JP2002060411A - Method for storing olefin polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for storing an olefin polymerization catalyst, which method is excellent in the ability to store an olefin polymerization catalyst and enables even an olefin polymerization catalyst stored long thereby to give an olefin polymer having a high bulk density and excellent particle properties without causing polymer particles to stick to each other to form lumps. SOLUTION: There is provided a method for storing an olefin polymerization catalyst obtained by bringing components [A] and [B] into contact with each other in the presence of an organoaluminum compound, component [A]: a compound of a transition metal of any one of groups 4-6 in the periodic table and having a conjugated five-membered ring ligand and component [B]: a solid component containing at least one member selected from the group consisting of (b-1) a microparticulate support carrying an aluminumoxy compound, (b-2) a microparticulate support carrying an ionic compound that can cationize component A by reaction therewith or carrying a Lewis acid, (b-3) solid acid microparticles, and (b-4) an ion-exchanging layered silicate microparticles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for preserving a catalyst for olefin polymerization, and more particularly, to a method for preserving an olefin polymerization catalyst with little deterioration of the catalyst over time and little decrease in activity.

[0002]

2. Description of the Related Art Periodic Tables 4 to 5 having a conjugated five-membered ring ligand
Group 6 transition metal compounds, so-called metallocene compounds,
Since a polymer having a high olefin polymerization activity and excellent stereoregularity can be obtained, it has been widely used as an olefin polymerization catalyst.

[0003] However, catalysts using metallocene compounds are difficult to store, and the polymerization activity decreases over time with storage, the amount of fine powder in the obtained polymer particles increases, Cohesion occurs to generate coarse particles,
There were problems such as a decrease in bulk density, which hindered processing such as purification and drying of the polymer.

[0004] The particle properties of the polymer particles largely depend on the particle properties of the olefin polymerization catalyst, and the deterioration of the particle properties of the polymer particles obtained by storage of the catalyst is caused by the deterioration of the catalyst particles during storage of the olefin polymerization catalyst. This is considered to be due to the deterioration of the particle properties.

[0005] Therefore, in order to enable long-term storage of the olefin polymerization catalyst and obtain polymer particles having excellent particle properties even after long-term storage, a storage method that does not impair the particle properties of the olefin polymerization catalyst is required. Development is important.

[0006]

DISCLOSURE OF THE INVENTION The present invention has excellent storage stability of an olefin polymerization catalyst. Even when a catalyst stored for a long period of time is used, polymer particles are not bound and aggregated. An object of the present invention is to provide a method for preserving an olefin polymerization catalyst capable of obtaining an olefin polymer having a high bulk density and excellent particle properties.

[0007]

SUMMARY OF THE INVENTION The present invention has been made as a result of intensive studies to solve the above-mentioned problems of the prior art.

That is, the present invention provides an olefin polymerization catalyst characterized by storing an olefin polymerization catalyst obtained by contacting the following components [A] and [B] in the presence of an organoaluminum compound. The present invention provides a method for storing a catalyst for use.

Component [A]: a transition metal compound of Groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand, Component [B]: from the following (b-1) to (b-4) A solid component containing one or more selected components, (b-1) a particulate carrier supporting an aluminum oxy compound, and (b-2) reacting with component [A] to convert component [A] to a cation. (B-3) solid acid fine particles (b-4) ion-exchange layered silicate fine particles, and the present invention provides an olefin polymerization catalyst comprising: An object of the present invention is to provide a method for preserving the above-mentioned olefin polymerization catalyst, which is obtained by bringing component [A], component [B] and component [C] into contact.

Component [A]: a transition metal compound of Groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand, Component [B]: from the following (b-1) to (b-4) A solid component containing one or more selected components, (b-1) a particulate carrier supporting an aluminum oxy compound, and (b-2) reacting with component [A] to convert component [A] to a cation. (B-3) solid acid fine particles (b-4) ion-exchangeable layered silicate fine particles, component [C] an organoaluminum compound, A method for storing the above-mentioned olefin polymerization catalyst in which the component [B] is an ion-exchange layered silicate, a method for storing the above-mentioned olefin polymerization catalyst in which the olefin polymerization catalyst is a prepolymerization catalyst previously contacted with an olefin, and , Catalyst tone An object of the present invention is to provide a method for preserving the above-mentioned olefin polymerization catalyst in which an aluminum compound is added by newly adding a component [D] an organoaluminum compound after the production.

Further, the present invention provides a method for preserving the above olefin polymerization catalyst wherein the olefin polymerization catalyst is dried in the presence of an organoaluminum compound; And a method for preserving the olefin polymerization catalyst described above.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The olefin polymerization catalyst of the present invention comprises the following components [A] and [B].

In the description of the present invention, “including”, “consisting of” and “combining” mean
As long as the effects of the present invention are not impaired, it means that compounds other than the listed compounds or components can be used in combination. The term "polymerization" is used to include not only homopolymerization but also copolymerization, and the term "polymer" is used to include not only homopolymers but also copolymers.

<Component [A]> The metallocene compound used in the present invention is a transition metal compound belonging to Groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand. Preferred as such a transition metal compound is the following general formula (1):
Compounds represented by (2), (3) and (4).

[0015]

Embedded image

Wherein A and A ′ represent a conjugated five-membered ring ligand which may have a substituent (A and A ′ may be the same or different in the same compound), and Q is A bonding group bridging the two conjugated five-membered ring ligands at an arbitrary position; Z represents a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom; A bonding group bridging any position of the five-membered ring ligand with Z;
Represents a metal atom selected from Groups 4 to 6 of the periodic table, and X and Y represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group. A) A and A ′ are conjugated five-membered ring ligands, which may be the same or different in the same compound, as described above. Specific examples of the conjugated five-membered ring ligand (A and A ′) include a conjugated five-membered ring ligand, that is, a cyclopentadienyl group. The cyclopentadienyl group may be one having five hydrogen atoms (C ₅ H ₅ —), and a derivative thereof, that is, one in which some of the hydrogen atoms are substituted with a substituent, Is also good. Examples of the substituent include a hydrocarbon group having 1 to 40, preferably 1 to 30 carbon atoms. Even if this hydrocarbon group is bonded to the cyclopentadienyl group as a monovalent group, when two or more of them are present, two of them are bonded at the other end (ω-end) to form cyclopentadienyl. It may form a ring with a part of the enyl. Examples of the latter are those in which two substituents are each bonded at the ω-terminal to share two adjacent carbon atoms in the cyclopentadienyl group to form a fused six-membered ring,
That is, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, and those forming a fused seven-membered ring,
That is, examples include an azulenyl group and a tetrahydroazulenyl group.

Specific examples of the conjugated five-membered ring ligand represented by A and A 'include a substituted or unsubstituted cyclopentadienyl group, an indenyl group, a fluorenyl group, and an azulenyl group. Among them, preferred is an azulenyl group.

As the substituent on the cyclopentadienyl group, in addition to the above-mentioned hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, a halogen atom group such as fluorine, chlorine, and bromine; To 12 alkoxy groups, for example, -Si (R
¹ ) a silicon-containing hydrocarbon group having 1 to 24 carbon atoms represented by (R ² ) (R ³ ); and 1 carbon atom represented by -P (R ¹ ) (R ² )
To 18 phosphorus-containing hydrocarbon groups, or -B (R ¹ )
Ageraru boron-containing hydrocarbon group having 1 to 18 carbon atoms represented by (R ^2). When there are a plurality of these substituents, each substituent may be the same or different. R described above
^{1 to} R ³ may be the same or different and each have ^{1 to 3} carbon atoms.
And 20 alkyl groups.

Q is a linking group bridging any two positions between the two conjugated five-membered ring ligands, and Q 'is bridging any position of the conjugated five-membered ring ligand to the group represented by Z. Represents a binding group.

Specific examples of Q and Q 'are (a)
Tylene group, ethylene group, isopropylene group, phenylme
Tylmethylene group, diphenylmethylene group, cyclohexyl
Alkylene groups such as a len group, (ii) dimethylsilylene
Group, diethylsilylene group, dipropylsilylene group,
Phenylsilylene group, methylethylsilylene group,
Phenylsilylene group, methyl-t-butylsilylene group,
Silylene such as silylene group and tetramethyldisilylene group
Group, (c) germanium, phosphorus, nitrogen, boron or
Hydrocarbon groups containing aluminum, more specifically,
(CH_Three)_TwoGe, (C₆H_Five)_TwoGe, (CH_Three) P, (C
₆H_Five) P, (C_FourH₉) N, (C₆H_Five) N, (C_FourH₉)
B, (C₆H_Five) B, (C₆H_Five) Al (C₆H_FiveO) with Al
And the like. Preferred are alkylene groups
And silylene groups.

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

Z represents 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. Specific examples of preferred compounds include an oxygen atom, a sulfur atom, a thioalkoxy group having 1 to 20, preferably 1 to 12 carbon atoms, and a thioalkoxy group having 1 to 4 carbon atoms.
0, preferably 1 to 18 silicon-containing hydrocarbon groups, 1 to 40 carbon atoms, preferably 1 to 18 nitrogen-containing hydrocarbon groups, 1 to 40 carbon atoms, preferably 1 to 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,
C1-20, preferably C1-10 hydrocarbon groups, C1-20, preferably C1-10 alkoxy groups, amino groups, diphenylphosphino groups, etc.
It is a phosphorus-containing hydrocarbon group having 0, preferably 1 to 12, or a silicon-containing hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms such as a trimethylsilyl group and a bis (trimethylsilyl) methyl group. X and Y may be the same or different. Of these, a halogen atom, a hydrocarbon group, particularly those having 1 to 8 carbon atoms, and an amino group are preferred.

In the olefin polymerization catalyst according to the present invention, the catalyst component [A] is represented by the general formula (1), (2),
Among the compounds represented by (3) or (4), particularly preferable ones have the following substituents.

A, A '= cyclopentadienyl, n-butylcyclopentadienyl, indenyl, 2-methyl-
Indenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl, 2-methyl-tetrahydroindenyl, 2-methylbenzoindenyl, 2,4-dimethyl-4H-azulenyl, 2-methyl-4-phenyl-4
H-azulenyl, 2-methyl-4- (2-naphthyl)-
4H-azulenyl, 2-methyl-4- (4-t-butylphenyl) -4H-azulenyl Q, Q '= ethylene, dimethylsilylene, isopropylidene Z = t-butylamide, phenylamide, cyclohexylamide, M = 4 group Transition metal, X, Y = chlorine, methyl, diethylamino.

Compounds represented by the general formulas (1) to (4)
Specific examples of the product are as follows. (A) As the compound represented by the general formula (1), for example,
(1) Bis (1,3-dimethylcyclopentadienyl)
Zirconium dichloride, (2) bis (1-ethyl-3
-Methylcyclopentadienyl) zirconium dichloride
And (3) bis (1-n-butyl-3-methylcyclope)
(Antadenyl) zirconium dichloride, (4) bis
(1-i-butyl-3-methylcyclopentadienyl)
Zirconium dichloride, (5) bis (1-t-butyl)
-3-methylcyclopentadienyl) zirconium dik
Loride, (6) bis (1,3-dimethylcyclopentadi
(Enyl) zirconium dimethyl, (7) bis (1-ethyl)
Ru-3-methylcyclopentadienyl) zirconiumdi
Methyl, (8) bis (1-n-butyl-3-methylcyclyl)
(Lopentadienyl) zirconium dimethyl, (9) bis
(1-i-butyl-3-methylcyclopentadienyl)
Zirconium dimethyl, (10) bis (1-t-butyl
-3-methylcyclopentadienyl) zirconium dime
Chill, (11) bis (1,3-dimethylcyclopentadi
Enyl) zirconium methyl chloride, (12) bis
(1-ethyl-3-methylcyclopentadienyl) zyl
Conium methyl chloride, (13) bis (1-n-butyl)
Ru-3-methylcyclopentadienyl) zirconium
Tyl chloride, (14) bis (1-i-butyl-3-meth)
Tylcyclopentadienyl) zirconium methyl chloride
, (15) bis (1-t-butyl-3-methylcyclo)
(Pentadienyl) zirconium methyl chloride, (1
6) bis (1,3-dimethylcyclopentadienyl) di
Ruconium diethyl, (17) bis (1-ethyl-3-
Methylcyclopentadienyl) zirconium diethyl,
(18) bis (1-n-butyl-3-methyl-cyclope)
(Ntadienyl) zirconium diethyl, (19) bis
(1-i-butyl-3-methyl-cyclopentadienyl
Ru) zirconium diethyl, (20) bis (1-t-butyl)
Tyl-3-methylcyclopentadienyl) zirconium
Diethyl, (21) bis (1,3-dimethylcyclopen
Tadienyl) zirconium diisobutyl, (22) bis
(1-ethyl-3-methylcyclopentadienyl) zyl
Conium diisobutyl, (23) bis (1-n-butyl
-3-Methyl-cyclopentadienyl) zirconiumdi
Isobutyl, (24) bis (1-i-butyl-3-methyl
Ru-cyclopentadienyl) zirconium diisobutyi
, (25) bis (1-t-butyl-3-methylcyclo)
(Pentadienyl) zirconium diisobutyl, (26)
Bis (1,3-dimethylcyclopentadienyl) zirco
Ium chloride monohydride, (27) bis (1-
Ethyl-3-methylcyclopentadienyl) zirconium
Muchloride monohydride, (28) bis (1-n-
Butyl-3-methyl-cyclopentadienyl) zirconi
Um chloride monohydride, (29) bis (1-i
-Butyl-3-methyl-cyclopentadienyl) zirco
Ium chloride monohydride, (30) bis (1-
t-butyl-3-methylcyclopentadienyl) zirco
Ammonium chloride monohydride, (31) bis (1,
3-dimethylcyclopentadienyl) zirconium diha
Idride, (32) bis (1-ethyl-3-methyl)
Clopentadienyl) zirconium dihydride,
(33) bis (1-n-butyl-3-methyl-cyclope)
(Antadienyl) zirconium dihydride, (34)
Bis (1-i-butyl-3-methyl-cyclopentadie)
Nyl) zirconium dihydride, (35) bis (1
-T-butyl-3-methylcyclopentadienyl) zyl
Conium dihydride, (36) bis (1,3-dimethyl
Tylcyclopentadienyl) zirconium dimethoxy
, (37) bis (1-ethyl-3-methylcyclopen)
Tadienyl) zirconium dimethoxide, (38) bis
(1-n-butyl-3-methyl-cyclopentadienyl
G) zirconium dimethoxide, (39) bis (1-i)
-Butyl-3-methyl-cyclopentadienyl) zirco
Ium dimethoxide, (40) bis (1-t-butyl-
3-methylcyclopentadienyl) zirconium dimethoate
Oxide, (41) bis (1,3-dimethylcyclopenta
Dienyl) zirconium bis (dimethylamide), (4
2) bis (1-ethyl-3-methylcyclopentadienyl)
B) zirconium bis (dimethylamide), (43)
(1-n-butyl-3-methyl-cyclopentadienyl)
G) zirconium bis (dimethylamide), (44)
(1-i-butyl-3-methyl-cyclopentadienyl)
B) zirconium bis (dimethylamide), (45)
(1-t-butyl-3-methylcyclopentadienyl)
G) zirconium (dimethylamide), (46) bis
(1,3-dimethylcyclopentadienyl) zirconium
Mbis (diethylamide), (47) bis (1-ethyl)
-3-methylcyclopentadienyl) zirconium bis
(Diethylamide), (48) bis (1-n-butyl-
3-methyl-cyclopentadienyl) zirconium bis
(Diethylamide), (49) bis (1-i-butyl-)
3-methyl-cyclopentadienyl) zirconium bis
(Diethylamide), (50) bis (1-t-butyl-
3-methylcyclopentadienyl) zirconium bis
(Diethylamide), (51) bis (1,3-dimethyl
Cyclopentadienyl) zirconium diethylamido
Nochloride, (52) bis (1-ethyl-3-methyl
Clopentadienyl) zirconium diethylamide mono
Chloride, (53) bis (1-n-butyl-3-methyl)
-Cyclopentadienyl) zirconium diethylamide
Monochloride, (54) bis (1-i-butyl-3-meth)
Tyl-cyclopentadienyl) zirconium diethyla
Midomonochloride, (55) bis (1-t-butyl-3)
-Methylcyclopentadienyl) zirconium diethyl
Amidomonochloride, (56) bis (1-methyl-3-
(Trifluoromethylcyclopentadienyl) zirconium
Mudichloride, (57) bis (1-methyl-3-trime
Tylsilylcyclopentadienyl) zirconium dichloro
Lido, (58) bis (1-cyclohexyl-3-methyl)
Cyclopentadienyl) zirconium dichloride, (5
9) Bis (1-methyl-3-phenylcyclopentadie)
Nyl) zirconium dichloride, (60) bis (1-
Nzir-3-methylcyclopentadienyl) zirconium
Mudichloride, (61) bis (1-n-butyl-3-to
Trifluoromethylcyclopentadienyl) zirconium
Dichloride, (62) bis (1-n-butyl-3-tri
Methylsilylcyclopentadienyl) zirconiumdic
Chloride, (63) bis (1-n-butyl-3-cyclohexyl)
Xylcyclopentadienyl) zirconium dichloride
, (64) bis (1-n-butyl-3-phenylcyclyl)
(Lopentadienyl) zirconium dichloride, (65)
Bis (1-benzyl-3-n-butylcyclopentadie
Nyl) zirconium dichloride. (B) Examples of the compound represented by the general formula (2) include
(1) Dimethylsilylenebis {1- (2-methyl-4H)
-Azulenyl) zirconium dichloride, (2) dime
Tylsilylenebis {1- (2,4-dimethyl-4H-A)
Zurenyl) zirconium dichloride, (3) dimethyl
Silylene bis {1- (2-methyl-4-isopropyl-)
4H-azulenyl) zirconium dichloride, (4)
Dimethylsilylenebis {1- (2-methyl-4-phenyl)
Ru-4H-azulenyl) zirconium dichloride,
(5) dimethylsilylenebis [1- {2-methyl-4-
(4-chlorophenyl) -4H-azulenyl}] zirco
Dichloride, (6) dimethylsilylenebis [1-
{2-methyl-4- (4-fluorophenyl) -4H-
Azulenyl｝] zirconium dichloride, (7) dimethyi
Lucirylene bis [1- {2-methyl-4- (3-chloro
Phenyl) -4H-azulenyl}] zirconium dichloro
Lido, (8) dimethylsilylenebis [1- {2-methyl
-4- (2,6-dimethylphenyl) -4H-azuleni
Ru]] zirconium dichloride, (9) dimethylsilyl
Bis-1- (2-methyl-4-sec-butyl-4H-
Azulenyl) zirconium dichloride, (9) dimethyi
Lucirylene bis {1- (2-methyl-4,6-diisop)
Ropyl-4H-azulenyl) zirconium dichloride
, (10) methylphenylsilylenebis {1- (2-
Methyl-4H-azulenyl) zirconium dichloride
(11) methylphenylsilylenebis {1- (2,
4-dimethyl-4H-azulenyl) zirconium dik
Chloride, (12) diphenylsilylenebis {1- (2-
Methyl-4-phenyl-4H-azulenyl) zirconi
Um dichloride, (13) methylphenylsilylenebis
{1- (2-methyl-4-phenyl-4H-azuleni)
Le) zirconium dichloride, (14) methylpheny
Rusilylenebis [1- {2-methyl-4- (1-naphthy
Ru) -4H-azulenyl}] zirconium dichloride,
(15) Methylphenylsilylene bis [1- {2-methyl
4- (4-chlorophenyl) -4H-azuleni
Ru]] zirconium dichloride, (16) methylphenyi
Lucirylene bis [1- {2-methyl-4- (4-fluoro
Lphenyl) -4H-azulenyl}] zirconium dik
Chloride, (17) methylphenylsilylenebis [1-
{2-methyl-4- (3-chlorophenyl) -4H-a
Zurenyl}] zirconium dichloride, (18) methyl
Phenylsilylenebis {1- (2-methyl-4-isoprop)
Ropyl-4H-azulenyl) zirconium dichloride
, (19) methylphenylsilylenebis {1- (2-
Methyl-4,6-diisopropyl-4H-azuleni
Le) zirconium dichloride, (20) diphenyl
Rylene bis {1- (2-methyl-4-phenyl-4H-)
Azulenyl) zirconium dichloride, (21) dime
Tylsilylenebis {1- (2-ethyl-4-phenyl)-
4H-azulenyl)｝ zirconium dichloride, (2
2) dimethylsilylenebis {1- (2-ethyl-4-i)
Sopropyl-4H-azulenyl) zirconium dichloride
Lido, (23) dimethylsilylenebis [1- ｛2-ethyl
Ru-4- (1-naphthyl) -4H-azulenyl}] zyl
Conium dichloride, (24) dimethylsilylenebis
[1- {2-ethyl-4- (4-chlorophenyl) -4]
H-azulenyl}] zirconium dichloride, (25)
Dimethylsilylene bis [1- {2-ethyl-4- (4-
Fluorophenyl) -4H-azulenyl}] zirconium
Mudichloride, (26) dimethylsilylenebis [1-
{2-ethyl-4- (3-chlorophenyl) -4H-a
Zurenyl}] zirconium dichloride, (27) dimethyi
Lucirylene bis {1- (2-ethyl-4-sec-butyl)
-4H-azulenyl) zirconium dichloride, (2
8) Dimethylsilylenebis {1- (2-ethyl-4-si)
Clohexyl-4H-azulenyl) zirconium dik
Chloride, (29) dimethylsilylenebis [1- {2-e
Tyl-4- (2-naphthyl) -4H-azulenyl {] di
Ruconium dichloride, (30) dimethylsilylenebis
[1- {2-ethyl-4- (1-anthracenyl) -4]
H-azulenyl}] zirconium dichloride, (31)
Dimethylsilylenebis [1- {2-ethyl-4- (2-
Anthracenyl) -4H-azulenyl}] zirconium
Dichloride, (32) dimethylsilylenebis [1- {2
-Ethyl-4- (9-anthracenyl) -4H-azure
Nil}] zirconium dichloride, (33) dimethyl
Rylene bis [1- {2-ethyl-4- (1-phenanthance)
Ril) -4H-azulenyl}] zirconium dichloride
, (34) dimethylsilylenebis [1- {2-ethyl}
-4- (9-phenanthryl) -4H-azulenyl}]
Zirconium dichloride, (35) dimethyl methylene bi
S1- [2-methyl-4- (4-biphenylyl) -4
H-azulenyl] zirconium dichloride, (36)
Dimethylgermylene bis {1- [2-methyl-4- (4
-Biphenylyl) -4H-azulenyl] zirconium
Dichloride, (37) ethylenebis {1- [2-methyl]
-4- (4-biphenylyl) -4H-azulenyl] di
Ruconium dichloride, (38) trimethylene bis ｛1
-[2-Methyl-4- (4-biphenylyl) -4H-a
Zurenyl] zirconium dichloride, (39) dimethyi
Lucirylene bis {1- [2-i-propyl-4- (4-
Biphenylyl) -4H-azulenyl] zirconium
Chloride, (40) dimethylsilylenebis {1- [2-me
Tyl-4- (2-fluoro-4-biphenylyl) -4H
-Azulenyl] zirconium dichloride, (41) di
Methylsilylenebis {1- [2-ethyl-4- (2-f
Fluoro-4-biphenylyl) -4H-azulenyl] di
Ruconium dichloride, (42) dimethylsilylenebis
{1- [2-methyl-4- (2 ′, 6′-dimethyl-4)
-Biphenylyl) -4H-azulenyl] zirconium
Dichloride, (43) dimethylsilylenebis {1- [2
-Methyl-4- (1-naphthyl) -4H-azuleni
Zirconium dichloride, (44) dimethylsilicone
Lenbis {1- [2-i-propyl-4- (1-naphthy
Ru) -4H-azulenyl] zirconium dichloride,
(45) dimethylsilylenebis {1- [2-ethyl-4]
-(2-naphthyl) -4H-azulenyl] zirconium
Mudichloride, (46) dimethylsilylenebis ｛1-
[2-i-propyl-4- (4-t-butylphenyl)
-4H-azulenyl] zirconium dichloride, (4
7) Dimethylsilylenebis {1- [2-ethyl-4-
(9-anthryl) -4H-azulenyl] zirconium
Mudichloride, (48) dimethylsilylene {1- [2-
Methyl-4- (4-biphenylyl) -4H-azuleni
]} 1- [2-methyl-4- (4-biphenylyl)
Indenyl] zirconium dichloride, (49)
Tylsilylenebis {1- [2-ethyl-4- (4-biph
Enylyl) -4H-5,6,7,8-tetrahydroaz
Renyl] zirconium dichloride, (50) dimethyl
Silylene {1- (2-ethyl-4-phenyl-4H-a)
Zulenyl) {1- (2-methyl-4,5-benzoin)
Denenyl) zirconium dichloride, (51) dimethyl
Silylenebis {1- (2-ethyl-4-phenyl-6)
Isopropyl-4H-azulenyl) zirconium dik
Chloride, (52) dimethylsilylenebis {1- (2-E)
Tyl-4,6-diphenyl-4H-azulenyl) zil
Conium dichloride, (53) dimethylsilylenebis
[1- {2-methyl-4- (pentafluorophenyl)]
-4H-azulenyl}] zirconium dichloride, (5
4) Dimethylsilylenebis {1- (2-ethyl-4-)
(Pentafluorophenyl) -4H-azulenyl) di
Ruconium dichloride, (55) dimethylsilylenebis
{1- (2-ethyl-4-phenyl-7-fluoro-4)
(H-azulenyl) zirconium dichloride, (56)
Dimethylsilylenebis {1- (2-ethyl-4-indo)
Ryl-4H-azulenyl) zirconium dichloride,
(57) dimethylsilylenebis {1- (2-dimethylbo)
Lano-4-indolyl-4H-azulenyl) zirconi
Um dichloride, (68) dimethylsilylenebis [1-
{2-ethyl-4- (3,5-bistrifluoromethyl)
Phenyl) -4H-azulenyl}] zirconium dichloro
Lido, (59) dimethylsilylenebis {1- (2-methyl)
4-phenyl-4H-azulenyl) zirconium
Dimethyl, (60) dimethylsilylenebis {1- (2-
Ethyl-4-phenyl-4H-azulenyl) zirconi
Dimethyl, (61) dimethylsilylenebis ｛1-
(2-methyl-4-phenyl-4H-azulenyl) di
Ruconium chlorodimethylamide, (62) dimethyl
Rylene bis {1- (2-methyl-4-phenyl-4H-)
Azulenyl) zirconium bis (trifluoromethane
Sulfonic acid), (63) dimethylsilylenebis {1-
(2-methylindenyl) zirconium dichloride,
(64) dimethylsilylenebis {1- (2,4-dimethyl)
Ruindenyl) zirconium dichloride, (65) di
Methylsilylene bis {1- (2-methyl-4-isopro)
Pyrindenyl) zirconium dichloride, (66)
Dimethylsilylenebis {1- (2-methyl-4-phenyl)
Ruindenyl) zirconium dichloride, (67) di
Methylsilylene bis {1- (2-methyl-4,5-ben)
Zoindenyl) zirconium dichloride, (68) di
Methylsilylene bis [1- {2-methyl-4- (1-na
Fthyl) indenyl}] zirconium dichloride, (6
9) Dimethylsilylenebis [1- {2-methyl-4-
(2,6-dimethylphenyl) indenyl}] zirconi
Um dichloride, (70) dimethylsilylene bis ｛1-
(2-methyl-4-sec-butylindenyl) zircon
Dichloride, (71) dimethylsilylene bis ｛1
-(2-methyl-4,6-diisopropylindenyl
Le) zirconium dichloride, (72) methylphenyi
Lucirylene bis {1- (2-methylindenyl)} zyl
Conium dichloride, (73) methylphenylsilylene
Bis {1- (2,4-dimethylindenyl)} zirconi
Um dichloride, (74) diphenylsilylene bis ｛1
-(2-methyl-4-phenylindenyl) zirconi
Um dichloride, (75) methylphenylsilylenebis
{1- (2-methyl-4-phenylindenyl)} zyl
Conium dichloride, (76) methylphenylsilylene
Bis {1- (2-methyl-4,5-benzoindenyl)
Le) zirconium dichloride, (77) methylphenyi
Rusilylenebis [1- {2-methyl-4- (1-naphthy
Le) indenyl}] zirconium dichloride, (78)
Methylphenylsilylenebis {1- (2-methyl-4-
Isopropylindenyl) zirconium dichloride,
(79) Methylphenylsilylenebis {1- (2-methyl)
-4,6-diisopropylindenyl) zirconium
Mudichloride, (80) diphenylsilylenebis @ 1-
(2-methyl-4-phenylindenyl) zirconium
Mudichloride, (81) dimethylsilylenebis @ 1-
(2-ethyl-4,5-benzoindenyl) zirconi
Um dichloride, (82) dimethylsilylenebis @ 1-
(2-ethyl-4-phenylindenyl) zirconium
Mudichloride, (83) dimethylsilylenebis @ 1-
(2-ethyl-4-isopropylindenyl) zircon
Dichloride, (84) dimethylsilylenebis [1
-{2-ethyl-4- (1-naphthyl) indenyl}]
Zirconium dichloride, (85) dimethylsilylene bi
S1- (2-ethyl-4-sec-butylindeni)
Z) zirconium dichloride, (86) dimethylsilicide
Lenbis {1- (2-ethyl-4-cyclohexylin)
Denenyl) zirconium dichloride, (87) dimethyl
Silylene bis [1- {2-ethyl-4- (2-naphthy
Le) indenyl}] zirconium dichloride, (88)
Dimethylsilylenebis [1- {2-ethyl-4- (1-
Anthryl) indenyl｝] zirconium dichloride,
(89) dimethylsilylenebis [1- {2-ethyl-4
-(2-anthryl) indenyl}] zirconium dik
Chloride, (90) dimethylsilylenebis [1- {2-e
Cyl-4- (9-anthryl) indenyl}] zirconi
Um dichloride, (91) dimethylsilylenebis ｛1-
(2-ethyl-α-acenaphthoindenyl) zirconi
Um dichloride, (92) dimethylsilylenebis [1-
{2-ethyl-4- (1-phenanthryl) indeni
｝] Zirconium dichloride, (93) dimethylsilyl
Lenbis [1- {2-ethyl-4- (9-phenanthry)
Ru) indenyl}] zirconium dichloride, (94)
Dimethylsilylene {1- (2-ethyl-4-phenyli)
Ndenyl) {1- (2-methyl-4,5-benzoin)
Denenyl) zirconium dichloride, (95) dimethyl
Silylenebis {1- (2-ethyl-4-phenyl-6)
Isopropylindenyl) zirconium dichloride,
(96) dimethylsilylenebis {1- (2-ethyl-)
4,6-diphenylindenyl) zirconium dichloro
Lido, (97) dimethylsilylenebis [1- {2-methyl
4- (pentafluorophenyl) indenyl}] di
Ruconium dichloride, (98) dimethylsilylenebis
{1- (2-ethyl-4- (pentafluorophenyl)}
Indenyl) zirconium dichloride, (99) dime
Tylsilylenebis {1- (2-ethyl-4-phenyl)
7-fluoroindenyl) zirconium dichloride,
(100) dimethylsilylenebis {1- (2-ethyl-)
4-Indolylindenyl) zirconium dichloride
, (101) dimethylsilylenebis {1- (2-dimension)
Cylborano-4-indolylindenyl) zirconium
Mudichloride, (102) dimethylsilylenebis [1-
{2-ethyl-4- (3,5-bistrifluoromethyl)
Phenyl) indenyl}] zirconium dichloride,
(103) dimethylsilylenebis {1- (2-methyl-
4,5-benzoindenyl) zirconium dimethyl,
(104) dimethylsilylenebis {1- (2-methyl-
4,5-benzoindenyl) zirconium methyl chloride
Lido, (105) dimethylsilylenebis {1- (2-E)
Cyl-α-acenaphthoindenyl)｝ zirconium dime
Chill, (106) dimethylsilylenebis {1- (2-meth
Tyl-4-phenylindenyl) zirconium dimethyl
, (107) dimethylsilylenebis {1- (2-ethyl)
Ru-4-phenylindenyl) zirconium dimethyi
, (108) dimethylsilylenebis {1- (2-methyl)
Ru-4-phenylindenyl) zirconium chlorodi
Methylamide, (109) dimethylsilylenebis {1-
(2-methyl-4-phenylindenyl) zirconium
Mbis (trifluoromethanesulfonic acid), (110)
Dimethylsilylenebis {1- (2-ethyl-4-phenyl)
Ruindenyl) zirconium bis (trifluorometa)
Sulfonic acid) (111) ethylene-1,2-bis @ 1
-(2-methylindenyl) zirconium dichloride
, (112) ethylene-1,2-bis ｛1- (2,4
-Dimethylindenyl) zirconium dichloride,
(113) Ethylene-1,2-bis {1- (2-methyl)
-4-phenylindenyl) zirconium dichloride
(114) ethylene-1,2-bis @ 1- (2-E)
Tyl-4-phenylindenyl) zirconium dichloro
Lido, (115) ethylene-1,2-bis @ 1- (2-
Methyl-4,5-benzoindenyl) zirconiumdi
Chloride, (116) ethylene-1,2-bis [1-
{2-methyl-4- (1-naphthyl) indenyl}] di
Ruconium dichloride, (117) isopropylidenebi
1- (2-methyl-4-phenylindenyl) di
Ruconium dichloride, (118) ethylene-1,2-
Bis {1- (2-ethyl-4-phenyl-6-isopro)
Pyrindenyl) zirconium dichloride, (11
9) Ethylene-1,2-bis {1- (2-ethyl-4-)
Indolyl indenyl) zirconium dichloride (1
20) Ethylene-1,2-bis {1- (2-methyl-4)
(H-azulenyl) zirconium dichloride, (12
1) Ethylene-1,2-bis {1- (2,4-dimethyl)
-4H-azulenyl) zirconium dichloride, (1
22) Ethylene-1,2-bis {1- (2-methyl-4)
-Phenyl-4H-azulenyl) zirconium dichloro
Lido, (123) ethylene-1,2-bis @ 1- (2-
Ethyl-4-phenyl-4H-azulenyl) zirconi
Umm dichloride, (124) ethylene-1,2-bis
[1- {2-methyl-4- (1-naphthyl) indene]
｝] Zirconium dichloride, (125) ethylene-
1,2-bis [1- {2-methyl-4- (4-chlorofu
Enyl) -4H-azulenyl}] zirconium dichloride
Do, (126) isopropylidenebis {1- (2-methyl)
4-phenyl-4H-azulenyl) zirconium
Dichloride, (127) ethylene-1,2-bis @ 1-
(2-ethyl-4-phenyl-6-isopropyl-4H
-Azulenyl) zirconium dichloride, (128)
Ethylene-1,2-bis {1- (2-ethyl-4-yne)
Drill-4H-azulenyl) zirconium dichloride
(129) Dimethylgermylene bis {1- (2-methyl)
-4-phenylindenyl) zirconium dichloride
, (130) dimethylgermylene bis {1- (2-E)
Tyl-4-phenylindenyl) zirconium dichloro
Lido, (131) dimethylgermylene bis {1- (2-
Methyl-4,5-benzoindenyl) zirconiumdi
Chloride, (132) methylaluminum bis {1-
(2-ethyl-4-phenylindenyl) zirconium
Mudichloride, (133) phenylphosphinobis ｛1
-(2-ethyl-4-phenylindenyl) zirconi
Umm dichloride, (134) ethyl holanobis
(2-methyl-4-phenylindenyl) zirconium
Mudichloride, (135) phenylaminobis {1-
(2-methyl-4-phenylindenyl) zirconium
Mudichloride and the like.

(C) Examples of the compound represented by the general formula (3) include (1) (tetramethylcyclopentadienyl) titanium (bis-t-butylamide) dichloride, and (2) (tetramethylcyclopentadienyl) ) Titanium (bisisopropylamide) dichloride, (3) (tetramethylcyclopentadienyl) titanium (biscyclododecylamide) dichloride, (4) (tetramethylcyclopentadienyl) titanium {bis (trimethylsilyl) amide) dichloride , (5) (2-methyl-4-phenyl-4H-azulenyl) titanium {bis (trimethylsilyl) amide} dichloride, (6) (2-methyl-4
-Phenyl-4H-azulenyl) zirconium {bis (trimethylsilyl) amide} dichloride, (7) (2
-Methylindenyl) titanium (bis-t-butylamido) dichloride, (8) (fluorenyl) titanium (bis-t-butylamido) dichloride, (9) (3,6
-Diisopropylfluorenyl) titanium (bis-t-
Butylamido) dichloride, (10) (tetramethylcyclopentadienyl) titanium (phenoxide) dichloride, (11) (tetramethylcyclopentadienyl) titanium (2,6-diisopropylphenoxide) dichloride and the like. (D) Examples of the compound represented by the general formula (4) include: (1) dimethylsilanediyl (tetramethylcyclopentadienyl) (t-butylamido) titanium dichloride, (2) dimethylsilanediyl (tetramethylcyclo) Pentadienyl) (cyclododecylamide) titanium dichloride, (3) dimethylsilanediyl (tetramethylcyclopentadienyl) (trimethylsilylamide)
Titanium dichloride, (4) dimethylsilanediyl (tetramethylcyclopentadienyl) (t-butylamido) titanium dimethyl, (5) dimethylsilanediyl (2-methylindenyl) (t-butylamido) titanium dichloride, (6) dimethyl Silanediyl (fluorenyl) (t-butylamido) titanium dichloride, (7) dimethylsilanediyl (3,6-diisopropylfluorenyl) (t-butylamido) titanium dichloride and the like can be mentioned.

<Component [B]> As the component [B], the following compounds are used.

(B-1) Fine particle carrier carrying aluminum oxy compound: The aluminum oxy compound is specifically represented by the following general formula (5), (6) or (7)
The compound represented by these is mentioned.

[0030]

Embedded image

In each of the above general formulas, R^FourIs a hydrogen atom or
Is a hydrocarbon residue, preferably 1 to 10 carbon atoms, particularly preferably
Or a hydrocarbon residue having 1 to 6 carbon atoms. Also multiple
R ^FourMay be the same or different. R^FiveIs
C1-C10 hydrocarbon residue or halogenated hydrocarbon
Represents an elementary group. Also, p is 0 to 40, preferably 2 to 30.
Indicates an integer.

The compounds represented by the general formulas (5) and (6) are compounds also called alumoxanes, and are obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminums with water. Specifically, (a) methylalumoxane, ethylalumoxane, propylalumoxane, butylalumoxane, isobutylalumoxane obtained from one type of trialkylaluminum and water, (b) two types of trialkylaluminum, Examples thereof include methylethylalumoxane, methylbutylalumoxane, and methylisobutylalumoxane obtained from water. Of these, methylalumoxane or methylisobutylalumoxane is preferred.

The above-mentioned alumoxanes can be used in combination of two or more in each group and between each group. The alumoxane can be prepared under various known conditions. Specifically, the following method can be exemplified. (A) A method in which a trialkylaluminum is directly reacted with water in the presence of a suitable organic solvent such as toluene, benzene, or ether. (B) A method of reacting a trialkylaluminum with a salt hydrate having water of crystallization, for example, a hydrate of copper sulfate or aluminum sulfate. (C) A method of reacting trialkylaluminum with water impregnated in silica gel or the like. (D) A method in which trimethylaluminum and triisobutylaluminum are mixed and then directly reacted with water in the presence of a suitable organic solvent such as toluene, benzene, or ether. (E) a salt hydrate having a mixture of trimethylaluminum and triisobutylaluminum and water of crystallization, for example,
A method of reacting a hydrate with copper sulfate and aluminum sulfate by heating. (F) A method in which silica gel or the like is impregnated with water, treated with triisobutylaluminum, and then additionally treated with trimethylaluminum. (G) A method in which methylalumoxane and isobutylalumoxane are synthesized by a known method, and a predetermined amount of these two components is mixed and reacted by heating. (H) A method in which a salt having water of crystallization such as copper sulfate pentahydrate and trimethylaluminum are added to an aromatic hydrocarbon solvent such as benzene and toluene and reacted at a temperature of about -40 to 40 ° C.

The amount of water used in the reaction is usually 0.5 to 1.5 in molar ratio to trimethylaluminum.
The methylalumoxane obtained by the above method is a linear or cyclic organoaluminum polymer.

The compound represented by the general formula (7) is prepared by mixing one kind of trialkylaluminum or two or more kinds of trialkylaluminums with an alkylboronic acid represented by the following general formula (8): It can be obtained by a 1: 1 (molar ratio) reaction. In the general formula (8), R ⁵ represents a hydrocarbon residue having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or a halogenated hydrocarbon group.

R ⁵ B (OH) ₂ (8) Specifically, the following reaction products can be exemplified. (A) Trimethylaluminum and methylboronic acid 2:
Reaction product 1 (b) 2: 1 reaction product of triisobutylaluminum and methylboronic acid (c) 1: 1: 1 reaction product of trimethylaluminum, triisobutylaluminum and methylboronic acid (d) 2: 2 reaction of trimethylaluminum and ethylboronic acid
1 Reactant (e) Triethylaluminum and butylboronic acid 2:
1 Reactant These aluminum oxy compounds are supported on a particulate carrier. The particulate carrier will be described later.

(B-2) A fine particle carrier carrying an ionic compound or Lewis acid capable of converting component (A) into a cation by reacting with component (A): First, react with component (A) The ionic compound and Lewis acid capable of converting the component (A) into a cation will now be described. The fine particle carrier will be described later. Some of the above-mentioned Lewis acids can be regarded as ionic compounds capable of reacting with the component (A) to convert the component (A) into a cation. Therefore, compounds belonging to both the above-mentioned Lewis acids and ionic compounds belong to either one.

The ionic compound capable of reacting with the component (A) to convert the component (A) into a cation includes a compound represented by the general formula (9).

[K] ^{e +} [Z] ^e-
(9) In the general formula (9), K is a cation component, for example,
Examples include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. In addition, metal cations and organic metal cations which are easily reduced by themselves are also included.

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

In the above general formula (9), Z is an anion component, which is a component (generally a non-coordinating component) which becomes a counter anion to the converted cation species of component (A). As Z, for example, an organic boron compound anion,
Organic aluminum compound anion, organic gallium compound anion, organic phosphorus compound anion, organic arsenic compound anion, organic antimony compound anion, and the like,
Specific examples include the following anions. (A) tetraphenylboron, tetrakis (3,4,5
-Trifluorophenyl) boron, tetrakis @ 3,5
-Bis (trifluoromethyl) phenyl} boron, tetrakis {3,5-di (t-butyl) phenyl} boron,
(B) tetraphenylaluminum, tetrakis (3,3)
4,5-trifluorophenyl) aluminum, tetrakis {3,5-bis (trifluoromethyl) phenyl}
Aluminum, tetrakis (3,5-di (t-butyl)
(C) tetraphenylgallium, tetrakis (3,4)
5-trifluorophenyl) gallium, tetrakis {3,5-bis (trifluoromethyl) phenyl} gallium, tetrakis {3,5-di (t-butyl) phenyl} gallium, tetrakis (pentafluorophenyl)
Gallium, etc. (d) tetraphenyl phosphorus, tetrakis (pentafluorophenyl) phosphorus, etc. (e) tetraphenyl arsenic, tetrakis (pentafluorophenyl) arsenic, etc. (f) tetraphenyl antimony, tetrakis (pentafluorophenyl) antimony, etc. (g) Decaborate,
Undecaborate, carbadodecaborate, decachlorodecaborate, etc. Examples of Lewis acids, particularly Lewis acids capable of converting component [A] into cations, include various organic boron compounds and metal halide compounds. Typical examples include the following compounds. (A) Organic boron compounds such as triphenylboron, tris (3,5-difluorophenyl) boron and tris (pentafluorophenyl) boron (b) Aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, magnesium bromide Metal halide compounds such as, magnesium iodide, magnesium chlorobromide, magnesium chloroiodide, magnesium bromoiodide, magnesium hydride, magnesium hydride, magnesium hydride, magnesium alkoxide, magnesium alkoxide, etc. b-3) Solid acid fine particles Examples of the solid acid fine particles include fine particles of a solid acid such as alumina and silica-alumina.

Here, (b-1) and (b-
The particulate carrier in 2) will be described.

The fine particle carrier of the present invention has an elemental composition,
The compound composition is not particularly limited. For example, the following compounds may be mentioned as the particulate carrier made of an inorganic or organic compound.

For example, inorganic carriers include typical metal oxides such as silica, alumina, silica-alumina, various zeolites and magnesia, typical metal halides such as aluminum chloride and magnesium chloride, copper oxide, zinc oxide, iron oxide, and the like. Examples thereof include transition metal compounds such as iron chloride, activated carbon, diatomaceous earth, ion-exchange layered compounds other than silicates, and inorganic silicates. Alternatively, a mixture thereof may be used.

Examples of the organic carrier include polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, styrene,
A fine particle carrier of a porous polymer composed of a polymer of an aromatic unsaturated hydrocarbon such as divinylbenzene is exemplified.
Alternatively, a mixture thereof may be used.

These fine particle carriers are usually 0.1 μm
-5 mm, preferably 1 μm-1 mm, more preferably 5 μm-200 μm.

(B-4) Ion-exchangeable phyllosilicate The phyllosilicate is a silicate compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force. In the present invention, the layered silicate is preferably ion-exchangeable. Here, ion exchangeability means that interlayer cations of the layered silicate can be exchanged. The term “layered” means having a layered structure.

Most ion-exchangeable phyllosilicates occur naturally mainly as a main component of clay minerals.
The ion-exchange layered silicate is not limited to natural ones,
It may be an artificial compound. Specific examples of the ion-exchangeable layered silicate include, for example, known layered silicates described in “Clay Mineralogy”, Asakura Shoten (1995) by Haruo Shiramizu, and include dickite, nacrite, kaolinite, and anoki. Kaolin group such as site, metahalloysite, halloysite, serpentine group such as chrysotile, lizardite, antigolite, montmorillonite, zaukonite, beidellite, nontronite, smectite group such as saponite, teniolite, hectorite, stevensite, vermiculite, etc. Vermiculite, mica,
Examples include mica such as illite, sericite, and chlorite, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, and chlorite. These may form a mixed layer.

Among these, montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite,
Smectites such as teniolite, vermiculites and mica are preferred.

Typical examples of the smectite family include:
Generally, it is montmorillonite, beidellite, saponite, nontrite, hectorite, sauconite and the like. "Benclay SL" (manufactured by Mizusawa Chemical Industries), "Kunipia", "Smecton" (all manufactured by Kunimine Industries), "Montmorillonite K10" (manufactured by Aldrich, Jute Chemie), "K-Catalysts"
Commercial products such as "Series" (manufactured by Jute Hemy) can also be used.

Representative mica tribes include muscovite,
Examples include paragonite, phlogopite, biotite, and lepidolite. Commercially available "synthetic mica somasif" (manufactured by Corp Chemical), "fluorphlogopite", "fluorine tetrasilicic mica",
Commercial products such as "Teniolite" (all manufactured by Topy Industries) can also be used.

In the present invention, Al atoms in the silicate and Mg
The molar ratio of atoms (Al / Mg ratio) is preferably 7.0 or less. Particularly preferred component [B] is Al / Mg.
It is a smectite with a ratio between 4.5 and 6.5.

These ion-exchange layered silicates are preferably subjected to a chemical treatment.

Here, the chemical treatment may be any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the crystal structure and chemical composition of the ion-exchange layered silicate. Specifically, (a) acid treatment, (b)
Alkali treatment, (c) salt treatment, and (d) organic substance treatment. These treatments remove surface impurities, exchange cations between layers, Al, F in the crystal structure.
Cations such as e and Mg are eluted, and as a result, ionic complexes, molecular complexes, organic derivatives and the like are formed, and the surface area, interlayer distance, solid acidity, and the like can be changed. These processes may be performed alone, or two or more processes may be combined.

As the (a) acid used in the chemical treatment,
Suitable inorganic or organic acids, preferably, for example,
Hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, etc.,
(B) Examples of the alkali include NaOH, KOH, NH _{3 and the} like. (C) The salts are selected from the group consisting of cations containing at least one atom selected from the group consisting of Group 2 to Group 14 atoms, and halogen atoms or anions derived from inorganic or organic acids. Compounds comprising at least one anion are preferred. (D) As organic substances, alcohols (aliphatic alcohols having 1 to 4 carbon atoms, preferably, for example, methanol, ethanol, propanol, ethylene glycol, glycerin, 6 carbon atoms)
To 8 aromatic alcohols, preferably phenol, for example, higher hydrocarbons (5 to 10 carbon atoms, preferably 5 to 10 carbon atoms).
8, things, preferably, for example, hexane, heptane, etc.)
Is raised. Also, formamide, hydrazine, dimethyl sulfoxide, N-methylformamide, N, N-
Dimethylaniline and the like are preferred.

The salts and acids may be two or more.
When the salt treatment and the acid treatment are combined, there are a method of performing the salt treatment and then performing the acid treatment, a method of performing the acid treatment and then performing the salt treatment, and a method of simultaneously performing the salt treatment and the acid treatment.

The conditions for treatment with salts and acids are not particularly limited, but usually the concentration of salts and acids is 0.1 to 50.
Wt%, treatment temperature is from room temperature to boiling point, treatment time is from 5 minutes to 2
It is preferable to select a condition of 4 hours and to elute at least a part of the substance constituting the ion-exchange layered silicate. Salts and acids are toluene, n-
If an organic solvent such as heptane or ethanol, or a salt or an acid is liquid at the treatment temperature, it can be used without a solvent, but is preferably used as an aqueous solution.

Usually, an ion-exchange layered silicate (component b-
For 4), it is desirable to use those from which these adsorbed water and / or interlayer water have been removed by heat treatment. The method of heat-treating the layered silicate for adsorbed water and interlayer water is not particularly limited, and methods such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used.

As a specific drying method, a method of filling in a closed vessel and dehydrating by heating under reduced pressure, or drying under heating using a so-called rotary kiln of a batch type or a continuous type generally used industrially, is used. A method in which nitrogen or the like is passed and dried is used.

The heating temperature is 50 ° C. or higher, preferably 100 ° C. or higher, particularly preferably 150 ° C. or higher so that interlayer water does not remain. Is not preferred. Preferably it is less than 400 ° C, more preferably less than 300 ° C.

The heating time varies depending on the amount of the ion-exchanged layered silicate to be dried, the water content before heating, the dewatering ability of the dryer, etc., but is usually 0.5 minutes or more, preferably 1 minute or more. And particularly preferably 3 minutes or more. At this time, the water content of the component (b-4) after the removal is 3% by weight or less when the water content is 0% by weight when dehydrated for 2 hours at a temperature of 200 ° C. and a pressure of 1 mmHg. , Preferably 1% by weight or less.

As an industrially preferred embodiment of drying, a predrying step of preliminarily drying to a moisture content of about 5% or less at a temperature of 50 to 150 ° C., and then a pre-dried ion-exchange layer The silicate is subjected to a heat treatment under a flow of an inert gas such as nitrogen or under reduced pressure to undergo a main drying step of drying to a predetermined moisture content.
If agglomerates of the ion-exchange layered silicate are formed in the predrying step, it is preferable to loosen the particles to a predetermined particle size to form particles, and then subject the particle-ionized ion-exchanged layered silicate to the main drying step. preferable.

The ion-exchangeable layered silicate of the present invention (component b
-4), when performing a chemical treatment, including the treatment process, at any time before, during, or after any of these processes, the particle properties are determined by pulverization, granulation, sizing, sorting, etc. Can be controlled. The method can be of any suitable purpose. In particular, for the granulation method, 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, Emulsion granulation and submerged granulation are exemplified. Particularly preferred granulation methods are spray granulation method, tumbling granulation method and compression granulation method. Among the above-mentioned components [B], particularly preferred is (b-4) an ion-exchangeable layered silicate.

The α-olefin polymerization catalyst of the present invention may contain, as an optional component other than the fine particle carrier, an active hydrogen-containing compound such as H ₂ O, methanol, ethanol and butanol, and an electron-donating compound such as ether, ester and amine. Compound, phenyl borate, dimethylmethoxyaluminum,
It can contain an alkoxy-containing compound such as phenyl phosphite, tetraethoxysilane, diphenyldimethoxysilane, and the like.

The optional components other than those described above include tri-lower alkylaluminums such as trimethylaluminum, triethylaluminum and triisobutylaluminum, halogen-containing alkylaluminums such as diethylaluminum chloride, diisobutylaluminum chloride and methylaluminum sesquichloride, and diethylaluminum. Alkyl aluminum hydrides such as hydrides,
Alkoxy-containing alkylaluminums such as diethylaluminum ethoxide and dimethylaluminum butoxide; and aryloxy-containing alkylaluminums such as diethylaluminum phenoxide are exemplified.

In the α-olefin polymerization catalyst of the present invention, (b-1) a fine particle carrier carrying an aluminum oxy compound, (b-2) reacts with component [A] to convert component [A] into a cation. A particulate carrier carrying an ionic compound or a Lewis acid capable of being converted, (b-
3) The solid acid fine particles or (b-4) the ion-exchange layered silicate fine particles can be used alone as the component (B), or can be used in an appropriate combination of these four components.

<Description of Component [C]> In the present invention, the catalyst for olefin polymerization can be prepared by combining an organic aluminum compound as an optional component in addition to the above-mentioned components [A] and [B]. it can.

Examples of the organoaluminum compound used as the component [C] include AlR ⁸ _j X _3-j (10) (in the formula (10), R ⁸ is a C ₁ -C ₂₀ hydrocarbon group, and X is Hydrogen, halogen, an alkoxy group, and j are represented by 0 <j ≦ 3). Specifically, it is a trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum or triisobutylaluminum, or a halogen or alkoxy-containing alkylaluminum such as diethylaluminum monochloride or diethylaluminum methoxide.

As the organoaluminum compound, an aluminum oxy compound represented by the following general formula (5), (6) or (7) can be used.

[0070]

Embedded image

(In each of the above general formulas, R ⁴ represents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably a hydrocarbon residue having 1 to 6 carbon atoms. R ⁴ may be the same or different.
⁵ represents a hydrocarbon residue having 1 to 10 carbon atoms or a halogenated hydrocarbon group. P is 0 to 40, preferably 2
Shows an integer of ~ 30. ) As specific compounds, the same compounds as described in the component (b-1) can be used.

Among these, a trialkylaluminum is preferable, and a trialkylaluminum compound having a branched structure in which R is β-position, such as triisobutylaluminum, is particularly preferable.

In the present invention, the catalyst is obtained by contacting the component [A], the component [B] and, if necessary, the component [C]. The contact of the component [A], the component [B] and, if necessary, the component [C] is not particularly limited. The component [A] is brought into contact with the component [B]. After contacting the component [A] with the component [B], the component [C]
Is added. After contacting the component [A] with the component [C], the component [B]
Is added. After contacting the component [B] with the component [C], the component [A]
Is added.

In addition, a method of contacting the three components simultaneously or a method of contacting the contact product of component [A] and component [C] with the contact product of component [B] and component [C] is also employed. obtain. Further, an aluminum oxy compound, an ionic compound capable of reacting with the component [A] to convert the component [A] into a cation, or a Lewis acid is used as the component (b-1).
It is not limited to the form of (b-2) and can be separately used in an arbitrary method.

Upon or after the contact of each component of the catalyst, a polymer such as polyethylene or polypropylene, silica,
Solids of inorganic oxides such as alumina may coexist or may be brought into contact.

The contact is carried out in an inert gas such as nitrogen, pentane,
It may be carried out in an inert hydrocarbon solvent such as hexane, heptane, toluene and xylene. Contact temperature is -20 ° C ~
The reaction is carried out between the boiling points of the solvent, particularly preferably between room temperature and the boiling point of the solvent.

The amount of each catalyst component used is 0.0001 to 10 mmol, preferably 0.001 to 5 mmol of component [A] per 1 g of component [C]. When component [B] is (b
In the case of -1), the atomic ratio of the transition metal in the component [A] to the aluminum in the component [B] is 1: 1 to 100,000, preferably 5 to 10,000, and the component [B] is ( b-
In the case of 2), the molar ratio of the transition metal in the component [A] to the component (b-2) is usually 0.1 to 1,000, preferably 0.5.
-100, more preferably 1-50. The atomic ratio of the transition metal in the component [A] to the aluminum in the component [C] is 1: 0.01 to 1,000,000.
0, preferably 0.1 to 100,000.

<Preliminary Polymerization> In the present invention, the olefin polymerization catalyst prepared by the above-mentioned method can be subjected to further treatment.

As one of the treatments, a method of pre-polymerizing by pre-contacting an olefin can be employed. Examples of usable monomers include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, and styrene. .

After the preliminary polymerization, washing is carried out as required. This preliminary polymerization with ethylene or the like provides ethylene or the like in an inert solvent under the contact of the above components to produce a polymer of 0.01 to 1000 g, preferably 0.1 to 100 g per 1 g of the solid catalyst component. It is desirable to do so. The prepolymerization temperature is -50 to 100C, preferably 0 to 100C, and the prepolymerization time is 0.1 to 100.
Time, preferably 0.1 to 20 hours.

The solid catalyst component obtained by the treatment as described above may be directly used for the polymerization reaction without washing.
It may be used after washing. When the reaction is carried out in a solvent such as an inert hydrocarbon, the slurry may be used as it is, or the solvent may be distilled off and dried to obtain a powder.

<Storage> The catalyst for olefin polymerization may be stored in a slurry state containing a solvent, a semi-dry state containing a small amount of the solvent, or a completely dry state containing the solvent completely removed. Here, the solvent refers to a single or a mixture of inert hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, toluene, xylene, and liquid paraffin. The slurry concentration is based on the components per mL of solvent.
[B] is 0.0001 g to 10 g, preferably 0.01 g
０．５0.5 g. In the case of a semi-dry state, the amount is 0.001 to 10 mmol, preferably 0.01 to 1 mmol per 1 g of the component [B].

The storage temperature of the catalyst for olefin polymerization is 90 ° C.
The temperature is preferably 50 ° C. or lower, and the effect is higher as the temperature is lower.

The organoaluminum compound to be present during storage of the olefin polymerization catalyst can be used without any particular limitation as long as the object of the present invention can be achieved, such as an aluminoxane and a trialkylaluminum compound.
When an aluminum oxy compound is used as the component (b-1) and an organoaluminum compound is used as the component [C] during the preparation of the olefin polymerization catalyst, or when an organoaluminum compound is added in the prepolymerization and they remain. Can be saved in that state. In the present invention, the aluminum oxy compound is treated as belonging to the organic aluminum compound.

When the olefin polymerization catalyst is stored in the presence of the organic aluminum, the molar ratio of the organic aluminum / component [A] is 0.1 to 1000, preferably 1 to 100. The amount of organic aluminum per 1 g of the component [B] is 0.00.
It is 1 to 10 mmol, preferably 0.01 to 5 mmol.

As a method for drying the olefin polymerization catalyst containing a solvent, methods such as heat removal, removal under gas flow, and removal under reduced pressure are used. Either method is performed in an atmosphere of an inert gas such as nitrogen or argon so that the catalyst does not come into contact with air or moisture.

The drying temperature is 80 ° C. or lower or the boiling point of the solvent or lower, preferably 0 ° C. to 50 ° C. As a gas used for drying under a gas flow, an inert gas such as nitrogen or argon is used. When removing the solvent by drying, the solid component in the catalyst slurry may be settled, and the supernatant may be removed in advance by decantation or the like. The initial concentration of the catalyst slurry for starting the drying is not particularly limited, but the solvent 1 m
The component [B] per L may be 0.0001 g to 10 g, preferably 0.01 g to 0.5 g.

When drying in the presence of organic aluminum, the concentration of aluminum in the solvent-containing catalyst is from 0.1 to 1000, preferably from 1 to 100, in terms of the molar ratio of organic aluminum / component [A]. The amount of organic aluminum per 1 g of the component [B] is 0.1.
001 to 10 mmol, preferably 0.01 to 5 mmol
l.

When the step of synthesizing the catalyst for olefin polymerization includes a step of bringing an organoaluminum compound into contact, it is advantageous to carry out washing without leaving a portion of the catalyst.

However, the component [D] organoaluminum compound may be newly added when storing the olefin polymerization catalyst.

<Component [D]> As the organoaluminum compound of the component (D), those represented by the following general formula (11) can be used.

[0092] AlR ⁹ of _a P _3-a (11) compound represented by the formula in the present invention alone, it is needless to say that may be used in or in combination as a mixture of two or more. This use can be used not only at the time of catalyst preparation but also at the time of prepolymerization or polymerization. In the formula, R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms;
Represents a halogen, hydrogen, an alkoxy group, an amino group or a siloxy group. a indicates a number greater than 0 and 3 or less.
R ⁹ is preferably an alkyl group, and P is chlorine when it is a halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group and 1 to 8 carbon atoms when it is an amino group. Is preferred. Therefore, specific examples of preferred compounds include trimethylaluminum, triethylaluminum, trinormal propyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, trinormal hexyl aluminum,
Trinormal octyl aluminum, tri normal decyl aluminum, diethyl aluminum chloride, diethyl aluminum sesquichloride, diethyl aluminum hydride, diethyl aluminum ethoxide, diethyl aluminum dimethyl amide, diisobutyl aluminum hydride, diisobutyl aluminum chloride and the like can be mentioned. Of these, preferably, a =
3, trialkylaluminum and dialkylaluminum hydride where a = 1. More preferably, R
⁹ is an alkyl aluminum having a branched structure at the β-position.

As the organoaluminum compound, an aluminum oxy compound represented by the following general formula (5), (6) or (7) can be used.

[0094]

Embedded image

(In each of the above general formulas, R ⁴ represents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably a hydrocarbon residue having 1 to 6 carbon atoms. R ⁴ may be the same or different.
⁵ represents a hydrocarbon residue having 1 to 10 carbon atoms or a halogenated hydrocarbon group. P is 0 to 40, preferably 2
Shows an integer of ~ 30. ) As specific compounds, the same compounds as described in the component (b-1) can be used.

When component [D] is added to the above-mentioned catalyst,
Any of a slurry state using an inert hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, xylene, and liquid paraffin as a solvent, a semi-dry state containing a small amount of the above solvent, or a completely dry state containing the solvent completely May be added. When adding the component [D] to the catalyst slurry or the solid catalyst, it is preferable to mix the components while performing operations such as stirring.

The type of the component [D] to be added to the catalyst may be the same as the component [C], but may be a mixture of different types.

When component [D] is added, neat or undiluted solution may be used, but hexane, heptane, pentane,
A solution diluted with an inert hydrocarbon such as cyclohexane, benzene, toluene, xylene, or liquid paraffin is preferred. The temperature at which the component [D] is added is 80 ° C. or lower, or the boiling point of the solvent or lower, preferably 50 ° C. or lower.

<Polymerization> The polymerization reaction of the olefin is carried out using the solid catalyst component obtained as described above, and an organoaluminum compound is used if necessary. At this time, as the organoaluminum compound to be used, the same compounds as the above-mentioned component [C] can be mentioned. The amount of the organoaluminum compound used at this time is selected so that the molar ratio of the transition metal in the catalyst component [A] to the aluminum in the organoaluminum compound is 1: 0 to 10,000.

In the present invention, the olefin polymer includes a homopolymer of olefin, a copolymer of olefin, and a copolymer of olefin and another copolymerizable monomer. Examples of the olefin that can be polymerized by the catalyst include ethylene, propylene, butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, vinylcycloalkane, styrene, and derivatives thereof.
Further, the copolymerization can be suitably applied to generally known random copolymerization and block copolymerization.

The polymerization reaction is carried out in the presence or absence of a solvent such as an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene and cyclohexane, or a liquefied α-olefin. The temperature is −50 to 250 ° C., and the pressure is not particularly limited, but preferably ranges from normal pressure to about 2000 kgf / cm ² . Further, hydrogen may be present as a molecular weight regulator in the polymerization system.

[0102]

The present invention will be described in more detail with reference to the following examples.
The present invention is not limited to the following examples.

The following operations were all performed in an inert gas atmosphere. The solvent used in the complex synthesis, catalyst preparation and polymerization was dehydrated and purified using molecular sieve 4A, and deoxygenated by bubbling with purified nitrogen.

A. Measurement of MFR Melt flow index (g / 10 min) is JIS-K
Measured according to -6758.

B. Measurement of melting point: 10 ° C. using DSC (“DSC6200” manufactured by Seiko Instruments Inc.)
After one temperature rise / fall to 20-200 ° C./min
It was determined by measurement at the time of the second temperature rise.

C. Evaluation of bulk density of polymer particles: The bulk density was measured by measuring the weight of a polymer particle flowing from a stainless steel funnel having a 5 mmφ outlet hole diameter into a 100 cc container, and expressed as the weight per 1 cc.

Example 1-1 (1) Synthesis of Component (A) [(r) -Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl] {] Zirconium] is disclosed in
No. 090, the method described in the examples.

Bromochlorobenzene (1.84 g, 9.
59 mmol) was dissolved in a mixed solvent of diethyl ether (10 mL) and hexane (10 mL), and a solution of t-butyllithium in pentane (11.7 mL, 19.18 mmol) was obtained.
1, 1.64N) was added dropwise at -78 ° C. 2 at -70 ° C
The mixture was stirred at -5 ° C for 1.5 minutes for 1.5 minutes. 2-Methylazulene (1.22 g, 8.63 mmol) was added to the solution, and the mixture was stirred at -5 ° C for 10 minutes and at room temperature for 1.5 hours. After cooling to 0 ° C., tetrahydrofuran (10 mL) was added, and N-methylimidazole (15 μL) and dimethyldichlorosilane (0.52 m
L, 4.31 mmol), and the mixture was heated to room temperature and stirred at room temperature for 1.5 hours. Thereafter, dilute hydrochloric acid was added, and the mixture was separated. The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane and hexane-dichloromethane 1: 1) to give dimethylbis1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -1,4. -Dihydroazulene) (2.06 g, 85
%)was gotten.

The azulene (1.27 g) obtained above was dissolved in diethyl ether (15 mL), and a hexane solution of normal butyl lithium (2.8 mL,
(1.6 mol / L) was added dropwise, the temperature was gradually raised, and the mixture was stirred at room temperature overnight. The solvent was distilled off, and toluene (5 mL) and diethyl ether (0.12 mL) were added. Cooled to -78 ° C and sublimated and purified zirconium tetrachloride (530mg)
, And the mixture was gradually heated and stirred at room temperature for 4 hours. The resulting solution was subjected to frit filtration using Celite, and toluene (3
mL) on a frit. The filtrate was extracted with dichloromethane and concentrated under reduced pressure to give dichloro [1,1 '.
A racemic / meso mixture of -dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4H-azulenyl)] zirconium (906 mg, including toluene) was obtained. The racemic-meso ratio was 6: 4.

Complex Purification The racemic-meso mixture (906 mg, including toluene) obtained above was suspended in dichloromethane (25 mL), and subjected to 40 spectral irradiation using a high-pressure mercury lamp (100 W). This solution was filtered using a frit, and the solvent was distilled off under reduced pressure. Toluene (7 mL) was added to the obtained solid, the mixture was allowed to stand, and the supernatant was removed. The same operation was performed with toluene (5 mL,
6 mL) and finally hexane (8 mL, 5 m
L). When dried under reduced pressure, a racemic body (275 mg) was obtained as a yellow powder. ¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.95
(S, 6H, SiMe ₂ ), 2.13 (s, 6H, 2-
Me), 4.83 (br s, 2H, 4-H), 5.7.
0-5.90 (m, 8H), 6.05-6.11 (m,
2H), 6.73 (d, 2H), 7.25-7.30.
(M, 8H, arom.). negative CI-
_{^{MS722 (M + C 36 H 32}} 35 Cl 4 Si 90 Zr). (2) Synthesis of component (B) (a) Acid treatment In a separable flask, 96% sulfuric acid (2500 g) was added to 3750 mL of pure water, and 1000 g of commercially available montmorillonite (Benclay SL, manufactured by Mizusawa Chemical Co., Ltd.) was added at 60 ° C.
To form a slurry while stirring. This slurry was heated to 90 ° C over 1 hour and reacted at 90 ° C for 5 hours,
The reaction slurry was cooled to room temperature for 1.5 hours and washed with distilled water until the washing solution (filtrate) reached pH 3. The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and further dried under reduced pressure at 200 ° C. for 6 hours to obtain 707.2 g of chemically treated smectite.

The composition of this chemically treated montmorillonite is A
l: 5.21 wt%, Si: 38.9 wt%, Mg:
0.80 wt%, Fe: 1.60 wt%, Na: <0.
2 wt%, and Al / Si = 0.139 [mol / m]
ol]. (B) Organic aluminum treatment of the above components 20.0 g of the chemically treated montmorillonite obtained in the above (a) was weighed into a glass reactor having an internal volume of 500 mL, and 73.7 mL of heptane and 84.0 mL of a heptane solution of triethylaluminum (50 mL) were added. 1.0 mmol) and add 1 at room temperature.
Stirred for hours. Thereafter, the resultant was washed with heptane, and finally, the slurry amount was adjusted to 200.0 mL. (3) Prepolymerization with propylene (r)-
87.2 mL of a heptane solution of dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium (30
0.37 μmol) and 4.26 mL of triisobutylaluminum in heptane (3003.58 μmol)
Was added at room temperature and stirred for 60 minutes.

This complex solution was added to the montmorillonite treated with triethylaluminum of the synthesis (2) of (2) and stirred at room temperature for 60 minutes. Next, the mixed slurry was added to a 1-liter stirred autoclave in which 209 mL of heptane had been introduced in advance, and the mixture was stirred. When the temperature in the autoclave was stabilized at 40 ° C., propylene was fed at 476.2 mmol / hr for 120 minutes. Subsequently, the temperature was raised to 50 ° C. at a rate of 1 ° C./min and maintained for 2 hours. Thereafter, the remaining gas was purged, and the prepolymerized catalyst was recovered from the autoclave. (4) Drying of Preliminary Polymerization Catalyst The catalyst slurry recovered in the above (3) was allowed to stand, and the supernatant was extracted. 17.02 mL (12.02 mmol) of a solution of triisobutylaluminum in heptane was added to the remaining solid component.
l) was added at room temperature, and the mixture was stirred at room temperature for 10 minutes, and dried under reduced pressure to recover 62.11 g of a solid catalyst component. (5) Copolymerization of propylene-ethylene 2.86 mL (40 mL) of a heptane solution of triisobutylaluminum was placed in a 3-liter stirred autoclave.
0 mg) and 45.6 m of the prepolymerized catalyst obtained above.
g, 750 g of liquefied propylene and 16.5 g of ethylene.
g and 34 NmL of hydrogen were introduced, and then the temperature inside the autoclave was raised to 70 ° C, and polymerization was carried out for 1 hour while maintaining the temperature at 70 ° C. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene-ethylene copolymer was 167.8 g. The amount of polymer produced per 1 g of the solid component per hour was 11,187 g. The MFR of the polymer was 4.83 g / 10 min, and the bulk density was 0.441.
g / cc, melting point: 139.4 ° C.

<Example 1-2> (1) The dried catalyst obtained in (4) of Example 1-1 was transferred to a Pyrex (registered trademark) pressure-resistant bottle under a nitrogen atmosphere, sealed, and then cooled at room temperature under nitrogen. Stored in sealed storage for 6 months. (2) Copolymerization of propylene-ethylene 2.86 mL (40 mL) of a heptane solution of triisobutylaluminum was placed in a 3-liter stirred autoclave.
0 mg) and 45.6 m of the prepolymerized catalyst obtained above.
g, 750 g of liquefied propylene and 16.5 g of ethylene.
g and 34 NmL of hydrogen were introduced, and then the temperature inside the autoclave was raised to 70 ° C, and polymerization was carried out for 1 hour while maintaining the temperature at 70 ° C. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene-ethylene copolymer was 177.0 g. The amount of polymer produced per 1 g of the solid component per hour was 11,800 g. The MFR of the polymer was 3.92 g / 10 min, and the bulk density was 0.369.
g / cc and the melting point was 135.7 ° C.

<Example 2-1> (1) Preliminary polymerization with propylene The above Example 1-1 (1) which had been prepared in advance
Synthetic (r) -dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H]
-Azulenyl}] zirconium in heptane 87.2
4.26 mL (3003.58 mL) of a solution of triisobutylaluminum in heptane was added to mL (300.37 μmol).
μmol) at room temperature and stirred for 60 minutes.

This complex solution was used in Example 1-1 (2) above.
(Ii) to montmorillonite treated with triethylaluminum, and stirred at room temperature for 60 minutes. Next, the mixed slurry was added to a 1-liter stirred autoclave in which 209 mL of heptane had been introduced in advance, and the mixture was stirred. When the temperature in the autoclave was stabilized at 40 ° C., propylene was fed at 476.2 mmol / hr for 120 minutes. Then at 50C at 1 ℃ / min
Then, the temperature was maintained for 2 hours, then the remaining gas was purged, and the prepolymerized catalyst was recovered from the autoclave. (2) Drying of the prepolymerized catalyst The catalyst slurry recovered in the above (1) was allowed to stand, and the supernatant was extracted. To the remaining solid component, 8.5 mL (6.01 mmol) of a triisobutylaluminum heptane solution was added at room temperature, stirred at room temperature for 10 minutes, and dried under reduced pressure to recover 53.72 g of a solid catalyst component. (3) Copolymerization of propylene-ethylene 2.86 mL (40 mL) of a heptane solution of triisobutylaluminum was placed in a 3 L stirred autoclave.
0 mg), 39.75 m of the prepolymerized catalyst obtained above.
g, 750 g of liquefied propylene and 16.5 g of ethylene.
g and 34 NmL of hydrogen were introduced, and then the temperature inside the autoclave was raised to 70 ° C, and polymerization was carried out for 1 hour while maintaining the temperature at 70 ° C. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene-ethylene copolymer was 178.0 g. The amount of polymer produced per 1 g of the solid component per hour was 11867 g. The MFR of the polymer was 3.73 g / 10 min, and the bulk density was 0.447.
g / cc, melting point 136.1 ° C.

<Example 2-2> (1) The dried catalyst obtained in (2) of Example 2-1 was transferred to a Pyrex pressure bottle under a nitrogen atmosphere, sealed, and stored at room temperature with a nitrogen seal. Stored in the warehouse for 4 months. (2) Copolymerization of propylene-ethylene 2.86 mL (40 mL) of a heptane solution of triisobutylaluminum was placed in a 3-liter stirred autoclave.
0 mg), 39.75 m of the prepolymerized catalyst obtained above.
g, 750 g of liquefied propylene and 16.5 g of ethylene.
g and 34 NmL of hydrogen were introduced, and then the temperature inside the autoclave was raised to 70 ° C, and polymerization was carried out for 1 hour while maintaining the temperature at 70 ° C. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene-ethylene copolymer was 191.2 g. The amount of polymer produced per 1 g of the solid component per hour was 12,747 g. The MFR of the polymer was 5.06 g / 10 min, and the bulk density was 0.452.
g / cc and the melting point was 137.1 ° C.

<Example 2-3> (1) The dried catalyst obtained in (2) of Example 2-1 was transferred to a Pyrex pressure bottle under a nitrogen atmosphere, sealed, and stored at room temperature with a nitrogen seal. It was kept in the storage for 7 months. (2) Copolymerization of propylene-ethylene 2.86 mL (40 mL) of a heptane solution of triisobutylaluminum was placed in a 3-liter stirred autoclave.
0 mg), 39.75 m of the prepolymerized catalyst obtained above.
g, 750 g of liquefied propylene and 16.5 g of ethylene.
g and 34 NmL of hydrogen were introduced, and then the temperature inside the autoclave was raised to 70 ° C, and polymerization was carried out for 1 hour while maintaining the temperature at 70 ° C. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene-ethylene copolymer was 192.7 g. The amount of polymer produced per 1 g of the solid component per hour was 12,847 g. The MFR of the polymer was 4.05 g / 10 min, and the bulk density was 0.468.
g / cc and melting point was 138.1 ° C.

<Comparative Example 1-1> (1) Drying of Preliminary Polymerization Catalyst The catalyst slurry recovered in Example 2-1 (1) was allowed to stand, and the supernatant was extracted. The remaining solid component was dried under reduced pressure without any addition to recover 52.53 g of a solid catalyst component. (2) Copolymerization of propylene-ethylene 2.86 mL (40 mL) of a heptane solution of triisobutylaluminum was placed in a 3-liter stirred autoclave.
0 mg) and 39.3 m of the prepolymerized catalyst obtained above.
g, 750 g of liquefied propylene and 16.5 g of ethylene.
g and 34 NmL of hydrogen were introduced, and then the temperature inside the autoclave was raised to 70 ° C, and polymerization was carried out for 1 hour while maintaining the temperature at 70 ° C. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene-ethylene copolymer was 165.0 g. The amount of polymer produced per 1 g of the solid component per hour was 11,000 g. The MFR of the polymer is 4.96 g / 10 min, and the bulk density is 0.310
g / cc and the melting point was 135.9 ° C.

<Comparative Example 1-2> (1) The dried catalyst obtained in Comparative Example 1-1 (1) was transferred to a Pyrex pressure-resistant bottle under a nitrogen atmosphere, sealed, and sealed at room temperature with nitrogen. For one month. (2) Copolymerization of propylene-ethylene 2.86 mL (40 mL) of a heptane solution of triisobutylaluminum was placed in a 3-liter stirred autoclave.
0 mg), 39.75 m of the prepolymerized catalyst obtained above.
g, 750 g of liquefied propylene and 16.5 g of ethylene.
g and 34 NmL of hydrogen were introduced, and then the temperature inside the autoclave was raised to 70 ° C, and polymerization was carried out for 1 hour while maintaining the temperature at 70 ° C. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene-ethylene copolymer was 35 g. The amount of the polymer produced per 1 g of the solid component per hour was 2,333 g. The MFR of the polymer was 13.9 g / 10 min, and the melting point was 137.0 ° C.

<Example 3> (1) Preliminary polymerization with propylene Example 1-1 (1) prepared in advance
Synthetic (r) -dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H]
-Azulenyl}] zirconium in heptane 87.2
4.26 mL (3003.58 mL) of a solution of triisobutylaluminum in heptane was added to mL (300.37 μmol).
μmol) at room temperature and stirred for 60 minutes.

This complex solution was used in Example 1-1 (2) above.
(Ii) to montmorillonite treated with triethylaluminum, and stirred at room temperature for 60 minutes. Next, the mixed slurry was added to a 1-liter stirred autoclave in which 209 mL of heptane had been introduced in advance, and the mixture was stirred. When the temperature in the autoclave was stabilized at 40 ° C., propylene was fed at 476.2 mmol / hr for 120 minutes. Then at 50C at 1 ℃ / min
Then, the temperature was maintained for 2 hours, then the remaining gas was purged, and the prepolymerized catalyst was recovered from the autoclave. (2) Drying of the prepolymerized catalyst The catalyst slurry recovered in the above (1) was allowed to stand, and the supernatant was extracted. To the remaining solid components, 10.0 mL (6.01 mmol) of a solution of triethylaluminum in heptane was added at room temperature, stirred at room temperature for 10 minutes, and dried under reduced pressure to recover 62.04 g of a solid catalyst component. (3) The dried catalyst obtained in the above (2) was transferred to a Pyrex pressure bottle under a nitrogen atmosphere, sealed, and stored at room temperature in a nitrogen-sealed storage for one month. (4) Copolymerization of propylene-ethylene 2.86 mL (40 mL) of a heptane solution of triisobutylaluminum was added to a 3-liter stirred autoclave.
0 mg), and the pre-polymerized catalyst obtained above was used for 46.05 m
g, 750 g of liquefied propylene and 16.5 g of ethylene.
g and 34 NmL of hydrogen were introduced, and then the temperature inside the autoclave was raised to 70 ° C, and polymerization was carried out for 1 hour while maintaining the temperature at 70 ° C. Thereafter, the unreacted residual gas was purged to stop the polymerization.

As a result, the amount of the obtained propylene-ethylene copolymer was 81.0 g. The amount of polymer produced per 1 g of the solid component per hour was 5,400 g. The MFR of the polymer was 5.34 g / 10 min, and the bulk density was 0.296.
g / cc and the melting point was 135.1 ° C.

<Example 4> (1) Preliminary polymerization with propylene Example 1-1 (1) prepared in advance
Synthetic (r) -dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H]
-Azulenyl}] zirconium in heptane 87.2
4.26 mL (3003.58 mL) of a solution of triisobutylaluminum in heptane was added to mL (300.37 μmol).
μmol) at room temperature and stirred for 60 minutes.

This complex solution was used in Example 1-1 (2) above.
(Ii) to montmorillonite treated with triethylaluminum, and stirred at room temperature for 60 minutes. Next, the mixed slurry was added to a 1-liter stirred autoclave in which 209 mL of heptane had been introduced in advance, and the mixture was stirred. When the temperature in the autoclave was stabilized at 40 ° C., propylene was fed at 476.2 mmol / hr for 120 minutes. Then at 50C at 1 ℃ / min
Then, the temperature was maintained for 2 hours, then the remaining gas was purged, and the prepolymerized catalyst was recovered from the autoclave. (2) Drying of the prepolymerized catalyst The catalyst slurry recovered in the above (1) was allowed to stand, and the supernatant was extracted. 15.4 mL (12.01 m) of a solution of diethylaluminum ethoxide in heptane was added to the remaining solid component.
mol) was added at room temperature, and the mixture was stirred at room temperature for 10 minutes, and dried under reduced pressure to recover 58.0 g of a solid catalyst component. (3) The dried catalyst obtained in the above (2) was transferred to a Pyrex pressure bottle under a nitrogen atmosphere, sealed, and stored at room temperature in a nitrogen-sealed storage for one month. (4) Copolymerization of propylene-ethylene 2.86 mL (40 mL) of a heptane solution of triisobutylaluminum was added to a 3-liter stirred autoclave.
0 mg) and 42.75 m of the prepolymerized catalyst obtained above.
g, 750 g of liquefied propylene and 16.5 g of ethylene.
g and 34 NmL of hydrogen were introduced, and then the temperature inside the autoclave was raised to 70 ° C, and polymerization was carried out for 1 hour while maintaining the temperature at 70 ° C. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the obtained propylene-ethylene copolymer was 93.3 g. The amount of the polymer produced per 1 g of the solid component per hour was 6,220 g. MF of polymer
R is 6.61 g / 10 min, bulk density is 0.336 g /
cc and the melting point was 137.0 ° C.

<Example 5-1> (1) Preliminary polymerization with propylene The above Example 1-1 (1) prepared in advance
Synthetic (r) -dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H]
-Azulenyl}] zirconium in heptane 87.2
4.26 mL (3003.58 mL) of a solution of triisobutylaluminum in heptane was added to mL (300.37 μmol).
μmol) at room temperature and stirred for 60 minutes.

This complex solution was used in Example 1-1 (2) above.
(Ii) to montmorillonite treated with triethylaluminum, and stirred at room temperature for 60 minutes. Next, the mixed slurry was added to a 1-liter stirred autoclave in which 209 mL of heptane had been introduced in advance, and the mixture was stirred. When the temperature in the autoclave was stabilized at 40 ° C., propylene was fed at 476.2 mmol / hr for 120 minutes. Then at 50C at 1 ℃ / min
Then, the temperature was maintained for 2 hours, then the remaining gas was purged, and the prepolymerized catalyst was recovered from the autoclave.

The concentration of the recovered catalyst slurry was 119.4.
It was 6 mg / mL and used for polymerization in a slurry state. (2) Copolymerization of propylene-ethylene 2.86 mL (40 mL) of a heptane solution of triisobutylaluminum was placed in a 3-liter stirred autoclave.
0 mg) and 43.8 m of the prepolymerized catalyst obtained above.
g, 750 g of liquefied propylene and 16.5 g of ethylene.
g and 34 NmL of hydrogen were introduced, and then the temperature inside the autoclave was raised to 70 ° C, and polymerization was carried out for 1 hour while maintaining the temperature at 70 ° C. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene-ethylene copolymer was 166.0 g. The amount of polymer produced per 1 g of the solid component per hour was 11067 g. The MFR of the polymer is 4.2 g / 10 min, and the bulk density is 0.464 g.
/ Cc and the melting point was 135.2 ° C.

<Example 5-2> (1) Preliminary polymerization with propylene The above Example 1-1 (1) which had been prepared in advance
Synthetic (r) -dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H]
-Azulenyl}] zirconium in heptane 87.2
4.26 mL (3003.58 mL) of a solution of triisobutylaluminum in heptane was added to mL (300.37 μmol).
μmol) at room temperature and stirred for 60 minutes.

This complex solution was used in Example 1-1 (2) above.
(Ii) to montmorillonite treated with triethylaluminum, and stirred at room temperature for 60 minutes. Next, the mixed slurry was added to a 1-liter stirred autoclave in which 209 mL of heptane had been introduced in advance, and the mixture was stirred. When the temperature in the autoclave was stabilized at 40 ° C., propylene was fed at 476.2 mmol / hr for 120 minutes. Then at 50C at 1 ℃ / min
Then, the temperature was maintained for 2 hours, then the remaining gas was purged, and the prepolymerized catalyst was recovered from the autoclave.

17.02 mL (12.02 mL) of a solution of triisobutylaluminum in heptane was added to the recovered catalyst slurry.
mmol) at room temperature and stirred for 10 minutes. The concentration of the catalyst slurry was 120.14 mg / mL, and the slurry was used for polymerization. (2) The slurry catalyst obtained in (1) was transferred to a Pyrex flask under a nitrogen atmosphere, sealed, and stored at room temperature in a nitrogen-sealed storage for one month. (3) Copolymerization of propylene-ethylene 2.86 mL (40 mL) of a heptane solution of triisobutylaluminum was placed in a 3 L stirred autoclave.
0 mg) and 45.6 m of the prepolymerized catalyst obtained above.
g, 750 g of liquefied propylene and 16.5 g of ethylene.
g and 34 NmL of hydrogen were introduced, and then the temperature inside the autoclave was raised to 70 ° C, and polymerization was carried out for 1 hour while maintaining the temperature at 70 ° C. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene-ethylene copolymer was 169.0 g. The amount of polymer produced per 1 g of the solid component per hour was 11,267 g. The MFR of the polymer was 6.55 g / 10 min, and the bulk density was 0.465.
g / cc and the melting point was 135.7 ° C.

<Comparative Example 2> (1) Preliminary polymerization with propylene Example 1-1 (1) prepared above in advance
Synthetic (r) -dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H]
-Azulenyl}] zirconium in heptane 87.2
4.26 mL (3003.58 mL) of a solution of triisobutylaluminum in heptane was added to mL (300.37 μmol).
μmol) at room temperature and stirred for 60 minutes.

This complex solution was used in Example 1-1 (2) above.
(Ii) to montmorillonite treated with triethylaluminum, and stirred at room temperature for 60 minutes. Next, the mixed slurry was added to a 1-liter stirred autoclave in which 209 mL of heptane had been introduced in advance, and the mixture was stirred. When the temperature in the autoclave was stabilized at 40 ° C., propylene was fed at 476.2 mmol / hr for 120 minutes. Then at 50C at 1 ℃ / min
Then, the temperature was maintained for 2 hours, then the remaining gas was purged, and the prepolymerized catalyst was recovered from the autoclave.

The concentration of the recovered catalyst slurry was 119.4.
It was 6 mg / mL and used for polymerization in a slurry state. (2) The slurry catalyst obtained in the above (1) was transferred to a Pyrex flask under a nitrogen atmosphere, sealed, and stored at room temperature in a nitrogen-sealed storage for one month. (3) Copolymerization of propylene-ethylene 2.86 mL (40 mL) of a heptane solution of triisobutylaluminum was placed in a 3 L stirred autoclave.
0 mg) and 43.8 m of the prepolymerized catalyst obtained above.
g, 750 g of liquefied propylene and 16.5 g of ethylene.
g and 34 NmL of hydrogen were introduced, and then the temperature inside the autoclave was raised to 70 ° C, and polymerization was carried out for 1 hour while maintaining the temperature at 70 ° C. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene-ethylene copolymer was 112.0 g. The amount of polymer produced per 1 g of the solid component per hour was 7,467 g. M of polymer
FR is 4.25 g / 10 min, bulk density is 0.462 g
/ Cc and the melting point was 137.0 ° C.

[0134]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a flowchart for helping to understand the present invention.

 ──────────────────────────────────────────────────の Continuing on the front page F term (reference) 4J028 AA01A AB00A AB01A AC01A AC08A AC09A AC10A AC26A AC27A AC28A BA00A BA01A BA01B BA02A BA03A BA04A BA05A BB01A BB01B BB02A BB03A BB04A BC13ABC BCBC BC BC BC BC BC BC CA15A CA16A CA18A CA19A CA25A CA27A CA28A CA30A CA49A CB09A DA01 DA02 DA03 DA04 DA05 DA06 DB02A DB02B DB02C DB04A DB04B DB04C DB08A DB08B DB08C EB01 EB02 EB04 EB05 EB10 EB21 EC01 EC09 FA07 GA07 GA07

Claims (7)

[Claims] An olefin polymerization catalyst obtained by contacting the following components [A] and [B] is stored in the presence of an organoaluminum compound. Method. Component [A]: transition metal compound of Groups 4 to 6 of the periodic table having at least one conjugated 5-membered ring ligand, Component [B]: selected from the following (b-1) to (b-4) A solid component containing at least one component, (b-1) a particulate carrier carrying an aluminum oxy compound, and (b-2) a component [A] which can be converted into a cation by reacting with the component [A]. (B-3) solid acid fine particles (b-4) ion-exchange layered silicate fine particles, 2. The method for preserving an olefin polymerization catalyst according to claim 1, wherein the olefin polymerization catalyst is obtained by contacting the following components [A], [B] and [C]. Component [A]: transition metal compound of Groups 4 to 6 of the periodic table having at least one conjugated 5-membered ring ligand, Component [B]: selected from the following (b-1) to (b-4) A solid component containing at least one component, (b-1) a particulate carrier carrying an aluminum oxy compound, and (b-2) a component [A] which can be converted into a cation by reacting with the component [A]. (B-3) solid acid fine particles (b-4) ion-exchange layered silicate fine particles, component [C] organoaluminum compound 3. The method according to claim 1, wherein the component [B] is an ion-exchange layered silicate. 4. The method for storing an olefin polymerization catalyst according to claim 1, wherein the olefin polymerization catalyst is a prepolymerization catalyst in which an olefin has been brought into contact in advance. 5. The method for preserving an olefin polymerization catalyst according to claim 1, wherein after the preparation of the catalyst, an aluminum compound is added by newly adding a component [D] an organoaluminum compound. 6. The olefin polymerization catalyst is dried in the presence of an organoaluminum compound.
The storage method of the olefin polymerization catalyst according to any one of the above. 7. The method for storing an olefin polymerization catalyst according to claim 1, wherein the organoaluminum compound has an alkyl group having a branched structure.