JPH10168110A - Catalyst for olefin polymerization and polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst capable of providing an olefin polymer with high activity and excellent granular character by comprising a transition metal compound, an ion exchangeable laminar compound, etc., except silicates, and an organoaluminum compound. SOLUTION: This catalyst for polymerization of a >=3C olefin is obtained by containing (A) a group IV to VI transition metal compound having a conjugated five-membered ligand, (B) at least one compound selected from the group consisting of (i) an ion exchangeable laminar compound except silicates and (ii) an inorganic silicate, which is prepared by treatment in the presence of both an acid selected from hydrochloric acid, nitric acid, sulfuric acid, phosphorus acid, acetic acid and oxalic acid and an salt such as a water-soluble compound which contains cation of an atom selected from group I to XIV atoms, and anion selected from anions of halogen, inorganic acid and organic acid or an acidic aqueous solution-soluble compound, and (C) an organoaluminum compound shown by the formula AlR<4> m X3-m (R<4> is a 1-20C hydrocarbon; X is H, a halogen, etc.; 0<(m)<=3), etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst and an olefin polymerization method, and more particularly, to an olefin polymer having 3 or more carbon atoms, which is suitable for producing an olefin polymer having a high activity. The present invention relates to a polymerization catalyst from which coalescence is obtained and a method for polymerizing an olefin using the catalyst.

[0002]

2. Description of the Related Art It is known to produce an olefin polymer by polymerizing an olefin in the presence of a catalyst comprising (1) a metallocene (2) a carrier (3) an organic Al compound (JP-A-61-31404). JP-A-61-108610,
JP-A-61-276805, JP-A-61-29600
8, JP-A-1-207303, JP-A-3-2347
No. 10, JP-A-5-132516, JP-A-5-194
635, JP-A-5-331230).

[0003] However, in these methods, the polymerization activity per solid component is insufficient, and the olefin polymer obtained often has poor bulk density and particle properties such as fine powder. The present inventors have solved these problems,
A method using a specific solid component has been proposed (JP-A-5-30).
1917, JP-A-7-309907, JP-A-8-1
No. 27613). However, even in these methods, the polymerization activity when applied to the polymerization of olefins having 3 or more carbon atoms is not always sufficient.

[0004]

Means for Solving the Problems The present inventors have made intensive studies in view of such a current situation, and as a result, have reached the present invention. That is, the present invention relates to a method for preparing 4 to 6 having [A] conjugated five-membered ring ligand.
At least one selected from the group consisting of (1) an ion-exchange layered compound excluding silicate, and (2) an inorganic silicate, obtained by performing a treatment in the coexistence of a group III transition metal compound, [B] acid and salts. And a catalyst for olefin polymerization having 3 or more carbon atoms, comprising the compound of formula (I) and [C] an organoaluminum compound, and homopolymerizing or copolymerizing an olefin having 3 or more carbon atoms in the presence of the polymerization catalyst. It lies in the method of polymerizing olefins.

Hereinafter, the present invention will be described in detail. (The periodicity of atoms in the present application is based on the group 18 system recommended by IUPAC in 1989.) It has a conjugated five-membered ring ligand, which is the component [A] used in the catalyst of the present invention. The group 4 to 6 transition metal compound is a transition metal compound having at least one conjugated five-membered ring ligand. It is already known that such transition metal compounds themselves and their use as catalyst components for olefin polymerization are known.

Preferred compounds as the component [A] are compounds represented by the following general formulas [1], [2] and [3]. _{(C 5 H 5-a R} 1 a) (C 5 H 5-b R 2 b) MXY [1] Q (C 5 H 4-c R 1 c) (C 5 H 4-d R 2 d) MXY _{[2] Q '(C 5} H 4-e R 3 e) ZMXY [3]

(Where Q is a bonding group bridging the two conjugated five-membered ring ligands, Q ′ is a bonding group bridging the conjugated five-membered ligand and the Z group, and M is a periodic group. X and Y each independently represent hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, A nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, wherein Z is oxygen, sulfur, an alkoxy group having 1 to 20 carbon atoms, A silicon-containing hydrocarbon group having 1 to 40 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, or a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms, wherein R ¹ , R ² and R ³ are each independently , Carbon number 1
To 20 hydrocarbon groups, halogen groups, halogen-containing hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups, aryloxy groups, silicon-containing hydrocarbon groups, phosphorus-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups or boron-containing hydrocarbon groups. Shows a hydrogen group. Further, two adjacent R ¹ , two R ² or two R ³ may be bonded to each other to form a C4 to C10 ring.
a, b, c, d and e are 0 ≦ a ≦ 5, 0 ≦ b ≦ 5,
It is an integer satisfying 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, and 0 ≦ e ≦ 4. A) a bonding group Q bridging between two conjugated five-membered ring ligands and a bonding group Q ′ bridging between the conjugated five-membered ligand and the Z group;
Specific examples include the following.

Alkylene groups such as methylene group and ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, alkylidene groups such as diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, dipropylsilylene Group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, silicon-containing cross-linking group such as tetramethyldisilylene group, dimethylgermylene group, diethylgermylene group, A germanium-containing crosslinking group such as a diphenylgermylene group and a methylphenylgermylene group; an alkylphosphine; an amine; Among these, an alkylene group, an alkylidene group, and a silicon-containing crosslinking group are particularly preferably used.

[0009] In the general _{formula, (C 5 H 5-a} R 1 a),
_{(C 5 H 5-b R} 2 b), (C 5 H 4-c R 1 c), (C 5 H
_4-d R ² _d) and (C ₅ H _4-e R conjugated five-membered ring ligands represented by ³ _e) may be the same or different. R ¹ , R ² and R ³ are methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl,
Octyl, nonyl, decyl, phenyl, chloromethyl,
A hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen group such as a chloroethyl group, a halogen group such as fluorine, chlorine, bromine and iodine, an alkoxy group such as methoxy, ethoxy, propoxy and butoxy groups, a phenoxy group, Aryloxy groups such as methylphenoxy and pentamethylphenoxy groups, silicon-containing hydrocarbon groups such as trimethylsilyl, triethylsilyl and triphenylsilyl groups, or phosphorus-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups, and boron-containing hydrocarbon groups is there. When a plurality of R ¹ (or R ² and R ³ ) are present, they may be the same or different.

When two R ¹ , two R ² or two R ³ are present at adjacent carbon atoms of a cyclopentagenenyl ring, they are mutually bonded to form a C 4 -C 10 ring. And
Indenyl, tetrahydroindenyl, fluorenyl,
It may be an octahydrofluorenyl, azulenyl, hexahydroazulenyl group or the like. a, b, c, d and e are 0 ≦ a ≦ 5, 0 ≦ b ≦ 5, 0 ≦ c ≦ 4, 0 ≦ d ≦
4, an integer satisfying 0 ≦ e ≦ 4.

M is titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, or the like, which is a transition metal belonging to Groups 4 to 6 of the periodic table. Preferred are titanium, zirconium and hafnium, and particularly preferred are titanium and zirconium. Z is oxygen (-O-), sulfur (-S-), carbon number
1-20, preferably 1-10 alkoxy groups, 1 carbon atom
-20, preferably 1-12 thioalkoxy groups, 1-40 carbon atoms, preferably 1-18 silicon-containing hydrocarbon groups, 1-40 carbon atoms, preferably 1-18 nitrogen-containing hydrocarbon groups, carbon It is a phosphorus-containing hydrocarbon group having the number of 1 to 40, preferably 1 to 18, and a part of the Z group is bonded to the Q ′ group which is a bonding group.

X and Y each represent hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkylamide group, Number 1 to 20, preferably 1
And a phosphorus-containing hydrocarbon group having 1 to 12 carbon atoms, preferably a silicon-containing hydrocarbon group having 1 to 12 carbon atoms. X and Y
May be the same or different. Of these, a halogen group, a hydrocarbon group and an alkylamide group are preferred.

Specific examples of the transition metal compound when M is zirconium include bis (2-phenylindenyl) zirconium dichloride and bis {2- (3,5- Ditrifluoromethylphenyl) indenyl dizirconium dichloride and the like.

Examples corresponding to the formula [2] include methylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium monohydride monochloride, ethylenebis (indenyl) methylzirconium monochloride, Ethylene bis (indenyl) zirconium monomethoxide mono-4-lide, ethylene bis (indenyl) zirconium diethoxide, ethylene bis (indenyl) zirconium dimethyl, ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride , Ethylene bis (2-methylindenyl) zirconium dichloride, ethylene bis (2-ethylindenyl) zirconium dichloride, ethylene bis (2,4-dimethyl Ruindenyl) zirconium dichloride, ethylenebis (2,4,7-trimethylindenyl) zirconium dichloride, ethylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, ethylenebis (2-ethyl-4-phenylindenyl) Zirconium dichloride, ethylene bis (2-methyl-4,5-benzoindenyl) zirconium dichloride, ethylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, ethylene (2-methyl-4-t
-Butylcyclopentadienyl) (3'-t-butyl-
5'-methylcyclopentadienyl) zirconium dichloride, ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (indenyl) ) Zirconium dichloride, isopropylidene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (2-methyl-4-t-butylcyclopentadienyl) (3'-t-
Butyl-5'-methylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium chloride hydride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dimethyl, methylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium diphenyl, methylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, isopropyl Riden (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride-A
Isopropylidene (cyclopentadienyl) (2,3
4,5-tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (2 -Methylcyclopentadienyl) (fluoren-5
-Le) zirconium dichloride, isopropylidene (3
-T-butylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, isopropylidene (3-t-
Butylcyclopentagenenyl) (2-methyl-4-phenylazulenyl) zirconium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (fluorenyl) zirconium Dichloride, ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,4 -Diethylcyclopentadienyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (2,5-
Dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, methylenebis (2-methyl-4-phenylazulenyl) zirconium dichloride, ethylenebis (4-methylazulenyl) zirconium dichloride, ethylenebis ( 2,
4-dimethylazulenyl) zirconium dichloride, ethylenebis (2-methyl-4-phenylazulenyl) zirconium dichloride, ethylenebis (2-ethyl-4)
-Phenylazulenyl) zirconium dichloride, ethylenebis (2-methyl-4-phenylhexahydroazulenyl) zirconium dichloride, ethylenebis (2-
Methyl-4-isopropylazulenyl) zirconium dichloride, cyclohexylidenebis (2,4,4, -trimethylazulenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5,6,7 -Tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethylindenyl) Zirconium dichloride, dimethylsilylenebis (2-methyl-4,
5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2-methyl- 4,4-dimethyl-4,5,6,7
-Tetrahydroindenyl) zirconium dichloride,
Dimethylsilylenebis (2-methyl-4,4-dimethyl-sila-4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4.5-benzoindenyl) zirconium dichloride, Dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dimethyl, dimethylsilylenebis (2-methyl-4-phenylazulenyl) zirconium dichloride ,
Dimethylsilylenebis (2-methyl-4-phenylazulenyl) zirconium dimethyl, dimethylsilylenebis (2-methyl-4-phenylhexahydroazulenyl)
Zirconium dichloride, dimethylsilylenebis (2-
Methyl-4,4-diphenylazulenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-
Isopropiroazulenyl) zirconium dichloride, phenylmethylsilylenebis (indenyl) zirconium dichloride, phenylmethylsilylenebis (2-methylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, phenylmethyl Silylene bis (4
5,6,7-tetrahydroindenyl) zirconium dichloride, phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, phenylmethylsilylene (2,3 , 5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, phenylmethylsilylenebis (tetramethylcyclopentadienyl) zirconium dichloride, phenylmethylsilylenebis (2, 4,4-trimethylazulenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, tetramethyldisilylenebis (indenyl) zirconium dichloride, tetramethyldisilylenebis (cyclopentadiene ) Zirconium dichloride, tetramethyl silylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,
4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl)
(3,4-diethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride Dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride , Dimethylsilylene (cyclopentadienyl) (2,7-di-t
-Butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2,
5-dimethylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, diethylsilylene (2-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (2,5-dimethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene ( Diethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride;
Dimethylsilylene (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (ethylcyclopentadienyl) (octahydro Fluorenyl) zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylgermylene bis (indenyl) zirconium dichloride, dimethylgermylene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride, dimethylgermylene bis (2,4,4-trimethylazulenyl) zirconium dichloride, phenylphosphinobis (indenyl) zirconium dichloride, phenylaminobis (indenyl) zirconium dichloride, phenylamino (cyclopentadienyl) ) (Fluorenyl) zirconium dichloride, ethylenebis {4- (3-methyl-1)
-Phenyl) indenyl zirconium dichloride, dimethylsilylenebis {4- (3-methyl-1-phenyl) indenyl} zirconium dichloride, dimethylsilylenebis {4- (3-methyl-1-phenyl) indenyl} zirconiumbis (dimethylamide) ), Dimethylsilylenebis {4- (3-ethyl-1-phenyl) indenyl} zirconium dichloride, dimethylsilylenebis [4- {3-methyl-1- (2-naphthyl)} indenyl] zirconium dichloride, dimethylsilylenebis [ 4- {3-methyl-1- (3-methylphenyl)} indenyl] zirconium dichloride, dimethylsilylenebis [4- {3-methyl-1- (3,5-dimethylphenyl)} indenyl] zirconium dichloride, dimethyl gel Millenvis ｛ - (3-methyl-1-phenyl)
Indenyl} zirconium dichloride, ethylenebis {4- (7-t-butyl) indenyl} zirconium dichloride, dimethylsilylenebis {4- (2-methylindenyl)} zirconium dichloride, ethylenebis {4- (2,7-dimethyl) Indenyl) zirconium dichloride.

Examples corresponding to the formula [3] include pentamethylcyclopentadienyl-bis (phenyl) amidozirconium dichloride, indenyl-bis (phenyl) amidozirconium dichloride, and pentamethylcyclopentadienyl-bis (trimethylsilyl). Amidozirconium dichloride, pentamethylcyclopentadienylphenoxyzirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) phenylamidozirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) t-butylamidozirconium dichloride, dimethylsilylene (indenyl) )
Cyclohexylamide zirconium dichloride, dimethylsilylene (tetrahydroindenyl) decylaminozirconium dichloride, dimethylsilylene (tetrahydroindenyl) ((trimethylsilyl) amino) zirconium dichloride, dimethylgermylene (tetramethylcyclopentadienyl) (phenyl) aminozirconium dichloride Etc. are exemplified.

Further, other Group 4, 5, and 6 transition metal compounds such as titanium compounds and hafnium compounds also include:
The same compounds as described above can be mentioned. Further, these mixtures may be used. Furthermore, it can be used together with a known solid catalyst containing titanium trichloride as a main component or a carrier-supported catalyst containing magnesium, titanium and halogen as essential components.

In the present invention, as the component [B], a component is selected from the group consisting of (1) an ion-exchange layered compound excluding silicate and (2) an inorganic silicate obtained by performing a treatment in the presence of an acid and a salt. At least one selected compound is used.
An ion-exchangeable layered compound other than silicates is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and the ions contained therein are exchangeable.

The ion-exchangeable layered compound except silicate is
Hexagonal close packing type, antimony type, CdCl ₂ type,
An ionic crystalline compound having a layered crystal structure such as CdI ₂ type can be exemplified. Specific examples of the ion-exchangeable layered compound having such a crystal structure include α-
Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ )
₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (H
PO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-
Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HP
O ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄
PO ₄ ) ₂ .H ₂ O and other polyvalent metal crystalline acid salts.

Examples of the inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. These may be a synthetic product or a naturally occurring mineral.
Specific examples of clay and clay minerals include allophanes such as allophane, dickite, nacrite, kaolinite,
Kaolin group such as anoxite, halloysite group such as metahalloysite, halloysite, serpentine group such as chrysotile, lizardite, antigorite, montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, smectite, vermiculite, etc. Vermiculite minerals, mica minerals such as illite, sericite, and chlorite, attapulgite, sepiolite, paigorskite, bentonite, kibushi clay, gairome clay, hisingelite, pyrophyllite, and ryokudeite group. These may form a mixed layer.

Examples of artificial synthetic products include synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, and the like. Among the specific examples of the component [B], preferably, kaolins such as deckite, nacrite, kaolinite, and anoxite, halosites such as metahalosite and halosite, serpentine stones such as chrysotile, lizardite, and antigolite are preferred. Tribe, montmorillonite, zaukonite, beidellite, nontronite, saponite, smectites such as hectorite, vermiculite minerals such as vermiculite, illite, sericite, mica minerals such as chlorite, synthetic mica, synthetic hectorite, synthetic saponite, synthetic Teniolites are particularly preferred, and particularly preferred are montmorillonite, zaukonite, beidellite, nontronite, saponite, smectites such as hectorite, vermiculite minerals such as vermiculite, synthetic mica, synthetic hectorite, and synthetic saponite. , Synthetic taeniolite.

By treating at least one compound selected from the group consisting of (1) an ion-exchange layered compound excluding silicate and (2) an inorganic silicate in the presence of an acid and a salt, ] Component is obtained. Examples of the acid used here include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, and oxalic acid. Usually, it is selected from hydrochloric acid, nitric acid and sulfuric acid.

The salts used here are 1 to 14
A compound containing a cation containing at least one atom selected from the group consisting of group atoms, preferably 1
A water-soluble compound comprising a cation containing at least one kind of atom selected from the group consisting of group XIV to XIV and at least one kind of anion selected from the group consisting of halogen atoms, inorganic acids and anions of organic acids; or an acidic aqueous solution-soluble compound, more preferably, a cation containing at least one atom selected from the group consisting of 1 to 14 group atoms, Cl, Br, I, F , PO 4, SO 4, N
O ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , C
H ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ ,
O (ClO ₄ ) ₂ , O (SO ₄ ), OH, O ₂ Cl ₂ ,
OCl ₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄
And at least one anion selected from the group consisting of C ₆ H ₅ O ₇ .

Specifically, LiCl, NaCl, KC
1, CaCl_Two, CaSO_Four, CaC _TwoO_Four, Ca (N
O_Three)_Two, Ca_Three(C₆H_FiveO₇)_Two, MgCl_Two, M
gBr _Two, MgSO_Four, Mg (PO_Four)_Two, Mg (Cl
O_Four)_Two, MgC_TwoO_Four, Mg (NO_Three)_Two, Mg (O
OCCH_Three)_Two, MgC_FourH_FourO_Four, Sc (OOCCH
_Three)_Two, Sc_Two(CO_Three)_Three, Sc_Two(C_TwoO_Four)_Three, Sc
(NO_Three)_Three, Sc_Two(SO _Four)_Three, ScF_Three, ScCl
_Three, ScBr_Three, ScI_Three, Y (OOCCH_Three)_Three, Y
(CH_ThreeCOCHCOCH_Three)_Three, Y_Two(CO_Three)_Three, Y
_Two(C_TwoO_Four)_Three, Y (NO_Three)_Three, Y (ClO_Four)_Three, Y
PO_Four, Y_Two(SO_Four)_Three, YF_Three, YCl_Three, La (O
OCCH_Three)_Three, La (CH_ThreeCOCHCOC
H_Three)_Three, La_Two(CO_Three)_Three, La (NO_Three)_Three, La
(ClO_Four)_Three, La_Two(C_TwoO_Four)_Three, LaPO _Four, La
_Two(SO_Four)_Three, LaF_Three, LaCl_Three, LaBr_Three, L
aI_Three, Sm (OOCCH_Three)_Three, Sm (CH_ThreeCOCH
COCH_Three)_Three, Sm_Two(CO_Three)_Three, Sm (NO_Three)_Three,
Sm (ClO_Four)_Three, Sm_Two(C_TwoO_Four)_Three, Sm_Two(S
O_Four)_Three, SmF_Three, SmCl_Three, SmI_Three, Yb (O
OCCH_Three)_Three, Yb (NO_Three)_Three, Yb (Cl
O_Four)_Three, Yb_Two(C_TwoO_Four)_Three, Yb_Two(SO_Four)_Three, Yb
F_Three, YbCl_Three, Ti (OOCCH_Three)_Four, Ti (C
O_Three)_Two, Ti (NO_Three)_Four, Ti (SO_Four)_Two, Ti
F_Four, TiCl_Four, TiBr_Four, TiI_Four, Zr (OO
CCH _Three)_Four, Zr (CH_ThreeCOCHCOCH_Three)_Four,
Zr (CO_Three)_Two, Zr (NO _Three)_Four, Zr (SO_Four)
_Two, ZrF_Four, ZrCl_Four, ZrBr_Four, ZrI_Four, Z
rOCl_Two, ZrO (NO_Three)_Two, ZrO (ClO_Four)
_Two, ZrO (SO_Four), Hf (OOCCH)_Three)_Four, Hf
(CO_Three)_Two, Hf (NO_Three)_Four, Hf (SO_Four)_Two,
HfOCl_Two, HfF_Four, HfCl_Four, HfBr_Four, H
fI_Four, V (CH _ThreeCOCHCOCH_Three)_Three, VOSO
_Four, VOCl_Three, VCl_Three, VCl_Four, VBr_Three, Nb
(CH_ThreeCOCHCOCH_Three)_Five, Nb_Two(C
O_Three)_Five, Nb (NO_Three)_Five, Nb_Two(SO_Four)_Five, N
bF_Five, NbCl₆, NbBr_Five, NbI_Five, Ta (O
OCCH_Three)_Five, Ta_Two(CO_Three)_Five, Ta (NO_Three)
_Five, Ta_Two(SO_Four)_Five, TaF_Five, TaCl_Five, Ta
Br_Five, TaI_Five, Cr (CH_ThreeCOCHCOCH_Three)
_Three, Cr (OOCH)_TwoOH, Cr (NO_Three)_Three, Cr
(ClO_Four)_Three, CrPO_Four, Cr_Two(SO_Four)_Three, C
rO_TwoCl_Two, CrF_Three, CrCl_Three, CrBr_Three, C
rI_Three, CrO_TwoCl_Two, CrF_Three, CrCl_Three, Cr
Br_Three, CrI_Three, MoOCl_Four, MoCl_Three, MoC
l_Four, MoCl₆, MoF₆, MoI_Two, WCl_Four, W
Cl₆, WF₆, WBr_Five, Mn (OOCCH_Three)_Two,
Mn (CH_ThreeCOCHCOCH_Three)_Two, MnCO_Three, M
n (NO_Three)_Two, MnO, Mn (ClO_Four)_Two, MnF
_Two, MnCl_Two, MnBr_Two, MnI_Two, Fe (OOC
CH_Three)_Two, Fe (CH_ThreeCOCHCOCH_Three)_Three, F
eCO_Three, Fe (NO_Three)_Three, Fe (ClO_Four)_Three, F
ePO_Four, FeSO_Four, Fe_Two(SO_Four)_Three, Fe
F_Three, FeCl_Three, FeBr_Three, FeI_Three, FeC₆H
_FiveO₇, Co (OOCCH_Three)_Two, Co (CH_ThreeCOC
HCOCH_Three)_Three, CoCO_Three, Co (NO_Three)_Two, C
oC_TwoO_Four, Co (ClO_Four)_Two, Co_Three(P
O_Four)_Two, CoSO_Four, CoF_Two, CoCl_Two, CoB
r_Two, CoI_Two, NiCO_Three, Ni (NO_Three)_Two, Ni
C_TwoO_Four, Ni (ClO_Four)_Two, NiSO_Four, NiC
l_Two, NiBr_Two, Pb (OOCCH_Three)_Two, Pb (N
O_Three)_Two, PbSO_Four, PbCl _Two, PbBr_Two, Cu
Cl_Two, CuBr_Two, Cu (NO_Three)_Two, CuC
_TwoO_Four, Cu (ClO_Four)_Two, CuSO_Four, Cu (OO
CCH_Three)_Two, Zn (OOCCH _Three)_Two, Zn (CH_Three
COCHCOCH_Three)_Two, Zn (OOCH)_Two, ZnC
O _Three, Zn (NO_Three)_Two, Zn (ClO_Four)_Two, Zn_Three
(PO_Four)_Two, ZnSO_Four, ZnF_Two, ZnCl_Two, Zn
Br_Two, ZnI_Two, Cd (OOCCH_Three)_Two, Cd (C
H_ThreeCOCHCOCH_Three)_Two, Cd (OCOCH_TwoCH
_Three)_Two, Cd (NO_Three)_Two, Cd (ClO_Four)_Two, Cd
SO_Four, CdF_Two, CdCl_Two, CdBr _Two, Cd
I_Two, AlF_Three, AlCl_Three, AlBr_Three, AlI_Three,
Al_Two(SO_Four)_Three, Al_Two(C_TwoO_Four)_Three, Al (CH
_ThreeCOCHCOCH_Three)_Three, Al (NO_Three)_Three, AlP
O_Four, GeCl_Four, GeBr_Four, GeI_Four, Sn (OO
CCH _Three)_Four, Sn (SO_Four)_Two, SnF_Four, SnCl
_Four, SnBr_Four, SnI_Four, Pb (OOCCH_Three)_Four,
PbCO_Three, PbCO_Three, Pb (NO_Three)_Two, PbHP
O_Four, Pb (ClO_Four)_Two, PbSO_Four, PbF_Two, P
bCl_Two, PbBr_Two, PbI_TwoAnd the like.

The acid and salt used in the treatment may be two or more. The feature of the present invention resides in the treatment in the coexistence of an acid and a salt, and it is important that the acid and the salt coexist. As the method, there are a method of treating by adding salts after acid treatment, a method of treating by adding acid after salt treatment, and a method of treating by adding acid and salts at the same time. High polymerization activity cannot be obtained by a method of washing after performing an acid treatment and then performing a salt treatment or a method of performing a washing after performing a salt treatment and then performing an acid treatment.

The conditions for the treatment in the coexistence of an acid and a salt are as follows:
Although not particularly limited, usually, the processing temperature is from room temperature to the boiling point,
The processing time is performed by selecting a condition of 5 minutes to 24 hours. The acids and salts are generally used in an aqueous solution. The ratio between the acid and the salt during the treatment in the coexistence of the acid and the salt is not particularly limited, but if the acid / salt molar ratio is large, the activity is undesirably reduced. The acid / salt molar ratio is usually 10 to 10.
0.1 is selected.

In the present invention, the treatment is carried out in the co-presence of the above-mentioned acid and salt. However, shape control such as pulverization and granulation may be performed before and after the treatment. In order to obtain an olefin polymer having excellent particle properties, it is preferable to perform granulation after the treatment. The component [B] after the above treatment is usually used after being dehydrated and dried.

Examples of the organoaluminum compound used as the component [C] in the present invention include AlR ⁴ _m X _3-m (where R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, X is hydrogen, halogen, An alkoxy group, an aryloxy group, and m is a compound represented by 0 <m ≦ 3), specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, or diethylaluminum monochromate. And halogen or alkoxy-containing alkylaluminums such as ride and diethylaluminum ethoxide. In addition, aluminoxanes such as methylaluminoxane can also be used. These may be used as a mixture. Of these, trialkyl aluminum is particularly preferred.

The component [A], the component [B] and the component [C] are brought into contact with each other to form a catalyst, but the contact method is not particularly limited. This contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin. A polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or alumina may coexist or may be brought into contact with each component of the catalyst or after the 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 solvents, particularly preferably between room temperature and the boiling point of the solvents. The amount of each component of the catalyst is 0.0001 to 10 mmol of the [A] component per 1 g of the [B] component,
It is preferably 0.001 to 5 mmol, and the component [C] is 0.01 to 10000 mmol, preferably 0.1 to 10 mmol.
100 mmol. Further, the atomic ratio of the transition metal in the component [A] to the aluminum in the component [C] is 1: 0.01.
~ 1,000,000, preferably 0.1 ~ 100000
It is.

The catalyst thus obtained may be used without washing, or may be used after washing. If necessary, the component [C] may be newly used in combination. The amount of the component [C] used at this time is selected so that the ratio of the transition metal in the component [A] to the atom of aluminum in the component [C] is 1: 0 to 10,000.

Before the polymerization, ethylene, propylene, 1-
Butene, 1-hexene, 1-octene, 4-methyl-1
An olefin such as -pentene, 3-methyl-1-butene, vinylcycloalkane, styrene or the like is preliminarily polymerized and, if necessary, washed, can be used as a catalyst. This preliminary polymerization is carried out at 0.0 g / g of solid catalyst.
It is desirable to carry out so as to produce 1 to 1000 g, preferably 0.1 to 100 g of the polymer.

The olefin having 3 or more carbon atoms used in the polymerization includes propylene, 1-butene, 1-hexene,
3-methyl-1-butene, 4-methyl-1-pentene,
Examples include vinylcycloalkane, styrene and derivatives thereof. The polymerization can be applied to not only homopolymerization but also random copolymerization and block copolymerization with generally known ethylene and other olefins having 3 or more carbon atoms.

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 ° C. to 250 ° C., and the pressure is not particularly limited.
It is in the range of 00 kg / cm ² . Further, hydrogen may be present as a molecular weight regulator in the polymerization system.

[0034]

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by these examples unless departing from the gist of the present invention. The following catalyst synthesis step and polymerization step were all performed in a purified nitrogen atmosphere. The solvent used was dehydrated by MS-4A and then deaerated by bubbling with purified nitrogen.

Example 1 (1) Synthesis of Component [A] (dimethylsilylenebis (2-
Methyl-4-phenylazulenyl) zirconium dichloride) The following reactions were all performed under an inert gas atmosphere, and the reaction solvent used was previously dried. Dissolve 2.22 g of 2-methylazulene in 30 ml of hexane and prepare a solution of phenyllithium in cyclohexane-diethyl ether 1
5.6 ml (1.0 equivalent) were added in small portions at 0 ° C. After stirring this solution at room temperature for 1 hour, it was cooled to -78 ° C and 30 ml of tetrahydrofuran was added. 0.95 ml of dimethyldichlorosilane was added to this solution, the temperature was raised to room temperature, and the mixture was further heated at 50 ° C. for 1.5 hours. Thereafter, an aqueous solution of ammonium chloride 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-dichloromethane 5: 1) to give 1.48 g of dimethylbis {1- (2-methyl-4-phenyl-1,4-dihydroazulenyl)} silane. Obtained.

The dimethylbis {1- (2-) obtained above
768 mg of methyl-4-phenyl-1,4-dihydroazulenyl) silane was dissolved in 15 ml of diethyl ether, and 1.98 ml (1.64 mol / L) of a hexane solution of normal butyllithium was added dropwise at -78 ° C. The mixture was heated and stirred at room temperature for 12 hours. After evaporating the solvent under reduced pressure, the obtained solid was washed with hexane and dried under reduced pressure. Toluene / diethyl ether (40: 1) 2
0 ml, and zirconium tetrachloride 325 m at -60 ° C.
g was added, the temperature was gradually raised, and the mixture was stirred at room temperature for 15 hours.

The resulting solution was concentrated under reduced pressure, and reprecipitated by adding hexane to obtain 150 mg of a diastereomer mixture of dimethylsilylenebis (2-methyl-4-phenylazulenyl) zirconium dichloride. The entire diastereomer mixture of dimethylsilylenebis (2-methyl-4-phenylazulenyl) zirconium dichloride was dissolved in 5 ml of methylene chloride and introduced into a pyrex glass reactor equipped with a 100 W high-pressure mercury lamp. This solution was irradiated with light for 10 minutes under normal pressure while stirring (3.
After that, methylene chloride was distilled off under reduced pressure. To the obtained tan solid, 7 ml of toluene was added, and the mixture was stirred and allowed to stand. Then, a yellow solid precipitated and the supernatant was removed. Further, the same operation was performed with 1 ml of toluene, 1 ml, and 1 ml of hexane, and the obtained solid was dried under reduced pressure to obtain a single diamine of dimethylsilylenebis (2-methyl-4-phenylazulenyl) zirconium dichloride. 75 mg of the stereomer was obtained.

(2) Production of Component [B] 11.7 g of commercially available montmorillonite (Kunimine F, Kunipia F) was dispersed in 93 ml of demineralized water in which 7.35 g of MgSO ₄ and 13.1 g of sulfuric acid were dissolved. The temperature was raised while stirring, and the boiling point treatment was performed for 2 hours. Then, it was sufficiently washed with demineralized water and dried to obtain the component [B].

(3) Synthesis of catalyst 1.24 g of the chemically treated montmorillonite obtained in (2) was collected in a 100 ml flask, and subjected to a heat treatment at 200 ° C. for 2 hours under reduced pressure. After cooling to room temperature, a toluene solution of triethylaluminum (0.4 mmol / m
5.5 ml of 1) was added, and the mixture was contacted at room temperature for 1 hour with stirring. Thereafter, the resultant was washed with toluene, and 30 ml of toluene was added to form a slurry. 2.8 ml of the above slurry (100 mg as a solid component) was collected in a 100 ml flask, and a toluene solution of dimethylsilylenebis (2-methyl-4-phenylazulenyl) zirconium dichloride (1.9) was obtained.
1.5 mol / ml) was added. Then, a toluene solution of triisobutylaluminum (0.01 mmol
1 / ml) was added thereto and contacted at room temperature for 5 minutes to obtain a catalyst component.

(4) Polymerization of Propylene The entire amount of the catalyst component obtained in (3) was added to a 2 L autoclave, 100 ml of liquefied propylene was introduced, and preliminary polymerization was carried out at room temperature for 5 minutes with stirring. Then, 1 ml of a toluene solution of triisobutylaluminum (0.5 mmol / ml) was added, and 1300 ml of liquefied propylene was introduced.
After the temperature was raised to 0 ° C, polymerization was carried out at 80 ° C for 1 hour. Thereafter, unreacted propylene was purged to terminate the polymerization. The amount of the obtained propylene polymer was 265 g. Solid component 1
g · The amount of polymer produced per hour was 2,650 g.

Example 2 (1) Production of Component [B] In Example 1 (2), Zn was used instead of MgSO _4.
Except for using SO ₄ · 7H ₂ O18.2g are examples -1
Chemical treatment was performed in the same manner as in (2) to obtain component [B].

(2) Synthesis of catalyst A catalyst component was obtained in the same manner as in Example 1 (3) except that the chemically treated montmorillonite obtained in (1) was used. (3) Polymerization of propylene 100 mg of the catalyst component obtained in (2) as a solid component
Except for using, propylene was polymerized in the same manner as in Example- (4). The obtained polymer weighs 280 g,
The amount of polymer produced per gram of solid component per hour was 280.
It was 0 g.

Example 3 (1) Production of Component [B] In Example 1 (2), TiO ₄ was used instead of MgSO _4.
Example 1 (2) except that 10.5 g of (SO ₄ ) ₂ was used.
Chemical treatment was performed in the same manner as described above to obtain the component [B].

(2) Synthesis of catalyst A catalyst component was obtained in the same manner as in Example 1 (3) except that the chemically treated montmorillonite obtained in (1) was used. (3) Polymerization of propylene 100 mg of the catalyst component obtained in (2) as a solid component
Except for using, propylene was polymerized in the same manner as in Example- (4). The obtained polymer was 220 g,
The amount of polymer produced per gram of solid component per hour was 220
It was 0 g.

Example 4 (1) Production of Component [B] In Example 1 (2), Zr was used in place of MgSO _4.
Chemical treatment was carried out in the same manner as in Example-1 (2), except that 22.4 g of (SO ₄ ) ₂ .4H ₂ O was used, to obtain a component [B]. (2) Synthesis of catalyst A catalyst component was obtained in the same manner as in Example-1 (3) except that the chemically treated montmorillonite obtained in (1) was used. (3) Polymerization of propylene 100 mg of the catalyst component obtained in (2) as a solid component
Except for using, propylene was polymerized in the same manner as in Example- (4). The obtained polymer was 160 g,
The amount of polymer produced per 1 g of the solid component per hour is 160
It was 0 g.

(Comparative Example 1) (1) Production of Component [B] Example 1 (2) was the same as Example 1 (2) except that the treatment was carried out using only sulfuric acid without using MgSO _4. Chemical treatment was performed in the same manner to obtain the component [B]. (2) Synthesis of catalyst A catalyst component was obtained in the same manner as in Example-1 (3) except that the chemically treated montmorillonite obtained in (1) was used. (3) Polymerization of propylene 100 mg of the catalyst component obtained in (2) as a solid component
Except for using, propylene was polymerized in the same manner as in Example- (4). The obtained polymer is 100 g,
The amount of polymer produced per 1 g of solid component per hour is 100
It was 0 g.

Comparative Example 2 (1) Production of Component [B] 2.0 g of the sulfuric acid-treated montmorillonite obtained in Comparative Example-1 (1) was added to 30 ml of deionized water in which 1.5 g of MgSO ₄ was dissolved. The mixture was dispersed, stirred at room temperature for 30 minutes, and then filtered. After repeating this operation once, the product was sufficiently washed with demineralized water and dried to obtain a chemically treated montmorillonite.

(2) Synthesis of catalyst A catalyst component was obtained in the same manner as in Example 1 (3) except that the chemically treated montmorillonite obtained in (1) was used. (3) Polymerization of propylene 100 mg of the catalyst component obtained in (2) as a solid component
Except for using, propylene was polymerized in the same manner as in Example- (4). The obtained polymer was 60 g, and the amount of polymer produced per 1 g of solid component per hour was 600 g.
Met.

[0049] (Comparative Example -3) (1) [B] Production Comparative Examples of component 2 (1), instead of MgSO ₄ solution, ZnSO ₄ · 7H ₂ Demineralized water 3 O3.2g dissolved
Except that 0 ml was used, a chemical treatment was carried out in the same manner as in Comparative Example-2 (1) to obtain a component [B]. (2) Synthesis of catalyst A catalyst component was obtained in the same manner as in Example-1 (3) except that the chemically treated montmorillonite obtained in (1) was used. (3) Polymerization of propylene 100 mg of the catalyst component obtained in (2) as a solid component
Except for using, propylene was polymerized in the same manner as in Example- (4). The obtained polymer was 70 g, and the amount of polymer produced per 1 g of solid component per hour was 700 g.
Met.

(Example-5) (1) Production of component [B] Example-1 (2) was the same as Example-1 (2) except that the boiling point treatment time was changed from 2 hours to 5 hours. Chemical treatment was performed in the same manner to obtain the component [B]. (2) Synthesis of catalyst A catalyst component was obtained in the same manner as in Example-1 (3) except that the chemically treated montmorillonite obtained in (1) was used. (3) Polymerization of propylene Example -1 except that polymerization was carried out at 80 ° C for 55 minutes using 91 mg of the catalyst component obtained in (2) as a solid component.
Propylene was polymerized in the same manner as in (4). The obtained polymer was 375 g, and the amount of the polymer produced per 1 g of the solid component per hour was 4,500 g.

(Example-6) (1) Production of component [B] In Example-1 (2), the amount of sulfuric acid used was 25.4 g.
Was carried out in the same manner as in Example-1 (2), except that the component [B] was used, to obtain the component [B]. (2) Synthesis of catalyst A catalyst component was obtained in the same manner as in Example-1 (3) except that the chemically treated montmorillonite obtained in (1) was used.

(3) Polymerization of Propylene Example 1 was repeated except that 95 mg of the catalyst component obtained in (2) was used as a solid component and polymerization was performed at 80 ° C. for 45 minutes.
Propylene was polymerized in the same manner as in (4). The obtained polymer was 338 g, and the amount of the polymer produced per 1 g of the solid component per hour was 4,750 g.

(Example-7) (1) Production of component [B] Commercially available montmorillonite (Kunimine F, 11) was placed in 45 ml of demineralized water in which 7.61 g of MgSO ₄ and 12.7 g of sulfuric acid were dissolved. 0.7 g was dispersed, and the temperature was raised with stirring to perform a boiling point treatment for 2 hours. Then, it was sufficiently washed with demineralized water and dried to obtain the component [B]. (2) Synthesis of catalyst A catalyst component was obtained in the same manner as in Example-1 (3) except that the chemically treated montmorillonite obtained in (1) was used.

(3) Polymerization of Propylene Example 1 was repeated except that 88 mg of the catalyst component obtained in (2) was used as a solid component for polymerization at 80 ° C for 45 minutes.
Propylene was polymerized in the same manner as in (4). The obtained polymer was 346 g, and the amount of the polymer produced per 1 g of the solid component per hour was 5230 g.

(Example-8) (1) Production of component [B] Commercially available montmorillonite (Kunimine Kogyo, Kunipia F) 11 was added to 35 ml of demineralized water in which 15.71 g of MgSO _{4 and} 12.8 g of sulfuric acid were dissolved. 0.7 g was dispersed, and the temperature was raised with stirring to perform a boiling point treatment for 2 hours. Then, it was sufficiently washed with demineralized water and dried to obtain the component [B].

(2) Synthesis of catalyst A catalyst component was obtained in the same manner as in Example 1 (3) except that the chemically treated montmorillonite obtained in (1) was used. (3) Polymerization of propylene 95.5 m as a solid component using the catalyst component obtained in (2) as a solid component
g was used to polymerize propylene in the same manner as in Example-1 (4), except that polymerization was performed at 80 ° C. for 35 minutes. The amount of the obtained polymer was 334 g, and the amount of the polymer produced per 1 g of the solid component per hour was 6000 g.

(Example-9) (1) Polymerization of propylene The catalyst component obtained in Example-8 (2) was used as a solid component in an amount of 96.5 mg, and polymerization was performed at 75 ° C for 1 hour. Propylene was polymerized in the same manner as in Example-1 (4). The amount of the obtained polymer was 347 g, and the amount of the polymer produced per 1 g of the solid component per hour was 3,600 g.

Example 10 (1) Production of Component [B] 13.0 g of MgCl ₂ .6H ₂ O and 13.8% of 36% hydrochloric acid
g of montmorillonite (Kunimine Kogyo Co., Ltd., Kunipia F) (11.8 g) was dispersed in 21 ml of deionized water in which g was dissolved, and the mixture was heated with stirring to perform a boiling point treatment for 2 hours. Then, it was sufficiently washed with demineralized water and dried to obtain the component [B].

(2) Synthesis of catalyst A catalyst component was obtained in the same manner as in Example 1 (3) except that the chemically treated montmorillonite obtained in (1) was used. (3) Polymerization of propylene Example -1 except that 90 mg of the catalyst component obtained in (2) was used as a solid component and polymerization was performed at 80 ° C for 55 minutes.
Propylene was polymerized in the same manner as in (4). The obtained polymer was 313 g, and the amount of polymer produced per 1 g of solid component per hour was 3,800 g.

Example 11 (1) Production of Component [B] 11.8 g of commercially available montmorillonite (Kunimine F, Kunipia F) was dispersed in 48 ml of demineralized water in which 7.5 g of MgSO ₄ was dissolved. The temperature was raised while stirring, and the boiling point treatment was performed for 1 hour. Thereafter, the temperature was lowered to 40 ° C., 13.5 g of sulfuric acid was added, and the temperature was raised with stirring to perform a boiling point treatment for 2 hours. Then wash thoroughly with demineralized water, dry,
[B] component was obtained. (2) Synthesis of catalyst A catalyst component was obtained in the same manner as in Example-1 (3) except that the chemically treated montmorillonite obtained in (1) was used.

(3) Polymerization of Propylene Example 1 was repeated except that 88 mg of the catalyst component obtained in (2) was used as a solid component and polymerization was performed at 80 ° C. for 55 minutes.
Propylene was polymerized in the same manner as in (4). The obtained polymer was 360 g, and the amount of the polymer produced per 1 g of solid component per hour was 4,470 g.

(Comparative Example-4) (1) Production of Component [B] In Example-11 (1), after treatment with MgSO ₄ ,
Example 11 except that sufficient washing with deionized water was performed.
[B] component was obtained in the same manner as in (1). (2) Synthesis of catalyst A catalyst component was obtained in the same manner as in Example-1 (3) except that the chemically treated montmorillonite obtained in (1) was used.

(3) Polymerization of propylene 100 mg of the catalyst component obtained in (2) was used as a solid component.
Example 1 was repeated except that the polymerization was carried out at 80 ° C. for 60 minutes.
Propylene was polymerized in the same manner as in 1 (4). The obtained polymer was 190 g, and the amount of the polymer produced per 1 g of the solid component per hour was 1,900 g.

(Example-12) (1) Synthesis of catalyst A catalyst component was obtained in the same manner as in Example-1 (3) using the chemically treated montmorillonite obtained in Example-8 (1). (2) Copolymerization of propylene and ethylene Example was carried out except that 50 mg of the catalyst component obtained in (1) was used as a solid component, and 15 g of ethylene was introduced before the temperature was raised to carry out polymerization at 75 ° C for 20 minutes. In the same manner as in -1 (4), propylene and ethylene were copolymerized. The amount of the obtained copolymer was 420 g, and the amount of the produced copolymer per 1 g of solid component per hour was 25,200 g.

Example 13 (1) Production of Component [B] Commercially available 90 ml of deionized water in which 19.1 g of Al ₂ (SO ₄ ) ₃ .14-18H ₂ O and 4.5 g of sulfuric acid were dissolved. 12.2 g of synthetic mica (manufactured by Corp Chemical Co., Ltd., ME-100) was dispersed and heated at 90 ° C. for 2 hours while stirring. Then wash thoroughly with demineralized water, dry,
[B] component was obtained.

(2) Synthesis of catalyst Using the chemically treated synthetic mica obtained in Example 13 (1), a catalyst component was obtained in the same manner as in Example 1 (3). (3) Polymerization of propylene 100 mg of the catalyst component obtained in (2) as a solid component
Example 1 was repeated except that the polymerization was carried out at 80 ° C. for 60 minutes.
Propylene was polymerized in the same manner as in 1 (4). The amount of the obtained polymer was 125 g, and the amount of the polymer produced per 1 g of the solid component per hour was 1,250 g.

(Comparative Example-5) (1) Production of Component [B] In Example-13 (1), Al ₂ (SO ₄ ) ₃ .14
Without the presence of an ~18H ₂ O, except for using only sulfuric acid,
A component [B] was obtained in the same manner as in Example-13 (1). (2) Synthesis of Catalyst Using the chemically treated synthetic mica obtained in Comparative Example-5 (1), a catalyst component was obtained in the same manner as in Example-1 (3).

(3) Polymerization of propylene 100 mg of the catalyst component obtained in (2) was used as a solid component.
Example 1 was repeated except that the polymerization was carried out at 80 ° C. for 60 minutes.
Propylene was polymerized in the same manner as in 1 (4). The amount of the obtained polymer was 35 g, and the amount of the polymer produced per 1 g of the solid component per hour was 350 g.

(Example-14) (1) Production of component [B] Commercially available synthetic mica (manufactured by Corp Chemical Co., Ltd., M) was added to 85 ml of deionized water in which 2.9 g of LiCl and 4.3 g of nitric acid were dissolved.
E-100) 15.3 g was dispersed, and the mixture was heated with stirring and subjected to a boiling point treatment for 2 hours. Then, it was sufficiently washed with demineralized water and dried to obtain the component [B].

(2) Synthesis of Catalyst A catalyst component was obtained in the same manner as in Example-1 (3) using the chemically treated synthetic mica obtained in Example-14 (1). (3) Polymerization of propylene 100 mg of the catalyst component obtained in (2) as a solid component
Example 1 was repeated except that the polymerization was carried out at 80 ° C. for 60 minutes.
Propylene was polymerized in the same manner as in 1 (4). The amount of the obtained polymer was 120 g, and the amount of the polymer produced per 1 g of the solid component per hour was 1200 g.

Example 15 (1) Synthesis of Component [A] (dimethylsilylenebis (2-
Methyl-4-phenylindenyl) zirconium dichloride) The synthesis of the above complex is described in Organometallics.
1994, 13, 954-963.

(2) Synthesis of catalyst In Example-1 (3), dimethylsilylenebis (2
-Methyl-4-phenylazulenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-
A catalyst component was obtained in the same manner as in Example-1 (3) except that 4-phenylindenyl) zirconium dichloride was used. (3) Polymerization of propylene 100 mg of the catalyst component obtained in (2) as a solid component
Example 1 was repeated except that the polymerization was carried out at 80 ° C. for 60 minutes.
Propylene was polymerized in the same manner as in 1 (4). The amount of the obtained polymer was 300 g, and the amount of the polymer produced per 1 g of the solid component per hour was 3000 g.

Comparative Example -6 (1) Synthesis of Catalyst The procedure of Example -15 (2) was repeated except that the chemically treated montmorillonite obtained in Comparative Example -1 (1) was used as the component [B]. A catalyst component was obtained in the same manner as in Example-15 (2). (2) Polymerization of propylene 100 mg of the catalyst component obtained in (1) as a solid component
Example 1 was repeated except that the polymerization was carried out at 80 ° C. for 60 minutes.
Propylene was polymerized in the same manner as in 1 (4). The amount of the obtained polymer was 60 g, and the amount of the polymer produced per 1 g of the solid component per hour was 600 g.

Example 16 (1) Production of Component [B] Commercially available montmorillonite (Kunimine Kogyo Co., Kunipia F) was added to 40 ml of deionized water in which 2.29 g of LiCl and 10.0 g of sulfuric acid were dissolved. 0 g was dispersed, and the temperature was raised with stirring to perform a boiling point treatment for 2 hours. Thereafter, the product was sufficiently washed with demineralized water and dried to obtain the component [B].

(2) Synthesis of Catalyst 0.65 g of the chemically treated montmorillonite obtained in (1) was sampled in a 100 ml flask and subjected to a heat treatment at 200 ° C. for 2 hours under reduced pressure. After cooling to room temperature, a toluene solution of triethylaluminum (0.4 mmol / m
1) 3.3 ml was added and contacted at room temperature for 1 hour with stirring. Thereafter, the resultant was washed with toluene, and 20 ml of toluene was added to obtain a slurry.

The above slurry was placed in a 100 ml flask.
0 ml (100 mg as a solid component) was collected and dimethylsilylenebis (2-methyl-4-phenylazulenyl) was collected.
Toluene solution of zirconium dichloride (1 μmol /
3) was added. Then, a toluene solution of triisobutylaluminum (0.01 mmol / ml) was added to 3
Then, the resulting mixture was contacted at room temperature for 5 minutes to obtain a catalyst component.

(3) Polymerization of Propylene The procedure of Example 1 (4) was repeated except that the catalyst obtained in (2) was used in its entirety in Example 1 (4) and polymerization was carried out at 80 ° C. for 40 minutes. Polymerization of propylene was carried out in the same manner as in 4). The obtained polymer was 340 g, and the amount of the polymer produced per 1 g of the solid component per hour was 5,100 g.

[0078]

According to the catalyst of the present invention and the polymerization method using the same, when polymerizing an olefin having 3 or more carbon atoms,
The polymerization activity per solid component can be made extremely high, and there is no need to remove the catalyst component from the obtained polymer, which is industrially useful.

Claims (5)

[Claims] 1. [A] 4 to 6 having a conjugated five-membered ring ligand
At least one selected from the group consisting of (1) an ion-exchange layered compound excluding silicate, and (2) an inorganic silicate, obtained by performing a treatment in the coexistence of a group III transition metal compound, [B] acid and salts. And a catalyst for polymerization of olefins having 3 or more carbon atoms, comprising the compound of formula (I) and [C] an organoaluminum compound. 2. The olefin polymerization catalyst according to claim 1, wherein the acid is selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid and oxalic acid. 3. The salt comprises at least one cation selected from the group consisting of atoms of groups 1 to 14 and at least one cation selected from the group consisting of halogen atoms, inorganic acids and anions of organic acids. A water-soluble compound containing an anion or an acidic aqueous solution-soluble compound,
The catalyst for olefin polymerization according to claim 1. 4. The component [C] is a compound represented by the general formula: AlR ⁴ _m X _3-m (wherein R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, X is hydrogen, a halogen, an alkoxy group, an aryloxy group, 2. The catalyst for olefin polymerization according to claim 1, wherein m is a compound represented by 0 <m ≦ 3). 5. A method for polymerizing olefins, comprising homopolymerizing or copolymerizing an olefin having 3 or more carbon atoms in the presence of the olefin polymerization catalyst according to claim 1.