JP2003105029A - Olefin polymer and its production process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefin polymer which has a narrow particle diameter distribution and uniform melting point properties on measuring the particle diameter of every product, and excels in the uniformity of a composition aspect, can reduce the trouble of fine powders such as agglomeration/adhesion to realize an industrial long-term, stable operation from the production aspect, and can produce molded articles having a reduced amount of gels, fish eyes and the like and excellent external appearance due to the possession of the above properties in film molding, blow molding, injection molding and the like, and a catalyst which has a high olefin polymerization activity, can quickly increase the particle diameter in a reactor to reduce the trouble of fine powders such as agglomeration/adhesion, and furthermore does not cause particle fragmentation. SOLUTION: The olefin polymer (particle) can be obtained by an olefin polymerization catalyst composed of [A1] a hafnium compound or zirconium compound which has at least one conjugated 5-membered cyclic ligand, [A2] a zirconium compound having at least one conjugated 5-membered cyclic ligand other than the compound [A1], and [B] a phyllosilicate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymer,
The present invention relates to polymer particles and a method for producing the same. More specifically, it relates to a polymer particle having a narrow particle size distribution and a uniform melting point characteristic measured for each particle size of a product, and a method for producing the same.

[0002]

2. Description of the Related Art In producing an olefin polymer by polymerizing an olefin, there has been proposed a method using a catalyst composed of (1) a metallocene compound, (2) an ion-exchange layered compound, an inorganic silicate, etc. Kaihei 5-301
No. 917 and No. 8-127613). In the polymerization method using these catalysts, a conventional so-called methylalumoxane is used by supporting it on a carrier such as an inorganic oxide such as silica or alumina, or an organic substance (JP-A-60-350).
No. 07, No. 61-31404, No. 61-108610.
No. 61-276805, No. 61-296008, etc.), the polymerization activity is higher not only per transition metal and per Al but also per solid component. There has also been an attempt to improve the fluidity of catalyst particles and product polymer particles by making a clay mineral, which is a co-catalyst, into a spherical shape by spray granulation (JP-A-7-228621, etc.).

However, when olefins are polymerized with these catalysts, the polymerization activity is still insufficient, or the reactivity at the initial stage of polymerization (so-called initial activity) is low, causing aggregation and adhesion in the reactor. Easily fine powder particles, that is, low-activity particles increase, which hinders stable polymerization operation, or causes low-melting point particles due to compositional variations between particles,
Agglomeration and adhesion were increased to form adhered polymer and agglomerated polymer on the inner wall surface of the reactor, the inner wall of the product withdrawing pipe, the piping for the polymerization gas circulation system, etc., and it was difficult to industrially perform the polymerization operation for a long time.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and provides an olefin polymer having no adhesion or blockage on the inner wall surface of a reactor or the inner wall surface of a pipe. . Further, the present invention is to provide a method for industrially stably producing such an olefin polymer over a long period of time.

[0005]

The present invention has been made as a result of extensive studies for achieving the above object, and its gist is the hafnium compound or zirconium compound having at least one conjugated five-membered ring ligand [ [A1], a zirconium compound having at least one conjugated five-membered ring ligand, a compound [A2] different from [A1], and an olefin polymerization catalyst in the presence of a layered silicate [B]. It exists in the olefin polymer obtained by Further, the present invention has a particle size range of 45 to 3000 μm, when the particle size distribution of the polymer is measured by a sieving method.
The average particle size is 100 to 2000 μm, the difference between the maximum temperature (maximum Tmx) and the minimum temperature (minimum Tmx) of the melting points measured according to the particle size of the polymer is 3.0 ° C. or less, and the minimum particle size is the melting point (Tms) of the polymer. ) And the average melting point (Tm ₀ ) of all polymers satisfy the following formula (1). -1.2 ≤ Tms-Tm ₀ (1) Still another subject matter of the present invention is a hafnium compound or zirconium compound [A1] having at least one conjugated five-membered ring ligand, a conjugated five-membered conjugate. A zirconium compound having at least one cyclic ligand, which is different from [A1], a compound [A2], a layered silicate [B], and an organoaluminum compound [C], and [A1] is a catalyst for olefin polymerization. In a method for producing an olefin polymer, the olefin is polymerized in the presence of a catalyst having a molar ratio of 0.05 to 0.95 with respect to the total amount of [A1] and [A2]. Exist. In the present specification, the “hafnium compound or zirconium compound having at least one conjugated five-membered ring ligand” may be referred to as [A1] or component [A1]. “A zirconium compound having at least one conjugated five-membered ring ligand, which is different from [A1]”,
It may be referred to as [A2] or component [A2]. [A
1] and [A2] may be collectively referred to as [A] or component [A]. The layered silicate may be referred to as [B] or component [B]. The organoaluminum compound may be referred to as [C] or component [C].

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION [[A]] <Hafnium compound or zirconium compound [A1] having at least one conjugated five-membered ring ligand> [A1] used in the present invention is represented by the following general formula [1] , [2],
It is a compound represented by [3] or [4]. [Wherein A and A ′ are ligands having the same or different conjugated five-membered ring structures, Q is a bonding group bridging two conjugated five-membered ring ligands at any position, and M is Hf atom or Zr
An atom, Z is a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom bonded to M, a hydrogen atom, a halogen atom or a hydrocarbon group, and Q'is a conjugated five-membered ring system. A bonding group bridging Z at any position of the ligand,
X and Y represent a hydrogen atom bonded to M, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group, respectively. ]

A and A'are conjugated five-membered ring ligands,
As described above, these may be the same or different in the same compound. A typical example of this conjugated five-membered ring ligand is a conjugated carbon five-membered ring ligand, that is, a cyclopentadienyl group. The cyclopentadienyl group may have 5 hydrogen atoms, or may be a derivative thereof, that is, some of the hydrogen atoms may be substituted with a substituent.

One specific example of this substituent has 1 to 1 carbon atoms.
Although it is a hydrocarbon group of 20, preferably 1 to 12, this hydrocarbon group may be bonded to a cyclopentadienyl group as a monovalent group, and when there are a plurality of these, two of them are Each of them may be bonded at the other end (ω-end) to form a ring together with a part of the cyclopentadienyl group. As a typical example of the latter, those in which two substituents are bonded at their ω-ends to share two adjacent carbon atoms in the cyclopentadienyl group to form a condensed six-membered ring That is, an indenyl group can be mentioned. Further, a fluorenyl group in which two condensed 6-membered rings are bonded to the conjugated position of a cyclopentadienyl group and an azulenyl group forming a condensed 7-membered ring can be mentioned.

Therefore, a typical example of the conjugated five-membered ring ligand can be a substituted or unsubstituted cyclopentadienyl group, indenyl group or fluorenyl group, and azulenyl group. As the substituent of the cyclopentadienyl group, in addition to the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a halogen atom (eg, fluorine, chlorine, bromine), an alkoxy group (eg, C _{1 to} C ₁₂ ), silicon-containing hydrocarbon groups (for example, a silicon atom containing —Si (R ¹ ))
(A group having about 1 to 24 carbon atoms in the form of (R ² ) (R ³ )),
Phosphorus-containing hydrocarbon group (e.g., a phosphorus atom -P (R ¹⁾
(A group having about 1 to 18 carbon atoms in the form of (R ² )), a nitrogen-containing hydrocarbon group (for example, a nitrogen atom is —N (R ¹ ) (R ² ).
In the form of a group having about 1 to 18 carbon atoms) or a boron-containing hydrocarbon group (for example, a boron atom containing -B (R ¹ )).
(A group having about 1 to 18 carbon atoms in the form of (R ² )).
When there are a plurality of these substituents, the respective substituents may be the same or different.

Q is a bonding group which bridges between two conjugated five-membered ring ligands at any position, and Q'is a bonding group which bridges between any position of the conjugated five-membered ring ligand and a Z group. Represents a group. Specifically, Q and Q ′ are (a) a methylene group, an ethylene group,
1 to 1 carbon atoms such as isopropylidene group, phenylmethylmethylene group, diphenylmethylene group and cyclohexylene group
20 alkylene groups, (b) silylene groups, dimethylsilylene groups, phenylmethylsilylene groups, diphenylsilylene groups, disilylene groups, silylene groups such as tetramethyldisiylene groups, (ha) germanium, phosphorus, nitrogen, boron or aluminum A hydrocarbon group containing, specifically (C
H _{3) 2} Ge _{group, (C 6 H 5) 2} Ge group, (CH ₃₎ P group,
(C ₆ H ₅ ) P group, (C ₄ H ₉ ) N group, (C ₆ H ₅ ) N group,
(CH ₃ ) B group, (C ₄ H ₉ ) B group, (C ₆ H ₅ ) B group,
(C ₆ H ₅₎ Al group, a (CH ₃ O) Al group. Preferred are alkylene groups and silylene groups.

Z is a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom bonded to M, a hydrogen atom, a halogen atom or a hydrocarbon group.
Specific examples of preferable Z include oxygen (—O).
-), Sulfur (-S-), an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and 1 to 40 carbon atoms, preferably 1 To 18 silicon-containing hydrocarbon groups, 1 to 4 carbon atoms
0, preferably 1-18 nitrogen-containing hydrocarbon groups, 1-40 carbon atoms, preferably 1-18 phosphorus-containing hydrocarbon groups,
It is a hydrogen atom, chlorine, bromine, or a hydrocarbon group having 1 to 20 carbon atoms.

X and Y are each hydrogen, a halogen atom,
1 to 20 carbon atoms, preferably 1 to 10 hydrocarbon groups, 1 to 20 carbon atoms, preferably 1 to 10 alkoxy groups, amino groups, 1 to 20 carbon atoms, preferably 1 to 12 phosphorus-containing hydrocarbons A group (specifically, for example, a diphenylphosphine group) or a carbon number of 1 to 20, preferably 1 to 12
Is a silicon-containing hydrocarbon group (specifically, for example, a trimethylsilyl group or a bis (trimethylsilyl) methyl group). X and Y may be the same or different. Of these, a halogen atom, a hydrocarbon group (especially one having 1 to 8 carbon atoms) and an amino group are preferable.

Therefore, among the compounds represented by the general formula [1], [2], [3] or [4] which are preferable as the component [A1] in the catalyst for olefin polymerization according to the present invention, particularly preferable ones are as follows. It has the respective substituents of the contents. A, A ′ = cyclopentadienyl, n-butyl-cyclopentadienyl, dimethyl-cyclopentadienyl, diethyl-cyclopentadienyl, ethyl-n-butyl-cyclopentadienyl, ethyl-methyl-cyclopenta Dienyl, n-butyl-methyl-cyclopentadienyl, indenyl, 2-methyl-
Indenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl, 2-methyl-tetrahydroindenyl, 2-methyl-benzoindenyl, 4-hydroazulenyl, 2,4-dimethylhexahydroazulenyl,
2-Methyl-4-phenyl-4H-azurenyl, 2-methyl-4-phenyl-hexahydroazurenyl (in the above, the position of the substituent is preferably the 1-position and / or the 3-position) Q, Q '= Ethylene, dimethylsilylene, isopropylidene, Z = t-butylamide, phenylamide, cyclohexylamide, X, Y = chlorine atom, methyl, diethylamino.

In the present invention, the component [A1] is used as a mixture of two or more compounds within a group of compounds represented by the same general formula and / or between compounds represented by different general formulas. You can Below, M
Specific examples of the compound are given when is a Hf atom.

(A) A compound represented by the general formula [1], that is, a hafnium compound having no conjugated group Q and two conjugated five-membered ring ligands: (1) Bis (cyclopentadienyl) Hafnium dichloride, (2) bis (methylcyclopentadienyl) hafnium dichloride, (3) bis (dimethylcyclopentadienyl) hafnium dichloride, (4) bis (trimethylcyclopentadienyl) hafnium dichloride,
(5) Bis (tetramethylcyclopentadienyl) hafnium dichloride, (6) bis (pentamethylcyclopentadienyl) hafnium dichloride, (7) bis (i
-Propylcyclopentadienyl) hafnium dichloride, (8) bis (n-butylcyclopentadienyl) hafnium dichloride, (9) bis (t-butylcyclopentadienyl) hafnium dichloride, (10) bis (ethyl-n) -Butyl-cyclopentadienyl) hafnium dichloride,

(11) Bis (ethyl-methyl-cyclopentadienyl) hafnium dichloride, (12) bis (n-butyl-methyl-cyclopentadienyl) hafnium dichloride, (13) (cyclopentadienyl)
(N-Butyl-cyclopentadienyl) hafnium dichloride, (14) (cyclopentadienyl) (ethyl-
Methyl-cyclopentadienyl) hafnium dichloride, (15) (n-butylcyclopentadienyl) (dimethylcyclopentadienyl) hafnium dichloride,
(16) Bis (indenyl) hafnium dichloride,
(17) Bis (tetrahydroindenyl) hafnium dichloride, (18) bis (2-methylindenyl) hafnium dichloride, (19) bis (2-methyltetrahydroindenyl) hafnium dichloride, (20) bis (fluorenyl) hafnium dichloride ,

(21) Bis (cyclopentadienyl) hafnium monochloride monohydride, (22) bis (cyclopentadienyl) methylhafnium monochloride, (23) bis (cyclopentadienyl) ethylhafnium monochloride, ( 24) bis (cyclopentadienyl) phenyl hafnium monochloride, (25) bis (cyclopentadienyl) hafnium dimethyl, (2)
6) bis (cyclopentadienyl) hafnium diphenyl, (27) bis (cyclopentadienyl) hafnium dinopentyl, (28) bis (cyclopentadienyl) hafnium dihydride, (29) (cyclopentadienyl) (Indenyl) hafnium dichloride,
(30) (cyclopentadienyl) (fluorenyl) hafnium dichloride, (31) (cyclopentadienyl) (azurenyl) hafnium dichloride, etc.,

(B) A compound represented by the general formula [2], that is, a hafnium compound having a binding group Q, for example, (b-1) Q = alkylene group: (1) methylenebis (indenyl) hafnium dichloride, (2) Ethylenebis (indenyl) hafnium dichloride, (3) ethylenebis (indenyl) hafnium monochloride monohydride, (4) ethylenebis (indenyl) methylhafnium monochloride, (5)
Ethylene bis (indenyl) hafnium monomethoxide monochloride, (6) ethylene bis (indenyl) hafnium diethoxide, (7) ethylene bis (indenyl) hafnium dimethyl, (8) ethylene bis (4,
5,6,7-Tetrahydroindenyl) hafnium dichloride, (9) ethylenebis (2-methylindenyl)
Hafnium dichloride, (10) ethylenebis (2-ethylindenyl) hafnium dichloride,

(11) ethylenebis (2,4-dimethylindenyl) hafnium dichloride, (12) ethylene (2,4-dimethylcyclopentadienyl) (3 ',
5'-dimethylcyclopentadienyl) hafnium dichloride, (13) ethylene (2-methyl-4-t-butylcyclopentadienyl) (3'-t-butyl-5'-
Methylcyclopentadienyl) hafnium dichloride,
(14) ethylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′-trimethylcyclopentadienyl) hafnium dichloride, (15) ethylenebis (4-indenyl) hafnium dichloride, ( 1
6) ethylenebis [4- (2,7-dimethylindenyl)] hafnium dichloride, (17) ethylenebis (4-phenylindenyl) hafnium dichloride,
(18) isopropylidene bis (indenyl) hafnium dichloride, (19) isopropylidene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylpentadienyl) hafnium dichloride, (20) ethylenebis (indenyl) ) Hafnium monochloride monohydride,

(21) Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) hafnium dichloride, (22) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) hafnium mono Chloride monohydride, (23) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) hafnium dimethyl, (24) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) hafnium Diphenyl, (25) methylene (cyclopentadienyl) (trimethylcyclopentadienyl) hafnium dichloride, (26) methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) hafnium dichloride, (27) isopropylidene (cyclopene) Dienyl) (3,4-dimethyl cyclopentadienyl) hafnium dichloride, (28)
Isopropylidene (cyclopentadienyl) (2,3,
4,5-Tetramethylcyclopentadienyl) hafnium dichloride, (29) isopropylidene (cyclopentadienyl) (3-methylindenyl) hafnium dichloride, (30) isopropylidene (cyclopentadienyl) (fluorenyl) hafnium Dichloride,

(31) isopropylidene (2-methylcyclopentadienyl) (fluorenyl) hafnium dichloride, (32) isopropylidene (3-t-butylcyclopentadienyl) (fluorenyl) hafnium dichloride, (33) isopropylidene (2,5-Dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) hafnium dichloride, (34) isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, ( 35)
Ethylene (cyclopentadienyl) (3,5-dimethylpentadienyl) hafnium dichloride, (36) ethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, (37) ethylene (2,5-dimethylcyclopentadienyl) ) (Fluorenyl) hafnium dichloride, (38) ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, (39) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) Hafnium dichloride, (40) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) hafnium dichloride, (41) cyclohexylidene (cyclopentadienyl) (fluorenyl) hafnium dichloride, 42) cyclohexylidene (2,5
-Dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) hafnium dichloride,
(43) Dimethylmethylenebis [2-methyl-4- (4
-Biphenylyl) -4H-azulenyl] hafnium dichloride, (44) trimethylenebis [2-methyl-4-]
(4-biphenylyl) -4H-azulenyl] hafnium dichloride,

(B-2) Compound having Q = silylene group: (1) dimethylsilylenebis (indenyl) hafnium dichloride, (2) dimethylsilylenebis (4,5,5)
6,7-Tetrahydroindenyl) hafnium dichloride, (3) Dimethylsilylenebis (2-methylindenyl) hafnium dichloride, (4) Dimethylsilylenebis (2,4-dimethylindenyl) hafnium dichloride, (5) Dimethylsilylene Bis (2-methyl-4,
5,6,7-Tetrahydroindenyl) hafnium dichloride, (6) dimethylsilylenebis (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) hafnium dichloride, (7) dimethyl Silylenebis (2-methyl-4,5-benzoindenyl) hafnium dichloride, (8) Dimethylsilylenebis (2-methyl-4-phenylindenyl) hafnium dichloride, (9) Dimethylsilylenebis (2-methyl-4) , 4-Dimethyl-4,5,6,7-tetrahydro-4-cyraindenyl) hafnium dichloride, (1
0) dimethylsilylenebis [4- (2-phenylindenyl)] hafnium dichloride,

(11) Dimethylsilylenebis [4- (2
-T-butylindenyl) hafnium dichloride, (1
2) Dimethylsilylene bis [4- (2-phenyl-3-
Methylindenyl)] hafnium dichloride, (13)
Dimethylsilylene bis [4- (2-methyl-4,5,5
6,7-Tetrahydroindenyl)] hafnium dichloride, (14) phenylmethylsilylenebis (indenyl) hafnium dichloride, (15) phenylmethylsilylenebis (4,5,6,7-tetrahydroindenyl) hafnium dichloride, (16) ) Phenylmethylsilylene (2,4-dimethylcyclopentadienyl)
(3 ′, 5′-Dimethylcyclopentadienyl) hafnium dichloride, (17) phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl)
(2 ′, 4 ′, 5′-trimethylcyclopentadienyl) hafnium dichloride, (18) phenylmethylsilylenebis (tetramethylcyclopentadienyl) hafnium dichloride, (19) diphenylsilylenebis (indenyl) hafnium dichloride, ( 20) tetramethyldisilylenebis (indenyl) hafnium dichloride,

(21) Tetramethyldisilylenebis (cyclopentadienyl) hafnium dichloride, (22)
Tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) hafnium dichloride, (23)
Dimethylsilylene (cyclopentadienyl) (3,4-
Dimethylcyclopentadienyl) hafnium dichloride, (24) dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) hafnium dichloride, (25) dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) hafnium Dichloride, (26) dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) hafnium dichloride, (27) dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) hafnium dichloride, (28) ) Dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) hafnium dichloride, (29) dimethylsilylene (cyclopentadienyl) (fluorenyl)
Hafnium dichloride, (30) dimethyl silylene (3
-T-butyl-cyclopentadienyl) (fluorenyl) hafnium dichloride,

(31) Dimethylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride, (32) Dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) hafnium Dichloride, (33) dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) hafnium dichloride, (34) dimethylsilylene (2,5-dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, (35) dimethylsilylene ( 2-ethylcyclopentadienyl) (fluorenyl) hafnium dichloride, (36) dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, (37) diethylsilylene (2-methylcyclopentadiene) Le) (2 ', 7'-di -t- butyl-fluorenyl) hafnium dichloride, (38) dimethylsilylene (2,5-dimethyl-cyclopentadienyl)
(2 ′, 7′-di-t-butylfluorenyl) hafnium dichloride, (39) dimethylsilylene (2-ethylcyclopentadienyl) (2 ′, 7′-di-t-butylfluorenyl) hafnium Dichloride, (40) dimethylsilylene (diethylcyclopentadienyl) (2 ',
7'-di-t-butylfluorenyl) hafnium dichloride,

(41) Dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) hafnium dichloride, (42) Dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) hafnium dichloride, (43) Dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) hafnium dichloride, (44) dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) hafnium dichloride, (45) dimethylsilylene bis [1- (2-methyl-4-phenyl-4
H-azurenyl)] hafnium dichloride, (46) dimethylsilylenebis [2-i-propyl-4- (4-biphenylyl) -4H-azurenyl] hafnium dichloride, (47) dimethylsilylenebis [2-methyl-4-
(2-fluoro-4-biphenylyl) -4H-azulenyl] hafnium dichloride, (48) dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azulenyl] hafnium dichloride,
(49) Dimethylsilylenebis [2-methyl-4- (4
-Chlorophenyl) -4H-azurenyl] hafnium dichloride, (50) dimethylsilylene bis [2-methyl-4- (2 ', 6'-dimethyl-4-biphenylyl)-
4H-azurenyl] hafnium dichloride,

(51) Dimethylsilylenebis [2-methyl-4- (1-naphthyl) -4H-azulenyl] hafnium dichloride, (52) Dimethylsilylenebis [2-
i-Propyl-4- (1-naphthyl) -4H-azulenyl]} hafnium dichloride, (53) dimethylsilylenebis [2-ethyl-4- (2-naphthyl) -4H-azulenyl] hafnium dichloride, (54) dimethyl Silylenebis [2-i-propyl-4- (4-t-butylphenyl) -4H-azurenyl] hafnium dichloride, (55) dimethylsilylenebis [2-ethyl-4-
(9-anthryl) -4H-azurenyl] hafnium dichloride, (56) dimethylsilylene-1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]-
1- [2-methyl-4- (4-biphenylyl) indenyl] hafnium dichloride, (57) dimethylsilylene bis [2-methyl-4- (4-biphenylyl) -4H-
5,6,7,8-tetrahydroazulenyl] hafnium dichloride, etc.

(B-3) Q = Compound of hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum: (1) dimethylgermylene bis (indenyl) hafnium dichloride, (2) dimethylgermylene (cyclopentadiene) (Enyl) (fluorenyl) hafnium dichloride,
(3) Methylaluminum bis (indenyl) hafnium dichloride, (4) Phenylaluminum bis (indenyl) hafnium dichloride, (5) Phenylphosphinobis (indenyl) hafnium dichloride, (6)
Ethylholanobis (indenyl) hafnium dichloride, (7) phenylaminobis (indenyl) hafnium dichloride, (8) phenylamino (cyclopentadienyl) (fluorenyl) hafnium dichloride,
(9) Dimethylgermylene bis [2-methyl-4- (4
-Biphenylyl) -4H-azulenyl] hafnium dichloride,

(C) A compound represented by the general formula [3], that is, a hafnium compound having no conjugated group Q'and one conjugated five-membered ring ligand: (1) pentamethylcyclopentadienyl -Bis (phenyl) aminohafnium dichloride, (2) indenyl-bis (phenyl) amido hafnium dichloride,
(3) Pentamethylcyclopentadienyl-bis (trimethylsilyl) aminohafnium dichloride, (4) Pentamethylcyclopentadienylphenoxyhafnium dichloride, (5) Cyclopentadienylhafnium trichloride, (6) Pentamethylcyclopentadichloride Enyl hafnium trichloride, (7) cyclopentadienyl hafnium benzyl dichloride, (8) cyclopentadienyl hafnium dichlorohydride, (9) cyclopentadienyl hafnium triethoxide, and the like.

(D) A compound represented by the general formula [4], that is, a hafnium compound having one conjugated five-membered ring ligand bridged with a bonding group Q ': (1) dimethylsilylene (tetramethylcyclopentadiene) (Enyl) phenylamido hafnium dichloride, (2)
Dimethylsilylene (tetramethylcyclopentadienyl) -t-butylamido hafnium dichloride, (3)
Dimethylsilylene (indenyl) cyclohexylamide hafnium dichloride, (4) dimethylsilylene (tetrahydroindenyl) decylamide hafnium dichloride, (5) dimethylsilylene (tetrahydroindenyl) ((trimethylsilyl) amino) hafnium dichloride, (6) dimethylgermylene (Tetramethylcyclopentadienyl) (phenyl) aminohafnium dichloride and the like are exemplified.

Further, it is also possible to use the compounds of the above (a) to (d) in which chlorine is replaced with bromine, iodine, hydride, methyl, phenyl, diethylamide group or the like. In the above example, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product includes 1,2,3- and 1,2,4-substituted products. Including. In addition, when asymmetric carbon is generated in these metallocene-based transition metal compounds, unless otherwise specified, the stereoisomeric 1
Or a mixture thereof (including a racemate). Two or more types of component [A1] may be used.

As above, as [A1], the general formula [1],
A large number of hafnium compounds (when M is Hf atom) represented by [2], [3] or [4] are exemplified. Although illustration is omitted, a zirconium compound in which M is a Zr atom can be similarly used. A preferable compound as the component [A1] is a hafnium compound represented by the general formula [1]. Further, preferred [A1] is represented by the general formula [1
0] is a hafnium compound. (CpR ¹ R ² ) ₂ HfX ¹ X ² ... [10] (wherein Cp represents a cyclopentadienyl group, R ¹ ,
R ² is independently a halogen, hydrogen, a silicon-containing group, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group, an alkoxy group, an aryloxy group or an amino group, and R ¹ and R ² are They may combine with each other to form a ring. Further, X ¹ and X ² each independently represent a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group, an alkoxy group, an aryloxy group or an amide group. Here, R ¹ and R ² are preferably at the 1- and / or 3-position of the cyclopentadienyl group. )

<Compound [A2] which is a zirconium compound having at least one conjugated five-membered ring ligand and is different from [A1]> [A2] used in the present invention is represented by the following general formulas [5] and [5]. 6], [7] or [8]. [Wherein A and A ′ are ligands having the same or different conjugated five-membered ring structures, Q is a bonding group bridging two conjugated five-membered ring ligands at any position, and Z is A ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom, a hydrogen atom, a halogen atom or a hydrocarbon group, which is bonded to Zr, and Q ′ is any conjugated five-membered ring ligand. Position and Z
And X and Y each 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 bonded to Zr. ]

General formula [5], [6], [7] or [8]
The compound of 1 is limited to zirconium as the central transition metal element, hafnium or zirconium, as compared with the compound of the above general formula [1], [2], [3] or [4] representing the component [A1]. Other than that, they have the same structure. Therefore, the general formulas [5], [6],
The detailed description of the zirconium compound of [7] or [8] will be omitted, and only the important points will be described below.

General formula [5], [6], [7] or [8]
In, preferred are A, A ′ = cyclopentadienyl, n-butyl-cyclopentadienyl, dimethyl-cyclopentadienyl, diethyl-cyclopentadienyl, ethyl-n-butyl-cyclopentadienyl, Ethyl-methyl-cyclopentadienyl, n-butyl-methyl-cyclopentadienyl, indenyl, 2-methyl-indenyl, 2-methyl-4-phenylindenyl,
Tetrahydroindenyl, 2-methyl-tetrahydroindenyl, 2-methyl-benzoindenyl, 4-hydroazurenyl, 2,4-dimethylhexahydroazurenyl, 2-methyl-4-phenyl-4H-azurenyl, 2
-Methyl-4-phenyl-hexahydroazurenyl (in the above, the position of the substituent is preferably the 1-position and / or the 3-position) Q, Q '= ethylene, dimethylsilylene, isopropylidene, Z = t-butylamide , Phenylamide, cyclohexylamide, X, Y = chlorine atom, methyl, diethylamino.

Among them, the preferable zirconium compound is represented by the general formula [5]. Further, a preferable zirconium compound can be represented by the general formula [11]. (CpR ¹ R ² ) ₂ ZrX ¹ X ² ... [11] (wherein Cp represents a cyclopentadienyl group, R ¹ ,
R ² is independently a halogen, hydrogen, a silicon-containing group, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group, an alkoxy group, an aryloxy group or an amino group, and R ¹ and R ² are They may combine with each other to form a ring. Further, X ¹ and X ² each independently represent a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group, an alkoxy group, an aryloxy group or an amide group. Here, R ¹ and R ² are preferably at the 1- and / or 3-position of the cyclopentadienyl group. )

Examples of such preferable zirconium compounds are as follows. (1) bis (cyclopentadienyl) zirconium dichloride, (2) bis (methylcyclopentadienyl) zirconium dichloride, (3) bis (dimethylcyclopentadienyl) zirconium dichloride, (4) bis (trimethylcyclopentadiene (Enyl) zirconium dichloride, (5) bis (tetramethylcyclopentadienyl) zirconium dichloride, (6) bis (pentamethylcyclopentadienyl) zirconium dichloride,
(7) Bis (i-propylcyclopentadienyl) zirconium dichloride, (8) Bis (n-butylcyclopentadienyl) zirconium dichloride, (9) Bis (t-butylcyclopentadienyl) zirconium dichloride, (10) ) Bis (ethyl-n-butyl-cyclopentadienyl) zirconium dichloride,

(11) Bis (ethyl-methyl-cyclopentadienyl) zirconium dichloride, (12) bis (n-butyl-methyl-cyclopentadienyl) zirconium dichloride, (13) (cyclopentadienyl)
(N-Butyl-cyclopentadienyl) zirconium dichloride, (14) (cyclopentadienyl) (ethyl-methyl-cyclopentadienyl) zirconium dichloride, (15) (n-butylcyclopentadienyl)
(Dimethylcyclopentadienyl) zirconium dichloride, (16) bis (indenyl) zirconium dichloride, (17) bis (tetrahydroindenyl) zirconium dichloride, (18) bis (2-methylindenyl) zirconium dichloride, (19) bis (2-methyltetrahydroindenyl) zirconium dichloride,
(20) Bis (fluorenyl) zirconium dichloride,

(21) Bis (cyclopentadienyl) zirconium monochloride Monohydride, (22) bis (cyclopentadienyl) methylzirconium monochloride, (23) bis (cyclopentadienyl) ethylzirconium monochloride, ( 24) bis (cyclopentadienyl) phenyl zirconium monochloride, (2
5) bis (cyclopentadienyl) zirconium dimethyl, (26) bis (cyclopentadienyl) zirconium diphenyl, (27) bis (cyclopentadienyl)
Zirconium Dineopentyl, (28) Bis (cyclopentadienyl) zirconium dihydride, (29)
(Cyclopentadienyl) (indenyl) zirconium dichloride, (30) (cyclopentadienyl) (fluorenyl) zirconium dichloride, (31) (cyclopentadienyl) (azurenyl) zirconium dichloride, etc.,

<Combination of Component [A1] and Component [A2]>
In the present invention, [A1] and [A2] are used in combination. The usage rate will be described later.

<Layered Silicate [B]> [B] used in the present invention accounts for the majority of clay minerals. It is preferably an ion-exchange layered silicate. A layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with weak bonding forces. Most of the layered silicates are naturally produced mainly as the main components of clay minerals, but these layered silicates are not limited to those of natural origin, and may be synthetic products.

Specific examples of the layered silicate include known layered silicates described in Haruo Shiramizu, “Clay Mineralogy”, Asakura Shoten (1995), such as dickite,
Kaolins such as nakrite, kaolinite, anoxite, metahalloysite, halloysite, serpentine family such as chrysotile, risaldite, antigorite, montmorillonite, sauconite, beidellite, nontronite, saponite, teniolite, hectorite, stevensite. , Smectites such as bentonite and sauconite, vermiculites such as vermiculite, micas such as mica, illite, sericite and glauconite,
Attapulgite, sepiolite, palygorskite,
Examples include bentonite, pyrophyllite, talc, and chlorite. These may form a mixed layer.

Among these, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite,
Preferred are smectites such as teniolite, vermiculites, and mica. Typical examples of the smectites are montmorillonite, beidellite,
They are saponite, nontrolite, hectorite, sauconite and the like. "Ben clay SL" (Mizawa Chemical Co., Ltd.), "Kunipia", "Smecton" (Kunimine Industries Co., Ltd.), "Montmorillonite K10" (Aldrich, Jute Chemie), "K-Catalysts series" (Jute Chemie) It is also possible to use a commercial product such as a product manufactured by the company. Typical examples of the mica group include muscovite, paragonite, phlogopite, biotite, and lepidrite. Commercially available "Synthetic mica somasif" (made by Corp Chemical), "Fluorine phlogopite", "Fluorotetrasilicon mica",
Commercially available products such as "Teniolite" (all manufactured by Topy Industries, Ltd.) can also be used. More preferred are smectites such as "Ben clay SL".

In general, natural products are often non-ion-exchangeable (non-swellable), and in that case, they have ion-exchangeable (or swellable) properties in order to have preferable ion-exchangeable (or swellable) properties. It is preferable to carry out a treatment for imparting the property. Among such treatments, the following chemical treatments are particularly preferable. That is, it is preferable that these silicates are chemically treated. Here, as the chemical treatment, both surface treatment for removing impurities adhering to the surface and treatment for affecting the crystal structure and chemical composition of the layered silicate can be used. Specifically, (a) acid treatment, (b) alkali treatment, (c) salt treatment, (d) organic substance treatment and the like can be mentioned.

These treatments remove impurities on the surface, exchange cations between layers, and Al and F in the crystal structure.
It acts to elute cations such as e and Mg, and as a result, forms an ionic complex, a molecular complex, an organic derivative, etc., and can change the surface area, interlayer distance, solid acidity, and the like. These treatments may be performed alone or two or more treatments may be combined. As the (a) acid used in the chemical treatment, a purposeful inorganic acid or organic acid,
Preferred examples include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and the like, and (b) alkalis include NaOH and K.
OH, NH _{3 and the} like can be mentioned. (C) As salt, 2
At least one selected from the group consisting of group 14 to group 14 atoms
A compound composed of a cation containing one kind of atom and at least one kind of anion selected from the group consisting of a halogen atom or an anion derived from an inorganic acid or an organic acid is preferable.

More preferred are Li, Mg, Ca,
Al, Ti, Zr, Hf, V, Nb, Ta, Cr, M
n, W, Mn, Fe, Co, Ni, Cu, Zn, B, A
1, an ion derived from 1, Ge or Sn is used as a cation, and an ion derived from Cl, SO ₄ , NO ₃ , OH, C ₂ H ₄ and PO ₄ is used as an anion. (D) Organic substances include alcohols (aliphatic alcohols having 1 to 4 carbon atoms, preferably methanol, ethanol, propanol, ethylene glycol, glycerin, aromatic alcohols having 6 to 8 carbon atoms, preferably phenol, for example), higher Hydrocarbons (having 5 to 10 carbon atoms, preferably 5 to 8 carbon atoms, preferably, for example, hexane, heptane, etc.) can be mentioned. Further, formamide, hydrazine, dimethylsulfoxide, N-methylformamide, N, N-dimethylaniline and the like are preferable. Two or more kinds of salts and acids may be used.

When the salt treatment and the acid treatment are combined, a method of performing the salt treatment and then the acid treatment, a method of performing the acid treatment and then the salt treatment, and a method of simultaneously performing the salt treatment and the acid treatment There is. The treatment conditions with salts and acids are not particularly limited, but usually, the salt and acid concentrations are 0.1 to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. Then, it is preferable to carry out under the condition that at least a part of the substance constituting the layered silicate is eluted. Further, salts and acids are toluene,
In an organic solvent such as n-heptane or ethanol, or if the salt or acid is liquid at the treatment temperature, it can be used without a solvent, but is preferably used as an aqueous solution.

Component [B] of the present invention is
During any of the following time points, crushing, granulating, sizing,
The particle properties can be controlled by fractionation or the like. The method can be any purposeful. In particular, if the granulation method is shown, for example, spray granulation method, tumbling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized bed granulation method, Examples thereof include an emulsion granulation method and a submerged granulation method. Particularly preferable granulation methods are the spray granulation method, the rolling granulation method and the compression granulation method among the above.

Component [A1], component [A2], component [B]
The contact is not particularly limited, but the contacts can be made in the following contact order. a1. After contacting the component [A1] and the component [A2], the component [B] is added. a2. The component [A1] and the component [A2] are brought into contact with each other and then added to the component [B]. b1. After bringing the component [A1] and the component [B] into contact with each other, the component [A2] is added. b2. The component [A1] and the component [B] are brought into contact with each other and then added to the component [A2]. c1. After bringing the component [A2] and the component [B] into contact with each other, the component [A1] is added. c2. The component [A2] and the component [B] are brought into contact with each other and then added to the component [A1]. In addition, the three components may be contacted at the same time.

The amounts of the components [A1] and [A2] used are 0.001 to 1,000 per 1 g of the component [B].
It is 0 mmol, preferably 0.01 to 100 mmol. Further, the usage ratio of the component [A1] and the component [A2] is a mol ratio with respect to the sum of the two, and is generally [A1] /
([A1] + [A2]) = 0.05 to 0.95, preferably 0.15 to 0.85, and more preferably 0.25.
Is about 0.75. However, when the polymerization activity of the active sites formed from the respective compounds of the component [A1] and the component [A2] and the component [B] is greatly different, the usage ratio is such that the component [A1], the component [A2], the component If the catalyst prepared by contacting [B] and the organoaluminum compound [C] as the case requires, is intended to limit the present invention by the range of the above-mentioned use ratio. Of course, this is not the case.

<Organoaluminum Compound [C]> In the present invention, [C] is a compound represented by the following general formula, which is used as necessary. Trimethylaluminum or triethyl represented by AlR ⁸ _j X _3-j (wherein, R ⁸ is a C _{1 to} C ₂₀ hydrocarbon group, X is hydrogen, halogen, an alkoxy group, and j is a number of 0 <j ≦ 3). aluminum,
Trialkylaluminum such as tripropylaluminum, triisobutylaluminum and trioctylaluminum, or halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monochloride and diethylaluminum methoxide. In addition, aluminoxane such as methylaluminoxane can be used. Of these, trialkylaluminum is particularly preferable. Component [A] when component [C] is used
The contact order of 1], component [A2], component [B], and component [C] is not particularly limited as long as it is purposeful.

Further, as a catalyst component, a boron compound such as a Lewis acid represented by tris (pentafluorophenyl) boron, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl). An anionic compound represented by borate can also be used.

The amount of the component [C] used is 0.01 to 10000 mmol, preferably 0.
1 to 100 mmol. Further, the atomic ratio of the transition metal including the component [A1] and the component [A2] and the aluminum in the component [C] is 1: 0.01 to 1,000,000, preferably 0.1 to 100,000.

Before using a catalyst comprising the components [A] and [B] as a catalyst for olefin polymerization (main polymerization), ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4- Olefin such as methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane and styrene can be preliminarily polymerized in a small amount (preliminary polymerization). Since the prepolymerized catalyst is stable during the main polymerization, it is possible to prevent the generation of fine powdered polymer due to particle crushing and to produce polymer particles having excellent fluidity. It is preferable because the polymerization reaction can be stably operated. The prepolymerization step also has the advantage of promoting the formation of active sites. That is, by carrying out preliminary polymerization, the component [B]
Is finely dispersed in the prepolymerized catalyst particles to increase its surface area and form new polymerization active precursor points, or the prepolymerized polymer contains the polymerization active points, thereby There is an advantage in industrial handling such that the contact between the spot and the poisonous substance is limited and the deactivation can be prevented.

The preliminary polymerization with ethylene or the like is carried out before, during, and after all steps unless the effect is lost.
After that, it can be carried out in any of the above, in an inert solvent or in the absence of a solvent (or in the case of using a liquid α-olefin for prepolymerization, it may be the α-olefin), under contact with each of the above components, if necessary. Then, an organoaluminum such as the above-mentioned component [C] is newly added, ethylene and the like are provided, and 0.01 to 1000 g, preferably 0.1 to 100 g of a polymer is produced per 1 g of the catalyst component. Is desirable. The prepolymerization temperature is −100 to 100 ° C., preferably −60 to 100 ° C., and the prepolymerization time is 0.1 to 100 hours, preferably 0.1 to 20 hours.

The olefin polymerization reaction is carried out using the catalyst component obtained above, but an organoaluminum compound is used if necessary. At this time, as the organoaluminum compound used, the same compounds as the above-mentioned component [C] can be mentioned. The amount of the organoaluminum compound used at this time is such that the molar ratio of the transition metal in the catalyst component [A] to the aluminum in the organoaluminum compound is 1: 0 to 10.
Is chosen to be 000. Examples of the olefin that can be polymerized by the above-mentioned olefin polymerization catalyst include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 3-methylbutene-1,3-methylpentene-
1,4-methylpentene-1, vinylcycloalkane,
Examples thereof include styrene and derivatives thereof. Further, diolefins such as 1,5-hexadiene and butadiene may also be mentioned. Further, the polymerization can be suitably applied to not only homopolymerization but also random copolymerization and block copolymerization.
Diolefins such as hexadiene and butadiene may be copolymerized with the above olefins. Preferred is copolymerization of ethylene with an α-olefin having 3 to 20 carbon atoms, particularly 6 to 20 carbon atoms, and particularly preferred is copolymerization of ethylene with 1-hexene (particularly gas phase polymerization). .

The polymerization reaction is carried out in the presence of a solvent such as an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene, cyclohexane or a liquefied α-olefin, or substantially no liquid phase of the solvent or monomer. In the state, it is preferable to carry out by gas phase polymerization. The gas phase polymerization can be carried out using a reactor such as a fluidized bed, a stirred bed, or a stirred fluidized bed equipped with a stirrer / mixer. The conditions such as polymerization temperature and polymerization pressure are not particularly limited, but the polymerization temperature is generally -5.
0 to 250 ° C, preferably 0 to 100 ° C, more preferably 60 to 95 ° C, and the polymerization pressure is usually atmospheric pressure to
About 2000 kgf / cm ² , preferably normal pressure to 200 k
gf / cm ² , more preferably normal pressure to 50 kgf / cm ^2.
Is the range. Further, hydrogen may be present as a molecular weight modifier in the polymerization system.

<Characteristics of Polymerization Reaction Behavior of the Catalyst of the Present Invention> The olefin polymerization catalyst of the present invention has a high polymerization activity and an appropriate degree when the following conditions (i) and (ii) are satisfied as the olefin polymerization performance of the catalyst. Olefin polymer particles having high initial activity and rapidly increasing the particle size in the reactor and capable of reducing troubles of fine powder such as aggregation / adhesion and having excellent fluidity can be produced, which is preferable. (I) The temperature rise value (ΔT; unit ° C) in the reaction system measured according to the "initial activity assay method" is the same as that of the catalyst produced by the same method except that the component [A2] is not included. 1.5 times or more and 14 times or less of (ΔT0; unit ° C). (Ii) Olefin polymerization catalyst obtained by contacting component [A1], component [B] and optionally used component [C], or component [A2], component [B] and, if necessary, Compared to the olefin polymerization catalyst obtained by contacting the used component [C], [A1], component [A2],
The olefin polymerization catalyst obtained by contacting the component [B] with the component [C] used as necessary has a higher olefin polymerization activity under the same polymerization conditions.

The conditions (i) and (ii) will be described below. The condition (i) is a polymerization activity pattern immediately after the catalyst is charged into the polymerization reactor (behavior of change in polymerization activity with time while staying in the reactor), that is, the amount of polymer particles in the reactor. It expresses a preferable characteristic regarding the progress of growth over time. In general, the catalyst particles immediately after being charged into the polymerization reactor have a smaller particle size than other polymer particles, so that the particles adhere to the reactor wall surface, the particles agglomerate, the particles scatter from the reactor, etc. Tend to occur, which tends to hinder stable operation of polymerization (for example, JP-A-6-30).
6117 publication). In order to prevent these obstacles, it is necessary that the catalyst introduced into the reactor rapidly undergoes the polymerization reaction and the particle size increases. In the present invention, various methods for predicting the polymerization activity pattern of the catalyst continuously fed into the continuous olefin polymerization reactor are investigated, and as a result, the initial polymerization activity pattern (initial activity ) Is useful for solving problems that occur in the actual manufacturing process.

<Catalyst Initial Activity Assay Method> A batch type olefin polymerization reactor having an internal volume of 1.2 L equipped with a temperature control jacket (volume 18.8 L) using water and steam as a heat medium was used. After drying under reduced pressure at a temperature of 90 ° C. for 45 minutes, the pressure was restored with dry nitrogen, and dried under reduced pressure at a temperature of 90 ° C. for 6 hours in advance at a density of 0.9.
80 g of ethylene / 1-hexene copolymer particles of 25 g / cm ³ are placed as a seed bed. Here, triisobutylaluminum (0.366m
mol / ml heptane solution 0.8 ml) and diethyl aluminum ethoxide DEAE (1.05 mmol /
0.57 ml of heptane solution is added with slow stirring so that it is evenly dispersed in the seed bed. The internal temperature is raised to the polymerization temperature, and a raw material gas such as a monomer is filled to a predetermined concentration. After maintaining the internal temperature at 3 ° C lower than the polymerization temperature (87 ° C when the polymerization temperature was 90 ° C) and confirming that the pressure was constant at the set value, the reactor was pseudo-insulated. The temperature control function is stopped so that it can be regarded as a system. Confirm that the temperature is less than ± 0.5 ° C for 4 minutes after stopping the temperature control function. Five minutes after the temperature control function was stopped, a fixed amount of the catalyst and 2 ml of heptane together with 2 ml of heptane were pressed into the reactor with argon gas to start the polymerization reaction. Then, the raw material gas for the amount consumed by the polymerization is supplied to keep the pressure constant and the polymerization is continued. During the polymerization, the temperature was recorded every second, the temperature (T100) was read 100 seconds after the lowest temperature (T0) was recorded after the catalyst was pressed, and the temperature was read.
ΔT (= T100-T0) was used as an initial activity index.

The above-mentioned initial activity index ΔT (° C./100
Sec) is a measurement value that can be changed depending on the shape, material, wall thickness, form of temperature control jacket, type of polymerized monomer, pressure, etc. of the reactor used, and therefore, in the present invention, it should be compared with the comparison target. A conventionally known catalyst consisting of component [A
2] is not included, and the catalyst produced by the same production method (at this time, the total amount of [A1] and [A2] used is the same amount) is evaluated under the same conditions, and the corresponding value is represented as ΔT0, ΔT / ΔT0 was used as a representative value representing the performance of the catalyst of the present invention. ΔT / ΔT0 is 1.5 or more 1
When it is 4 times or less, the particle size is rapidly increased in the reactor, and fine powder troubles such as aggregation and adhesion can be reduced, and olefin polymer particles having excellent fluidity can be produced.
If ΔT / ΔT0 is less than 1.5, agglomeration or adhesion of catalyst particles or ungrown particles will occur, resulting in a molten sheet or a molten lump, and in the worst case, product extraction failure or temperature control becomes impossible. Not preferable. Also, ΔT / ΔT0
Is larger than 14, violent particle growth occurs in the initial stage of polymerization, and fine particles increase due to crushing and disintegration of particles, and particle melting due to poor heat removal at a locally exothermic site is not preferable. ΔT / ΔT0 is preferably 2.0 or more and 13 or less,
More preferably, it is 3.0 or more and 11 or less. Moreover, the experimental conditions (ethylene-1-hexene copolymerization described in the present invention.
The sum of 1-hexene partial pressure and ethylene partial pressure 18kg / c
m ² -G, partial pressure ratio 10% by weight), the range of ΔT is 0.75 to 7.0 ° C., preferably 1.0 to 6.
5 ° C, more preferably 1.5 to 5.5 ° C, most preferably 2.0 to 5.0 ° C.

(Ii) Olefin polymerization catalyst obtained by contacting component [A1], component [B] and optionally component [C], or component [A2], component [B] and necessary Than the catalyst for olefin polymerization obtained by contacting the component [C] used according to
1], the component [A2], the component [B] and the component [C] used as the case requires, the olefin polymerization catalyst has higher olefin polymerization activity under the same polymerization conditions. . The condition (ii) also relates to the performance of the catalyst with respect to the polymerization activity, and the component [A1], the component [A
2] Olefin polymerization activity under the same conditions is higher than that of a catalyst produced by the same production method except that only one of them is used (the sum of the amounts of [A1] and [A2] used is the same) That is. This is the ingredient [A
By coexisting 1] and component [A2] on the same catalyst, it means that the improvement of the activation efficiency, which could not be achieved by each component alone, can be realized only by the synergistic effect of the two components. This is a very advantageous property.

<Characteristics of Polymer Particles> The olefin polymerization catalyst of the present invention has the following properties (ii) as physical properties of the olefin polymer particles produced by contacting the catalyst with an olefin.
When i) and (iv) are satisfied, it is possible to manufacture product particles with a narrow distribution of composition (melting point, molecular weight) for each particle size, and the formation of adhered polymer on the inside wall of the reactor, inside wall, and inside wall of piping Since it is possible to produce an olefin polymer stably over a long period of time industrially without the formation of olefins, and the olefin polymer or olefin copolymer has a narrow melting point distribution for each particle, particular attention is paid to it. It is more preferable because a molded product having excellent composition uniformity can be produced without passing through various kneading conditions, and the appearance of gel, fish eyes, etc. can be improved.

(Iii) The olefin polymer particles produced by using the catalyst were mixed with openings 45, 75, 125, 212,
The melting point of each particle size obtained by fractionating each particle size with each sieve of 500, 850 and 1700 μm and measuring the fractionated particles on the sieve by TSC (x = 0, 45, 75, 125, 2
12,500, 850, 1700) (° C), the difference between the minimum temperature and the maximum temperature is 3.0 ° C or less.

(Iv) The melting point of the olefin polymer produced by using the catalyst is Tm ₀ (° C.), and the olefin polymer on the sieve with the smallest opening among the particle size fractionated particles described in the above condition (iii) is used. When the melting point of the fractionated particles on the sieve is Tms (° C.), the following formula (1) −1.2 ≦ Tms−Tm ₀ (1) is satisfied.

The condition (iii) means that the distribution of the copolymerizable composition for each particle size of the olefin polymer particles produced by using the catalyst of the present invention is very small. That is, DS
It defines that the variation of the melting point for each particle size obtained by C measurement is within a certain temperature range. The distribution of the composition by particle size is mainly due to the nonuniformity of the catalyst particle size distribution, the polymerization activity distribution for each catalyst particle, the polymerization conditions (polymerization temperature, polymerization pressure, gas composition, catalyst concentration, etc.) in the polymerization tank. Occurs. Further, in the case of a continuous polymerization device, it occurs due to residence time distribution and the like. Here, the variation of the melting point by particle size obtained by the DSC measurement is the molecular weight distribution in the homopolymerization, the stereoregularity distribution in the stereoregular polymerization, and the copolymerization in the copolymerization of two or more olefins. The cause can be determined for each distribution of the polymerization composition.

When the difference between the minimum temperature and the maximum temperature of the melting point for each particle size is 3.0 ° C. or less, it is possible to prevent the formation of adhered polymer and the formation of blocked lumps in the reactor, the inner wall surface and the inner wall surface of the pipe. . In addition, the olefin polymer or olefin copolymer can be formed into a molded article having excellent uniformity without performing special kneading and molding which require a particularly high energy cost. The difference between the minimum temperature and the maximum temperature of the melting point for each particle size is preferably 2.5 ° C. or less, more preferably 2.0 ° C. or less.

In addition to the condition (iii), a preferable condition for satisfying the melting point for each particle size is as described in the condition (iv), as described in the above condition (iii) as compared with the melting point Tm ₀ (° C.) of the product. Of the fractional particles classified by particle size, the melting point Tms (° C.) of the fractionated particles on the sieve with the smallest opening sieve is within a certain range, that is, the following formula (1) −1.2 ≦ Tms−Tm. _0: It is within the temperature range of (1).

As described above in the explanation of the condition (i), particles having a small particle size are apt to adhere and aggregate. not to mention,
If the adverse condition of low melting point overlaps with this, agglomeration
The risk of sticking increases. Although there are exceptions, of course, as far as the inventors know, in most cases, the smaller the particle size, the lower the melting point tends to be, and a detailed study was carried out on the basis of copolymerization of ethylene and α-olefin. As a result, it has been found that this tendency has a close correlation with the polymerization activity behavior in the reactor, and can be avoided by using the catalyst in which the initial activity index ΔT is controlled within a preferable certain range as described above. The correlation between the ΔT value and the (Tms-Tm ₀ ) value is remarkable in the case of copolymerization of ethylene with an α-olefin having 3 or more carbon atoms, particularly in the case of copolymerization of ethylene with an α-olefin having 6 or more carbon atoms. Appear in.

The (Tms-Tm ₀ ) value is preferably -1.
It is 1 ° C or higher and 0.5 ° C or lower, and more preferably -1.0 ° C or higher and 0.0 ° C or lower. If the (Tms-Tm ₀ ) value is smaller than this range, particles having a small particle size and a low melting point increase, and aggregation and adhesion occur, which is not preferable. (Tms-T
If the m ₀ ) value is larger than this range, fine powder due to crushing of particles is increased, and aggregation and adhesion of fine powder polymer having a bad shape occurs, which is also not preferable. The average particle size of the olefin polymer particles produced by contacting the olefin polymerization catalyst of the present invention with olefin (total on the sieve: 50%
(Particle size) is due to the convenience of production with industrial scale manufacturing equipment,
Preferably 100-2000 μm, more preferably 20
It is 0 to 1000 μm.

Further, the polymer particles of the present invention have the following condition (v):
It is preferable to satisfy. That is, the olefin polymer particles are made to have openings 45, 75, 125, 212, 500, 85.
The ΔTs value, which represents the distribution of the amount of the low melting point component contained in the polymer particles of the minimum particle size when fractionated by particle size with each of 0, 1700 μm sieves, is related to the density (D) of the polymer. It is preferable that the following expression (2) is further satisfied. ΔTs ≦ −2544D + 2377 (2) ΔTs ≦ −2544D + 2375 (3) (wherein, ΔTs value is the melting point (Tm of the minimum particle size polymer.
s) and the temperature Ts (1/2 min) defined below.
Ts (1/2 min) is a straight line perpendicular to the DSC curve of the polymer having the smallest particle size, which intersects perpendicularly with the perpendicular line drawn from the maximum peak apex indicating the melting point (Tms) to the baseline, and the DSC curve. Is the lowest temperature among the intersections on the lower temperature side than the melting point (Tms). )

1 and 2, ΔTs, Tms, Ts (1
It is an example of a DSC curve showing the relationship of / 2 min), and is a definition diagram of ΔTs in the present invention. In the figure, the horizontal axis is the temperature (° C), the vertical axis is the thermal energy difference (mW) that flows in and out of the sample cell and the reference cell from the heat source per unit time, and the melting start point and the melting end point are linear. It is common to set the line that connects the lines as the baseline, but if the melting start point is unclear, the extrapolation line of the straight line portion after the melting end point is used as the baseline. As a reference, edited by the Chemical Society of Japan, "New Experimental Chemistry Course 2, Basic Technology 1 Heat and Pressure"
(Maruzen 1977) 109 pages (Susumu Mita), RSPo
rter and FE Jhonson Eds. `` Analytical Calorimetry
(Plenum Press, New York: 1968) ”209 pages (APGray),“ Thermal analysis (Kodansha Scientific 1975) ”70 pages (Kobe Hirotaro), Kinki Chapter edited by the Japan Society for Analytical Chemistry,“ Instrument Analysis Experimental Method Addendum (1970
) "(Kenji Uede), Textile Society of Japan 25 (1969) 5
All known publications on DSC measurement, such as page 3 (Kenji Uede), are mentioned.

As described above in the explanation of the condition (iv), although there are exceptions, as far as the present inventors know, in many cases, the smaller the particle size, the lower the melting point. There is a tendency that the DSC melting curve of the minimum particle size polymer broadly swells to the low temperature side at the same time as the decrease of Tms defined above. Will have. The index for expressing the distribution of the amount of the low melting point component contained in such a polymer having the minimum particle size is ΔTs. The polymer particles satisfying the formula (2) means that ethylene and α having 3 or more carbon atoms are used.
-It is extremely important in the case of copolymerization with olefin, especially in the case of copolymerization of ethylene and α-olefin having 6 or more carbon atoms.

Further, the polymer particles of the present invention have the following condition (v
It is preferable to satisfy i). That is, since the particle morphology of the polymer being melted is maintained up to a higher temperature by the presence of an appropriate amount of the high melting point component in the polymer, aggregation of particles or fusion to the reactor wall is suppressed. . The presence of this high melting point component is represented by the following formula (4), preferably (5), such that the average melting point (Tm ₀ ) of all polymers is at a relatively high temperature in relation to the density (D) of the polymer. ) Is indicated by the range. Tm ₀ > 400D-250 ... (4) Tm ₀ > 400D-248 ... (5) Even if the polymer particles do not satisfy the formula (4), a higher temperature is used instead of the melting point Tm _0. When the second peak, the third peak, etc. existing on the side satisfy the formula (4), the effect of suppressing the aggregation of particles and the fusion to the reactor wall is exhibited by the same mechanism.

[0075]

EXAMPLES The present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. The polymerization activity of the catalyst was represented by the polymer production amount (gram number) per 1 g of the component [B]. The physical properties of the polymer are measured by the following methods.

<MI and FR measurement> MI is JIS K6
According to 760, it was measured at 190 ° C. under a load of 2.16 kg. FR is a ratio of melt index I _{10 kg} and MI, similarly measured under the conditions of 190 ° C. and a load of _{10 kg} ,
Calculated from FR (= I _{10 kg} / MI).

<Measurement of Density> The density is measured according to JIS K71.
In accordance with No. 12, the strand obtained at the time of measuring the melt index is heat-treated at 100 ° C. for 1 hour, and further at room temperature for 1 hour.
It is measured by the density gradient tube method after being left for a time. <Product Bulk Density> JIS K7365
The apparent density of a polymer according to

<Measurement of Sieve Particle Size> Six standard sieves having an inner diameter of 75 mm (opening 75 μm, 125 μm, 212 μm, 500 μm)
m, 850 μm, 1700 μm,) 100 g of product particles
Was added and the mixture was shaken for 20 minutes, and the 50% integrated value under the sieve was taken as the average particle diameter.

<Melting point measurement by DSC> JIS K71
It measured based on 21. As the sample, a sheet prepared by pressing 0.1 g or more of particles at a temperature of 160 ° C. for 2 minutes and cutting out a required amount was used. Sample 5mg at 170 ℃
After melting for 5 minutes, cool down to 20 ℃ at a rate of 10 ℃ / minute,
After holding for 1 minute, the melting curve is measured up to 170 ° C. at a temperature rising rate of 10 ° C./min, and the peak top temperature (° C.) is determined by the melting point (T
m).

Example 1 (1) Acid Treatment of Clay Minerals Granulated and classified product of commercially available swelling montmorillonite (“Ben clay SL”, Mizusawa Chemical Co., Ltd., average particle size 27 μm) 37 k
g in 25% sulfuric acid 148 kg and dispersed at 90 ° C for 2
Stir for hours. This was filtered and washed with demineralized water. (2) Titanium salt treatment of clay mineral and drying Commercially available titanyl sulfate aqueous solution (Ti, Sakai Chemical Industry Co., Ltd., Ti
(Containing 7.5% as O _{2 and} 25.6% as SO ₄ )
The sulfuric acid-treated montmorillonite cake obtained in (1) above was totally dispersed in 236 kg, and the mixture was stirred at 30 ° C. for 3 hours. After filtering and washing this with demineralized water to pH 3.5, the obtained water-containing solid cake was preliminarily dried at 110 ° C. for 10 hours to obtain a titanium salt-treated montmorillonite. Of this pre-dried montmorillonite, the aperture is 15
The particles that passed through the 0 mesh sieve were further subjected to a countercurrent nitrogen stream (nitrogen flow rate 49 Nm ³ / hr) at a speed of 3 kg / hr (retention time 10 minutes) using a rotary kiln. It was continuously dried and collected under dry nitrogen.

(3) Preparation of catalyst and prepolymerization In a nitrogen atmosphere, a reactor with an induction stirring device having a volume of 1 L was charged with n.
-164 ml of heptane and 10 g of dried montmorillonite particles (component [B]) obtained in (2) were added to n-heptane 250.
It was made into a slurry with ml and introduced into the reactor. The system was maintained at 30 ° C., and triethylaluminum 9.6 mmol (1.0
96 g) was added and stirred for 10 minutes. Subsequently, while maintaining the temperature, bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride as a component [A2] (1.20 mmol, that is, a solution in which 0.5191 g is dispersed in 173.0 ml of n-heptane) And bis (n-butylcyclopentadienyl) hafnium dichloride (1.20 mmol, that is, a solution of 0.5902 g dispersed in 196.7 ml of n-heptane) as component [A1] were continuously added, and then the temperature of the system was changed. Was heated to 78 ° C. After reacting at 78 ° C. for 10 minutes, ethylene gas was introduced at a rate of 1.0 NL / min for 57 minutes to carry out prepolymerization. The supply of ethylene was stopped and the ethylene gas in the reactor was replaced with nitrogen. (4) Washing and Drying of Prepolymerized Catalyst The prepolymerized catalyst slurry obtained in (3) above was transferred to a flask and washed with n-heptane at 60 ° C up to a washing rate of 1/15. Then, the solvent was distilled off by heating to 70 ° C. and drying under reduced pressure to give 81.7 g of prepolymerized catalyst powder.
Was recovered.

(5) Copolymerization of ethylene / 1-hexene Using the prepolymerized catalyst powder of (4) above, ethylene / 1
-Hexene gas phase copolymerization was performed. That is, the above-mentioned (4 51 mg / h as the component [B]
r, triisobutylaluminum and diethylaluminum ethoxide were 100 mg / hr and 68 mg / hr, respectively.
Was supplied intermittently. The polymerization reaction conditions were 90 ° C., ethylene partial pressure 18 kg / cm ² , and average residence time 4.1 hours. The average polymerization rate of the produced polyethylene after lapse of 12 hours from the start of the supply of the prepolymerization catalyst was 294 g /
It was hr. The results of polymerization are shown in Table 1, and after 18 hours,
Table 2 shows the physical properties of the products measured by collecting the products manufactured over time.

Example 2 As component [A2], bis (1
-N-butyl-3-methylcyclopentadienyl) zirconium dichloride (0.48 mmol or 0.2
A solution in which 076 g was dispersed in 69.2 ml of n-heptane)
Example 1 (3) )
A prepolymerized catalyst was produced in the same manner as in (4), and 79.2 g of the prepolymerized catalyst powder was recovered. Using this prepolymerized catalyst powder, ethylene.1- was prepared in the same manner as in Example 1 (5).
Hexene copolymerization was performed. The polymerization results are shown in Table 1, and the product properties are shown in Table 2.

[Comparative Example 1] As component [A2], bis (1
-N-butyl-3-methylcyclopentadienyl) zirconium dichloride (2.40 mmol or 1.0
382 g was dispersed in n-heptane 346.1 ml) and the component [A1] was not used.
A prepolymerized catalyst was produced in the same manner as in Example 1 (3) and (4), and 79.9 g of prepolymerized catalyst powder was recovered. Using this prepolymerized catalyst powder, ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1 (5). The polymerization results are shown in Table 1, and the product properties are shown in Table 2.

[Comparative Example 2] Component [A2] was not used, and bis (n-butylcyclopentadienyl) hafnium dichloride (2.40 mmol, that is, 1.1803 g was added to 393.4 ml of n-heptane as Component [A1]. A prepolymerized catalyst was produced in the same manner as in Example 1 (3) (4) except that the dispersed solution) was used, and the prepolymerized catalyst powder 8
6.8g was recovered. Using this prepolymerized catalyst powder, ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1 (5). After starting the supply of the prepolymerization catalyst, 11
After a lapse of time, the polymer lump was blocked in the product polymer discharge line, so that the operation could not be continued. Table 1 shows the polymerization results obtained by recovering the product manufactured 1 hour before the operation was stopped, and Table 2 shows the physical properties of the product.

[Example 3] Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (1.20 mmol or 0.4181) was used as the component [A2].
g in a solution of 139.4 ml of n-heptane),
Example 1 (3) (except that bis (n-butylcyclopentadienyl) hafnium dichloride (1.20 mmol, that is, a solution of 0.5902 g dispersed in 196.7 ml of n-heptane) was used as the component [A1]. Prepolymerization catalyst was produced in the same manner as 4), and prepolymerization catalyst powder 7
5.8g was recovered. Using this prepolymerized catalyst powder, ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1 (5). The polymerization results are shown in Table 1, and the product properties are shown in Table 2.

[Example 4] Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (0.48 mmol or 0.1672) was used as the component [A2].
g was dispersed in 55.7 ml of n-heptane) and bis (n-butylcyclopentadienyl) hafnium dichloride (1.92 mmol or 0.9442 g) was dispersed in 314.7 ml of n-heptane as the component [A1]. A prepolymerized catalyst was produced in the same manner as in Example 1 (3) and (4) except that the solution) was used.
8.3 g was recovered. Using this prepolymerized catalyst powder, ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1 (5). The polymerization results are shown in Table 1, and the product properties are shown in Table 2.

[Comparative Example 3] Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (2.40 mmol or 0.8362) was used as the component [A2].
Example 1 except that component [A1] was not used, and a solution in which g was dispersed in 278.8 ml of n-heptane was used.
(3) A prepolymerized catalyst was produced in the same manner as in (4), and 82.1 g of prepolymerized catalyst powder was recovered. Using this prepolymerized catalyst powder, ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1 (5). Thirteen hours after starting the supply of the prepolymerization catalyst, the polymer lump was blocked in the product polymer discharge line, so that the operation could not be continued. Table 1 shows the polymerization results obtained by recovering the product manufactured 1 hour before the operation was stopped, and Table 2 shows the physical properties of the product.

Example 5 (1) Acid Treatment of Clay Minerals Granulated and classified product of commercially available swelling montmorillonite (“Ben clay SL”, manufactured by Mizusawa Chemical Co., Ltd., average particle size 38 μm) 40 k
g in 250% sulfuric acid 160 kg and dispersed at 90 ° C for 2
Stir for hours. This is filtered with demineralized water to pH 3.5.
After washing, the water-containing solid cake obtained was washed at 110 ° C. for 10 minutes.
The acid-treated montmorillonite was preliminarily dried for an hour.
Particles of this pre-dried montmorillonite that have passed through a sieve having a mesh size of 150 mesh are further subjected to a countercurrent nitrogen stream at a temperature of 200 ° C. using a rotary kiln (nitrogen flow rate 4
9 Nm ³ / hr), speed of 3 kg / hr (residence time 1
It was continuously dried at 0 min) and collected under dry nitrogen.

(2) Catalyst Preparation and Prepolymerization Under a nitrogen atmosphere, 2.47 L of n-heptane and 100 g of dried montmorillonite particles (component [B]) obtained in (1) were placed in a reactor having a capacity of 10 L and equipped with an induction stirrer. It was slurried with 1.00 L of n-heptane and introduced into the reactor. System 2
Keep at 0 ° C, triethylaluminum 96.0 mmol
(10.96 g) was added and stirred for 10 minutes. Subsequently, while maintaining the temperature, bis (1-
n-Butyl-3-methylcyclopentadienyl) zirconium dichloride (12.00 mmol or 5.1
91 g of a solution obtained by dispersing 0.45 L of n-heptane),
After continuously adding bis (n-butylcyclopentadienyl) hafnium dichloride (12.00 mmol, that is, a solution in which 5.900 g was dispersed in 0.45 L of n-heptane) as the component [A1], the system temperature was adjusted to 78. The temperature was raised to ° C. After reacting at 78 ° C. for 10 minutes, ethylene gas was introduced at a rate of 10.0 NL / min for 61 minutes to carry out prepolymerization. The supply of ethylene was stopped and the ethylene gas in the reactor was replaced with nitrogen.

(3) Washing of prepolymerized catalyst The prepolymerized catalyst slurry obtained in (2) above was cooled to 60 ° C., and 5.0 L of n-heptane was added. At this time, the total volume of the preliminary polymerization catalyst slurry liquid was 10.4 L. After stirring at 60 ° C. for 5 minutes, the stirring was stopped and the mixture was allowed to settle for 15 minutes, and 7.0 L of the supernatant was extracted. The process of adding 6.5 L of n-heptane again, stirring at 60 ° C. for 5 minutes, allowing to sediment for 15 minutes and extracting 6.5 L of the supernatant was repeated 3 times. Finally, n-heptane was added so that the total amount became 5.0 L. (4) Drying of prepolymerized catalyst The whole amount of the slurry of prepolymerized catalyst washed in (3) was taken out in a nitrogen atmosphere into a 15 L tank vibrating vacuum dryer equipped with a steam jacket for conductive heat reception. 4 L of heptane was added to the reactor and all the contents remaining in the reactor were extracted into a dryer. The prepolymerized catalyst slurry transferred to the dryer was allowed to stand still to remove about 5 L of the supernatant liquid, and then the solvent was distilled off by drying under reduced pressure while heating at 70 ° C. While maintaining the temperature, it was visually confirmed that the solvent had been almost distilled off, and then dried under reduced pressure for 2 hours, and as a result, 791 g of the prepolymerized catalyst powder was recovered. (5) Polymerization evaluation Ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1 (5) using the preliminary polymerization catalyst powder obtained in (4) above. The polymerization results are shown in Table 1, and the product properties are shown in Table 2.

[Comparative Example 4] As the component [A2], bis (1
-N-butyl-3-methylcyclopentadienyl) zirconium dichloride (24.00 mmol or 1
A solution prepared by dispersing 0.382 g in 0.90 L of n-heptane) was used, and component [A1] was not used.
A prepolymerized catalyst was produced in the same manner as in Example 5 (2) (3) (4), and 775 g of prepolymerized catalyst powder was recovered. Using this preliminary polymerization catalyst powder, polymerization evaluation was carried out in the same manner as in Example 5 (5). The polymerization results are shown in Table 1, and the product properties are shown in Table 2.

[Comparative Example 5] Component [A2] was not used, and bis (n-butylcyclopentadienyl) hafnium dichloride (24.00 mmol or 11.80 g as n-heptane 0.90 L) was used as component [A1]. The prepolymerized catalyst was produced in the same manner as in Example 5 (2) (3) (4) except that the dispersed solution) was used.
50 g was recovered. Using this prepolymerized catalyst powder,
Polymerization was evaluated in the same manner as in Example 5 (5). Ten hours after starting the supply of the prepolymerization catalyst, the polymer lump was blocked in the product polymer discharge line, so that the operation could not be continued. Table 1 shows the polymerization results obtained by recovering the product manufactured 1 hour before the operation was stopped, and Table 2 shows the physical properties of the product.

Example 6 As component [A2], bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (12.00 mmol or 4.181) was used.
g) in a solution of 0.45 L of n-heptane) and bis (n-butylcyclopentadienyl) hafnium dichloride (12.00 mmol or 5.900 g) as a component [A1] in 0.45 L of n-heptane. A prepolymerized catalyst was produced in the same manner as in Example 5 (2) (3) (4) except that the solution) was used, and prepolymerized catalyst powder 6
85 g was recovered. Using this prepolymerized catalyst powder,
Polymerization was evaluated in the same manner as in Example 5 (5). The polymerization results are shown in Table 1, and the product properties are shown in Table 2.

[Comparative Example 6] Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (24.00 mmol or 8.362) was used as the component [A2].
Example 5 except that a solution prepared by dispersing g in 0.90 L of n-heptane) was used and the component [A1] was not used.
(2) A prepolymerized catalyst was produced in the same manner as in (3) and (4), and 878 g of prepolymerized catalyst powder was recovered. Using this preliminary polymerization catalyst powder, polymerization evaluation was carried out in the same manner as in Example 5 (5). Twelve hours after starting the supply of the prepolymerization catalyst, the polymer lump was blocked in the product polymer discharge line, so that the operation could not be continued. Table 1 shows the polymerization results obtained by recovering the product manufactured 1 hour before the operation was stopped, and Table 2 shows the physical properties of the product.

Example 7 (1) Acid Treatment of Clay Minerals 8 kg of commercially available montmorillonite (“Kunipia F”, manufactured by Kunimine Industries Co., Ltd.) was crushed by a vibrating ball mill, and 50 kg of demineralized water in which 10 kg of magnesium chloride was dissolved was crushed. The mixture was dispersed and stirred at 80 ° C. for 1 hour. The obtained solid component was washed with water, then dispersed in 56 L of an aqueous solution of 8.2% hydrochloric acid, stirred at 90 ° C. for 2 hours, and washed with demineralized water. The thus-obtained montmorillonite 4.6 kg water slurry liquid was prepared to have a solid content concentration of 15.2%, and spray granulated by a spray dryer. The shape of the particles obtained by granulation was spherical. (2) chromium salts of the clay mineral and drying was then separated granulated montmorillonite obtained in the above (1) to the flask of 1L, then chromium nitrate nonahydrate _{(Cr (NO 3) 3 ·} 9H ₂ O) 48 g was dispersed in 400 ml of demineralized water and stirred at 90 ° C. for 3 hours.
After the treatment, this solid component was washed with demineralized water and pre-dried to obtain treated montmorillonite. Put this pre-dried chromium treated montmorillonite in a 200 ml flask and
A heat dehydration treatment was performed at 200 ° C. for 2 hours under a reduced pressure of mmHg.

(3) Preparation of catalyst and prepolymerization In a nitrogen atmosphere, a reactor with an induction stirrer having a volume of 1 L was charged with n.
-Heptane 374 ml and dry montmorillonite particles obtained in (2) 10 g (component [B]) were added to n-heptane 250
It was made into a slurry with ml and introduced into the reactor. The system was maintained at 30 ° C., and triethylaluminum 9.6 mmol (1.0
96 g) was added and stirred for 10 minutes. Subsequently, while maintaining the temperature, biscyclopentadienyl zirconium dichloride (0.40 mmol, that is, a solution in which 0.1170 g was dispersed in 40 ml of toluene) was used as the component [A2], and ethylene bis (4,5,5) was used as the component [A1].
After continuously adding 6,7-tetrahydroindenyl) zirconium dichloride (0.40 mmol, that is, a solution in which 0.1714 g was dispersed in 40 ml of toluene),
The system temperature was raised to 78 ° C. After reacting at 78 ° C for 10 minutes, ethylene gas was added at a rate of 1.0 NL / min to 57
It was introduced for a period of time to carry out prepolymerization. The supply of ethylene was stopped and the ethylene gas in the reactor was replaced with nitrogen. (4) Drying of prepolymerized catalyst The prepolymerized catalyst slurry obtained in (3) above was transferred to a flask, heated to 70 ° C., and the solvent was distilled off by vacuum drying to obtain prepolymerized catalyst powder 80. 5 g was recovered.

(5) Copolymerization of ethylene / 1-butene Using the prepolymerized catalyst powder of (4) above, ethylene / 1
-Butene slurry copolymerization was performed. That is, 1.5 L of n-heptane, 2.5 mmol of triethylaluminum, and 100 ml of 1-butene were added to a 3 L autoclave, and the temperature was raised to 65 ° C. Then, 100 mg of the prepolymerized catalyst obtained in (4) was introduced together with ethylene as the component [B], and ethylene and 1-
While supplying a mixed gas of butene (1-butene / ethylene = 7.0% by weight), the total pressure was kept at 22 kg / cm ² -G, and polymerization was carried out at 65 ° C. for 2 hours. After 2 hours, ethanol was added to terminate the polymerization. The obtained ethylene / 1-butene copolymer was 218 g. The polymerization results are shown in Table 3 and the product properties are shown in Table 4.

[Comparative Example 7] As the component [A1], ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride (0.80 mmol, 0.3
Example 7 except that a solution in which 428 g was dispersed in 80 ml of toluene) was used and the component [A2] was not used.
(3) A prepolymerized catalyst was produced in the same manner as in (4), and 82.5 g of prepolymerized catalyst powder was recovered. Polymerization evaluation was carried out in the same manner as in Example 7 (5) using this preliminary polymerization catalyst powder. The polymerization results are shown in Table 3 and the product properties are shown in Table 4.

[Comparative Example 8] Biscyclopentadienyl zirconium dichloride (0.80 m) was used as the component [A2].
mol, that is, a solution in which 0.2339 g was dispersed in 80 ml of toluene) was used, and the component [A1] was not used. 79.0 g of the polymerization catalyst powder was recovered.
Polymerization evaluation was carried out in the same manner as in Example 7 (5) using this preliminary polymerization catalyst powder. The polymerization results are shown in Table 3 and the product properties are shown in Table 4.

Example 8 Ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 5 (5). However, a mixed gas of ethylene, 1-hexene, and hydrogen is used as 1-hexene /
Ethylene = 3.3 mol%, hydrogen / ethylene = 0.017
It was defined as mol%. The polymerization results are shown in Table 5, and the product properties are shown in Table 6.

[Comparative Example 9] In the same manner as in Comparative Example 4, ethylene / 1-hexene copolymerization was carried out. However, the mixed gas of ethylene, 1-hexene and hydrogen is 1-hexene / ethylene = 3.8 mol%, hydrogen / ethylene = 0.025 mol%
And 10 hours after starting the supply of the prepolymerization catalyst,
The polymer mass clogged the product polymer discharge line, making it impossible to continue operation. Table 5 shows the polymerization results obtained by collecting the products produced one hour before the operation was stopped, and Table 6 shows the product properties.

Example 9 (1) Organoaluminum Treatment of Clay Minerals Under a nitrogen atmosphere, 1.01 L of n-heptane was added to a reactor equipped with an induction stirrer with a capacity of 10 L and the dried montmorillonite obtained in Example 5 (1). 100 g of particles (component [B]) was slurried with 1.00 L of n-heptane and introduced into the reactor.
The system was maintained at 30 ° C., 0.489 L of an n-heptane solution of triethylaluminum (concentration 0.613 mol / L) was added, and the temperature was raised to 40 ° C. 1 while keeping the temperature
After the reaction was carried out for a period of time, the steps of adding n-heptane, separating by sedimentation and removing the supernatant were repeated 4 times for washing. The cleaning rate at this time was 1/69. Finally, n-heptane was added to prepare a total amount of 3.47 L.

(2) Preparation of Catalyst and Preliminary Polymerization Subsequent to (1), 96.0 mmol (10.96 g) of triethylaluminum was added at a temperature of 20 ° C. and the mixture was stirred for 10 minutes. Continue to maintain the temperature,
2] as bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride (12.00 m
mol or 5.191 g of n-heptane 0.45 L
And a bis (n-butylcyclopentadienyl) hafnium dichloride (1) as the component [A1].
A solution in which 2.00 mmol, that is, 5.900 g, was dispersed in 0.45 L of n-heptane) was continuously added, and then the temperature of the system was raised to 78 ° C. After reacting at 78 ° C. for 10 minutes, ethylene gas was added at a rate of 3.3 NL / min for 185
It was introduced for a period of time to carry out prepolymerization. The supply of ethylene was stopped and the ethylene gas in the reactor was replaced with nitrogen.

(3) Washing of prepolymerized catalyst The prepolymerized catalyst slurry obtained in (2) above was cooled, and the prepolymerized catalyst was washed and dried in the same manner as in Example 5 (3) (4). did. However, toluene was used instead of n-heptane as the washing solvent, and the temperature in the system at the time of washing was changed from 60 ° C to 30 ° C. As a result, 749 g of the prepolymerized catalyst powder was recovered. (4) Polymerization Evaluation Using the prepolymerized catalyst powder obtained in (3) above, ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1 (5). However, the mixed gas of ethylene, 1-hexene and hydrogen was 1-hexene / ethylene = 4.5 mol% and hydrogen / ethylene = 0.032 mol%. The polymerization results are shown in Table 5, and the product properties are shown in Table 6.

Example 10 (1) Organoaluminum Treatment of Clay Minerals Under a nitrogen atmosphere, 0.3441 L of n-heptane was added to a 2 L flask equipped with a stirrer, and 100 g of dry montmorillonite particles obtained in Example 5 (1) (component) [B]) was introduced. The system was maintained at 30 ° C., and 0.489 L of an n-heptane solution of triethylaluminum (concentration 0.613 mol / L) was added. After the reaction was carried out for 1 hour while maintaining the temperature, washing with n-heptane was performed until the washing rate became 1/70, and then the total amount was adjusted to 0.20 L.

(2) Following catalyst preparation (1), bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride (12.00 mmol or 5.191 g) as component [A2] at a temperature of 30 ° C. Was dispersed in 0.45 L of toluene) and bis (n-butylcyclopentadienyl) hafnium dichloride (12.00 mm) as the component [A1].
(i.e., a solution in which 5.900 g was dispersed in 0.45 L of toluene) was continuously added, and then the reaction was continued for 1 hour while maintaining the temperature. After stirring was stopped, the mixture was allowed to stand for 30 minutes to settle, and 1.80 L of the supernatant was extracted, and then the same amount of toluene as the amount to be extracted was added to wash the catalyst slurry as a catalytic reaction product, which was repeated 4 times, and finally the total amount. Is 2.00
Toluene was added until L was reached.

(3) Prepolymerization In a nitrogen atmosphere, in a reactor with a capacity of 10 L induction stirrer
2.37 L of n-heptane and the catalyst slurry obtained in (2) above.
The entire amount of Lee was introduced. Keep the system at 20 ° C and
Luminium 96.0 mmol (10.96 g) was added.
And stirred for 10 minutes. Raise the system temperature to 40 ° C and
Reaction was carried out for a minute. Continue ethylene prepolymerization
It was That is, the first step is 3.3 NL / min at a temperature of 40 ° C.
After introducing ethylene gas at a rate of 60 minutes, the second step
As the temperature of the system is raised at an average of 0.8 ° C / min.
20 minutes after increasing the introduction rate of ren gas to 6.6 NL / min
For 10 NL / min as the third stage
Up to 0.14 NL / min on average ²Rate of ethylene introduction
Was increased for a total of 120 minutes of prepolymerization. Echi
Stop supplying ethylene and replace ethylene gas in the reactor with nitrogen.
Replaced. By cooling the resulting prepolymerized catalyst slurry,
The prepolymerized catalyst was dried in the same manner as in Example 5 (4).
did. As a result, 863 g of the prepolymerized catalyst powder was recovered.
It was (4) Polymerization evaluation Using the prepolymerized catalyst powder obtained in (3) above,
Ethylene / 1-hexene copolymerization as in Example 1 (5)
I went together. However, ethylene, 1-hexene and hydrogen
1-hexene / ethylene = 3.4 mol% mixed water, water
Element / ethylene = 0.037 mol%. Table of polymerization results
5 and the product physical properties are shown in Table 6.

[Example 11] (1) Production of prepolymerized catalyst 858 g of prepolymerized catalyst powder was recovered in the same manner as in Example 10 (1) to (3). However, after introducing ethylene gas for 60 minutes at a temperature of 40 ° C. at a rate of 3.3 NL / min as the first step of the prepolymerization, while raising the temperature of the system at an average of 1.0 ° C./minute as the second step. The ethylene gas introduction rate was increased to 6.6 NL / min and the reaction was carried out for 12 minutes. Then, as a third step, the ethylene introduction rate was increased to 10 NL / min to carry out a preliminary polymerization for a total of 110 minutes. (4) Polymerization evaluation Using the preliminary polymerization catalyst powder obtained in the above (1), ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1 (5). However, the mixed gas of ethylene, 1-hexene and hydrogen was 1-hexene / ethylene = 3.7 mol% and hydrogen / ethylene = 0.032 mol%. The polymerization results are shown in Table 5, and the product properties are shown in Table 6.

[0110]

[Table 1] Table 1

[0111]

[Table 2] Table 2 (1)

[0112]

[Table 3] Table 2 (Part 2)

[0113]

[Table 4] Table 2 (Part 3)

[0114]

[Table 5] Table 3

[0115]

[Table 6] Table 4

[0116]

[Table 7] Table 5

[0117]

[Table 8] Table 6 (Part 1)

[0118]

[Table 9] Table 6 (Part 2)

[0119]

[Table 10] Table 6 (Part 3)

[0120]

EFFECT OF THE INVENTION The olefin polymer of the present invention is a polymer having a narrow particle size distribution and a uniform melting point characteristic measured for each product particle size. Since no low-melting point particles are generated, the distribution of the melting point of each particle becomes narrow. As a result, it is possible to manufacture a molded product having excellent compositional uniformity, reduce fine powder troubles such as aggregation and adhesion, and realize industrial long-term stable operation. Furthermore, when the obtained olefin polymer is subjected to film molding, blow molding, injection molding or the like, it is possible to produce a molded product having less gel and fish eyes and having an excellent appearance. Such a polymer can be produced by using a specific mixed catalyst of Hf and Zr. Since the catalyst of the present invention has a high olefin polymerization activity, the particle size can be rapidly increased in the reactor to reduce fine powder troubles such as agglomeration and adhesion, and further, since particle crushing does not occur, it is industrially Long-term stable operation can be realized.

[Brief description of drawings]

FIG. 1 is an example of a DSC curve, and ΔT in the present invention.
It is a definition diagram of s.

FIG. 2 is another example of the DSC curve and is a definition diagram of ΔTs in the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J015 DA07                 4J100 AA02P AA02Q AA03P AA03Q                       AA04P AA04Q AA16P AA16Q                       AA17P AA17Q AA18P AA18Q                       AB02P AB02Q AB07P AB07Q                       CA01 CA04 DA24 EA09                 4J128 AA02 AB00 AC01 AC28 AD05                       AD06 AD07 AD08 AD11 AD13                       BA00A BA00B BA01B BB00A                       BB00B BB01B BC15B BC16B                       BC24B BC25B CA30C DA01                       EA01 EB02 EB04 EB05 EB07                       EB08 EB09 EB10 EB13 EB15                       EB21 EC01 EC02 ED01 ED02                       ED03 ED04 ED05 ED08 ED09                       GA05 GA07 GA08 GA09 GA19                       GA24 GB01 GB07

Claims (14)

[Claims] 1. A hafnium compound or zirconium compound [A1] having at least one conjugated five-membered ring ligand,
A zirconium compound having at least one conjugated five-membered ring ligand, which is obtained by polymerizing an olefin in the presence of an olefin polymerization catalyst comprising a compound [A2] different from [A1] and a layered silicate [B]. The obtained olefin polymer. 2. A hafnium compound or zirconium compound [A1] having at least one conjugated five-membered ring ligand,
A zirconium compound having at least one conjugated five-membered ring ligand, which is obtained by polymerizing an olefin in the presence of an olefin polymerization catalyst comprising a compound [A2] different from [A1] and a layered silicate [B]. The obtained olefin polymer particles. 3. When the particle size distribution of the polymer is measured by the sieving method, the particle size range is 45 to 3000 μm and the average particle size is 100.
The olefin polymer particles according to claim 2, wherein the olefin polymer particles have a particle size of ˜2000 μm. 4. The difference between the maximum temperature (maximum Tmx) and the minimum temperature (minimum Tmx) of the melting points measured by the particle size of the polymer is 3.0.
The olefin polymer particles according to claim 2 or 3, wherein the temperature is not higher than ° C. 5. The melting point (Tms) of the minimum particle size polymer and the average melting point (Tm ₀ ) of all the polymers satisfy the following formula (1). Olefin polymer particles. −1.2 ≦ Tms−Tm ₀ (1) 6. A ΔTs value representing the distribution of the amount of the low melting point component contained in the minimum particle size polymer particles satisfies the following formula (2) in relation to the density (D) of the polymer. The olefin polymer particles according to any one of claims 2 to 5. ΔTs ≦ −2544D + 2377 (2) (wherein ΔTs value is the melting point (Tm of the minimum particle size polymer.
s) and the temperature Ts (1/2 min) defined below.
Ts (1/2 min) is a straight line perpendicular to the DSC curve of the polymer having the smallest particle size, which intersects perpendicularly with the perpendicular line drawn from the maximum peak apex indicating the melting point (Tms) to the baseline, and the DSC curve. Is the lowest temperature among the intersections on the lower temperature side than the melting point (Tms). ) 7. The olefin polymer comprises ethylene and 3 to 10 carbon atoms.
An olefin polymer particle according to any one of claims 2 to 6, which is a copolymer with 20 α-olefins. 8. A hafnium compound or zirconium compound [A1] having at least one conjugated five-membered ring ligand,
A catalyst for olefin polymerization comprising a zirconium compound having at least one conjugated five-membered ring ligand, which is different from [A1], and a layered silicate [B], wherein [A1] is [A1] The method for producing an olefin polymer according to claim 1, wherein the olefin is polymerized in the presence of a catalyst that is 0.05 to 0.95 (molar ratio) with respect to the total amount of [A2] and [A2]. 9. [A1] is represented by the general formula [1] (In the formula, A and A ′ are ligands having the same or different conjugated five-membered ring structure, and X and Y are hydrogen atoms bonded to Hf, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, and a phosphorus group. 9. The method for producing an olefin polymer according to claim 1, which is a metallocene compound represented by each of a containing hydrocarbon group and a silicon-containing hydrocarbon group. 10. [A2] is represented by the general formula [5]. (In the formula, A and A ′ are ligands having the same or different conjugated five-membered ring structure, and X and Y are hydrogen atoms bonded to Zr, halogen atoms, hydrocarbon groups, alkoxy groups, amino groups and phosphorus. 9. The method for producing an olefin polymer according to claim 1, which is a metallocene compound represented by each of a containing hydrocarbon group and a silicon-containing hydrocarbon group. 11. The polymer has a particle size range of 45 to 3000 μm and an average particle size of 10 as measured by a sieving method.
0 to 2000 μm, the difference between the maximum temperature (maximum Tmx) and the minimum temperature (minimum Tmx) of the melting point measured according to the particle size of the polymer is 3.0 ° C. or less, and the minimum particle size of the polymer melting point (Tms) and total weight An olefin polymer particle characterized in that the average melting point (Tm ₀ ) of the coalescence satisfies the following formula (1). −1.2 ≦ Tms−Tm ₀ (1) 12. The ΔTs value, which represents the distribution of the amount of the low melting point component contained in the minimum particle size polymer particles, is the density (D) of the polymer.
The olefin polymer particles according to claim 11, wherein the following formula (2) is satisfied in relation to. ΔTs ≦ −2544D + 2377 (2) (wherein ΔTs value is the melting point (Tm of the minimum particle size polymer.
s) and the temperature Ts (1/2 min) defined below.
Ts (1/2 min) is a straight line perpendicular to the DSC curve of the polymer having the smallest particle size, which intersects perpendicularly with the perpendicular line drawn from the maximum peak apex indicating the melting point (Tms) to the baseline, and the DSC curve. Is the lowest temperature among the intersections on the lower temperature side than the melting point (Tms). ) 13. The olefin polymer is ethylene and has 3 carbon atoms.
The olefin polymer particles according to claim 11 or 12, wherein the olefin polymer particles are a copolymer of 20 to 20 α-olefins. 14. A melt index of 0.1 to 50 g /
The olefin polymer particle according to any one of claims 11 to 13, which has a density of 0.900 to 0.940 g / cm ³ for 10 minutes.