JP2006008983A - Propylenic polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylenic polymer having good heat resistance and good impact resistance in spite of having a low melting point. <P>SOLUTION: This polymer is composed of a portion (D<SB>sol</SB>) soluble in n-decane at room temperature and a portion (D<SB>insol</SB>) insoluble in n-decane at room temperature, is obtained from propylene (M<SB>p</SB>) and one or more olefins (M<SB>x</SB>) selected from ethylene and ≥4C α-olefins, and simultaneously satisfies the following requirements (1) to (3). (1) GPC mol. wt. distributions (M<SB>w</SB>/M<SB>n</SB>) of D<SB>sol</SB>and D<SB>insol</SB>are ≤4.0, respectively. (2) The melting point (T<SB>m</SB>) of D<SB>insol</SB>is in a range of 140 to 155°C. (3) A heat distortion temperature HDT (load 0.45 MPa) and the amount W<SB>sol</SB>(wt%) of the portion soluble in n-decane at room temperature satisfy a relational expression: 100-W<SB>sol</SB>≤HDT≤120-W<SB>sol</SB>. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a propylene-based polymer, and more particularly to a propylene-based block copolymer having good heat resistance and impact resistance despite having a low melting point.

  Highly crystalline polypropylene obtained by polymerizing propylene using a Ziegler-type catalyst has a wide range of applications as a material having excellent rigidity and heat resistance as a thermoplastic resin, but it is particularly heat resistant in applications such as high retort and semi-retort. In addition, impact resistance and heat sealability are required.

  Here, propylene-ethylene block copolymer with improved impact resistance at low temperatures, which is a drawback of polypropylene, is produced by propylene-ethylene block copolymerization, in which polymerization or copolymerization of propylene and ethylene is performed in two or more stages. It is known to be manufactured. In addition, using a Ziegler-type catalyst, the polymerization of propylene or a mixture of propylene and a small amount of ethylene is continuously performed in the former stage, and the copolymerization of propylene and ethylene is continuously performed in the latter stage and the amorphous propylene. A method for producing an ethylene copolymer and continuously producing a propylene-ethylene block copolymer having an excellent balance between impact resistance and rigidity is known. However, in the step of carrying out the block copolymerization, in addition to a copolymer of propylene and ethylene soluble in a solvent such as n-decane or paraxylene, a copolymer of propylene and ethylene insoluble in these solvents, polyethylene, Polypropylene is by-produced.

  It is known that the solvent-insoluble component in the block copolymerization step causes a decrease in physical properties such as the elastic modulus of the propylene copolymer. Therefore, in the second step in which block copolymerization is performed, the appearance of a propylene-ethylene copolymer insoluble in solvents such as n-decane and paraxylene, and a propylene-ethylene copolymer in which polyethylene and polypropylene are not by-produced is desired. It is.

In JP-A-2003-206325 and JP-A-2003-147035, a block copolymer is produced using a metallocene catalyst. In the above invention, although there are few by-products such as propylene-ethylene copolymer insoluble in n-decane and paraxylene in the step of performing block copolymerization, the propylene block copolymer itself has a high melting point and low temperature heat sealability. There's a problem.
JP 2003-206325 A Japanese Patent Laid-Open No. 2003-147035

  The present invention relates to a propylene-based polymer, and more particularly to a propylene-based block copolymer having good heat resistance and impact resistance despite having a low melting point.

That is, the present invention is a propylene polymer that simultaneously satisfies the following requirements (1) to (3), specifically, one or more selected from propylene ( _MP ) and ethylene and an α-olefin having 4 or more carbon atoms. The present invention relates to a propylene-based block copolymer obtained from an olefin (M _X ), and various molded products obtained by molding the propylene-based polymer.

Consists of a part soluble in room temperature n-decane (D _sol ) and a part insoluble in room temperature n-decane (D _insol ), selected from propylene (M _P ) and ethylene and α-olefins with 4 or more carbon atoms A propylene-based polymer which is a polymer obtained from one or more olefins (M _X ) and simultaneously satisfies the following requirements (1) to (3).
(1) Both D _sol and D _insol have a GPC molecular weight distribution (Mw / Mn) of 4.0 or less.
(2) The melting point (Tm) of D _insol is in the range of 140 to 155 ° C.
(3) The heat distortion temperature HDT (load 0.45 MPa) and the amount W _sol (wt%) of the portion soluble in room temperature n-decane satisfy the following relational expression.

  Although the propylene-based block copolymer of the present invention has a low melting point, it has good heat resistance and impact resistance, and is suitably used in fields requiring low-temperature heat sealability, heat resistance, and impact resistance. can do.

Hereinafter, the present invention will be described in detail.
Propylene-based polymer The propylene-based polymer of the present invention, that is, a propylene-based block copolymer obtained from propylene (M _P ) and at least one olefin (M _X ) selected from ethylene and an α-olefin having 4 or more carbon atoms. Consists of a room temperature n-decane insoluble part (D _insol ) and a room temperature n-decane soluble part (D _sol ). From the viewpoint of chemical structure, the propylene-based polymer of the present invention is composed of a propylene homopolymer and a copolymer selected from propylene, ethylene and an α-olefin having 4 or more carbon atoms. Corresponds mainly to a component insoluble in room temperature n-decane (D _insol ) or a component insoluble in orthodichlorobenzene at 90 ° C. and soluble in 135 ° C. orthodichlorobenzene, having propylene and ethylene and / or having 4 or more carbon atoms The copolymer part composed of α-olefin corresponds to a component soluble in n-decane at room temperature (D _sol ) or a component soluble in orthodichlorobenzene at 40 ° C. Hereinafter, requirements (1) to (3) included in the propylene polymer of the present invention will be described in detail.

  The α-olefin having 4 or more carbon atoms used in the present invention is preferably an α-olefin having 4 to 20 carbon atoms, such as 1-butene, 1-pentene, 3-methyl-1-butene, and 1-hexene. 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. The amount of ethylene or α-olefin in the copolymer part is 10 to 80 mol%, preferably 20 to 80 mol%, more preferably 30 to 80 mol%. Further, the α-olefin in the copolymer may be one type or two or more types, and ethylene, 1-butene, and 1-hexene are particularly preferable.

[Requirement (1)]
The propylene polymer of the present invention has a GPC molecular weight distribution (Mw / Mn) of a component soluble in n-decane at room temperature (D _sol ) of 4.0 or less, preferably 2.0 to 4.0.

[Requirement (2)]
The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the component (D _insol ) insoluble in room temperature n-decane of the propylene polymer of the present invention is 1.0 to 4.0, preferably 2.0-4.0. The melting point (Tm) of the component insoluble in room temperature n-decane (D _insol ) is 140 to 155 ° C, preferably 145 to 155 ° C. When Tm is 155 ° C. or higher, the low temperature heat sealability is deteriorated, and when Tm is 140 ° C. or lower, the heat resistance is lowered. The _total amount of components insoluble in room temperature n-decane (D _insol ) and components insoluble in orthodichlorobenzene at 90 ° C. and soluble in 135 ° C. orthodichlorobenzene described below is approximately equal to the amount of propylene homopolymer based on experience. .

[Requirement (3)]
Requirement (3) is a stipulation regarding the heat resistance rigidity of the propylene-based polymer of the present invention. That is, the propylene-based polymer of the present invention is characterized in that the heat distortion temperature HDT (load 0.45 MPa) and the amount W _sol (wt%) of the portion soluble in room temperature n-decane satisfy the following relational expression. .

In the above formula (Eq-1), when HDT is smaller than (100−W _sol ), the heat resistance is deteriorated and it is not suitable for heat sterilization such as retort treatment.

  The propylene-based polymer of the present invention preferably satisfies the following requirement (4) in addition to the above requirements (1) to (3).

[Requirement (4)]
The sum of the amount of 2,1-insertion bonds and the amount of 1,3-insertion bonds in the component of the propylene polymer of the present invention that is insoluble in orthodichlorobenzene at 90 ° C. and soluble in 135 ° C. orthodichlorobenzene is 0.2 mol. % Or less, preferably 0.1 mol% or less. When the amount of 2,1-insertion bond and 1,3-insertion bond are large, the heat resistance of the propylene polymer is lowered. Here, the amount of 2,1-insertion bond and the amount of 1,3-insertion bond were calculated according to the method described in JP-A-7-145212.

The propylene polymer of the present invention preferably satisfies the following requirements (1 ′) to (4 ′) in addition to the above requirements (1) to (3) and (4).
(1 ′) The ratio W ₀ / W ₄₀ of the amount W ₀ of the component soluble in 0 ° C. orthodichlorobenzene and the amount W ₄₀ of the component soluble in 40 ° C. orthodichlorobenzene is 0.88 or more.
(2 ′) The ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the component soluble in 0 ° C. orthodichlorobenzene is 1.0 to 4.0.
(3 ′) Mw of the 0 ° C. orthodichlorobenzene soluble component is 2 × 10 ⁵ or more.
(4 ′) Mw / Mn of a component insoluble in orthodichlorobenzene at 90 ° C. and soluble in orthodichlorobenzene at 135 ° C. is 1.0 to 4.0.

Hereinafter, each requirement (1 ′) to (4 ′) will be described in detail.
[Requirement (1 ')]
If the ratio W ₀ / W ₄₀ of the amount W ₀ of the component soluble in 0 ° C orthodichlorobenzene and the amount W ₄₀ of the component soluble in 40 ° C orthodichlorobenzene, W ₀ / W ₄₀ is 0.88 or more, preferably 0.90 or more. Here, when W ₀ / W ₄₀ is 0.87 or less, the crystal component in the copolymer part increases, and the rigidity and impact resistance decrease.

[Requirement (2 ')]
The ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the component soluble in 0 ° C. orthodichlorobenzene is 1.0 to 4.0, preferably 1.0 to 3.5, more preferably 1.0 to 3.0. If Mw / Mn exceeds 4.0, the impact resistance may decrease.

[Requirement (3 ')]
The weight average molecular weight (Mw) of the component soluble in 0 ° C. orthodichlorobenzene is 2.0 × 10 ⁵ , preferably 2.5 × 10 ⁵ . If Mw is less than 2.0 × 10 ⁵ , impact resistance may be lowered.

[Requirement (4 ')]
The ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the components insoluble in orthodichlorobenzene at 90 ° C and soluble in 135 ° C orthodichlorobenzene is 1.0 to 4.0, preferably 2.0 to 4.0. is there.

  The propylene polymer of the present invention preferably satisfies the following requirement (5 ') in addition to the above (1) to (3), (4) and (1') to (4 ').

[Requirement (5 ')]
The temperature at which 20% of W _90-135 elutes with _respect to the amount of components insoluble in 90 ° C orthodichlorobenzene and soluble in 135 ° C orthodichlorobenzene (W _90-135 ) is T ₂₀ (° C), W _{90 When} the temperature at which 80% of _-135 elutes is T ₈₀ (° C), it is desirable to satisfy the following formula (Eq-2).

In the above formula (Eq-2), when (T ₈₀ -T ₂₀ ) exceeds 8, the heat resistance of the propylene-based block copolymer is lowered.

Propylene Polymer Production Method A polymerization catalyst for producing the propylene polymer of the present invention, a polymerization method, an additive that may be added to the polymer, and a method for molding the polymer will be described in this order.

★ Polymerization catalyst
The propylene polymer according to the present invention can be produced with a metallocene catalyst. The metallocene catalyst is
(A) a transition metal compound,
(B) (B-1) Organometallic compound,
(B-2) an organoaluminum oxy compound, and
(B-3) a compound that reacts with the transition metal compound (A) to form an ion pair,
At least one compound selected from:
Is a polymerization catalyst containing as an essential component.

Hereinafter, these catalyst components will be described in detail.
(A) Transition metal compound The transition metal compound used in the present invention is not particularly limited as long as it is a transition metal compound having a known olefin polymerization ability, but is preferably a transition metal compound of Groups 4 to 6 in the periodic table. For example, transition metal halides, transition metal alkylates, transition metal alkoxylates, non-crosslinkable or crosslinkable metallocene compounds of Groups 4 to 6 of the periodic table.

  More preferred are transition metal halides, transition metal alkylates, transition metal alkoxylates, non-crosslinkable or crosslinkable metallocene compounds of Group 4 of the periodic table. Specific examples of these transition metal compounds (A) include transition metal halides, transition metal alkylates, and transition metal alkoxylates. Specific examples include titanium tetrachloride, dimethyltitanium dichloride, tetrabenzyl titanium, tetrabenzyl. Examples include zirconium and tetrabutoxy titanium.

  Preferably, it is a non-crosslinkable or crosslinkable metallocene compound which is a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, and examples thereof include compounds represented by the following general formula [I].

  In the formula, M represents one kind of transition metal atom selected from Group 4 of the periodic table, preferably zirconium, titanium or hafnium.

x is the valence of the transition metal and represents the number of L. L represents a ligand or group coordinated to the transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and other than the ligand having the cyclopentadienyl skeleton. L is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO ₃ R (where R is a carbon which may have a substituent such as halogen) A hydrocarbon group having 1 to 8 atoms), a halogen atom, and one group or atom selected from the group consisting of hydrogen atoms.

  Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, an alkyl-substituted cyclopentadienyl group, an indenyl group, an alkyl-substituted indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. Groups, alkyl-substituted fluorenyl groups, and the like. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

  Particularly preferably, when the compound represented by the general formula [I] includes two or more ligands having a cyclopentadienyl skeleton, the ligands having two cyclopentadienyl skeletons are , A crosslinkable metallocene compound bonded (crosslinked) through an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, or the like.

Specifically describing the crosslinkable metallocene compound, 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, rac-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-phenylethyl) Indenyl)} 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, rac-diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindene) Nyl)} 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 dichlorine Rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-i-propyl) Indenyl)} 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-propylindene Nyl)} 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-hexylindene Nyl)} 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-dimethyl Silylene-bis {1- (2,3,7-trimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-phenyldichloromethyl) Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-di Tylsilylene-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 dichloro Lido, 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-dimethylsilylene-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-methylindenyl)} zirconium-bi (Methanesulfonato), rac-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-dimethylsilylene-bis {1- (2 -Methyl-4-i-propyl-7-methylindenyl)} titani Mujikurorido, rac- dimethylsilylene - bis {1- (2-methyl -4-i-propyl-7-methylindenyl)} and the like hafnium dichloride.
Furthermore, a crosslinkable metallocene compound represented by the general formula [II] is also preferably used.

In the general formula [II], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ are hydrogen. , Hydrocarbon groups and silicon-containing groups, which may be the same or different. Such hydrocarbon groups include methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n- Linear hydrocarbon groups such as nonyl group and n-decanyl group; isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1 -Branched hydrocarbon groups such as methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group; Cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; phenyl group, tolyl group, naphthyl group, biphenyl group, phenanthryl group, Cyclic unsaturated hydrocarbon groups such as entracenyl group; saturated hydrocarbon groups substituted with cyclic unsaturated hydrocarbon groups such as benzyl group, cumyl group, 1,1-diphenylethyl group, triphenylmethyl group; methoxy group, ethoxy group And hetero atom-containing hydrocarbon groups such as phenoxy group, furyl group, N-methylamino group, N, N-dimethylamino group, N-phenylamino group, pyryl group and thienyl group. Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group. Moreover, the adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group, etc. Can be mentioned.

In the general formula [II], R ¹ , R ² , R ³ and R ⁴ substituted on the cyclopentadienyl ring are preferably hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the aforementioned hydrocarbon groups. More preferably, R ³ is a hydrocarbon group having 1 to 20 carbon atoms.

In the general formula [II], R ⁵ to R ¹² substituted on the fluorene ring are preferably hydrocarbon groups having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the aforementioned hydrocarbon groups. The adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring.

In the general formula [II], Y that bridges the cyclopentadienyl ring and the fluorenyl ring is preferably a Group 14 element, more preferably carbon, silicon, or germanium, and further preferably a carbon atom. R ¹³ and R ¹⁴ substituted for Y are preferably a hydrocarbon group having 1 to 20 carbon atoms. These may be the same or different from each other, and may be bonded to each other to form a ring. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the aforementioned hydrocarbon groups. More preferably, R ¹⁴ is an aryl group having 6 to 20 carbon atoms. Examples of the aryl group include the above-mentioned cyclic unsaturated hydrocarbon group, a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group, and a heteroatom-containing cyclic unsaturated hydrocarbon group. R ¹³ and R ¹⁴ may be the same or different from each other, and may be bonded to each other to form a ring. As such a substituent, a fluorenylidene group, a 10-hydroanthracenylidene group, a dibenzocycloheptadienylidene group, and the like are preferable.

  In the general formula [II], M is preferably a Group 4 transition metal, more preferably Ti, Zr, Hf and the like. Q is selected from the same or different combinations from halogen, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other. Specific examples of the halogen include fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group include those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy. And ethers such as ethane. It is preferable that at least one Q is a halogen or an alkyl group.

Specifically, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) ( 2,7-dimethylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) Methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium Dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-n-butylphenyl) methylene (Cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-n-butylphenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride Di (p-n-butylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7 -Ditert-butylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) ) (3,6-Ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zyl Nium dichloride, (p-tolyl) (phenyl) methylene (cyclopentadienyl) (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) ) (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (cyclopentadienyl) (octamethyloctahydrodibenzofluorene) Nyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, (p-tolyl) (phenyl) methylene (cyclopentadiene) Enyl) (2,7-ditert-butylfluorenyl) zirconium di Loride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (2 , 7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dimethyl, (p-tolyl) (phenyl) ) Methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) ) Zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadiene) Nyl) (3,6-ditert-butylfluorenyl) zirconium dimethyl, (p-tert-butylphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium Dichloride, (p-tert-butylphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, (p-tert-butylphenyl) (phenyl) methylene (cyclopentadienyl) ) (3,6-ditert-butylfluorenyl) zirconium dichloride, (p-n-ethylphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride (P-n-ethylphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, (p-n-ethylphenyl) (phenyl) methylene (cyclopenta (Dienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (4-biphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, ( 4-biphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, (4-biphenyl) (phenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Clopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, Adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Cyclohexylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Cyclopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, cyclohexylidene Clopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, cyclopentylidene ( (Cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, adamantylidene ( Cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) ) (3,6-Dimethyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-dimethyl) Fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dichloride, cyclopropyl Liden (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) ) (3,6-ditert-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6 -Di-tert-fluorenyl) zirconium dichloride, cyclopropyl Den (cyclopentadienyl) (3,6-dicumyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-dicumyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) ( 3,6-dicumyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-dicumyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-dicumyl-fluorenyl) ) Zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-di (trimethylsilyl) -fluorenyl) zirconium Dichloride, cyclopentylidene (Si Lopentadienyl) (3,6-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) ) (3,6-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-diphenyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6 -Diphenyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-diphenyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-diphenyl-fluorenyl) zirconium dichloride, Siku Heptylidene (cyclopentadienyl) (3,6-diphenyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-dibenzyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) ( 3,6-dibenzyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-dibenzyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-dibenzyl-fluorenyl) Zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-dibenzyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-difluoro-fluorenyl) zirconium dichloride, cyclobutylidene ( Cyclope Tadienyl) (3,6-difluoro-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-difluoro-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-difluoro -Fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-difluoro-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-dibromo-fluorenyl) zirconium dichloride, cyclo Butylidene (cyclopentadienyl) (3,6-dibromo-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-dibromo-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-Dibromo Fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-dibromo-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dibromide, Cyclobutylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dibromide, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dibromide, cyclohexylidene ( (Cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dibromide, cycloheptylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dibromide, cyclopropylidene (cyclopentadiene) Enyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cyclobutylide (Cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentadienyl) ( 3,6-dimethyl-fluorenyl) zirconium dimethyl, cycloheptylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cyclopropylidene (cyclopentadienyl) (3,6-ditert- Fluorenyl) hafnium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) hafnium dichloride,
Cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) hafnium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) hafnium dichloride, cycloheptylidene (cyclo Pentadienyl) (3,6-ditert-fluorenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) titanium dichloride, cyclobutylidene (cyclopentadienyl) (3 , 6-Ditert-fluorenyl) titanium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-ditert- Fluorenyl) titanium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) titanium Mudichloride, cyclopropylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadiene) Dienyl) (2,7-dimethyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7 -Dimethyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium Dichloride, cyclopentylidene (cyclo Pentadienyl) (2,7-ditert-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2, 7-ditert-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-dicumyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-dicumyl-fluorenyl) zirconium Dichloride, cyclopentylidene (cyclopentadienyl) (2,7-dicumyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-dicumyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclohexane) Pentadienyl) (2,7-dicumyl-fluorenyl) di Luconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-di (trimethylsilyl) -fluorenyl) zirconium Dichloride, cyclopentylidene (cyclopentadienyl) (2,7-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-di (trimethylsilyl) -fluorenyl) zirconium dichloride, Cycloheptylidene (cyclopentadienyl) (2,7-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-diphenyl-fluorenyl) zirconium dichloride, cyclobutylidene ( Cyclopentadi Enyl) (2,7-diphenyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-diphenyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-diphenyl) -Fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-diphenyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride, cyclo Butylidene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-Divenge -Fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-difluoro-fluorenyl) zirconium dichloride, cyclo Butylidene (cyclopentadienyl) (2,7-difluoro-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-difluoro-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-difluoro-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-difluoro-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-dibromo- Fluorenyl) zirco Nium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-dibromo-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-dibromo-fluorenyl) zirconium dichloride, cyclohexylidene (cyclohexane) Pentadienyl) (2,7-dibromo-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-dibromo-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2, 7-ditert-fluorenyl) zirconium dibromide, cyclobutylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dibromide, cyclopentylidene (cyclopentadienyl) (2,7-ditert -Fluorenyl) zirconium dibromide, cyclohexylidene (cyclope Tadienyl) (2,7-ditert-fluorenyl) zirconium dibromide, cycloheptylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dibromide, cyclopropylidene (cyclopentadienyl) ( 2,7-dimethyl-fluorenyl) zirconium dimethyl, cyclobutylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) Zirconium dimethyl, cyclohexylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dimethyl, cycloheptylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dimethyl, cyclopropylidene ( Cyclopentadienyl) (2,7-ditert-fluorenyl) hafnium dic Lido, cyclobutylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) hafnium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) hafnium dichloride, cyclohexylidene ( Cyclopentadienyl) (2,7-ditert-fluorenyl) hafnium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) titanium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) titanium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-di tert-fluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) Titanium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclo Butylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadiene) (Enyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclopropylide (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclopentylidene (cyclopentadiene (Enyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cycloheptylidene (cyclopentadienyl) ( Octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclobutylidene (cyclopentadienyl) ) (Octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentadienyl) (octamethyloctahydro) Dibenzofluorenyl) zirconium dimethyl, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Hafnium dichloride, cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Hafnium dichloride, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodihydrate) Benzofluorenyl) hafnium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Titanium dichloride, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Titanium dichloride, cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, cyclopentylidene (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium Dichloride, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, di-n-butylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopenta Dienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butyl Methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) ) (Dibenzofluorenyl) zirconium dichloride, di -Butylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diisobutylmethylene (cyclopenta Dienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) ) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride,
Diisobutylmethylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclo Pentafluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (benzofluorenyl) zirconium Dichloride, dibenzylmethylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) ( Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (3, 6-ditert-butylfluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (benzofluorenyl) Nyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadiene) Enyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclo Pentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (benz Drill) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) ( Octahydrodibenzofluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (fluorenyl) zirconium Dichloride, di (cumyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (3,6-ditert-butylfull Oleenyl) zirconium Chloride, di (cumyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (cumyl) Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) ( Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl- Ethyl) methylene (cyclopentadi Enyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (1- Phenyl-ethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (1-phenyl- Ethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (Cyclohexylmethyl) methylene (cycl Lopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (cyclohexylmethyl) ) Methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclo Pentadienyl) (dibenzofluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadi) Nyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) ) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di ( 1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, Di (1-cyclohexyl) Ethyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (1-cyclohexyl-) Ethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride , Di (cyclopentylmethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl Zirconi Um dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (cyclopentylmethyl) Methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (1-cyclopentyl- Ethyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride Lido, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (octa Methyloctahydrodibenzofluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (Dibenzofluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (Octamethyltetrahydride Dicyclopentafluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopenta Dienyl) (benzofluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (octahydrodibenzofur Oleenyl) zirconium dichroic , Di (naphthylmethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (biphenylmethyl) ) Methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium Dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di ( Biphenylmethyl) Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, (benzyl) (phenethyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (benzyl) (phenethyl) methylene (cyclopentadienyl) (2, 7-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (phenethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (phenethyl) methylene ( Cyclopen Tadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (benzyl) (n-butyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (benzyl) (n-butyl) methylene (cyclopentadienyl) ) (2,7-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (n-butyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl ) (N-butyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorene) Nyl) zirconium dichloride,
(Benzyl) (cumyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride,
(Benzyl) (cumyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (benzyl) (cyclohexylmethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfur Olenyl) zirconium dichloride, (benzyl) (cyclohexylmethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (cyclohexylmethyl) methylene (cyclopentadienyl) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, dibenzylmethylene (cyclopentadienyl) (3, 6-ditert-butylfluorenyl) titanium Chloride, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di Benzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, dibenzylmethylene ( Cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dibromide, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dibromide, dibenzyl Methylene (cyclopentadienyl) (octamethyloctahydrodiben Zofluorenyl) Zirconium dibromide, dibenzylmethylene (cyclopentadienyl) (2,7-di tert-butylfluorenyl) Zirconium dimethyl, dibenzylmethylene (cyclopentadienyl) (3,6-di tert-butylfur) Olenyl) zirconium dimethyl, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium Dimethyl, dimethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, dimethylmethylene ( Cyclopentadienyl) (benzofluorene) ) Zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) ( Octamethyltetrahydrodicyclopentafluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3,6- Di-tert-butylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (benzofluorenyl) zirconium Dichloride, dimethylmethylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (octamethyltetrahydro Dicyclopentafluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride Lido, dimethylsilylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octamethyltetrahydro Dicyclopentafluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (benzofluorenyl) zirconium dimethyl, dimethyl Silylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopenta Fluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butyl Fluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (2,7-ditert- Butylfluorenyl) zirconium dichloride, dimethyl Methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p -Tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, Cyclopentylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Adamantylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, monophenylmonomethyl Methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene ( Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Diethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, cyclohexyl Silidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, adamantylidene Tadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, dimethylmethylene (cyclopentadiyl) Enyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene ( Cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, diethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, cyclopentylidene (cyclo Pentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (2,7 Ditert-butylfluorenyl) titanium dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (2,7 -Ditert-butylfluorenyl) titanium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di tert-butylfluorenyl) titanium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, diethylmethylene (cyclopentadienyl) (2, 7-ditert-butylfluorenyl) titanium dichloride, isopropylidene (3,5-dimethyl-cyclopentadienyl) Oleenyl) zirconium dichloride, isopropylidene (3,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (3,5-dimethyl-cyclopentadienyl) ( 3,6-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (3,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl -5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, Isopropylidene (3-tert -Butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethylocta Hydrodibenzofluorenyl) zirconium dichloride, isopropylidene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3- (2-adamantyl) -5-methyl- Cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (3,6-ditert-butyl) Fluorenyl) zirconium dichloride, isopropylidene (3- (2-adama) Til) -5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-ethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropyl Liden (3-tert-butyl-5-ethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-ethyl-cyclopentadienyl) ) (3,6-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-ethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, isopropylidene (3-tert- Til-2,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluorene) Nyl) zirconium dichloride, isopropylidene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl- 2,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (3,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride,
Diphenylmethylene (3,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3,5-dimethyl-cyclopentadienyl) (3,6-di tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-) Cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3- tert-Butyl-5-methyl-si Lopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenyl Methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (2,7- Ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene ( 3- (2-adamantyl) -5-me Til-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert -Butyl-5-ethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (3,6 -Di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (3-tert- Spotted -2,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) ) Zirconium dichloride, diphenylmethylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-2) , 5-Dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (3,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di ( p-Tolyl) methylene (3,5-dimethyl-cyclopentadieny ) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3,5-dimethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium Dichloride, di (p-tolyl) methylene (3,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5- Methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium Dichloride, di (p-tolyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6 -Di-tert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di ( p-tolyl) methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (3- (2-adamantyl) -5-methyl-cyclo Pentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (3,6- Di-tert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (fluorenyl) zirconium Dichloride, di (p-tolyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3 -Tert-butyl-5-ethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-ethyl-cyclopenta) Dienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p Tolyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadi) Enyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (3,6-ditert -Butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p -Tert-butylphenyl) methylene (3,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium Dichloride, di (p-tert-butylphenyl) methylene (3,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3,5-Dimethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3,5-dimethyl-cyclopentadienyl) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tert) -Butylphenyl) methylene (3-tert-butyl-5-methyl-cycl Pentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-di) tert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (P-tert-butylphenyl) methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3- (2-adamantyl) ) -5-methyl-cyclopentadienyl) (2,7-ditert- Tylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (P-tert-butylphenyl) methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (2 , 7-Ditert-butylfluorenyl) zirconium di Lido, di (p-tert-butylphenyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert- Butylphenyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl- 2,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (2,7- Ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) Nyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3- tert-butyl-2,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) ) (Fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (methyl) ( Phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) 3,6-ditert-butylfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride , (P-tolyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, (p-tolyl) (phenyl) methylene (3-tert-butyl-5- Methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3 , 6-Ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) ( Phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dibenzylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) ) (Fluorenyl) zirconium dichloride, dibenzylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (3-tert- Butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethylocta Hydrodibenzofluorenyl) zirconium Lorid,
Fluorenylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, fluorenylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfullyl) Olenyl) zirconium dichloride, fluorenylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, fluorenylidene (3-tert-butyl-5-methyl) -Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dimethyl, diphenylmethylene (3-tert- Til-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dimethyl, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6- Di-tert-butylfluorenyl) zirconium dimethyl, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, diphenylmethylene (3-tert-butyl) -5-methyl-cyclopentadienyl) (fluorenyl) titanium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, Diphenylmethylene (3-tert-butyl-5-methyl Ru-cyclopentadienyl) (3,6-ditert-butylfluorenyl) titanium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) ) Titanium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7 -Ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (3 -Tert-butyl-5-methyl-cyclo Ntajieniru) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride and the like, but the transition metal compound used in the present invention is not intended to be limited to the above exemplified compounds.

(B-1) Organometallic Compound As the (B-1) organometallic compound used in the present invention, specifically, the groups 1, 2 and 12 as shown in (B-1a) to (B-1c) , Group 13 organometallic compounds are used.

(B-1a) General formula: R ^a _m Al (OR ^b ) _n H _p X _q
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0 < m ≦ 3, n is 0 ≦ n <3, p is a number of 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3). Specific examples of such compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride and the like.

(B-1b) General formula: M ² AlR ^a ₄
(Wherein, ^{M 2} represents a Li, Na or K, ^{R a} is a carbon number 1 to 15, preferably a 1-4 hydrocarbon group) complex of Group 1 metal and aluminum represented by Alkylates. Examples of such compounds include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

(B-1c) General formula: R ^a R ^b M ³
(In the formula, R ^a and R ^b may be the same as or different from each other, and each represents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd) A dialkyl compound of a Group 2 or Group 12 metal represented by: Of the organometallic compounds (B-1), organoaluminum compounds are preferred. Moreover, such an organometallic compound (B-1) may be used individually by 1 type, and may be used in combination of 2 or more type.

(B-2) Organoaluminum Oxy Compound The organoaluminum oxy compound (B-2) used in the present invention may be a conventionally known aluminoxane or as exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound.

A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
[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, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the above suspension of the hydrocarbon medium.
[2] A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, diethyl ether or tetrahydrofuran.
[3] A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent. Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (B-1a). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. The above organoaluminum compounds are used singly or in combination of two or more.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms. That is, those which are insoluble or hardly soluble in benzene are preferred. These organoaluminum oxy compounds (B-2) are used singly or in combination of two or more.

(B-3) Compound that reacts with transition metal compound to form ion pair (B-3) Compound that reacts with transition metal compound (A) to form ion pair (hereinafter referred to as “ionization”) Examples of the ionic compound ”) include JP-A-1-501950, JP-A-1-502036, JP-A-3-17905, JP-A-3-179006, JP-A-3-207703, Examples include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-207704 and US5321106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. Such ionized ionic compounds (B-3) are used singly or in combination of two or more. When the transition metal compound of the present invention is used as an olefin polymerization catalyst, when an organoaluminum oxy compound (B-2) such as methylaluminoxane as a co-catalyst component is used in combination, the olefin compound exhibits a particularly high polymerization activity.

  Further, the olefin polymerization catalyst according to the present invention comprises the above transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-2) an ionized ionic compound. A carrier (C) can be used together with at least one selected compound (B), if necessary.

(C) Carrier The carrier (C) used in the present invention is an inorganic or organic compound and is a granular or particulate solid. Among these, as the inorganic compound, porous oxides, inorganic chlorides, clays, clay minerals or ion-exchangeable layered compounds are preferable.

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or the like, or a composite or mixture containing these is used, for example using natural or synthetic _zeolites, SiO _{2 -MgO,} etc. _{SiO 2 -Al 2 O 3, SiO} 2 -ZrO 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -ZrO 2 -MgO can do. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferable. Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 5 to 300 μm, more preferably 6 to 75 μm, and a specific surface area of 50 to 50 μm. 1000 m ² / g, more preferably in the range of 100~700m ² / g, it is desirable that the pore volume is in the range of 0.3~3.0cm ³ / g. Such a carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic chloride, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic chloride may be used as it is or after being pulverized by a ball mill or a vibration mill. In addition, an inorganic chloride dissolved in a solvent such as alcohol and then precipitated in a fine particle form by a precipitant can be used.

The clay used in the present invention is usually composed mainly of clay minerals. The ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the contained ions can be exchanged. . Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used. Further, as clay, clay mineral, or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal close-packed packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. Can be illustrated. Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite , Halloysite and the like, and as the ion-exchangeable layered compound, α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Zr (HPO ₄ ) ₂ and crystalline acid salts of polyvalent metals such as γ-Zr (NH ₄ PO ₄ ) ₂ .H ₂ O. The clay and clay mineral used in the present invention are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment.

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchange property. . Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Introducing another substance between layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as ZrCl ₄ , metal alkoxides such as Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ (R is a hydrocarbon group, etc.), [ Examples thereof include metal hydroxide ions such as Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , and [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ . These compounds are used alone or in combination of two or more. Moreover, when intercalating these compounds, obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.) Polymers, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers. Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

  Examples of the organic compound include granular or fine particle solids having a particle size in the range of 5 to 300 μm. Specifically, a (co) polymer produced from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene as a main component, vinylcyclohexane and styrene. The (co) polymer produced | generated as a main component and those modifications can be illustrated.

  The catalyst for olefin polymerization according to the present invention comprises the transition metal compound (A), (B-1) organometallic compound, (B-2) organoaluminum oxy compound, and (B-3) ionized ionic compound of the present invention. A specific organic compound component (D) as described later can be included together with at least one selected compound (B) and, if necessary, the carrier (C) as necessary.

(D) Organic Compound Component In the present invention, the (D) organic compound component is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, sulfonates, and the like.

In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.
[1] A method of adding the component (A) alone to the polymerization vessel.
[2] A method in which component (A) and component (B) are added to the polymerization vessel in any order.
[3] A method in which the catalyst component having component (A) supported on carrier (C) and component (B) are added to the polymerization vessel in any order.
[4] A method in which the catalyst component having component (B) supported on carrier (C) and component (A) are added to the polymerization vessel in any order.
[5] A method in which a catalyst component in which component (A) and component (B) are supported on a carrier (C) is added to a polymerization vessel.

  In each of the above methods [2] to [5], at least two or more of the catalyst components may be contacted in advance. In each of the above methods [4] and [5] in which the component (B) is supported, the unsupported component (B) may be added in any order as necessary. In this case, the components (B) may be the same or different. The solid catalyst component in which the component (A) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) are prepolymerized with olefin. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.

  In the present invention, when a polypropylene resin is produced using the catalyst as described above, prepolymerization can be performed in advance.

  Examples of the prepolymerized olefin include linear olefins such as ethylene, propylene, 1-butene, 1-octene, 1-hexadecene and 1-eicocene; 3-methyl-1-butene, 3-methyl-1-pentene, 1-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1- Hexene, 3-ethyl-1-hexene, allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes, etc. An olefin having a branched structure can be used, and these may be copolymerized. Of these, ethylene and propylene are particularly preferably used.

  The prepolymerization is preferably carried out under mild conditions by adding the prepolymerized olefin and the catalyst component to an inert hydrocarbon medium.

  Examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; benzene Aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof. In particular, it is preferable to use an aliphatic hydrocarbon.

★ Polymerization method In the method for producing an olefin polymer according to the present invention, an olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst as described above.

When the olefin polymerization is carried out using the olefin polymerization catalyst as described above, the component (A) is usually 10 ⁻⁸ to 10 ⁻² mol, preferably 10 ⁻⁷ to 10 ⁻³ per liter of the reaction volume. It is used in such an amount that it becomes a mole. Component (B-1) has a molar ratio [(B-1) / M] of component (B-1) to all transition metal atoms (M) in component (A) of usually 0.01 to 5,000. The amount is preferably 0.05 to 2,000. Component (B-2) has a molar ratio [(B-2) / M] of aluminum atoms in component (B-2) to all transition metals (M) in component (A) of usually 10-5. 2,000, preferably 20 to 2,000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to transition metal atom (M) in component (A) of usually 1 to 10, preferably 1. Used in an amount such that it is ˜5.

  When component (B) is component (B-1), component (D) has a molar ratio [(D) / (B-1)] of usually 0.01 to 10, preferably 0.1 to 5. When the component (B) is the component (B-2), the molar ratio [(D) / (B-2)] is usually 0.01 to 2, preferably 0.005. When the component (B) is the component (B-3) in such an amount that it becomes 1, the molar ratio (D) / (B-3)] is usually 0.01 to 10, preferably 0.1 to 5. Is used in such an amount that

  Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. The molecular weight of the resulting olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the component (B) to be used. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

  Next, the olefin supplied to the polymerization reaction of the propylene-based copolymer in the present invention will be described in detail. The propylene-based polymer of the present invention uses a polymerization apparatus in which two or more, preferably two, reactors are connected in series, and the following two steps ([Step 1] and [Step 2]) are continuously performed. It is obtained by carrying out.

  [Step 1] comprises (co) polymerizing propylene (Mp) and, if necessary, one or more olefins (Mx) selected from ethylene and α-olefins having 4 or more carbon atoms, It is a manufacturing process. The α-olefin having 4 or more carbon atoms is a linear or branched α-olefin having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, such as 1-butene, 1-pentene, 3-methyl-1 -Butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene Etc. Also, cyclic olefins having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8- Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; polar monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2 , 2,1) -5-heptene-2,3-dicarboxylic anhydride and other α, β-unsaturated carboxylic acids and their sodium, potassium, lithium, zinc, magnesium, calcium salts, etc. Metal salts of: methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate Α, β-unsaturated carboxylic acid esters such as 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; vinyl acetate, propionic acid Vinyl esters such as vinyl, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; unsaturated glycidyl such as glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, etc. Can do. Aromatic vinyl compounds such as vinylcyclohexane, diene or polyene, such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene Mono- or polyalkyl styrene such as p-ethylstyrene; functionalities such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, ο-chlorostyrene, p-chlorostyrene, divinylbenzene Polymerization can also be carried out by allowing a group-containing styrene derivative; and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like to coexist in the reaction system. In the present invention, the olefin used in [Step 1] is propylene alone, or a mixed olefin of propylene and ethylene is a preferred embodiment, and propylene alone is a more preferred embodiment.

  [Step 2] is a step of producing a copolymer part by copolymerizing propylene and one or more olefins selected from ethylene and an α-olefin having 4 or more carbon atoms. As the one or more olefins selected from ethylene and an α-olefin having 4 or more carbon atoms used in [Second Step], the olefins exemplified in [First Step] can be used as they are. Further, the olefin used in the [second step] may be the same as or different from the olefin used in the [first step].

  In the production of the propylene-based polymer in the present invention, the amount distribution of the polymer produced in the above [Step 1] and [Step 2] will be described with reference to the following examples. Examples include two steps of producing a propylene polymer: (1) a step of producing a propylene homopolymer (= [Step 1]) and (2) a step of producing a propylene / ethylene copolymer (= [Step 1]. ]) Is carried out continuously for production. This example is a three-stage polymerization in which the [first step] is performed in two steps and the [second step] is performed in one step. That is, in the first stage, a propylene homopolymer is produced at a polymerization temperature of 0 to 100 ° C., a polymerization pressure of normal pressure to 5 MPa gauge pressure, and then in a second stage of a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa. Propylene homopolymer is finally produced at a gauge pressure in a polypropylene resin in which the content of the first and second stages is 95 to 50% by weight. In the third stage, the polymerization temperature is 0 It is preferable to produce the propylene-ethylene block copolymer in an amount of 50 to 5% by weight in the finally obtained polypropylene resin at -100 ° C. and normal pressure of polymerization to 5 MPa gauge pressure. As shown in the above example, each step may be composed of two or more polymerization stages.

  After completion of the polymerization, a propylene polymer is obtained as a powder by performing post-treatment steps such as a known catalyst deactivation treatment step, a catalyst residue removal step, and a drying step as necessary.

★ Additives Propylene polymer powders obtained as described above are added to antioxidants, UV absorbers, antistatic agents, nucleating agents, lubricants, flame retardants, antiblocking agents, colorants, inorganic or organic substances. Various additives such as fillers and various synthetic resins are blended as necessary, melt-kneaded, and pelletized to form pellets for use in the production of various molded products.

  Moreover, you may add an elastomer and an inorganic filler to the propylene-type polymer of this invention. Examples of elastomers include ethylene / α-olefin random copolymers, ethylene / α-olefin / non-conjugated polyene random copolymers, hydrogenated block copolymers, other elastic polymers, and mixtures thereof. Examples of the filler include talc, clay, calcium carbonate, mica, silicates, carbonates, and glass fibers. Among these, talc and calcium carbonate are preferable, and talc is particularly preferable. The average particle size of talc is 1 to 5 μm, preferably 1 to 3 μm. A filler can also be used individually by 1 type and can also be used in combination of 2 or more type.

★ Molding Method To blend the propylene-based polymer of the present invention with a predetermined amount of each of the above-mentioned various additives, a normal kneading apparatus such as a Henschel mixer, a ribbon blender, or a Banbury mixer can be used. The melt-kneading and pelletizing are performed by melt-kneading at 170 to 300 ° C., preferably 190 to 250 ° C., using a normal single-screw extruder or twin-screw extruder, Brabender or roll, and pelletizing. The obtained propylene-based polymer composition is produced by various molding methods such as injection molding, extrusion molding, injection blow molding, and blow molding. It can be processed into a film, sheet, blow molded product, injection blow molded product for injection molded products and retort applications.

  In particular, since the propylene polymer of the present invention has a low melting point, it has heat resistance and good impact resistance, and therefore can be suitably used for a retort film.

  EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to this Example at all.

(i) Cross chromatographic fractionation measurement (CFC)
Analysis of components soluble in orthodichlorobenzene at each temperature was performed by cross-chromatographic fractionation measurement (CFC). CFC was measured under the following conditions using the following apparatus equipped with a temperature rising elution fractionation (TREF) part for performing composition fractionation and a GPC part for carrying out molecular weight fractionation, and the amount at each temperature was calculated.

Measuring apparatus: CFC T-150A type, Mitsubishi Yuka Co., Ltd., trademark Column: Shodex AT-806MS (x3)
Dissolved solution: o-dichlorobenzene Flow rate: 1.0 ml / min
Sample concentration: 0.3 wt% / vol% (with 0.1% BHT)
Injection volume: 0.5ml
Solubility: Complete dissolution Detector: Infrared absorption detection method, 3.42 μ (2924 cm ⁻¹ ), NaCl plate Elution temperature: 0 to 135 ° C., 28 fractions
0, 10, 20, 30, 40, 45, 50,
55, 60, 65, 70, 75, 80, 85,
90, 94, 97, 100, 103, 106, 109,
112, 115, 118, 121, 124, 127, 135 (° C)

  To describe the details of the measurement, the sample was heated and dissolved at 145 ° C for 2 hours, held at 135 ° C, then held at 10 ° C / hr up to 0 ° C and further held at 0 ° C for 60 minutes. Coated. The temperature rising elution column capacity is 0.83 ml, and the pipe capacity is 0.07 ml. The detector was an infrared spectrometer MIRAN 1A CVF type (CaF2 cell) manufactured by FOXBORO, and infrared light of 3.42 μm (2924 cm −1) was detected by setting the absorbance mode with a response time of 10 seconds. The elution temperature ranged from 0 ° C. to 135 ° C. into 25 to 40 fractions. All temperature indications are integers. For example, the elution fraction at 94 ° C. indicates a component eluted at 91 to 94 ° C. The molecular weight of components not coated even at 0 ° C. and the fraction eluted at each temperature were measured, and the molecular weight in terms of PP was determined using a general-purpose calibration curve. The SEC temperature is 135 ° C., the internal standard injection volume is 0.5 ml, the injection position is 3.0 ml, and the data sampling time is 0.50 seconds. Data processing was performed using the analysis program “CFC data processing (version 1.50)” included with the device. Cross-fractionation (CFC) itself is said to be an analytical method that reproduces the results with high analytical accuracy if the measurement conditions are exactly the same. Is more preferable.

(ii) Room temperature n-decane soluble part (D _sol )
200 ml of n-decane was added to 5 g of a sample of the final product (that is, the propylene polymer of the present invention) and dissolved by heating at 145 ° C. for 30 minutes. It was cooled to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (hereinafter, n-decane insoluble part: D _insol ) was filtered off. The filtrate was put in about 3 times the amount of acetone to precipitate the components dissolved in n-decane. The precipitate (A) and acetone were separated by filtration, and the precipitate was dried. Even when the filtrate side was concentrated to dryness, no residue was observed. The amount of n-decane soluble part was determined by the following equation.
n-decane soluble part amount (wt%) = [precipitate (A) weight / sample weight] × 100

(Iii) The amount of skeleton derived from α-olefin contained in the n-decane soluble part (D _sol ) The n-decane soluble part separated in the above (i) The amount of α-olefin-derived skeleton contained in the n-decane soluble part was measured by resonance analysis ( ¹³ C-NMR). Propylene, ethylene, and α-olefin were quantified in the same manner as in (ii).

(iv) Intrinsic viscosity measurement The intrinsic viscosity was measured at 135 ° C using a decalin solvent. About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After diluting the decalin solution with 5 ml of decalin solvent, the specific viscosity ηsp was measured in the same manner. This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity.
[Η] = lim (ηsp / C) (C → 0)

(v) GPC molecular weight distribution (Mw / Mn)
It measured as follows using GPC-150C Plus made from Waters. The separation columns were TSKgel GMH6-HT and TSKgel GMH6-HTL, the column size was 7.5 mm in inner diameter and 600 mm in length, the column temperature was 140 ° C., and o-dichlorobenzene (Wako Pure Chemical Industries) was used as the mobile phase. Industry) and BHT (Wako Pure Chemical Industries) 0.025% by weight as an antioxidant, moved at 1.0 ml / min, the sample concentration was 0.1% by weight, the sample injection volume was 500 microliters, A differential refractometer was used as a detector. Standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

(vi) Melting point (Tm)
Measurement was performed using a differential scanning calorimeter (DSC, manufactured by PerkinElmer). Here, the endothermic peak in the third step was defined as the melting point (Tm).

(Measurement condition)
First step: The temperature is raised to 240 ° C. at 10 ° C./min and held for 10 min.
Second step: Decrease the temperature to 60 ° C at 10 ° C / min.
Third step: Increase the temperature to 240 ° C at 10 ° C / min.

(vii) 1,2-insertion, 1,3-insertion measurement
^{Using 13} C-NMR, the amount of 1,2-insertion bond and 1,3-insertion bond was measured according to the method described in JP-A-7-152212.

(viii) MFR (Melt Flow Rate)
MFR was measured according to ASTM D1238 (230 ° C., load 2.16 kg).

(ix) Heat distortion temperature (HDT)
The heat distortion temperature was measured according to ASTM D648.
<Test conditions>
Test piece: 12.7 mm (width) x 6.4 mm (thickness) x 127 mm (length)
Load: 0.45 MPa
Test piece thickness: 1/4 inch

(x) Izod impact strength (IZ)
Izod impact strength (IZ) was measured under the following conditions in accordance with ASTM D256.
<Test conditions>
Temperature: 23 ° C, -30 ° C
Test piece: 12.7 mm (width) x 6.4 mm (thickness) x 64 mm (length)
Notch machined

(1) Production of solid catalyst support 300 g of SiO ₂ (manufactured by Dokai Chemical Co., Ltd.) was sampled in a 1 L branch flask, and 800 mL of toluene was added to make a slurry. Next, the solution was transferred to a 5 L four-necked flask, and 260 mL of toluene was added. 2830 mL of methylaluminoxane (hereinafter referred to as MAO) -toluene solution (Albemarle 10 wt% solution) was introduced. The mixture was stirred for 30 minutes while remaining at room temperature. The temperature was raised to 110 ° C. over 1 hour, and the reaction was carried out for 4 hours. After completion of the reaction, it was cooled to room temperature. After cooling, the supernatant toluene was extracted and replaced with fresh toluene until the replacement rate reached 95%.

(2) Production of solid catalyst (support of metal catalyst component on support)
In a glove box, 2.0 g of diphenylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride is weighed in a 5 L four-necked flask. It was. The flask was taken out, 0.46 liters of toluene and 1.4 liters of MAO / SiO2 / toluene slurry prepared in 1) were added under nitrogen, and the mixture was stirred for 30 minutes to carry. The obtained diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-tert-butylfluorenyl) zirconium dichloride / MAO / SiO2 / toluene slurry was replaced with 99% by n-heptane. The final slurry volume was 4.5 liters. This operation was performed at room temperature.

(3) Production of prepolymerization catalyst 202 g of the solid catalyst component prepared in the above (2), 109 mL of triethylaluminum, and 100 L of heptane were inserted into an autoclave with a stirrer having an internal volume of 200 L, and the internal temperature was maintained at 15 to 20 ° C. to give 2020 g of ethylene. Inserted and allowed to react with stirring for 180 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 2 g / L. This prepolymerized catalyst contained 10 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization The catalyst slurry produced in 50 kg / hour of propylene, 5 NL / hour of hydrogen and 3) in a tubular polymerization vessel having an internal volume of 58 L is 3.1 g / hour as a solid catalyst component, 1.7 g / hour of triethylaluminum. Was continuously fed and polymerized in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization vessel, propylene was supplied at 50 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.05 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization reactor, propylene was supplied at 12 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.05 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.05 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L to carry out copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, ethylene was supplied at 12 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.16 mol%. Polymerization was performed at a polymerization temperature of 52 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based polymer. The resulting propylene polymer was vacuum dried at 80 ° C.

  Table 1 shows the physical properties of the propylene polymer.

  Heat stabilizer IRGANOX 1010 (trade name, Ciba Geigy Co., Ltd.) 0.1 part by weight, heat stabilizer IRGAFOS168 (trade name, Ciba Geigy Co., Ltd.) 0.1 part by weight, calcium stearate with respect to 100 parts by weight of the obtained propylene polymer After mixing 0.1 parts by weight with a tumbler, melt-kneading with a twin screw extruder to prepare a pellet-shaped polypropylene resin composition, and ASTM with an injection molding machine [Part No. IS100, manufactured by Toshiba Machine Co., Ltd.] A test piece was molded. Table 2 shows the physical properties of the molded product.

<Melting and kneading conditions>
Same-direction biaxial kneader: Product number NR2-36, manufactured by Nakatani Machinery Co., Ltd. Kneading temperature: 230 ° C
Screw rotation speed: 200rpm
Feeder rotation speed: 500 rpm

<Injection molding conditions>
Injection molding machine: Part number IS100, manufactured by Toshiba Machine Co., Ltd. Cylinder temperature: 230 ° C
Mold temperature: 40 ℃

The polymerization was performed in the same manner as in Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal capacity of 58 L, propylene is 50 kg / hour, hydrogen is 5 NL / hour, the catalyst slurry produced in (3) of Example 1 is used as a solid catalyst component, 3.1 g / hour, triethylaluminum. 1.7 g / hour was continuously fed, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. Propylene was supplied to the polymerization vessel at 50 kg / hour, ethylene was supplied at 0.3 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.05 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.
The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization reactor, propylene was supplied at 12 kg / hour, ethylene was supplied at 0.2 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase became 0.05 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, ethylene was supplied at 0.1 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.05 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L to carry out copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, ethylene was supplied at 12 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.16 mol%. Polymerization was performed at a polymerization temperature of 50 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based polymer. The resulting propylene polymer was vacuum dried at 80 ° C.

  Table 1 shows the physical properties of the propylene polymer.

  Thermal stabilizer IRGANOX 1010 (Ciba Geigy Co., Ltd.) 0.1 part by weight, thermal stabilizer IRGAFOS168 (Ciba Geigy Co., Ltd.) 0.1 part by weight with respect to 100 parts by weight of the obtained propylene-based block copolymer, After mixing 0.1 parts by weight of calcium stearate with a tumbler, melt-kneading with a twin screw extruder to prepare a polypropylene resin composition in the form of a pellet, and using an injection molding machine [Part No. IS100, manufactured by Toshiba Machine Co., Ltd.] An ASTM test piece was molded. Table 2 shows the physical properties of the molded product.

[Comparative Example 1]
(1) Preparation of solid titanium catalyst component 952 g of anhydrous magnesium chloride, 4420 ml of decane and 3906 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to obtain a homogeneous solution. To this solution, 213 g of phthalic anhydride was added, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

  After cooling the homogeneous solution thus obtained to 23 ° C., 750 ml of this homogeneous solution was dropped into 2000 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 52.2 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours. Held on. Subsequently, the solid part was collected by hot filtration, and the solid part was resuspended in 2750 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours.

  After the heating, the solid part was again collected by hot filtration, and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.

  The solid titanium catalyst component prepared as described above was stored as a hexane slurry. A part of the catalyst was dried to examine the catalyst composition. The solid titanium catalyst component contained 2% by weight of titanium, 57% by weight of chlorine, 21% by weight of magnesium and 20% by weight of DIBP.

(2) Production of prepolymerization catalyst 56 g of transition metal catalyst component, 20.7 mL of triethylaluminum, 7.0 mL of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, and 80 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 L. Then, maintaining the internal temperature at 5 ° C., 560 g of propylene was inserted, and the reaction was carried out with stirring for 60 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the transition metal catalyst component concentration was 0.7 g / L. This prepolymerized catalyst contained 10 g of polypropylene per 1 g of the transition metal catalyst component.

(3) Main polymerization The mixture was sent to a vessel polymerization reactor with an internal volume of 1000 L and equipped with a stirrer, and propylene was supplied at 127 kg / hour and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.30 mol%. The catalyst slurry produced in (2) of Comparative Example 1 was continuously supplied as a solid catalyst component at 1.2 g / hour, triethylaluminum 16.2 g / hour, and dicyclopentyldimethoxysilane 2.3 mL / hour, and a polymerization temperature of 75 Polymerization was carried out at a pressure of 3.3 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 25 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.3 mol%. Polymerization was carried out at a polymerization temperature of 74 ° C. and a pressure of 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at 25 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 4.0 mol%. Polymerization was carried out at a polymerization temperature of 73 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L to carry out copolymerization. Propylene was supplied to the polymerization vessel at 15 kg / hour, ethylene was supplied at 17 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 2.7 mol%. Polymerization was performed at a polymerization temperature of 56 ° C. and a pressure of 3.0 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based polymer. The resulting propylene polymer was vacuum dried at 80 ° C.

  Table 1 shows the physical properties of the propylene-based polymer.

  Heat stabilizer IRGANOX 1010 (trade name, Ciba Geigy Co., Ltd.) 0.1 part by weight, heat stabilizer IRGAFOS168 (trade name, Ciba Geigy Co., Ltd.) 0.1 part by weight, calcium stearate with respect to 100 parts by weight of the obtained propylene polymer After mixing 0.1 parts by weight with a tumbler, melt-kneading with a twin screw extruder to prepare a pellet-shaped polypropylene resin composition, and ASTM with an injection molding machine [Part No. IS100, manufactured by Toshiba Machine Co., Ltd.] A test piece was molded. Table 2 shows the physical properties of the molded product.

  Although the propylene-based polymer of the present invention has a low melting point, it has good heat resistance and impact resistance, and is suitable for a film for retort that requires low-temperature heat sealability, heat resistance, and impact resistance. Can be used.

FIG. 4 is a schematic CFC diagram showing parameters W ₀ and W ₄₀ used for defining the propylene-based polymer of the present invention in an easy-to-understand manner.

These are CFC schematic diagrams showing parameters T ₂₀ and T ₈₀ used for defining the propylene-based polymer of the present invention in an easy-to-understand manner.

Claims (9)

Consists of a part soluble in room temperature n-decane (D _sol ) and a part insoluble in room temperature n-decane (D _insol ), selected from propylene (M _P ) and ethylene and α-olefins with 4 or more carbon atoms A propylene-based polymer which is a polymer obtained from one or more olefins (M _X ) and simultaneously satisfies the following requirements (1) to (3).
(1) Both D _sol and D _insol have a GPC molecular weight distribution (Mw / Mn) of 4.0 or less.
(2) The melting point (Tm) of D _insol is in the range of 140 to 155 ° C.
(3) The heat distortion temperature HDT (load 0.45 MPa) and the amount W _sol (wt%) of the portion soluble in room temperature n-decane satisfy the following relational expression.

  The sum of the amount of 2,1-bond and 1,3-bond in a component insoluble in orthodichlorobenzene at 90 ° C and soluble in 135 ° C orthodichlorobenzene is 0.2 mol% or less. 1. The propylene polymer according to 1. The propylene polymer according to claim 1 or 2, wherein the following requirements (1 ') to (4') are simultaneously satisfied.
(1 ′) The ratio W ₀ / W ₄₀ of the amount W ₀ of the component soluble in 0 ° C. orthodichlorobenzene and the amount W ₄₀ of the component soluble in 40 ° C. orthodichlorobenzene is 0.88 or more.
(2 ′) The ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the component soluble in 0 ° C. orthodichlorobenzene is 1.0 to 4.0.
(3 ′) Mw of the 0 ° C. orthodichlorobenzene soluble component is 2 × 10 ⁵ or more.
(4 ′) Mw / Mn of a component insoluble in orthodichlorobenzene at 90 ° C. and soluble in orthodichlorobenzene at 135 ° C. is 1.0 to 4.0. The temperature at which 20% of W _90-135 elutes is T ₂₀ (° C.) and W _90-135 for the amount of W _90-135 that is insoluble in ortho dichlorobenzene at 90 ° C. and soluble in ortho dichlorobenzene at 135 ° C. 4. The propylene polymer according to claim 3, wherein the following formula (Eq-2) is satisfied, where T ₈₀ (° C.) is a temperature at which 80% of the eluate is dissolved.

  An injection-molded article obtained by molding the propylene-based polymer according to any one of claims 1 to 4.   The film obtained by shape | molding the propylene-type polymer of any one of Claims 1-4.   The sheet | seat obtained by shape | molding the propylene-type polymer of any one of Claims 1-4.   The blow molding container obtained by shape | molding a propylene-type polymer in any one of Claims 1-4.   An injection blow molded container obtained by molding a propylene polymer according to any one of claims 1 to 4.

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