JP2002275225A - Propylene-based polymer and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene-based polymer having high transparency, flexibility and mechanical strength and no waxiness, and to provide a method for producing the above polymer at low cost. SOLUTION: This propylene-based polymer essentially composed of block (I): a propylene homopolymer >=155 deg.C in melting point determined by DSC and block (II): a copolymer of a propylene containing 0.5-20 mol% of an α-olefin and a 2-20C α-olefin, is obtained by polymerization using a metallocene catalyst substantially constituted of metallocene singly. The propylene-based polymer thus obtained has the following characteristics: the low-crystalline component eluting at <40 deg.C when the polymer is put to temperature rising elution fractionation with o-dichlorobenzene accounts for <=10 wt.% of the whole polymer, and the melting point is lower than that of the polymer constituting the block (I).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a propylene-based polymer in the presence of a metallocene catalyst.

[0002]

2. Description of the Related Art A propylene-based block copolymer obtained by stepwise polymerizing propylene with ethylene or another α-olefin can improve the balance between rigidity and impact resistance. In order to meet performance requirements, various manufacturing methods have been proposed to improve the balance between the rigidity and the impact resistance.

Further, a production method has been proposed in which propylene-based block copolymerization is carried out in the presence of a catalyst comprising a metallocene compound and a co-catalyst to improve the physical properties such as low-temperature impact resistance (Japanese Patent Application Laid-Open No. Hei 4-1992). 337308, JP-A-5-202152, JP-A-6-206921, JP-T8-510491, WO95 / 27
740, WO95 / 27741, etc.).

The present applicant has also proposed an improved propylene block copolymer using a metallocene compound and / or a method for producing a propylene block copolymer (JP-A-6-287257, JP-A-11-22861).
No. 2, JP-A-11-240929).

[0005] In these proposals, a rubbery copolymer having a high ethylene content is produced in the second stage polymerization step, and an incompatible polymer blend is substantially mixed with the polymer produced in the first stage. It can be seen that it is formed in a specific way.

On the other hand, when a copolymer having a relatively low ethylene content is polymerized in the second stage polymerization step, a compatible polymer blend is formed together with the polymer produced in the first stage. It is thought possible. In addition, such polymers can generally have improved transparency and flexibility as compared to incompatible polymer blends produced by the prior art.

Japanese Patent Publication No. 2001-500176 proposes a method for producing such a polymer by using a metallocene catalyst.
Since the polymer was produced using various metallocenes, the operation was complicated, and the melting point of propylene homopolymer, which is a constituent component of the polymer, was as low as less than 151 ° C.

[0008]

According to the present invention, a propylene-based polymer which is excellent in transparency, flexibility and mechanical strength and has no stickiness can be obtained, and the propylene-based polymer can be obtained at low cost. It is intended to provide a manufacturing method.

[0009]

Means for Solving the Problems The present inventors have found that a metallocene catalyst is used to provide a propylene-based polymer which is excellent in transparency, flexibility and mechanical strength and has no stickiness, and
As a result of intensive studies on a method for producing the propylene-based polymer at low cost, the present invention has been reached.

That is, the present invention relates to a propylene polymer essentially consisting of the following block (I) and block (II) and polymerized using a metallocene catalyst substantially composed of a single metallocene. When the polymer was fractionated at elevated temperature by elution with orthodichlorobenzene, the low crystalline component eluted at less than 40 ° C. was 10% by weight based on the total amount of the polymer.
The present invention provides a propylene-based polymer, wherein the melting point of the polymer measured by DSC is lower than the melting point of the polymer forming the block (I) measured by DSC.

Block (I): A propylene homopolymer having a melting point of 155 ° C. or higher as measured by DSC.

Block (II): Propylene having an α-olefin content of 0.5 to 20 mol% and ethylene and / or
Or a copolymer with an α-olefin having 4 to 20 carbon atoms.

[0013] The present invention also relates to a propylene homopolymer in the first stage in the presence of the above-mentioned propylene polymer wherein the α-olefin is ethylene, substantially a single metallocene catalyst, The α-olefin content is 0.5 to 2 in the presence of the first stage catalyst and polymer.
A process for producing a propylene-based polymer, characterized by obtaining the above-mentioned propylene-based polymer by copolymerizing 0 mol% of propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms, The catalyst is
[A] Metallocene, [B] a co-catalyst component selected from an ion-exchange layered compound other than silicate or an inorganic silicate, and if necessary, [C] an auxiliary component comprising an organoaluminum compound And a method for producing the propylene-based polymer wherein the metallocene is a transition metal compound represented by the following general formula (1c): Is provided.

[0014]

Embedded image

(In the general formula (1c), A ¹ and A ^{2 each} represent a conjugated 5-membered ring ligand (A ¹ and A ² may be the same or different in the same compound) The carbon of the conjugated five-membered ring that is not bonded to the group Q may have a substituent, and at least one conjugated five-membered ring ligand is bonded to an adjacent substituent on the conjugated five-membered ring. A condensed ring of 7 to 10 members formed including two atoms of a 5-membered ring, and Q is a bonding group bridging two conjugated 5-membered ring ligands at any position, M
Represents a transition metal atom selected from Group 4 of the periodic table, and X and Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an amino group, a halogenated hydrocarbon group bonded to M. , An oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, and a silicon-containing hydrocarbon group. )

Further, the present invention relates to a method for producing an organic aluminum compound represented by the general formula (4):

AlR ¹ _m Z _3-m (4)

Wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, Z is hydrogen, a halogen, an alkoxy group or an aryloxy group, and m is a number satisfying 0 <m ≦ 3. Certain methods for producing the propylene-based polymer described above,
An object of the present invention is to provide a method for producing the above-mentioned propylene-based polymer in which the polymerization in the step and the second step is performed in a liquid monomer mainly composed of propylene.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The propylene polymer of the present invention comprises:
It consists essentially of block (I) and block (II). Here, “consisting substantially of block (I) and block (II)” means that, in addition to a so-called true block copolymer in which block (I) and block (II) are each present on a unit polymerized chain, Also includes physical mixtures of blocks.

In general, a method of first producing a block (I) (first stage polymerization step) and then producing a block (II) in a second stage polymerization step is often used. In the propylene-based polymer of the present invention, the weight average molecular weight is 10,000 to 1,500,000, preferably 3
0.00-1,000,000, more preferably,
By controlling the molecular weight in the range of 50,000 to 800,000, excellent mechanical properties and moldability can be satisfied.

Block (I) is essentially a propylene homopolymer and has a melting point of 155 as measured by DSC.
° C or higher. In the present invention, the melting point measured by DSC is defined as a peak top temperature of a melting point peak. As described above, by making the high melting point propylene homopolymer a block (I), not only the mechanical strength of the polymer is improved, but also the block (I)
Is produced (first-stage polymerization step), and then, when the method of producing block (II) in the second-stage polymerization step is used, in the second-stage polymerization tank, block (I) replaces block (II). Since the morphology is included, the block (I) having high crystallinity covers the polymer particle surface, and the stickiness of the particle can be effectively suppressed.

The block (II) is a random copolymer of propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms.
The α-olefin content of 0 is 0.5 to 20 mol%. By keeping the content of the α-olefin at such a low level, the compatibility with the block (I) can be improved. Note that, as the α-olefin, ethylene or 1-butene is preferable, and ethylene is most preferable.

The propylene polymer of the present invention is polymerized using a metallocene catalyst substantially composed of a single metallocene. In the present invention, a substantially single metallocene means a substantially single metallocene in chemical constitution and steric structure. However, the racemate itself is treated as a single metallocene.

In the propylene polymer of the present invention, when the polymer is fractionated at elevated temperature by elution with orthodichlorobenzene, a low crystalline component eluted at a temperature lower than 40 ° C. is 10% by weight based on the total amount of the polymer. % Or less. This is because the metallocene catalyst is essentially a single site, and unlike a titanium trichloride-based catalyst or a magnesium chloride-supported titanium-based catalyst, the amount of low-crystalline components generated during polymerization is small.

Even when a metallocene catalyst is used, when a plurality of metallocene catalysts are used, the hydrogen response of each metallocene and the controllability of the molecular weight at the time of copolymerization are different. May occur. In the present invention, since substantially a single metallocene catalyst is used, it can be considered that such a problem does not occur in principle.

Further, the propylene-based polymer of the present invention is characterized in that the melting point of the polymer measured by DSC is lower than the melting point of the polymer forming the block (I). This can be considered to indicate that the compatibility between the block (II) and the block (I) is good.

Examples of the metallocene compound used in the present invention include compounds represented by the following general formulas (1a) and (1b).

[0028] ^{_{R 2 k (CpR 3 n)}} (CpR 3 n) MR 4 2 (1a) [R 2 k (CpR 3 n) (CpR 3 n) MR 4 (R 5) x] + [R 6] - (1b)

In the formula, each CpR ³ _n represents a cyclopentadienyl group or a substituted cyclopentadienyl group which may be the same or different, and R ² represents a covalent bond containing any of carbon, silicon and germanium. A crosslinking group,
³ is hydrogen, halogen, which may be the same or different,
A silicon-containing group, a hydrocarbon group having 1 to 20 carbon atoms which may have a halogen substituent, an alkoxy group, or an aryloxy group, wherein two R ³ are two adjacent groups of a cyclopentadienyl ring. When it is present at a carbon atom, it is bonded to each other and has 4 carbon atoms including 2 atoms of a cyclopentadienyl ring.
And 10 to 10 rings may be formed. R ⁴ is hydrogen which may be the same or different, halogen, a silicon-containing group, a hydrocarbon group having 1 to 20 carbon atoms which may have a halogen substituent, an alkoxy group, an aryloxy group, and k is 0 or 1, each n is a non-negative integer satisfying k + n = 5, M is a metal of Group 4 of the periodic table, and R ⁵ is M
Is a neutral ligand capable of coordinating with x> 0, and [R
⁶ ] represents a counter anion capable of stabilizing a metal cation.

Specific examples of R ² include methylene, alkylene such as ethylene, ethylidene, propylidene, isopropylidene, phenylmethylidene,
Alkylidene group such as diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methylisopropylsilylene group, methyl-t- Silicon-containing cross-linking groups such as butylsilylene groups, dimethylgermylene groups, diethylgermylene groups, dipropylgermylene groups, diisopropylgermylene groups, diphenylgermylene groups, methylethylgermylene groups, methylphenylgermylene groups, methyl Examples thereof include a germanium-containing cross-linking group such as an isopropylgermylene group and a methyl-t-butylgermylene group.

Specific examples of R ³ include halogen such as hydrogen, fluorine, chlorine, bromine and iodine, silicon-containing groups such as trimethylsilyl, triethylsilyl and triphenylsilyl, methyl, ethyl and n-. Propyl group, isopropyl group, n-butyl group, isobutyl group, t
-Alkyl groups such as butyl group, n-pentyl group, isopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, and decyl group, phenyl group, tolyl group, and naphthyl group. Aryl group, chloromethyl group, halohydrocarbon group containing halogen such as chloroethyl group, methoxy group, ethoxy group, propoxy group, alkoxy group such as butoxy group,
An aryloxy group such as a phenoxy group, a methylphenoxy group, and a pentamethylphenoxy group can be given. When two R ³ are present at two adjacent carbon atoms of a cyclopentadienyl ring, they are bonded to each other to form an indenyl group, a tetrahydroindenyl group, a fluorenyl group, an octahydrofluorenyl group. And so on. Among them, R ³ is preferably hydrogen, a methyl group, an ethyl group, an indenyl group formed by combining two R ³ , a tetrahydroindenyl group,
It is a fluorenyl group.

Specific examples of R ⁴ include halogen such as hydrogen, fluorine, chlorine, bromine and iodine, silicon-containing groups such as trimethylsilyl, triethylsilyl and triphenylsilyl, methyl, ethyl and n-. Propyl group, isopropyl group, n-butyl group, isobutyl group, t
-Alkyl groups such as butyl group, n-pentyl group, isopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, and decyl group, phenyl group, tolyl group, and naphthyl group. Aryl group, chloromethyl group, halohydrocarbon group containing halogen such as chloroethyl group, methoxy group, ethoxy group, propoxy group, alkoxy group such as butoxy group,
An aryloxy group such as a phenoxy group, a methylphenoxy group, and a pentamethylphenoxy group can be given. Among them, R ⁴ is preferably hydrogen, chlorine or methyl.

Specific examples of R ⁵ include neutral ligands such as tetrahydrofuran, dimethyl ether and diethyl ether.

Specific examples of R ⁶ include anions such as tetraphenylborate, tetra (p-tolylborate), tetra (pentafluorphenyl) borate, carbadodecaborate and dicarboundecaborate.

When M is zirconium, specific examples of the transition metal compound include: (1) dichloro [1,1′-dimethylsilylenebis (2
-Methylindenyl) zirconium] (2) Dichloro [1,1′-dimethylsilylenebis (2,4-dimethylindenyl) zirconium] (3) Dichloro [1,1′-dimethylsilylenebis (2
-Methyl-4-phenylindenyl) zirconium] (4) Dichloro [1,1′-dimethylsilylenebis (2
-Methyl-4-isopropylindenyl) zirconium] (5) Dichloro [1,1′-dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium] (6) Dichloro [1,1′-dimethylsilylenebis (2
-Ethyl-4-methylindenyl) zirconium] (7) dichloro [1,1′-dimethylsilylenebis (2
-Ethyl-4-phenylindenyl) zirconium] (8) Dichloro [1,1′-ethylenebis (2-methylindenyl) zirconium] (9) Dichloro [1,1′-ethylenebis (2,4-dimethyl) (Indenyl) zirconium] (10) dichloro [1,1′-ethylenebis (2-methyl-4-phenylindenyl) zirconium] (11) dichloro [1,1′-ethylenebis (2-methyl-4-isopropyl) (12) Dichloro [1,1'-ethylenebis (2-methyl-4-naphthylindenyl) zirconium] (13) Dichloro [1,1'-ethylenebis (2-ethyl-4-methyl) (14) Dichloro [1,1′-ethylenebis (2-ethyl-4-phenylindenyl) zirconium] ( 5) Dichloro [1,1′-dimethylsilylenebis (2-methyltetrahydroindenyl) zirconium] (16) Dichloro [1,1′-dimethylsilylenebis (2,4-dimethyltetrahydroindenyl) zirconium] (17) Dichloro [1,1'-dimethylsilylenebis (2-methyl-4-phenyltetrahydroindenyl)
Zirconium] (18) Dichloro [1,1′-dimethylsilylenebis (2-methyl-4-isopropyltetrahydroindenyl) zirconium] (19) Dichloro [1,1′-dimethylsilylenebis (2-methyl-4-naphthyl) Tetrahydroindenyl)
Zirconium] (20) Dichloro [1,1′-dimethylsilylenebis (2-ethyl-4-methyltetrahydroindenyl) zirconium] (21) Dichloro [1,1′-dimethylsilylenebis (2-ethyl-4-phenyl) Tetrahydroindenyl)
Zirconium] (22) Dichloro [1,1′-ethylenebis (2-methyltetrahydroindenyl) zirconium] (23) Dichloro [1,1′-ethylenebis (2,4-
Dimethyltetrahydroindenyl) zirconium] (24) Dichloro [1,1′-ethylenebis (2-methyl-4-phenyltetrahydroindenyl) zirconium] (25) Dichloro [1,1′-ethylenebis (2-methyl- 4-isopropyltetrahydroindenyl) zirconium] (26) dichloro [1,1'-ethylenebis (2-methyl-4-naphthyltetrahydroindenyl) zirconium] (27) dichloro [1,1'-ethylenebis (2- Ethyl-4-methyltetrahydroindenyl) zirconium] (28) Dichloro [1,1′-ethylenebis (2-ethyl-4-phenyltetrahydroindenyl) zirconium] (29) Chloro [1,1′-dimethylsilylenebis (Indenyl) zirconium] (tetraphenylborate)
(Tetrahydrofuran) (30) Chloro [1,1′-ethylenebis (indenyl) zirconium] (tetraphenylborate) (tetrahydrofuran) and the like. Also, titanium compounds,
As for other Group 4 transition metal compounds such as hafnium compounds, the same compounds as described above can be mentioned.

Among the metallocene compounds used in the present invention, a particularly preferred compound is a compound represented by the following formula (1c).

[0037]

Embedded image

(In the general formula (1c), A ¹ and A ^{2 each} represent a conjugated 5-membered ring ligand (A ¹ and A ² may be the same or different in the same compound) The carbon of the conjugated five-membered ring that is not bonded to the group Q may have a substituent, and at least one conjugated five-membered ring ligand is bonded to an adjacent substituent on the conjugated five-membered ring. A condensed ring of 7 to 10 members formed including two atoms of a 5-membered ring, and Q is a bonding group bridging two conjugated 5-membered ring ligands at any position, M
Represents a transition metal atom selected from Group 4 of the periodic table, and X
And Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an amino group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, 1 shows a silicon-containing hydrocarbon group. )

Typical examples of the conjugated 5-membered ring ligand include a substituted cyclopentadienyl group. Specific examples of the substituent include those having usually 1 carbon atom.
-20, preferably 1-15 hydrocarbon groups. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, phenyl group, naphthyl group, Butenyl, butadienyl, and triphenylcarbyl groups.

The substituents other than the above hydrocarbon groups include
Examples include hydrocarbon residues containing atoms such as silicon, oxygen, nitrogen, phosphorus, boron, and sulfur. Typical examples include methoxy, ethoxy, phenoxy, furyl, trimethylsilyl, diethylamino, diphenylamino, pyrazolyl, indolyl, carbazolyl, dimethylphosphino, diphenylphosphino, diphenylboron. , A dimethoxyboron group, a thienyl group and the like.

Other substituents include a halogen atom or a halogen-containing hydrocarbon group. Typical examples are chlorine, bromine, iodine, fluorine, trichloromethyl, chlorophenyl, chlorobiphenyl,
Examples thereof include a chloronaphthyl group, a trifluoromethyl group, a fluorophenyl group, a fluorobiphenyl group, a fluoronaphthyl group, and a pentafluorophenyl group.

As described above, at least one of A ¹ and A ² is bonded to an adjacent substituent on the conjugated 5-membered ring ligand, and has at least one of 7 to 10 members including 2 atoms of the 5-membered ring. To form a fused ring. Specific examples of such compounds include compounds such as azulene and derivatives thereof.

More specifically, a hydroazulenyl group,
Methylhydroazulenyl group, ethylhydroazulenyl group, dimethylhydroazulenyl group, methylethylhydroazulenyl group, methylisopropylhydroazulenyl group, methylphenylisopropylhydroazulenyl group,
Hydrogenated forms of various azulenyl groups, bicyclo- [6.3.0]
-Undecanyl group, methyl-bicyclo- [6.3.0]
-Undecanyl group, ethyl-bicyclo- [6.3.0]
-Undecanyl group, phenyl-bicyclo- [6.3.
0] -undecanyl group, methylphenyl-bicyclo-
[6.3.0] -undecanyl group, ethylphenyl-bicyclo- [6.3.0] -undecanyl group, methyldiphenyl-bicyclo- [6.3.0] -undecanyl group,
Methyl-bicyclo- [6.3.0] -undecadienyl group, methylphenyl-bicyclo- [6.3.0] -undecadienyl group, ethylphenyl-bicyclo- [6.
3.0] -undecadienyl group, methylisopropyl-
A bicyclo- [6.3.0] -undecadienyl group, a bicyclo- [7.3.0] -dodecanyl group and derivatives thereof,
Examples include a bicyclo- [7.3.0] -dodecadienyl group and its derivative, a bicyclo- [8.3.0] -tridecanyl group and its derivative, and a bicyclo- [8.3.0] -tridecadienyl group and its derivative. Is done.

Examples of the substituent of each of the above groups include the above-mentioned hydrocarbon groups, hydrocarbon groups containing atoms such as silicon, oxygen, nitrogen, phosphorus, boron and sulfur, halogen atoms and halogen-containing hydrocarbon groups. No.

Q represents a linking group that bridges the two conjugated 5-membered ring ligands at any position. That is, Q is a divalent linking group, and crosslinks A ¹ and A ² . Although there is no particular limitation on the type of Q, specific examples thereof include (a) a divalent hydrocarbon group or halogenated hydrocarbon group having usually 1 to 20, preferably 1 to 12 carbon atoms, specifically, Alkylene group, cycloalkylene group, unsaturated hydrocarbon group such as arylene, haloalkylene group, halocycloalkylene group,
(B) a silylene group or an oligosilylene group, (c) a silylene group or an oligosilylene group having a hydrocarbon group or a halogenated hydrocarbon group having usually 1 to 20, preferably 1 to 12 carbon atoms as a substituent, (d) ) Germylene group,
And (e) a germylene group having a hydrocarbon group or a halogenated hydrocarbon group having usually 1 to 20 carbon atoms as a substituent. Among them, a silylene group or a germylene group having an alkylene group, a cycloalkylene group, an arylene group, or a hydrocarbon group as a substituent is preferable.

M represents a transition metal atom selected from Group 4 of the periodic table, and is preferably zirconium or hafnium.

X and Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an amino group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a phosphorus-containing group bonded to M. It represents a hydrocarbon group or a silicon-containing hydrocarbon group. The number of carbon atoms in each of the above hydrocarbon groups is usually 1 to 20, preferably 1 to 12. Among these, a hydrogen atom, a chlorine atom, a methyl group, an isobutyl group, a phenyl group, a dimethylamino group, and a diethylamino group are preferred.

Specific examples of the compound represented by the general formula (1c) include the following compounds. (31) dichloro [1,1′-dimethylsilylenebis (2-methyl-4H-azulenyl)] hafnium (32) dichloro [1,1′-dimethylsilylenebis (2,4-dimethyl-4H-azulenyl)] hafnium (33) dichloro [1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4H-azulenyl)] hafnium (34) dichloro [1,1′-dimethylsilylenebis (2-methyl-4-isopropyl-) 4H-azulenyl)] hafnium (35) dichloro [1,1′-dimethylsilylenebis (2-methyl-4-cyclohexyl-4H-azulenyl)] hafnium (36) dichloro [1,1′-dimethylsilylenebis (2- Methyl-4-naphthyl-4H-azulenyl)] hafnium (37) dichloro [1,1′-dimethylsilylene bi (2-Ethyl-4H-azulenyl)] hafnium (38) Dichloro [1,1′-dimethylsilylenebis (2-ethyl-4-methyl-4H-azulenyl)] hafnium (39) Dichloro [1,1′-dimethyl Silylenebis (2-ethyl-4-phenyl-4H-azulenyl)] hafnium (40) dichloro [1,1′-dimethylsilylenebis (2-ethyl-4-isopropyl-4H-azulenyl)] hafnium (41) dichloro [ 1,1′-dimethylsilylenebis (2-ethyl-4-cyclohexyl-4H-azulenyl)] hafnium (42) dichloro [1,1′-dimethylsilylenebis (2-ethyl-4-naphthyl-4H-azulenyl)] Hafnium (43) dichloro [1,1′-ethylenebis (2-methyl-4H-azulenyl)] hafnium ( 4) dichloro [1,1'-ethylenebis (2,4
Dimethyl-4H-azulenyl)] hafnium (45) Dichloro [1,1'-ethylenebis (2-methyl-4-phenyl-4H-azulenyl)] hafnium (46) Dichloro [1,1'-ethylenebis (2- Methyl-4-isopropyl-4H-azulenyl)] hafnium (47) dichloro [1,1′-ethylenebis (2-methyl-4-cyclohexyl-4H-azulenyl)] hafnium (48) dichloro [1,1′-ethylene Bis (2-methyl-4-naphthyl-4H-azulenyl)] hafnium (49) dichloro [1,1′-ethylenebis (2-ethyl-4H-azulenyl)] hafnium (50) dichloro [1,1′-ethylene Bis (2-ethyl-4-methyl-4H-azulenyl)] hafnium (51) dichloro [1,1′-dimethylsilylenebis 2-ethyl-4-phenyl-4H-azulenyl)] hafnium (52) dichloro [1,1′-dimethylsilylenebis (2-ethyl-4-isopropyl-4H-azulenyl)] hafnium (53) dichloro [1,1 '-Ethylenebis (2-ethyl-4-cyclohexyl-4H-azulenyl)] hafnium (54) dichloro [1,1'-ethylenebis (2-ethyl-4-naphthyl-4H-azulenyl)] hafnium (55) dichloro [1,1′-dimethylsilylenebis (2-benzyl-4-phenyl-4H-azulenyl)]
Hafnium (56) dichloro [1,1'-dimethylsilylenebis (2-heptyl-4-phenyl-4H-azulenyl)]
Hafnium (57) dichloro [1,1'-dimethylsilylenebis (2-octyl-4-phenyl-4H-azulenyl)]
Hafnium (58) dichloro {1,1'-dimethylsilylenebis [2- (1-phenylethyl) -4-phenyl-4H-
Azulenyl] {hafnium (59) dichloro} 1,1'-dimethylsilylenebis [2- (2-phenylethyl) -4-phenyl-4H-
Azulenyl] @hafnium (60) dichloro [1,1'-dimethylsilylenebis (2-methyl-4-phenyl-6-isopropyl-4H
-Azulenyl)] hafnium (61) dichloro [1,1′-dimethylsilylenebis (2-ethyl-4-phenyl-6-isopropyl-4H)
-Azulenyl)] hafnium (62) dichloro [1,1′-dimethylsilylenebis (2-propyl-4-phenyl-6-isopropyl-4)
H-azulenyl)] hafnium (63) dichloro [1,1′-dimethylsilylenebis (2-isopropyl-4-phenyl-6-isopropyl-4H-azulenyl)] hafnium (64) dichloro [1,1′-dimethylsilylene Bis (2-phenyl-4-phenyl-6-isopropyl-4
H-azulenyl)] hafnium (65) dichloro [1,1′-dimethylsilylenebis (2-methyl-4-phenyl-7-isopropyl-4H)
-Azulenyl)] hafnium (66) dichloro [1,1′-dimethylsilylenebis (2-ethyl-4-phenyl-7-isopropyl-4H)
-Azulenyl)] hafnium (67) dichloro [1,1′-dimethylsilylenebis (2-propyl-4-phenyl-7-isopropyl-4)
H-azulenyl)] hafnium (68) dichloro [1,1′-dimethylsilylenebis (2-isopropyl-4-phenyl-7-isopropyl-4H-azulenyl)] hafnium (69) dichloro [1,1′-dimethylsilylene Bis (2-phenyl-4-phenyl-7-isopropyl-4
H-azulenyl)] hafnium (70) dichloro {1,1 ′-[di (chloromethyl) silylene] bis (2-methyl-4-phenyl-4H-azulenyl} hafnium (71) dichloro} 1,1 ′-[ Di (4-chlorophenyl) silylene] bis (2-methyl-4-phenyl-4H
-Azulenyl {hafnium (72) dichloro} 1,1'-dimethylmethylenebis [2-methyl-4- (4-biphenylyl) -4H-azulenyl] {hafnium (73) dichloro} 1,1'-dimethylsilylenebis [ 2-methyl-4- (4-biphenylyl) -4H-azulenyl] {hafnium (74) dichloro {1,1′-dimethylgermylene bis [2-methyl-4- (4-biphenylyl) -4H-azulenyl]} Hafnium (75) dichloro {1,1'-ethylenebis [2-methyl-4- (4-biphenylyl) -4H-azulenyl]}
Hafnium (76) dichloro {1,1'-trimethylenebis [2-
Methyl-4- (4-biphenylyl) -4H-azulenyl] {hafnium (77) dichloro} 1,1'-dimethylsilylenebis [2-ethyl-4- (4-biphenylyl) -4H-azulenyl]} hafnium (78 ) Dichloro {1,1′-dimethylsilylenebis [2-isopropyl-4- (4-biphenylyl) -4H]
-Azulenyl] {hafnium (79) dichloro} 1,1′-dimethylsilylenebis [2-n-propyl-4- (4-biphenylyl) -4H
-Azulenyl] {hafnium (80) dichloro} 1,1′-dimethylsilylenebis [2-phenyl-4- (4-biphenylyl) -4H-azulenyl] {hafnium (81) dichloro} 1,1′-dimethylsilylenebis [2-Methyl-4- (2-fluoro-4-biphenylyl) -4H-azulenyl] {hafnium (82) dichloro} 1,1'-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4- Biphenylyl) -4H-azulenyl] {hafnium (83) dichloro} 1,1'-dimethylsilylenebis [2-isopropyl-4- (2-fluoro-4-biphenylyl) -4H-azulenyl] {hafnium (84) dichloro} 1,1′-dimethylsilylenebis [2-n-propyl-4- (2-fluoro-4-biphenylyl) -4H-azuleni Hafnium (85) dichloro} 1,1′-dimethylsilylenebis [2-phenyl-4- (2-fluoro-4-biphenylyl) -4H-azulenyl] {hafnium (86) dichloro} 1,1′- Dimethylsilylenebis [2-methyl-4- (2,6-difluoro-4-biphenylyl) -4H-azulenyl] {hafnium (87) dichloro} 1,1′-dimethylsilylenebis [2-methyl-4- (2 , 6-Dichloro-4-biphenylyl) -4H-azulenyl] {hafnium (88) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (2,6-dimethyl-4-biphenylyl) -4H- Azulenyl] {hafnium (89) dichloro} 1,1′-dimethylsilylenebis [2-methyl-4- (2,6-diethyl-4-biphenylyl) -4H -Azulenyl] {hafnium (90) dichloro} 1,1′-dimethylsilylenebis [2-methyl-4- (2′-fluoro-4-biphenylyl) -4H-azulenyl] {hafnium (91) dichloro} 1,1 '-Dimethylsilylenebis [2-methyl-4- (3'-fluoro-4-biphenylyl) -4H-azulenyl] {hafnium (92) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- ( 4'-fluoro-4-biphenylyl) -4H-azulenyl] {hafnium (93) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (2 ', 6'-difluoro-4-biphenylyl)- 4H-azulenyl] {hafnium (94) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (2 ', 6'-dichloro-4-biphenylyl) 4H-azulenyl] {hafnium (95) dichloro {1,1'-dimethylsilylenebis [2-methyl-4- (4'-chloro-2 ', 6'-difluoro-4-biphenylyl) -4H-azulenyl]} Hafnium (96) dichloro {1,1′-dimethylsilylenebis [2-methyl-4- (2 ′, 4 ′, 6′-trichloro-
4-biphenylenyl) -4H-azulenyl] {hafnium (97) dichloro} 1,1′-dimethylsilylenebis [2-methyl-4- (2 ′, 4 ′, 6′-trimethyl-
4-biphenylyl) -4H-azulenyl] {hafnium (98) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (4'-chloro-2 ', 6'-dimethyl-4-biphenylyl)- 4H-azulenyl] {hafnium (99) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (3-biphenylyl) -4H-azulenyl] {hafnium (100) dichloro} 1,1'-dimethylsilylene Bis [2-ethyl-4- (3-biphenylyl) -4H-azulenyl] {hafnium (101) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (2-fluoro-3-biphenylyl)- 4H-azulenyl] {hafnium (102) dichloro} 1,1'-dimethylsilylenebis [2-ethyl-4- (2-fluoro-3-biphenyli) Le) -4H-azulenyl] {hafnium (103) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (1-naphthyl) -4H-azulenyl] {hafnium (104) dichloro} 1,1 ' -Dimethylsilylenebis [2-ethyl-4- (1-naphthyl) -4H-azulenyl] {hafnium (105) dichloro} 1,1'-dimethylsilylenebis [2-isopropyl-4- (1-naphthyl) -4H -Azulenyl] {hafnium (106) dichloro} 1,1′-dimethylsilylenebis [2-n-propyl-4- (1-naphthyl) -4H-azulenyl] {hafnium (107) dichloro} 1,1′-dimethyl Silylene bis [2-phenyl-4- (1-naphthyl) -4H-azulenyl] {hafnium (108) dichloro} 1,1'-dimethyl Lenbis [2-methyl-4- (2-naphthyl) -4H-azulenyl] {hafnium (109) dichloro} 1,1'-dimethylsilylenebis [2-ethyl-4- (2-naphthyl) -4H-azulenyl] {Hafnium (110) dichloro} 1,1′-dimethylsilylenebis [2-isopropyl-4- (2-naphthyl) -4H-azulenyl]} hafnium (111) dichloro {1,1′-dimethylsilylenebis [2- n-propyl-4- (2-naphthyl) -4H-azulenyl] {hafnium (112) dichloro} 1,1'-dimethylsilylenebis [2-phenyl-4- (2-naphthyl) -4H-azulenyl]} hafnium (113) Dichloro {1,1′-dimethylsilylenebis [2-methyl-4- (4-fluoro-1-naphthyl)-
4H-azulenyl] {hafnium (114) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (4-chloro-1-naphthyl) -4
H-azulenyl] {hafnium (115) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (4-methyl-1-naphthyl) -4
H-azulenyl] {hafnium (116) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (4-t-butyl-1-naphthyl)
-4H-azulenyl] {hafnium (117) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (5-fluoro-1-naphthyl)-
4H-azulenyl] {hafnium (118) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (5-chloro-1-naphthyl) -4
H-azulenyl] {hafnium (119) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (4-fluoro-2-naphthyl)-
4H-azulenyl] {hafnium (120) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (4-chloro-2-naphthyl) -4
H-azulenyl] {hafnium (121) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (5-fluoro-2-naphthyl)-
4H-azulenyl] {hafnium (122) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (5-chloro-2-naphthyl) -4
H-azulenyl] {hafnium (123) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (6-fluoro-2-naphthyl)-
4H-azulenyl] {hafnium (124) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (6-chloro-2-naphthyl) -4
H-azulenyl] {hafnium (125) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (7-fluoro-2-naphthyl)-
4H-azulenyl] {hafnium (126) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (7-chloro-2-naphthyl) -4
H-azulenyl] {hafnium (127) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (2,4,6-trimethylphenyl) -4H-azulenyl] {hafnium (128) dichloro} 1, 1'-dimethylsilylenebis [2-ethyl-4- (2,4,6-trimethylphenyl) -4H-azulenyl] {hafnium (129) dichloro} 1,1'-dimethylsilylenebis [2-isopropyl-4- (2,4,6-trimethylphenyl) -4H-azulenyl] {hafnium (130) dichloro} 1,1′-dimethylsilylenebis [2-n-propyl-4- (2,4,6-trimethylphenyl)- 4H-azulenyl] {hafnium (131) dichloro} 1,1'-dimethylsilylenebis [2-phenyl-4- (2,4,6-trimethyl Phenyl) -4H-azulenyl] {hafnium (132) dichloro} 1,1′-dimethylsilylenebis [2-methyl-4- (4-t-butylphenyl) -4H
-Azulenyl] {hafnium (133) dichloro} 1,1′-dimethylsilylenebis [2-ethyl-4- (4-t-butylphenyl) -4H
-Azulenyl] {hafnium (134) dichloro} 1,1'-dimethylsilylenebis [2-isopropyl-4- (4-t-butylphenyl)]
-4H-azulenyl] {hafnium (135) dichloro} 1,1'-dimethylsilylenebis [2-n-propyl-4- (4-t-butylphenyl)
-4H-azulenyl] {hafnium (136) dichloro} 1,1'-dimethylsilylenebis [2-phenyl-4- (4-t-butylphenyl) -4
H-azulenyl] {hafnium (137) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (4-t-butyl-3-chlorophenyl) -4H-azulenyl] {hafnium (138) dichloro} 1 , 1′-Dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-chlorophenyl) -4H-azulenyl] {hafnium (139) dichloro} 1,1′-dimethylsilylenebis [2-n- Propyl-4- (4-t-butyl-3-chlorophenyl) -4H-azulenyl] {hafnium (140) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (2,4,6-tri Isopropylphenyl) -4H-azulenyl] {hafnium (141) dichloro} 1,1′-dimethylsilylenebis [2-methyl-4- (3-t-butyl) Ruphenyl) -4H
-Azulenyl] {hafnium (142) dichloro} 1,1'-dimethylsilylenebis [2-methyl-4- (4-t-butyl-2-fluorophenyl) -4H-azulenyl] {hafnium (143) dichloro} 1 , 1'-Dimethylsilylenebis [2-methyl-4- (4-biphenylyl) -4H-5,
6,7,8-tetrahydroazulenyl] {hafnium (144) dichloro} 1,1′-dimethylsilylenebis [2-ethyl-4- (4-biphenylyl) -4H-5
6,7,8-tetrahydroazulenyl] {hafnium (145) dichloro} 1,1′-dimethylsilylenebis [2-isopropyl-4- (4-biphenylyl) -4H
-5,6,7,8-tetrahydroazulenyl] {hafnium (146) dichloro} 1,1'-dimethylsilylenebis [2-n-propyl-4- (4-biphenylyl) -4H
-5,6,7,8-tetrahydroazulenyl] {hafnium (147) dichloro} 1,1'-dimethylsilylenebis [2-phenyl-4- (4-biphenylyl) -4H-
5,6,7,8-tetrahydroazulenyl] {hafnium (148) dichloro} 1,1′-dimethylsilylenebis [2-methyl-4- (4-t-butylphenyl) -4H
-5,6,7,8-tetrahydroazulenyl] {hafnium (149) dichloro} 1,1'-dimethylsilylenebis [2-ethyl-4- (4-t-butylphenyl) -4H
-5,6,7,8-tetrahydroazulenyl] {hafnium (150) dichloro} 1,1'-dimethylsilylenebis [2-isopropyl-4- (4-t-butylphenyl)
-4H-5,6,7,8-tetrahydroazulenyl]}
Hafnium (151) dichloro {1,1'-dimethylsilylenebis [2-n-propyl-4- (4-t-butylphenyl)]
-4H-5,6,7,8-tetrahydroazulenyl]}
Hafnium (152) dichloro {1,1′-dimethylsilylenebis [2-phenyl-4- (4-t-butylphenyl) -4]
H-5,6,7,8-tetrahydroazulenyl] @hafnium

In the above compound, one or both of the dichlorides forming the X and Y moieties are a hydrogen atom, a fluorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an isobutyl group, a phenyl group, a fluorophenyl group. Compounds substituted for a group, benzyl group, methoxy group, dimethylamino group, diethylamino group and the like can also be exemplified.

Further, compounds in which the central metal (M) of the compounds exemplified above is replaced by titanium or zirconium instead of hafnium can also be exemplified. Among these, zirconium and hafnium are preferred, and hafnium is particularly preferred.

In the present invention, an organic aluminum oxy compound represented by the following general formulas (2a), (2b) and (2c) can be used as the component [B].

[0052]

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In each of the formulas, R ⁷ represents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably a hydrocarbon residue having 1 to 6 carbon atoms. A plurality of R ⁷ may be the same or different. P represents an integer of 0 to 40, preferably 2 to 30.

The compounds represented by the general formulas (2a) and (2b) are compounds also called aluminoxanes, and are obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminums with water. Specifically, (a) methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane obtained from one kind of trialkylaluminum and water, (b) obtained from two kinds of trialkylaluminum and water Can be
Methyl ethyl aluminoxane, methyl butyl aluminoxane, methyl isobutyl aluminoxane and the like can be mentioned. Among these, methylaluminoxane and methylisobutylaluminoxane are preferred. The above aluminoxanes may be used in combination of two or more. The above aluminoxane can be prepared under various known conditions.

The compound represented by the general formula (2c) can be obtained by mixing one or more trialkylaluminums or two or more trialkylaluminums with an alkylboronic acid represented by the following general formula (2d). It can be obtained by a 1: 1 (molar ratio) reaction.

R ⁸ -B (OH) ₂ (2d)

In the general formula (2d), R ⁸ has 1 to 1 carbon atoms.
0, preferably a hydrocarbon residue having 1 to 6 carbon atoms or a halogenated hydrocarbon group.

Specifically, the following reaction products: (a) a 2: 1 reactant of trimethylaluminum and methylboronic acid, (b) a 2: 1 reactant of triisobutylaluminum and methylboronic acid, (C) 1: 1: 1 reactant of trimethylaluminum, triisobutylaluminum and methylboronic acid, (d) 2: 1 reactant of trimethylaluminum and ethylboronic acid, (e) 2: 1 reactant of triethylaluminum and butylboronic acid And the like.

Further, as a component of the metallocene catalyst of the present invention, an ionic compound which can react with the metallocene to convert the metallocene into a cation may be used. Examples of such a compound include a compound represented by the general formula (3).

[K] ^{n +} [Z] ⁿ⁻ (3)

In the general formula (3), K is a cation component, for example, carbonium cation, tropylium cation, ammonium cation, oxonium cation,
Examples include a sulfonium cation and a phosphonium cation. 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 cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, Dicyclohexylammonium, triphenylphosphonium, trimethylphosphonium, tris (dimethylphenyl) phosphonium, tris (dimethylphenyl) phosphonium, tris (methylphenyl) phosphonium, triphenylsulfonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, Silver ion, gold ion, platinum ion, copper ion, palladium ion, mercury ion, ferrocenium ion And the like.

In the above general formula (3), Z is an anion component, which is a component (generally a non-coordinating component) that becomes a counter anion to the cation species to which the metallocene has been converted. As Z, for example, an organic boron compound anion,
Examples thereof include an organic aluminum compound anion, an organic gallium compound anion, an organic arsenic compound anion, and an organic antimony compound anion. Specific examples include the following compounds. That is, (a) tetraphenylboron, tetrakis (3,4,5-trifluorophenyl) boron, tetrakis @ 3,5-bis (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-bis (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-bis (trifluoromethyl) phenyl} gallium, tetrakis {3,5-di (t-butyl) phenyl} gallium, tetrakis (pentafluorophenyl)
Gallium, etc., (d) tetraphenyl phosphorus, tetrakis (pentafluorophenyl) phosphorus, etc., (e) tetraphenyl arsenic, tetrakis (pentafluorophenyl) arsenic, etc., (f) tetraphenyl antimony, tetrakis (pentafluorophenyl) antimony, etc. , (G) decaborate, undecaborate, carbadodecaborate, decachlorodecaborate and the like.

Further, as a component of the metallocene catalyst of the present invention, a Lewis acid, particularly a Lewis acid capable of converting a metallocene into a cation may be used. Specifically, various organic boron compounds, metal halide compounds, solid acids and the like are exemplified, and more specifically, the following compounds can be exemplified. That is, (a) triphenylboron,
Organic boron compounds such as tris (3,5-difluorophenyl) boron and tris (pentafluorophenyl) boron, (b) aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, magnesium bromide, magnesium iodide, chloride Metal halide compounds such as magnesium bromide, magnesium chloride iodide, magnesium bromide iodide, magnesium chloride hydride, magnesium chloride hydroxide, magnesium bromide hydroxide, magnesium chloride alkoxide, magnesium bromide alkoxide, (c) alumina, silica -Solid acids such as alumina can be used.

As the component [B] constituting the metallocene catalyst of the present invention, a component selected from ion-exchange layered compounds other than silicates or inorganic silicates can be used.

Ion-exchangeable layered compound except silicate
Are surfaces whose surfaces are weakly
A compound that has a crystal structure stacked in parallel with the resultant force.
In which the ions contained are exchangeable. Specifically
Is hexagonal close packing type, antimony type, CdCl_Two
Type, CdI_TwoIonic crystal with layered crystal structure such as type
Compounds and the like. More specifically
Is α-Zr (HAsO_Four)_TwoH _TwoO, α-Zr (HP
O_Four)_Two, Α-Zr (KPO_Four)_Two・ 3H_TwoO, α-Ti
(HPO_Four)_Two, Α-Ti (HAsO_Four)_Two・ H_TwoO, α-
Sn (HPO_Four)_Two・ H_TwoO, γ-Zr (HPO_Four)_Two, Γ
-Ti (HPO_Four)_Two, Γ-Ti (NH_FourPO_Four)_Two・ H_TwoO
And other crystalline salts of polyvalent metals.

Examples of the inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. They are,
A synthetic product may be used, or a naturally occurring mineral may be used.

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, mica minerals, such as chlorite, attapulgite, sepiolite, paigorskite, bentonite , Kibushi clay, gairome clay, hisingelite, pyrophyllite, ryokudeite group and the like. These may form a mixed layer.

Examples of artificial synthetic products include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

Of these specific examples, kaolins such as dickite, nacrite, kaolinite, and anoxite, halosites such as metahalosite and halosite, serpentine members such as chrysotile, lizardite, and antigolite are preferable. , Montmorillonite, zaukonite, beidellite, nontronite, saponite, hectorite and other smectites, vermiculite and other vermiculite minerals, illite, sericite, mica minerals and the like,
Synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, and particularly preferably montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite and other smectites, vermiculite and other vermiculite minerals, synthetic mica, synthetic hectorite, Synthetic saponite and synthetic teniolite.

These ion-exchange layered compounds other than silicates or inorganic silicates may be used as they are, but may be subjected to acid treatment with hydrochloric acid, nitric acid, sulfuric acid and / or the like, and / or
LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ ,
Li ₂ SO ₄ , MgSO ₄ , ZnSO ₄ , Ti (SO ₄ ) ₂ ,
It is preferable to perform a salt treatment such as Zr (SO ₄ ) ₂ and Al ₂ (SO ₄ ) ₃ . In the treatment, the corresponding acid and base may be mixed to form a salt in the reaction system, and the treatment may be performed. Further, shape control such as pulverization and granulation may be performed, and granulation is preferably performed in order to obtain a block copolymer having excellent particle properties. The above components are usually used after being dehydrated and dried.

In the present invention, the above components [A] and
Can be treated with an organoaluminum compound as an optional component [C] in accordance with the component [B], examples of the organic aluminum ^{_{compound, AlR 1 m Z 3-m}} (4) ( In the formula, R ^1, carbon The hydrocarbon group of the number 1 to 20, Z is
And hydrogen, a halogen, an alkoxy group or an aryloxy group, and m is a number 0 <m ≦ 3.

Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, or halogen or alkoxy-containing alkylaluminums such as diethylaluminum monochloride and diethylaluminum ethoxide, or diethylaluminum hydride And hydrogen-containing organoaluminum compounds such as diisobutylaluminum hydride. In addition, aluminoxanes such as methylaluminoxane shown as the component [B] can also be used. Of these, particularly preferred is trialkylaluminum. These optional components may be used in combination of two or more.

Furthermore, in the present invention, after the start and end of the first stage of the prepolymerization and polymerization, and before and after the start of the second stage of polymerization, the component [D] organoaluminum compound is newly added. Can be added.

As the [A] organoaluminum compound used as necessary, the same compounds as those exemplified in the section of the organoaluminum compound used as the component [C] can be used. When component [D] is used, component [C] and component [D] may be the same or different. Further, a plurality of components [D] may be used.

When the catalyst of the present invention is obtained by contacting the component [A], the component [B], the optional component [C], and the optional component [D], the contact method is not particularly limited.
This contact may be performed not only at the time of preparing the catalyst, but also at the time of prepolymerization with α-olefin or at the time of polymerization of α-olefin.

At the time of contact of each component of the catalyst or after the contact, a solid of a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or alumina may be coexistent or contacted.

The contact is carried out in an inert gas such as nitrogen, pentane,
It may be carried out in an inert hydrocarbon solvent such as hexane, heptane, toluene and xylene. It is preferable to use those solvents which have been subjected to an operation for removing poisonous substances such as water and sulfur compounds. The contact temperature is from 20 ° C. to the boiling point of the solvent to be used, particularly preferably from room temperature to the boiling point of the solvent to be used.

The amount of each component of the catalyst is such that when an ion-exchangeable layered compound other than silicate or an inorganic silicate is used as component [B], the amount of component [A] is 0 g per 1 g of component [B]. 0.0001 to 10 mmol, preferably 0.1 to 10 mmol.
001-5 mmol, and component [C] is 0-10,0
00 mmol, preferably 0.01 to 100 mmol. Further, the atomic ratio of the transition metal in the component [A] to the aluminum in the component [C] is 1: 0 to 1,000,000,
Preferably, it is 1: 0.1 to 100,000.

The catalyst thus obtained may be used after washing with an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene, or may be used without washing.

At the time of washing, a new component [C] may be used in combination as needed. The amount of the component [C] used at this time is 1: 0 to 10,000 in terms of the atom of aluminum in the component [C] with respect to the transition metal in the component [A].
It is preferable that

As the catalyst, ethylene, propylene, 1-
Butene, 1-hexene, 1-octene, 4-methyl-1
Α-Olefins such as -pentene, 3-methyl-1-butene, vinylcycloalkane, and styrene are preliminarily polymerized and, if necessary, washed and used.
This prepolymerization may be carried out in an inert gas such as nitrogen, or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene.

In the present invention, the production of the propylene polymer can be carried out in two stages. The polymerization reaction is carried out in the presence or absence of a liquid such as an inert hydrocarbon such as propane, butane, hexane, heptane or toluene or a liquefied α-olefin. Of these, polymerization is preferably carried out in a liquefied α-olefin or in the substantial absence of a solvent.

As described above, when the production of a propylene-based polymer is carried out in two stages, in the first stage, a propylene homopolymer is produced in the presence of the above-mentioned metallocene catalyst.
Usually, the polymerization temperature and the polymerization time are selected so that the amount of the polymer obtained in the first step is 5 to 95% by weight of the total amount of the produced polymer. The polymerization temperature is usually selected from the range of 20 to 150 ° C, preferably 0 to 100 ° C. Hydrogen is preferred as the molecular weight regulator.

In the present invention, the MFR of the polymer produced in the first step is 0.1 to 10,000 g / 10 min,
Preferably, 0.2 to 1,000 g / 10 min, DS
The catalyst and polymerization conditions are set so that the melting point measured at C is 155 ° C. or higher. When the MFR is out of the above range, the quality of the finally obtained polymer is deteriorated and the moldability is poor. Further, when the melting point measured by DSC is out of the above range, it is not preferable because it may cause a reduction in rigidity and a stickiness of a finally obtained resin product.

As a method for controlling the MFR of a polymer,
Examples include (1) a method of controlling the hydrogen concentration, (2) a method of controlling the polymerization temperature, and (3) a method of controlling the type and supply amount of a chain transfer agent such as organozinc. From these, select a preferred method according to the purpose,
The MFR of the polymer can be controlled alone or in combination of two or more. A commonly used method is to control the MFR by controlling the hydrogen concentration.

The methods for controlling the melting point measured by DSC to be 155 ° C. or more include (1) a method for controlling the structure of metallocene, (2) a method for controlling the polymerization temperature, and (3) a method for controlling the polymerization temperature. And a method of controlling the MFR. Among these, the melting point of the polymer can be controlled by using a preferred method according to the purpose alone or by combining a plurality of methods. Of these,
The methods commonly used are (1) a method for controlling the structure of the metallocene and (2) a method for controlling the polymerization temperature, and particularly preferably (1) a method for controlling the structure of the metallocene. In controlling the melting point by controlling the structure of the metallocene, it is generally considered that (a)
(B) the position and structure of the substituent on the 5-membered ring ligand; Resconi et al. , Ch
em. Rev .. , 100, 1253-1345 (200
0), etc., and serve the purpose (a),
(B) can be selected.

Next, in the second step, propylene is copolymerized with ethylene and / or an α-olefin having 4 to 20 carbon atoms in the presence of the metallocene catalyst-containing polymer produced in the first step to obtain an α-olefin. Content is 0.5 to 20 mol%
Is produced. As for the amount of the polymer obtained in the second step, the polymerization temperature and the polymerization time are usually selected so as to be 5 to 95% by weight based on the total amount of the produced polymer. The polymerization temperature is generally selected from the range of 0 to 100 ° C, preferably 20 to 90 ° C.

In the present invention, the melting point measured by DSC of the polymer obtained after the completion of the second polymerization step is lower than the melting point measured by DSC of the polymer formed in the first step;
The temperature is preferably at least 2 ° C, more preferably at least 5 ° C, particularly preferably at least 10 ° C.

In the present invention, the MFR of the polymer
Is from 0.01 to 1,000 g / 10 min,
It is desirable to set the polymerization conditions. If the MFR is out of this range, it is not preferable because physical properties and moldability are reduced.

In the propylene polymer of the present invention,
When the polymer is fractionated at elevated temperature by elution with orthodichlorobenzene, the low-crystalline component eluted at a temperature lower than 40 ° C. is at most 10% by weight, preferably at most 5% by weight, more preferably at most 5% by weight, based on the total amount of the polymer. 2% by weight or less, particularly preferably 0.1% by weight.
1% by weight or less. If the amount of the low-crystalline component is larger than this, stickiness is likely to occur in the finally obtained resin product, which is not preferable.

[0092]

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not restricted by these examples unless departing from the gist of the present invention.

In the examples, the separation of the polymer by heating and elution was performed using Mitsubishi Chemical CFC-T-102L. Also, orthodichlorobenzene was used as a solvent.

The melting point of the polymer was determined by the following method using a thermal analysis system TA2000 manufactured by DuPont. After melting the sample (about 5 to 10 mg) at 200 ° C. for 3 minutes, the temperature was lowered to 30 ° C. at a rate of 10 ° C./min.
The temperature was raised to 200 ° C. at a rate of 10 ° C./min to obtain a melting curve.

Example 1 (1) Dichloro {1,1′-dimethylsilylenebis [2
-Ethyl-4- (2-fluoro-4-biphenylyl)-
Synthesis of racemic [4H-azulenyl]} hafnium 2-fluoro-4-bromobiphenyl (6.35 g, 2
5.3 mmol) in a mixed solvent of diethyl ether (50 ml) and n-hexane (50 ml), and a solution of t-butyllithium in n-pentane (33 ml, 50.6
(mmol, 1.54N) at 78 ° C. The mixture was stirred at 10 ° C for 2 hours, and 2-ethylazulene (3.5
5g, 22.8 mmol) and stirred at room temperature for 2 hours. n-Hexane (30 ml) was added, and the supernatant was removed by decantation. This operation was repeated once. To the obtained yellow precipitate, n-hexane (30 ml) and tetrahydrofuran (40 ml) were added at 0 ° C. Then, N-methylimidazole (50 ml) and dimethyldichlorosilane (1.4 ml, 11.4 mmol)
l) was added, and the mixture was heated to room temperature and stirred at room temperature for 1 hour.
Thereafter, dilute hydrochloric acid was added, and the mixture was separated. The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-
A crude product (8.3 g) of biphenyl) -1,4-dihydroazulene) was obtained.

Next, the crude product obtained above was dissolved in diethyl ether (30 ml), and n-butyllithium n-hexane solution (14.9 ml, 22.8 m
mol, 1.53N), the temperature was gradually raised, and the mixture was stirred at room temperature overnight. Further, toluene (200 ml) was added, the mixture was cooled to 70 ° C., and hafnium tetrachloride (3.6 g, 1 g) was added.
(1.4 mmol), and the mixture was gradually heated and stirred at room temperature for 4 hours. Most of the solvent was distilled off from the obtained slurry under reduced pressure, diethyl ether (50 ml) was added, and the obtained slurry was filtered. Diethyl ether (5 ml
× 2), ethanol (15 ml × 2), and n-hexane (10 ml × 2).
Racemic / meso mixture of dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azulenyl]｝ hafnium (4.53 g, 42% yield)
was gotten. The obtained racemic / meso mixture was treated with ¹ H-NM
As a result of analysis by R, racemic 76.6%, meso 23.
It was found to be a 4% mixture.

The racemic / meso mixture obtained here (4.
5 g) was suspended in dichloromethane (35 ml) and irradiated with light using a high-pressure mercury lamp (100 W) for 1 hour. The solvent was distilled off under reduced pressure, and toluene (25 ml) and dichloromethane (11 ml) were added to the obtained solid. Dichloromethane was distilled off under reduced pressure to precipitate crystals. The obtained crystals were filtered, washed twice with hexane (5 ml), and dried under reduced pressure to obtain a racemic form (1.79 g).

(2) Production of Component [B] and Contact of Component [C] 55.85 g of demineralized water, 32.70 g of sulfuric acid and 8.01 g of lithium hydroxide were added to a 500-ml round bottom flask, and the mixture was stirred. (Mizusawa Smectite manufactured by Mizusawa Chemical Co., Ltd.) was added, and the mixture was heated and refluxed under reflux.
Treated for 0 minutes. After adding 300 ml of demineralized water and performing suction filtration, the solid component was dispersed in 600 ml of demineralized water and suction filtered. This operation was repeated once more. The residue obtained by filtration was dried at 100 ° C. to obtain chemically treated montmorillonite.

[0099] 1.05 g of the chemically treated montmorillonite obtained here was collected in a 100 ml round bottom flask, and dried by heating at 200 ° C under reduced pressure for 2 hours. A toluene solution of triethylaluminum (0.5 mmol / m
l) was added under purified nitrogen (4.0 ml) and the mixture was added at room temperature for 30 minutes.
After the reaction for 2 minutes, the mixture was washed twice with 30 ml of toluene to obtain a toluene slurry containing the component [B].

(3) Preliminary polymerization The slurry obtained in Example 1 (2) (solid content: 91%)
(Containing 4.2 mg), toluene was extracted, and the amount of residual toluene was adjusted to 1.0 ml. A slurry of triisobutylaluminum in toluene (0.5 mmol /
ml, 0.5 ml), and dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azulenyl] synthesized in Example 1 (1). A racemic solution of hafnium in toluene (3.0 mmol / ml, 9.2 ml) was added, and the mixture was stirred at room temperature for 1 hour to obtain a catalyst slurry.

Into a 2-liter induction-stirring autoclave, 40 ml of toluene and the entire amount of the catalyst slurry were introduced under purified nitrogen. 11.0 g of propylene was introduced under stirring, and prepolymerization was performed at 30 ° C. for 2 hours and then at 50 ° C. for 0.5 hour. After the pre-polymerization, unreacted propylene was purged and the pressure was replaced by 0.5 MPa with purified nitrogen twice, and then the pre-polymerization catalyst was taken out. This contained 9.7 g of polymer per 1 g of component [B].

(4) Polymerization A 2-liter induction-stirring autoclave having a built-in stirrer was replaced with purified nitrogen, and then 750 g of liquefied propylene was charged at 25 ° C. Triisobutylaluminum in toluene (0.1 mmol / ml, 5.0
ml) at the same temperature, and the temperature was raised to 70 ° C.
Then, 51.3 mg of the catalyst slurry obtained in Example 1 (3) was added as the component [B] to initiate the first stage polymerization. After 1 hour, the total pressure was 3.36 MPa. Next, ethylene was added so that the total pressure became 3.67 MPa, and the second stage polymerization was started. Thirty minutes after the start of the second stage polymerization, unreacted ethylene and propylene were purged to terminate the polymerization. The amount of the obtained propylene-based polymer was 167 g.

(5) Analysis of Polymer The melting point of a small amount of the propylene homopolymer extracted during the polymerization in the first stage was measured by DSC and found to be 158.1 ° C. As a result of monitoring the amount of generated heat, the amount of the catalyst extracted with the polymer was small, and the extraction operation did not substantially affect the polymerization.

The second polymer contained in the finally obtained polymer
The content of the copolymer obtained in the step was calculated from the generated heat of polymerization, and was 42.8% by weight. ¹³ C-NM
The ethylene content in the finally obtained polymer was measured by R, and the ethylene content in the copolymer obtained in the second step was determined from the result and the content of the copolymer obtained in the second step. It was 2.4 mol% as determined.

The amount of low-crystalline components (components eluted at a temperature of less than 40 ° C. when the polymer is fractionated at elevated temperature with o-dichlorobenzene) contained in the finally obtained polymer is 0%. 0.0% by weight. The weight average molecular weight of the polymer finally obtained was 64,000, and the number average molecular weight was 1
It was 68,000.

Example 2 (1) Polymerization Example 1 was repeated except that the polymerization time in the second stage was 1 hour.
Polymerization was performed in the same manner as in (4). The yield of the polymer finally obtained was 228 g.

(2) Analysis of Polymer The melting point of a small amount of the propylene homopolymer extracted during the polymerization in the first stage was 158.1 ° C. as measured by DSC. As a result of monitoring the amount of generated heat, the amount of the catalyst extracted with the polymer was small, and the extraction operation did not substantially affect the polymerization.

The second polymer contained in the finally obtained polymer
The content of the copolymer obtained in the step was calculated from the amount of polymerization heat generated, and was 58.4% by weight. ¹³ C-NM
The ethylene content in the finally obtained polymer was measured by R, and the ethylene content in the copolymer obtained in the second step was determined from the result and the content of the copolymer obtained in the second step. The calculated value was 3.4 mol%.

The amount of low-crystalline components (components eluted at a temperature of less than 40 ° C. when the polymer is separated by heating and eluting with orthodichlorobenzene) contained in the finally obtained polymer is 0%. 0.0% by weight. The weight average molecular weight of the finally obtained polymer was 58,900, and the number average molecular weight was 1
It was 550,000.

Comparative Example 1 (1) Production of Component [B] and Contact of Component [C] In a 500 ml round bottom flask, 196.50 g of demineralized water, 51.25 g of sulfuric acid and 12.45 g of lithium hydroxide were added and stirred. Thereafter, 51.65 g of montmorillonite (Mizusawa Chemical, Mizusawa Smectite) was added, and the mixture was heated and refluxed for 280 minutes. After adding 1600 ml of deionized water and centrifuging, the supernatant was removed. After removal, this operation was repeated twice more, and the residue was filtered. The residue obtained by filtration was dried at 100 ° C. to obtain chemically treated montmorillonite.

0.5 g of the chemically treated montmorillonite obtained here was collected in a 100 ml round bottom flask,
It was dried by heating at 200 ° C. for 2 hours. To this was added a toluene solution of triethylaluminum (0.45 mmol / m
l) was added under purified nitrogen (2.3 ml), and the mixture was added at room temperature for 30 minutes.
After reacting for 2 minutes, the mixture was washed twice with 20 ml of toluene to obtain a toluene slurry containing the component [B].

(2) Preparation of catalyst The dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4) synthesized in Example 1 (1) was used.
-Biphenylyl) -4H-azulenyl] {a solution of racemic hafnium in toluene (1.0 mmol as racemic)
l / ml, 1.8 ml) in a toluene solution of triisobutylaluminum (10 mmol / ml, 1.8 m2).
l) was added and stirred at room temperature for 5 minutes. The slurry containing component [B] prepared in Comparative Example 1 (1) (2.6) was added to this solution.
The resulting mixture was stirred at room temperature for 40 minutes to obtain a catalyst slurry.

(3) Polymerization A 2-liter induction stirring autoclave having a built-in anchor type stirring blade was replaced with purified nitrogen, and 61.0 mg of the catalyst slurry obtained in Comparative Example 1 (2) was added as a solid catalyst component. Next, 50 g of liquefied propylene was charged. Then, the mixture was stirred at 35 ° C for 10 minutes. Triisobutylaluminum in toluene (0.1 mmol / ml, 3.0
ml), and 625 g of liquefied propylene were charged.
The temperature was raised to 5 ° C. over 6 minutes, and at 65 ° C., a mixed gas of hydrogen and nitrogen (30 ml as hydrogen in a standard state) was supplied to initiate polymerization. The above-mentioned mixed gas of nitrogen and hydrogen was added at an interval of 10 minutes from the start of the polymerization to keep the hydrogen concentration in the system almost constant. After one hour, unreacted propylene,
Hydrogen and nitrogen were purged to terminate the first stage polymerization. The hydrogen concentration in the first stage, that is, the ratio of hydrogen / (hydrogen + propylene) in the gas phase of the autoclave was 0.076 mol% on average. The polymer yield in the first stage was weighed and the yield of polypropylene was determined to be 327 g. The melting point by DSC of this first stage polymer was 156.0 ° C.

After 35 g of the obtained polypropylene was withdrawn under a flow of purified nitrogen, the temperature was raised to 65 ° C. with stirring, and propylene gas and ethylene gas were heated at 65 ° C. so that the total polymerization pressure became 2.0 MPa. To the second
The stage polymerization was started. A mixed gas of propylene and ethylene was supplied so that the total polymerization pressure was kept constant at 2.0 MPa, and a polymerization reaction was performed at 65 ° C. for 27 minutes. The molar ratio between propylene and ethylene in the supplied mixed gas was 6
It was 5/35. The molar ratio of propylene to ethylene in the autoclave was 43/56 on average.

After completion of the polymerization, unreacted propylene and ethylene were purged to obtain 352 g of a white powdery propylene / ethylene / block copolymer. The content of the copolymer obtained in the second step contained in the obtained block copolymer was 17.0% by weight, and the ethylene content in the copolymer was 35 mol%. The amount of the low-crystalline component (the component which elutes at a temperature lower than 40 ° C. when the polymer is separated by heating and eluting with orthodichlorobenzene) contained in the finally obtained polymer is 18.4% by weight. %.

[0116]

According to the present invention, it is possible to produce a propylene-based polymer which is free from stickiness due to a low crystallinity component and has high flexibility and transparency at a low cost. Therefore, the present invention is industrially valuable.

Continued on front page F-term (reference) 4J026 HA04 HA27 HA32 HA41 HB02 HB04 HB27 4J028 AA01A AB00A AB01A AC01A AC10A AC20A BA00A BA01B BA02B BB00A BB01B BB02B BC05B BC11B BC12B BC14B BC25B BC39 EC02 GA01 EB01 EB01 AB01 AC01 AC10 AC20 AD00 BA00A BA01B BA02B BB00A BB01B BB02B BC05B BC11B BC12B BC14B BC25B BC42B CA07C CA30C EA02 EB04 EC01 ED01 ED02 ED03 ED04 GA18 GA19

Claims (7)

[Claims] 1. A propylene polymer which is essentially composed of the following block (I) and block (II) and is polymerized using a metallocene catalyst substantially composed of a single metallocene. Is less than 40% by weight based on the total amount of the polymer when eluted at elevated temperature with o-dichlorobenzene, and the melting point of the polymer measured by DSC is less than block (I). A propylene-based polymer having a melting point lower than the melting point measured by DSC of the polymer forming Block (I): a propylene homopolymer having a melting point of 155 ° C. or higher as measured by DSC. Block (II): α-olefin content is 0.5 to 20
A copolymer of propylene, which is mol%, and an α-olefin having 2 to 20 carbon atoms. 2. The propylene polymer according to claim 1, wherein the α-olefin is ethylene. 3. In the presence of a substantially sole metallocene catalyst,
In the first stage, propylene homopolymerization is performed,
In the stage, in the presence of the catalyst and the polymer of the first stage, α
-The propylene polymer according to claim 1 is obtained by copolymerizing propylene having an olefin content of 0.5 to 20 mol% with ethylene and / or an α-olefin having 4 to 20 carbon atoms. A method for producing a propylene polymer. 4. A metallocene catalyst comprising: [A] a metallocene;
[B] a product obtained by contacting a co-catalyst component selected from an ion-exchangeable layered compound other than silicate or an inorganic silicate and, if necessary, an auxiliary component comprising [C] an organoaluminum compound The method for producing a propylene-based polymer according to claim 3, comprising: [5] The metallocene represented by the following general formula (1c):
The method for producing a propylene-based polymer according to claim 3 or 4, which is a transition metal compound represented by the following formula: Embedded image (In the general formula (1c), A ¹ and A ^{2 each} represent a conjugated five-membered ring ligand (A ¹ and A ² may be the same or different in the same compound). The carbon of the conjugated 5-membered ring that is not bonded may have a substituent, and at least one conjugated 5-membered ring ligand is formed by bonding an adjacent substituent on the conjugated 5-membered ring to form a 5-membered ring. Has a 7-10 membered condensed ring formed including two ring atoms, Q is a bonding group bridging two conjugated 5-membered ring ligands at any position, and M is a periodic table X represents a transition metal atom selected from Group 4;
Each independently a hydrogen atom, a halogen atom, a hydrocarbon group, an amino group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a silicon-containing hydrocarbon bonded to M Represents a group. ) 6. The organic aluminum compound represented by the general formula (4): AlR ¹ _m Z _3-m (4) wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and Z is
The method for producing a propylene-based polymer according to claim 4 or 5, wherein the compound is a compound represented by hydrogen, a halogen, an alkoxy group or an aryloxy group, and m is a number satisfying 0 <m ≦ 3. 7. The process for producing a propylene-based polymer according to claim 3, wherein the polymerization in the first and second stages is carried out in a liquid monomer mainly composed of propylene.