JPH09302015A - Polypropylene having high melting point and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polypropylene having a superior heat resistance to that of a conventional polypropylene. SOLUTION: This polypropylene has a melting point (Tm) of 168 deg.C or higher, as measured using a differential scanning calorimeter, and has a value of molecular weight distribution (Mw/Mn) of 3 or smaller. This polypropylene can be obtained by polymerizing propylene at a temperature of -100 to 0 deg.C in the presence of a catalyst formed from (A) a metallocene compound having two ligands containing a cyclopentadienyl skeleton which are bonded to each other through a divalent group; and (B) at least one cocatalyst selected from the group consisting of (B-1) an organoaluminum compound, (B-2) an organoaluminumoxy compound and (B-3) a Lewis acid or an ionic compound containing a boron atom.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to polypropylene having a high melting point and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Polypropylene has been conventionally used for various purposes because of its excellent mechanical strength and chemical resistance. However, depending on the application, the heat resistance is not sufficient, and its industrial use was limited.

Therefore, attempts have been made to obtain polypropylene having a high melting point. The melting point of a single crystal of isotactic polypropylene is theoretically said to be 184 ° C (Flory, PJ Principles of Polymer Chemistr
y; Cornell University Press: Ithaca, NY, 1953 p568
), It is theoretically possible to obtain polypropylene with a high melting point. However, conventional polypropylene is not necessarily high in regioselectivity and stereoregularity, and there is a limit in raising the melting point. The melting point of industrial grade ordinary polypropylene (without additives) is 16
It is about 4 to 165 ° C.

It is known that polypropylene having a high melting point can be produced by using an olefin polymerization catalyst containing a metallocene compound. For example, JP-A-7-14
Japanese Patent No. 5203 discloses an example in which polypropylene is polymerized at a polymerization temperature of 5 ° C. using a catalyst component composed of a metallocene compound having a C1 symmetry and a non-coordinating ionic compound, and the melting point is the highest. 167.2 ° C.

Under such a situation in the prior art,
The present inventors have conducted extensive studies to obtain polypropylene having a high melting point by using a metallocene-based olefin polymerization catalyst, and as a result, by appropriately selecting the kind of ligand of the metallocene catalyst, the polymerization temperature and other conditions, The present invention has been completed by finding that polypropylene having a high melting point which is unknown is obtained.

[0006]

An object of the present invention is to provide a high melting point polypropylene having excellent heat resistance and a method for producing the same.

[0007]

SUMMARY OF THE INVENTION The polypropylene according to the present invention has a melting point (Tm) measured by a differential scanning calorimeter of 168 ° C. or higher.

This polypropylene has a molecular weight distribution (Mw
It is desirable that the value of / Mn) is 3 or less. Since the polypropylene according to the present invention has a high melting point, it can be used in applications where high heat resistance is required, which was not possible with conventional polypropylene.

The method for producing polypropylene according to the present invention comprises (A) a metallocene compound in which two ligands having a cyclopentadienyl skeleton are bonded via a divalent bonding group; B-1) Organoaluminum compound, (B-2) Organoaluminum oxy compound, (B-3) At least one selected from a Lewis acid or ionic compound containing a boron atom
-100 in the presence of a catalyst formed from the seed cocatalyst
It is characterized by polymerizing propylene at a temperature of ~ 0 ° C.

The method for producing polypropylene of the present invention can produce polypropylene having a high melting point (Tm).

[0011]

DETAILED DESCRIPTION OF THE INVENTION The high melting point polypropylene and the method for producing the same according to the present invention will be specifically described below.

The high melting point polypropylene according to the present invention has a melting point (Tm) measured by a differential scanning calorimeter of 168 ° C. or higher, preferably 168 to 175 ° C. The melting point (Tm) is measured as follows.

Differential scanning calorimeter (DSC-2 manufactured by Seiko
20C), first, the sample is heated from 20 ° C to 200 ° C at a rate of 10 ° C / min, held at 200 ° C for 2 minutes, and then cooled to -40 ° C at a rate of 10 ° C / min. -4
The temperature at the top of the endothermic peak obtained when the temperature was held at 0 ° C. for 5 minutes and then raised to 200 ° C. at a rate of 10 ° C./minute was taken as the melting point.

This polypropylene has a molecular weight distribution (Mw
It is desirable that the value of / Mn) is 3 or less. The value of the molecular weight distribution (Mw / Mn) is measured as follows.

Gel permeation chromatography (SSC7100) manufactured by Senshu Chemical Co., Ltd. was used as a solvent.
The measurement was performed at 145 ° C. using o-dichlorobenzene. A polystyrene standard was used for calibration.

The polypropylene according to the present invention is a ¹³ C--N
[Mmmm] pentad isotacticity measured by MR is 95 to 100%, preferably 97 to 100%
It is desirable to be in the range of.

The polypropylene according to the present invention is not limited to isotactic, but includes syndiotactic and the like, and the production method is not limited to the method using a metallocene compound as a catalyst. Among them, (A) cyclopentadiene A metallocene compound in which two ligands having an enyl skeleton are bonded via a divalent bonding group (hereinafter simply referred to as “metallocene compound”), (B) (B-1) organoaluminum compound, ( B-2) at least one selected from organoaluminum oxy compounds, (B-3) a boron acid-containing Lewis acid or ionic compound
It is desirable to make it by polymerizing propylene in the presence of a catalyst formed from a seed cocatalyst.

The respective components forming the propylene polymerization catalyst used in the present invention will be sequentially described below. (A) Metallocene compound As the metallocene compound, for example, a compound represented by the following formula (I) is used.

[0019]

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In the formula, M ¹ represents a transition metal atom of Group IV to VIB of the periodic table, specifically, zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, Preferred is zirconium, titanium or hafnium.

R ¹ , R ² , R ³ and R ^{4, which} may be the same or different, are hydrocarbon groups having 1 to 20 carbon atoms and halogenated hydrocarbon groups having 1 to 20 carbon atoms. , A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a hydrogen atom or a halogen atom. Of the groups represented by R ¹ , R ² , R ³ and R ⁴ ,
Part of the groups adjacent to each other may be bonded to each other to form a ring with the carbon atom to which the groups are bonded. Note that R
^{Although 1} , R ² , R ³ and R ⁴ are shown at two places respectively, for example, R ¹ and R ¹ may be the same group or different groups. The same suffixes among the groups represented by R indicate preferred combinations in the case where they are joined to form a ring.

As the hydrocarbon group having 1 to 20 carbon atoms, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and eicosyl; cyclopentyl, cyclohexyl, norbornyl,
Cycloalkyl groups such as adamantyl; alkenyl groups such as vinyl, propenyl, cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl And aryl groups such as methylnaphthyl, anthryl, and phenanthryl.

The ring formed by combining these hydrocarbon groups is a benzene ring, a naphthalene ring, an acenaphthene ring,
Examples thereof include a condensed ring group such as an indene ring, and a group in which a hydrogen atom on the condensed ring group is substituted with an alkyl group such as methyl, ethyl, propyl and butyl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Examples of the silicon-containing group include monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, and dimethylphenylsilyl ,
Trihydrocarbon-substituted silyl such as methyldiphenylsilyl, tritolylsilyl, trinaphthylsilyl; silyl ether of hydrocarbon-substituted silyl such as trimethylsilyl ether; silicon-substituted alkyl group such as trimethylsilylmethyl; silicon-substituted aryl group such as trimethylphenyl Can be mentioned.

Examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; an arylalkoxy group such as phenylmethoxy and phenylethoxy. To be

Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing group is replaced with sulfur. Amino group as nitrogen-containing group; alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino;
Phenylamino, diphenylamino, ditolylamino,
Examples thereof include arylamino groups such as dinaphthylamino and methylphenylamino, and alkylarylamino groups.

Examples of the phosphorus-containing group include phosphino groups such as dimethylphosphino and diphenylphosphino. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Of these, a hydrocarbon group having 1 to 20 carbon atoms is preferable, and a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl, or a hydrocarbon group is preferably bonded. The hydrogen atom on the benzene ring formed by combining the benzene ring and the hydrocarbon group is methyl, ethyl, n-propyl, iso-propyl, n-butyl, is
It is preferably a group substituted with an alkyl group such as o-butyl and tert-butyl.

X ¹ and X ² may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group,
It represents a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom.

Examples of the hydrocarbon group having 1 to 20 carbon atoms, the halogenated hydrocarbon group having 1 to 20 carbon atoms, the oxygen-containing group and the halogen atom include the same groups and atoms as the above R ^{1 to} R ^4. be able to.

Examples of the sulfur-containing group include the same groups as R ^{1 to} R ⁴ , and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl. Sulfonate groups such as benzene sulphonate, triisobutylbenzene sulphonate, p-chlorobenzene sulphonate, pentafluorobenzene sulphonate; methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenes Examples include sulfinate groups such as ruffinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate.

Examples of the silicon-containing group include the same silicon-substituted alkyl groups and silicon-substituted aryl groups as those described above for R ^{1 to} R ⁴ . Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a sulfonate group is preferable.

Y¹Is a divalent carbon having 1 to 20 carbon atoms
Hydrogenated group, divalent halogenated carbon having 1 to 20 carbon atoms
Hydrogen-containing group, divalent silicon-containing group, divalent germanium-containing group
Group, divalent tin-containing group, -O-, -CO-, -S-,
-SO-, -SO_Two-, -Ge-, -Sn-, -NR^Five
-, -P (R^Five)-, -P (O) (R^Five)-, -BR ^Five
-Or-AlR^Five-[However, R^FiveAre identical to each other
Hydrocarbon water having 1 to 20 carbon atoms
Elementary groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms,
A hydrogen atom or a halogen atom].

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include methylene, dimethylmethylene and 1,2-
Ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-
Examples include alkylene groups such as cyclohexylene; arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene.

Specific examples of the divalent halogenated hydrocarbon group having 1 to 20 carbon atoms include halogenated groups of the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene. Is mentioned.

As the divalent silicon-containing group, silylene,
Methyl silylene, dimethyl silylene, diethyl silylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenyl silylene, diphenyl silylene, di (p-tolyl) silylene, di (p- Alkylsilylylene groups such as chlorophenyl) silylene; Alkylarylsilylene groups; Arylsilylene groups; Tetramethyl-1,2-disilirene, tetraphenyl-1,2-disilylene and other alkyldisilylene groups; Alkylaryldisilylene groups; Aryldiyl Examples thereof include a silylene group.

Examples of the divalent germanium-containing group include groups obtained by substituting germanium for silicon in the divalent silicon-containing group. Examples of the divalent tin-containing group include groups obtained by substituting tin for silicon in the divalent silicon-containing group.

Of these, substituted silylene groups such as dimethylsilylene, diphenylsilylene and methylphenylsilylene are particularly preferred. R ⁵ is the above R ^{1 to} R ⁴
The same halogen atom, hydrocarbon group having 1 to 20 carbon atoms, and halogenated hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of the metallocene compound represented by the above formula (I) are shown below. ethylene
-Bis (indenyl) dimethyl zirconium, ethylene-
Bis (indenyl) zirconium dichloride, ethylene
-Bis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylene-bis (indenyl) zirconium bis (methanesulfonato), ethylene-bis (indenyl) zirconium bis (p-toluenesulfonato), ethylene-bis (indenyl) Zirconium bis (p-chlorobenzene sulfonate), ethylene-bis (4,
5,6,7-Tetrahydroindenyl) zirconium dichloride, isopropylidene-bis (cyclopentadienyl)
(Fluorenyl) zirconium dichloride, isopropylidene-bis (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (methylcyclopentadienyl) Zirconium dichloride, dimethylsilylene-bis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (indenyl) zirconium dichloride, dimethylsilylene-bis (indenyl) zirconium bis (Trifluoromethanesulfonato), dimethylsilylene-bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethyl Rylene-bis (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilylene-bis (indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,5-trimethyl) Cyclopentadienyl)
Zirconium dichloride, rac-Dimethylsilylene-bis (2,4,7-trimethylcyclopentadienyl) Zirconium dichloride, rac-Dimethylsilylene-bis (2-methyl-
4-tert-butylcyclopentadienyl) zirconium dichloride, isopropylidene- (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene- (3-tert-butylcyclopentadienyl)
(Indenyl) zirconium dichloride, isopropylidene- (4-methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene
-(4-tert-Butylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene
-(4-tert-Butylcyclopentadienyl) (3-tert-butylindenyl) zirconium dichloride, dimethylsilylene- (4-methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene- ( 4-tert-butylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene- (4-tert-butylcyclopentadienyl) (3-tert-
Butylindenyl) zirconium dichloride, dimethylsilylene- (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene- (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, etc.

In addition, compounds in which zirconium in the above compounds is replaced with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten can be given.

In the present invention, among the metallocene compounds represented by the above formula (I), the following general formula (II) or (III)
At least 1 selected from the metallocene compounds represented by
It is desirable to use certain metallocene compounds.

[0042]

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In the formula, M ² represents a transition metal atom of Group IVB of the Periodic Table, specifically titanium, zirconium or hafnium, preferably zirconium. R ^{11 s} may be the same or different from each other and represent a hydrocarbon group having 1 to 6 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- Examples thereof include alkyl groups such as butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl and cyclohexyl; alkenyl groups such as vinyl and propenyl.

Of these, an alkyl group having a primary carbon atom bonded to an indenyl group is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are particularly preferable.

R ¹² , R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different from each other and represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms similar to R ¹¹ . R ^13's may be the same or different from each other and represent a hydrogen atom or an aryl group having 6 to 16 carbon atoms,
Specifically, phenyl, α-naphthyl, β-naphthyl, anthryl, phenanthryl, pyrenyl, acenaphthyl,
Examples include phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like. Of these, phenyl, naphthyl, anthryl, and phenanthryl are preferable.

These aryl groups include halogen atoms such as fluorine, chlorine, bromine and iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl,
Alkyl groups such as nonyl, dodecyl, eicosyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl , Propylphenyl, biphenyl,
Hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as α- or β-naphthyl, methylnaphthyl, anthryl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl and biphenylyl. It may be substituted with an organic silyl group such as trimethylsilyl, triethylsilyl and triphenylsilyl.

X ³ and X ⁴ may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group,
It represents a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom, and specific examples thereof include the same atoms or groups as those of X ¹ and X ² .

Of these, halogen atom or carbon source
It is preferably a hydrocarbon group having a child number of 1 to 20. Y
^TwoIs a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon
Divalent halogenated hydrocarbon group having 1 to 20 atoms, divalent
A silicon-containing group, a divalent germanium-containing group, a divalent sulfur
Group containing group, -O-, -CO-, -S-, -SO-, -S
O_Two-, -Ge-, -Sn-, -NR^Five-, -P
(R^Five)-, -P (O) (R^Five)-, -BR ^Five-Or
-AlR^Five-[However, R^FiveAre the same or different
A hydrocarbon group having 1 to 20 carbon atoms,
Halogenated hydrocarbon group having 1 to 20 elementary atoms, hydrogen atom
Or a halogen atom].
Y¹And the same atom or group as.

Of these, a divalent silicon-containing group, a divalent germanium-containing group, and more preferably a divalent silicon-containing group, are alkylsilylene, alkylarylsilylene or arylsilylene. Is more preferable.

Specific examples of the metallocene compound represented by the above general formula (II) are shown below. rac-dimethylsilylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2
-Methyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛ 1- (2-methyl-
4- (1-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (2
-Anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (9-
Anthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-methyl-4- (pentafluorophenyl) indenyl) )} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (p-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (m-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (o-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (o, p-dichlorophenyl) phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1
-(2-Methyl-4- (p-bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1
-(2-Methyl-4- (p-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-methyl-4- (o
-Tolyl) indenyl)} zirconium dichloride, rac
-Dimethylsilylene-bis {1- (2-methyl-4- (o, o'-dimethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p -
Ethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (pi
-Propylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-)
(p-benzylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (p-biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m
-Biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-
Trimethylsilylenephenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-
Methyl-4- (m-trimethylsilylenephenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-phenyl-4-phenylindenyl)} zirconium dichloride, rac-diethylsilylene-bis {1-
(2-Methyl-4-phenylindenyl)} zirconium dichloride, rac-di- (i-propyl) silylene-bis {1- (2
-Methyl-4-phenylindenyl) zirconium dichloride, rac-di- (n-butyl) silylene-bis {1- (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dicyclohexylsilylene-bis} 1- (2-methyl-4-phenylindenyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2-methyl-
4-phenylindenyl)} zirconium dichloride, ra
c-diphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} Zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-methyl-4-phenylindenyl) )} Zirconium dichloride, rac-ethylene-bis {1- (2-methyl-4-)
Phenylindenyl) zirconium dichloride, rac-
Dimethylgermylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-Dimethylstanylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac- Dimethyl silylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dibromide, rac-dimethylsilylene-bis {1- (2
-Methyl-4-phenylindenyl)} zirconium dimethyl, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium methyl chloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride SO ₂ Me, rac-Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride OSO ₂ Me, rac-dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (5-acenaphthyl) indenyl) ｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (o-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (m-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (p-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,4-dimethylphenyl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (2,5-dimethylphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl- 4- (2,4,6-trimethylphenyl) indenyl)｝ zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,6
-Dichlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4-
(3,5-dichlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (2-bromophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (3-bromophenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (4-bromophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (4-biphenylyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4
-(4-trimethylsilylphenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis
(2-n-propyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-n-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl
-4- (2-methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl-4- (5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethyl Silylene-bis ｛1- (2-n-
Propyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-
Propyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1-
(2-i-propyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-i-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl
-4- (8-methyl-9-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4- (5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethyl Silylene-bis ｛1- (2-i-
Propyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-
Propyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1-
(2-s-butyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl
-4- (α-naphthyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4-
(Β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4- (2
-Methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4)
-(5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4)
-(9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4-
(9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-pentyl)
-4-Phenylindenyl)} zirconium dichloride, r
ac-dimethylsilylene-bis ｛1- (2-n-pentyl-4- (α-
Naphthyl) indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-n-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (α-naphthyl) indenyl) )｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-butyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (5- Acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-butyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n -Butyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4-phenylindenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis
-(2-i-butyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-
i-butyl-4- (2-methyl-1-naphthyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-i-butyl-4- (5-acenaphthyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-i-butyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-i-butyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-neopentyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-neopentyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛ 1- (2-n-
Hexyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-hexyl)
-4- (α-naphthyl) indenyl) zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2-ethyl
-4-Phenylindenyl)} zirconium dichloride, r
ac-methylphenylsilylene-bis ｛1- (2-ethyl-4- (α
-Naphthyl) indenyl)} zirconium dichloride, r
ac-methylphenylsilylene-bis {1- (2-ethyl-4- (9-
Anthryl) indenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-ethyl-4- (9
-Phenanthryl) indenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2-ethyl-4-
Phenylindenyl) zirconium dichloride, rac-
Diphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-anthryl) indenyl)} zirconium Dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (4-biphenylyl) Indenyl) {zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4-phenylindenyl)}
Zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium Dichloride, rac-ethylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-ethylene-bis
-(2-n-propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylgermyl-bis ｛1-
(2-ethyl-4-phenylindenyl) zirconium dichloride, rac-dimethylgermyl-bis ｛1- (2-ethyl-4-
(Α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylgermyl-bis ｛1- (2-n-propyl-4-)
Phenylindenyl) zirconium dichloride.

Further, a compound in which zirconium in the above compounds is replaced by titanium or hafnium can also be mentioned. In the present invention, the racemic metallocene compound represented by the general formula (II) is usually used as the catalyst component, but R type or S type can also be used.

Such a metallocene compound represented by the general formula (II) is described in Journal of Organometallic Chem.
985), pages 63-67, European Patent Application Publication No. 0,320,76.
It can be produced according to the specification and Example.

Next, the metallocene compound represented by the general formula (III) will be described.

[0054]

Embedded image

In the formula, M ³ represents a transition metal atom of Group IVB of the Periodic Table, specifically titanium, zirconium or hafnium, preferably zirconium. R ²¹ and R ²² may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, A sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a hydrogen atom or a halogen atom, and specifically, the above R
The same atom or group as ^{1 to} R ⁴ can be mentioned.

Of these, R ²¹ has 1 to 2 carbon atoms.
It is preferably a hydrocarbon group having 0, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl.

R ²² has a hydrogen atom or a carbon atom number of 1 to
20 hydrocarbon groups are preferred, and particularly hydrogen atom or methyl, ethyl, propyl having 1 carbon atom
It is preferably from 3 to 3 hydrocarbon groups.

R ²³ and R ^{24, which} may be the same or different, each represents an alkyl group having 1 to 20 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, Examples include isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl and the like.

Of these, R ²³ is preferably a secondary or tertiary alkyl group. X ⁵ and X ⁶ may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group. A group, a hydrogen atom or a halogen atom is shown, and specific examples thereof include the same atom or group as those of X ¹ and X ² .

Y^ThreeIs a divalent carbon having 1 to 20 carbon atoms
Hydrogenated group, divalent halogenated carbon having 1 to 20 carbon atoms
Hydrogen-containing group, divalent silicon-containing group, divalent germanium-containing group
Group, divalent tin-containing group, -O-, -CO-, -S-,
-SO-, -SO_Two-, -Ge-, -Sn-, -NR^Five
-, -P (R^Five)-, -P (O) (R^Five)-, -BR ^Five
-Or-AlR^Five-[However, R^FiveAre identical to each other
Hydrocarbon water having 1 to 20 carbon atoms
Elementary groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms,
A hydrogen atom or a halogen atom],
Is Y¹And the same atom or group as.

Specific examples of the metallocene compound represented by the above general formula (III) are shown below. rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1
-(2,7-Dimethyl-4-n-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7
-Dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis { 1- (2,7-dimethyl-4-
sec-Butylindenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-pentylindene) Nil)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindenyl) )} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-) Trimethylsiloxymethylindenyl)} zirconium dichloride, ra
c-Diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl) silylene-bis {1- (2,7-dimethyl-4) -i-
Propylindenyl) zirconium dichloride, rac-
Di (n-butyl) silylene-bis {1- (2,7-dimethyl-4-i-
Propylindenyl) zirconium dichloride, rac-
Di (cyclohexyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,7-dimethyl-4-i- Propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7 -Dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7-dimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2,7-dimethyl-4-i -Propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1 -(2-Methyl-4-i-propyl-7-ethylindenyl)} zirconium dibromide rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-
4-Ethylindenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-i- Propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2, 3,7-Trimethyl-4-sec-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride, rac- Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-pentylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-methylcyclohexylindenyl)} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-
Trimethylsiloxymethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-
Trimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,
3,7-Trimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-diethylsilylene
-Bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl)
Silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (n-butyl) silylene-bis {1- (2,3,7-trimethyl- 4-i-Propylindenyl)} zirconium dichloride, rac-di (cyclohexyl) silylene-bis {1- (2,3,7-trimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-Methylphenylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7
-Trimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2,3,7
-Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethyl silylene
-Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium dimethyl, rac-dimethylsilylene-
Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium methyl chloride, rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindene Nyl)} zirconium-bis (methanesulfonato), r
ac-Dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium-bis (p-phenylsulfinato), rac-dimethylsilylene-bis {1-
(2-Methyl-3-methyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4,6-di-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-phenyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methylindenyl)} zirconium dichloride, rac-ethylene- Bis {1- (2,4,7-trimethylindenyl)} zirconium dichloride, rac-isopropylidene-bis {1- (2,4,7-trimethylindenyl)}
Zirconium dichloride, etc.

Further, a compound in which zirconium in the above compounds is replaced by titanium or hafnium can also be mentioned. Among these, i-propyl and sec- in the 4th position
Those having a branched alkyl group such as a butyl or tert-butyl group are particularly preferable.

In the present invention, a racemic metallocene compound represented by the general formula (III) is usually used as a catalyst component, but R type or S type can also be used. The metallocene compound represented by the general formula (III) as described above can be prepared by a known method from an indene derivative, for example, JP-A-4-
It can be synthesized by the method described in Japanese Patent No. 268307.

Furthermore, in the present invention, Japanese Patent Laid-Open No. 7-1452.
C1 symmetric metallocene compounds disclosed in Japanese Patent Application No. 03, such as threo-isopropylidene (3-tert-butyl-
Cyclopentadienyl) (3-tert-butyl-indenyl)
Zirconium dimethyl or the like can also be used.

The metallocene compound (A) is
-1) Used for polymerization of propylene together with at least one cocatalyst selected from organoaluminum compound, (B-2) organoaluminum oxy compound and (B-3) Lewis acid containing boron atom or ionic compound .

(B-1) Organoaluminum Compound (B-1) Examples of the organoaluminum compound (hereinafter sometimes referred to as “component (B-1)”) include compounds represented by the following formula (I
The organoaluminum compound represented by V) can be exemplified.

[0067] In ^{_{R a n AlX 3-n ...}} (IV) formula, R ^a represents a hydrocarbon group, for example an alkyl group, a cycloalkyl group or an aryl group having 1 to 12 carbon atoms, specifically, Examples include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl and tolyl.

X represents a halogen atom or a hydrogen atom,
n is 1 to 3. Specific examples of such an organoaluminum compound include the following compounds.

Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri 2-
Trialkylaluminums such as ethylhexylaluminum and tridecylaluminum; Alkenylaluminums such as isoprenylaluminum; Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide; Methylaluminum sesquichloride, Ethyl aluminum sesquichloride,
Alkyl aluminum sesquihalides such as isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide; diethyl aluminum hydride, diisobutyl aluminum Alkyl aluminum hydride such as hydride.

As the organoaluminum compound (B-1), a compound represented by the following general formula (V) can also be used. During ^{_{R a n AlY 3-n ...}} (V) ( wherein, R ^a is as defined above, Y is -OR ^b group, -
OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -S
a iR ^f ₃ group or -N (R ^g) AlR ^h ₂ group, n is ^{1~2, R b, R c,} R d and R ^h are each methyl, ethyl, isopropyl, isobutyl, A cyclohexyl group, a phenyl group, etc., wherein ^Re is a hydrogen atom,
Examples include a methyl group, an ethyl group, an isopropyl group, a phenyl group, and a trimethylsilyl group, and R ^f and R ^g are a methyl group, an ethyl group, and the like. ) As such an organoaluminum compound, the following compounds are specifically used. (I) compounds represented by R ^a _n Al (OR ^b ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, and (ii) R ^a _n Al (OSiR ^c ₃ ) ₃ a compound represented by _-n , for example, Et ₂ Al (OSiMe ₃ ), (iso-B
u) ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (O
SiEt ₃ ), etc., (iii) R ^a _n Al (OAlR ^d ₂ ) _3-n
A compound represented by, for example, Et ₂ AlOAlEt ₂ ,
(Iso-Bu) ₂ AlOAl (iso-Bu) ₂ etc., (iv)
^{_{R a n Al (NR e 2}} ) a compound represented by _3-n, e.g., M
e ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNH
Et, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ Al
(V) R ^a _n Al (SiR ^f ₃ ) such as N (SiMe ₃ ) ₂
A compound represented by _3-n , for example, (iso-Bu) ₂ AlS
iMe _3, etc., such as (vi) R ^a _n Al [N (R ^g ) AlR ^h ₂ ].
A compound represented by _3-n , for example, Et ₂ AlN (Me)
AlEt ₂ , (iso-Bu) ₂ AlN (Et) Al (iso-
Bu) ₂ etc.

Among the organoaluminum compounds represented by the above general formulas (IV) and (V), the general formulas R ^a ₃ Al, R
Organoaluminum compounds represented by ^a _n Al (OR ^b ) _3-n and R ^a _n Al (OAlR ^d ₂ ) _3-n can be given as preferable examples, wherein R ^a is an isoalkyl group and n = 2.
Are particularly preferred. These organoaluminum compounds can be used as a mixture of two or more kinds.

(B-2) Organoaluminum Oxy Compound (B-2) Organoaluminum Oxy Compound (hereinafter referred to as “Component (B-
2) ”may be described. ) May be a conventionally known aluminoxane, or may be a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-2-78687.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of, and reacting the organoaluminum compound with adsorption water or crystallization water. (2) A method in which water, ice, or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the preparation of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum and triisobutylaluminum.
sec-Butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc. trialkylaluminums; tricyclohexylaluminum, tricyclooctylaluminum, etc. Dialkyl aluminum halides such as diethyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; diethyl Rumi bromide phenoxide, and the like dialkylaluminum Ally Loki Sid such.

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferable.
Further, as the organoaluminum compound used in the production of aluminoxane, isoprenylaluminum represented by the following general formula (VI) can also be used.

[0077] _{(i-C 4 H 9)} X Al y (C 5 H 10) Z ... (VI) ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Above Such organoaluminum compounds may be used alone or in combination.

The solvent used for the preparation of the aluminoxane includes aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides Among these, hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

(B-3) A Lewis acid containing a boron atom, or
Examples of the ionic compound (B-3) Lewis acid or ionic compound containing a boron atom (hereinafter sometimes referred to as “component (B-3)”) include the following compounds.

As the Lewis acid containing a boron atom,
Examples thereof include compounds represented by the following general formula (VII). BR ₃ (VII) However, in the above formula (VII), R is a phenyl group which may have a substituent such as fluorine, a methyl group or a trifluoromethyl group, or fluorine.

Specific examples of the compound represented by the general formula (VII) include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,
5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) Boron and the like. Of these, tris (pentafluorophenyl) boron is preferred.

Examples of the ionic compound containing a boron atom include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts and triarylphosphonium salts.

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron and trimethylammonium tetra. (P-Tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethyl) Phenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron, etc. are listed as N, N-dialkylanilinium salts. , For example, N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron, etc. Examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Triarylphosphonium salts such as triphenylphosphonium tetra Examples thereof include (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron and tri (dimethylphenyl) phosphonium tetra (phenyl) boron.

As the ionic compound containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) boronate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate Can also be mentioned.

Further, the following compounds can be exemplified as the ionic compound containing a boron atom. (In the ionic compounds listed below, the counter ion is, but not limited to, tri (n-butyl) ammonium.) Salts of anions, for example, bis [tri (n-butyl) ammonium] nonaborate, bis [tri (N-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl)
Ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate, tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (N-Butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, etc .; borane, carborane complex compounds , Salts of carborane anions, such as decaborane (14), 7,8-dicarbaundecaborane (13), 2,7-dicarbaundecaborane (13), undecahydride-7,8-dimethyl-7,8- Dicarbaundecaborane, Dodecahydride-11-Methyl-2,7-dicarbaundecaborane, Tri (n-butyl) ammoni Um 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl)
Ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7,8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarbaundecaborate (12), tri (N-Butyl) ammonium dodecahydride-8-methyl 7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride 8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) Ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-
Butyl) ammonium undeca hydride-8-allyl-
7,9-Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,
8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate, etc .; carboranes, salts of carboranes such as 4-carbanonaborane (14), 1,3- Dicarbano Naborane (13), 6,9-Dicarbadecaborane (14), Dodeca Hydride-1-Phenyl-1,3-Dicarbano Naborane, Dodeca Hydride-1-Methyl-1,3-Dicarbanona Examples of the ionic compound further containing a boron atom, such as borane and undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, include the following compounds.
(Note that the counter ion in the ionic compounds listed below is, but not limited to, tri (n-butyl) ammonium.) A salt of metal carborane and a metal borane anion, for example, tri (n-butyl) ammonium bis (nona). Hydride-1,3-dicarbanonaborate) Cobaltate (III),
Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (ferrate) (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dical) Boundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl)
Ammonium bis (undecahydride-7,8-dicarbaundecaborate) cubrate (cuprate) (II
I), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (metal salt) (III), tri (n-butyl) ammonium bis (nonahydride-7,8- Dimethyl-7,8-dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (chromate) ( III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl)
Ammonium bis (dodecahydride dicarbadodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III), tris [tri (n-butyl) ammonium] bis ( Undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) manganate (I
V), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-cal Bounce carbate) Nickelate (IV) and the like.

Two or more kinds of the above-mentioned Lewis acid or ionic compound containing a boron atom can be mixed and used. The propylene polymerization catalyst used in the present invention can also be used as a solid catalyst in which a part or all of the above metallocene compound and cocatalyst are supported on the following carrier.

(C) Carrier The (C) carrier used (hereinafter sometimes referred to as “component (C)”) is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably Is 20-2
Granules or fine particles of solid of 00 μm are used. Among them, a porous oxide is preferable as the inorganic carrier, and specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ ,
TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂
Or a mixture thereof, such as SiO ₂ --MgO,
SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V
Examples include ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , and SiO ₂ —TiO ₂ —MgO. Of these, those containing, as a main component, at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ .

The above inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ )
_It does not matter if it contains a carbonate, a sulfate, a nitrate or an oxide component such as ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O.

The properties of such a carrier (C) differ depending on its type and production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ³ / g. , The pore volume is 0.3 ~
It is preferably 2.5 cm ³ / g. The carrier is, if necessary, 100 to 1000 ° C, preferably 150 to 7 ° C.
It is used after firing at 00 ° C.

Further, the carrier (C) has a particle size of 10
A granular or fine particle solid of an organic compound having a particle size of up to 300 μm can be mentioned. As these organic compounds, ethylene, propylene, 1-butene, 4-methyl-1-pentene, and the like, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms, or vinylcyclohexane, Examples thereof include polymers or copolymers containing styrene as a main component.

Catalyst for Propylene Polymerization The catalyst for propylene polymerization used in the present invention comprises the metallocene compound (A) and the organoaluminum compound (B-1).
, A organoaluminum oxy compound (B-2) and at least one cocatalyst (B) selected from a Lewis acid containing a boron atom or an ionic compound (B-3), and may be a metallocene. It may be a solid catalyst in which a part or all of the compound (A) and the cocatalysts (B-1) to (B-3) are carried on the carrier (C), and propylene is prepolymerized on the solid catalyst (component). It may be a prepared prepolymerization catalyst.

The solid catalyst (component) can be prepared by mixing and contacting the above components in an inert solvent. The prepolymerization catalyst can be obtained by introducing propylene into an inert hydrocarbon solvent in the presence of each of the above components, preferably in the presence of the solid catalyst (component).

Specific examples of the inert hydrocarbon medium used for preparing the propylene polymerization catalyst include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, Examples thereof include alicyclic hydrocarbons such as cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

When the component (A), the component (B-1), the component (B-2), the component (B-3) and the component (C) are mixed and contacted, the concentration of the component (A) is about 10 ^{−. It is in the range of 4 to} 2 × 10 ^-2 mol / liter (solvent), preferably 2 × 10 ^-4 to 10 ^-2 mol / liter (solvent). Component (A) is component (C) 1
It is usually used in an amount of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ mol per g. Ingredient (B-
The atomic ratio (Al / transition metal) of aluminum of 1) to the transition metal in the component (A) is usually 10 to 500, preferably 20 to 200. Aluminum atom of component (B-2) (Al _B-2 ) and aluminum atom of component (B-1) (A
The atomic ratio of (l _B-1 ) (Al _B-2 / Al _B-1 ) is usually 0.0
It is in the range of 2-3, preferably 0.05-1.5. Molar ratio of component (A) and component (B-3) (component (A) / component (B
-3)) is usually 0.01 to 10, preferably 0.5 to 5.
Range.

The mixing temperature for mixing and contacting the component (A), the component (B-1), the component (B-2), the component (B-3) and the component (C) is usually -50 to 150 ° C. Preferably -20 to 120
And the contact time is 1 minute to 50 hours, preferably 10
Minutes to 25 hours.

The catalyst for propylene polymerization in which the component (A), the component (B-1) to the component (B-3) obtained as described above are carried on the component (C), is used per 1 g of the component (C). The transition metal atom derived from the component (A) is supported in an amount of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ gram atom, and the component (B-1) And aluminum atoms derived from the component (B-2) are supported in an amount of 10 ^{−3 to} 5 × 10 ⁻² gram atom, preferably 2 × 10 ⁻³ to 2 × 10 ⁻² gram atom,
Boron atom derived from the component (B-3) is 5 × 10 ^{−8 to} 5 × 1
It is desirable that it is supported in an amount of 0 ^-2 gram atom, preferably 5 x 10 ^{-7 to} 5 x 10 ^-3 gram atom.

The propylene polymerization catalyst is obtained by prepolymerizing propylene in the presence of component (A), component (B-1), component (B-2), component (B-3) and component (C). It may be a prepolymerization catalyst. The prepolymerization is carried out in the presence of the above-mentioned component (A), component (B-1), component (B-2), component (B-3) and component (C) in propylene in an inert hydrocarbon solvent. Can be carried out by introducing

In the prepolymerization, the above component (A) is
It is usually used in an amount of 10 ^{−6 to} 2 × 10 ⁻² mol / liter (solvent), preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / liter (solvent). The component (A) is usually 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 ×, per 1 g of the component (C).
Used in an amount of 10 ⁻⁴ mol. The atomic ratio (Al / transition metal) of aluminum as the component (B-1) to the transition metal in the component (A) is usually 10 to 500, preferably 20 to 200. Atomic ratio of component aluminum atom (Al _{B- 2)} and components (B-2) (B- 1) Aluminum atom (Al _B-1) (A
1 _B-2 / Al _B-1 ) is usually 0.02 to 3, preferably 0.05 to 1.5. Ingredient (A) and ingredient (B-
The molar ratio with (3) (component (A) / component (B-3)) is usually 0.01 to 10, preferably 0.5 to 5.

The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 10 ° C.
It is 0 hours, preferably about 1 to 50 hours. The amount of the propylene polymer produced by the prepolymerization is 0.1 to 500 g, preferably 0.2 to 300 g, and more preferably 0.5 to 200 g per 1 g of the carrier (C). Further, in the prepolymerization catalyst, the component (A) is present as a transition metal atom in an amount of about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ per 1 g of the carrier (C).
The aluminum atom (Al) derived from the component (B-1) and the component (B-2) is supported in the component (A) in an amount of gram atom, preferably 10 ^{−5 to} 2 × 10 ⁻⁴ gram atom. In a molar ratio (Al / M) to the transition metal atom (M) of 5 to 20
The component (B-3) is supported in an amount of 0, preferably 10 to 150, and the component (B-3) is 5 × 10 5 as a boron atom in the component (B-3).
^{-8 to} 5 x 10 ^-2 gram atom, preferably 5 x 10 ^{-7 to} 5
It is desirable to be loaded in an amount of × 10 ^-3 gram atom.

The prepolymerization can be carried out either batchwise or continuously, and can be carried out under reduced pressure, normal pressure or under pressure. In the present invention, the polymerization of propylene is carried out in the gas phase or in the slurry liquid phase. In the slurry polymerization, an inert hydrocarbon may be used as the solvent, or propylene itself may be used as the solvent.

Specific examples of the inert hydrocarbon solvent used in the slurry polymerization include butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, and other aliphatic hydrocarbons; cyclopentane, methylcyclopentane. , Cyclohexane,
Alicyclic hydrocarbons such as cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; gasoline;
Examples include petroleum fractions such as kerosene and light oil. Among these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferred.

Upon polymerization, the metallocene compound (A)
Is used in an amount of usually 10 ^-8 to 10 ^-3 gram atom / liter, preferably 10 ^-7 to 10 ^-4 gram atom / liter, as the concentration of the transition metal atom in the metallocene compound (A) in the polymerization system. Is desirable. When the organoaluminum compound (B-1) is used as the cocatalyst, the atomic ratio (Al / transition metal) of aluminum in the component (B-1) to the transition metal in the component (A) is usually 5 to 10,000. , And preferably in the range of 10 to 5000. When an organoaluminum oxy compound (B-2) is used as a cocatalyst, the component (B-2)
The atomic ratio (Al / transition metal) between the aluminum contained therein and the transition metal contained in the component (A) is usually 5 to 10000, preferably 10 to 5000. When a Lewis acid containing a boron atom or an ionic compound (B-3) is used as a cocatalyst, the molar ratio of the component (A) to the component (B-3) [(A
-1) / (B-3)] is usually in the range of 0.01 to 10, preferably 0.5 to 5.

When a solid catalyst or a prepolymerization catalyst is used for the polymerization, the same organoaluminum compound as the component (B-1) and / or an organoaluminum oxy compound as the component (B-2) may be added. Good. At this time, the atomic ratio of the aluminum atom (Al) derived from the organoaluminum compound and the organoaluminum oxy compound to the transition metal atom (M) in the (A) metallocene compound (Al
/ M) is in the range of 5-300, preferably 10-200, more preferably 15-150.

Polymerization Method In the present invention, when the polymerization is carried out, the polymerization temperature is usually in the range of -100 to 0 ° C.

The polymerization pressure is usually atmospheric pressure to 100 kg /
It is under a pressure condition of cm ² , preferably ² to 50 kg / cm ² , and the polymerization can be carried out in any of batch system, semi-continuous system and continuous system.

It is also possible to carry out the polymerization in two or more stages under different reaction conditions. By polymerizing propylene in the presence of the catalyst for propylene polymerization as described above under the conditions as described above, polypropylene having a melting point (Tm) measured by a differential scanning calorimeter of 168 ° C. or higher can be produced. .

[0107]

EFFECT OF THE INVENTION The polypropylene according to the present invention has a higher melting point than conventional polypropylenes and is therefore excellent in heat resistance, and can be used in applications requiring high heat resistance, which cannot be used with conventional polypropylenes.

According to the method for producing polypropylene of the present invention, polypropylene having a melting point higher than that of conventional polypropylene can be produced.

[0109]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0110]

Example 1 26.7 ml of toluene distilled and dehydrated on calcium hydroxide was introduced into a 100 ml stainless steel autoclave whose atmosphere was replaced with nitrogen, and then the system was cooled with liquid nitrogen to obtain a toluene solution of triisobutylaluminum 1.0.
ml (1.0 mol / liter), ethylene-bis {1-
0.005 mmol of (2,4,7-trimethylindenyl)} zirconium dichloride is introduced. Furthermore, after introducing 1.0 mmol of triphenylcarbenium tetrakispentafluorophenylborate, propylene 7.0
Polymerization was started by introducing liter, and the temperature was -78 ° C.
The reaction was allowed to stir for 2 days while cooling to room temperature. After the completion of the polymerization, the system was returned to room temperature, propylene was purged, the contents were put into methanol acidified with hydrochloric acid, and the produced polymer was recovered by filtration.

The melting point of the produced polymer was measured by a differential scanning calorimeter and found to be 168.9 ° C. The number average molecular weight (Mn) measured by gel permeation chromatography (GPC) was 1.36 million, and the ratio of the weight average molecular weight (Mw) to Mn (Mw / Mn) was 1.85.

[0112]

Example 2 Propylene was polymerized in the same manner as in Example 1 except that polymerization was carried out at -30 ° C for 2 hours instead of at -78 ° C for 2 days.

The melting point of the produced polymer was measured by a differential scanning calorimeter and found to be 168.0 ° C. Also, GP
The number average molecular weight (Mn) measured by C was 1,1010,000, and the ratio of the weight average molecular weight (Mw) to Mn (Mw / Mn) was 1.86.

Claims (3)

[Claims] 1. A melting point (T) measured by a differential scanning calorimeter.
m) is 168 ° C. or higher, polypropylene. 2. The polypropylene according to claim 1, which has a molecular weight distribution (Mw / Mn) value of 3 or less. 3. (A) a metallocene compound in which two ligands having a cyclopentadienyl skeleton are bound via a divalent linking group; and (B) (B-1) an organoaluminum compound, (B-2) at least one selected from organoaluminum oxy compounds, (B-3) Lewis acid containing a boron atom or ionic compound
-100 in the presence of a catalyst formed from the seed cocatalyst
A method for producing polypropylene, which comprises polymerizing propylene at a temperature of ~ 0 ° C.