JP2006124452A - Propylene polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polypropylene polymer containing little ethylene chain component to cause the deterioration of physical properties. <P>SOLUTION: The propylene copolymer is composed of a part (D<SB>sol</SB>) soluble in n-decane at room temperature and a part (D<SB>insol</SB>) insoluble in n-decane at normal temperature. The GPC molecular weight distributions (Mw/Mn) of both D<SB>sol</SB>and D<SB>insol</SB>are ≤4.0, the P(E3)/P(E5) ratio of the 720 cm<SP>-1</SP>peak height P(E5) and the 730 cm<SP>-1</SP>peak height P(E3) in the IR measurement of the polymer is ≥0.9, D<SB>sol</SB>/(D<SB>sol</SB>+D<SB>insol</SB>)×100 is ≥5%, and the intrinsic viscosity ([η](dl/g)) of D<SB>sol</SB>is ≥1.5. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a propylene-based polymer, more specifically to a propylene-based copolymer, and more specifically to a propylene-based copolymer having good performance of a polymer rubber during propylene-ethylene copolymerization.

  High crystalline polypropylene obtained by polymerizing propylene using a stereoregular catalyst has a wide range of uses as a material excellent in rigidity and heat resistance as a thermoplastic resin. On the other hand, a propylene-ethylene block copolymer with improved impact resistance at low temperatures, which is a drawback of polypropylene, is produced by a propylene-ethylene block copolymerization method in which propylene and ethylene are polymerized or copolymerized in two or more stages. It is known that In addition, using a stereoregular 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 thereafter to produce an amorphous A method for producing a propylene-ethylene copolymer and continuously producing a propylene-ethylene block copolymer having an excellent balance between impact resistance and rigidity is known. However, an ethylene chain is formed in the block copolymerization step.

  It is known that the ethylene chain component in the step of performing block copolymerization causes a decrease in physical properties such as the elastic modulus of the propylene copolymer. Therefore, the appearance of a propylene-ethylene copolymer having few ethylene chains is desired in the second step of performing block copolymerization.

  The problem to be solved by the present invention is to provide a propylene-based copolymer having a small amount of ethylene chain components that cause deterioration of physical properties.

The propylene-based copolymer of the present invention comprises a part soluble in room temperature n-decane (D _sol ) and a part insoluble in room temperature n-decane (D _insol ), and the following requirements (1) to (4) These are propylene polymer particles satisfying
1) The GPC molecular weight distribution (Mw / Mn) of D _sol and D _insol must both be 4.0 or less.
2) ratio P (E3 of peak height P of the peak of 720 cm ^-1 in the IR measurement of the polymer height P and ^{(E5) 730cm -1 (E3)} ) / P (E5) ≧ 0.9 be satisfied.
3) D _sol / (D _sol + D _insol ) × 100 ≧ 5%.
4) The intrinsic viscosity ([η] (dl / g)) of D _sol is 1.5 or more.

  The propylene-based copolymer of the present invention uses a polymerization apparatus in which two or more reactors are connected in series, and continuously performs the following two steps ([Step 1] and [Step 2]). It is characterized by being obtained.

  [Step 1] A step of producing a propylene (co) polymer by (co) polymerizing propylene and, if necessary, one or more olefins selected from ethylene and an α-olefin having 4 or more carbon atoms.

  [Step 2] A step of producing a propylene (co) polymer by copolymerizing propylene and ethylene. An α-olefin having 4 or more carbon atoms as described in [Step 1] can also be used in combination.

  The propylene-based copolymer of the present invention is a propylene-based copolymer having excellent physical properties such as an elastic modulus and having few ethylene chains in the rubber component produced in [Step 2], that is, the block copolymerization step.

The propylene-based copolymer of the present invention comprises a part soluble in room temperature n-decane (D _sol ) and a part insoluble in room temperature n-decane (D _insol ), and the following requirements (1) to (4) These are propylene polymer particles satisfying
1) The GPC molecular weight distribution (Mw / Mn) of D _sol and D _insol must both be 4.0 or less.
2) ratio P (E3 of peak height P of the peak of 720 cm ^-1 in the IR measurement of the polymer height P and ^{(E5) 730cm -1 (E3)} ) / P (E5) ≧ 0.9 be satisfied.
3) D _sol / (D _sol + D _insol ) × 100 ≧ 5%.
4) The intrinsic viscosity ([η] (dl / g)) of D _sol is 1.5 or more.

  The propylene-based copolymer of the present invention uses a polymerization apparatus in which two or more reactors are connected in series, and continuously performs the following two steps ([Step 1] and [Step 2]). It is characterized by being obtained.

  [Step 1] A step of producing a propylene (co) polymer by (co) polymerizing propylene and, if necessary, one or more olefins selected from ethylene and an α-olefin having 4 or more carbon atoms.

  [Step 2] A step of producing a propylene (co) polymer by copolymerizing propylene and ethylene.

  The present invention will be described in detail below.

-Propylene-based copolymer-
The propylene-based copolymer of the present invention has a portion (D _sol ) soluble in normal decane at room temperature (hereinafter sometimes referred to as “room temperature n-decane”) and a portion insoluble in room temperature n-decane. (D _insol ), which is a polymer obtained from propylene and one or more olefins selected from ethylene and α-olefins having 4 or more carbon atoms. The α-olefin having 4 or more carbon atoms used in the propylene-based copolymer of the present invention is the olefins described in detail in the “polymerization method” described later, and among these, ethylene is preferably used. That is, the preferred propylene-based copolymer of the present invention is a copolymer produced from two types of olefins, propylene and ethylene.

The propylene-based copolymer of the present invention is a propylene-based polymer characterized by satisfying the following requirements (1) to (4) simultaneously.
1) The GPC molecular weight distribution (Mw / Mn) of D _sol and D _insol must both be 4.0 or less.
2) the ratio of the peak height P of the peak of 720 cm ^-1 in the IR measurement of the polymer height P and (E5) 730cm ^-1 (E3) is, P (E3) / P ( E5) ≧ 0.9 be satisfied.
3) D _sol / (D _sol + D _insol ) × 100 ≧ 5%.
4) The intrinsic viscosity ([η] (dl / g)) of D _sol is 1.5 or more.

-Polymerization catalyst-
All of the propylene homopolymer and the copolymer obtained from propylene and the olefin constituting the propylene-based copolymer of the present invention can be obtained by polymerizing the monomer in the presence of a metallocene catalyst. The metallocene catalyst according to the present invention 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,
Polymerization catalyst containing as an essential component at least one compound selected from
It is.

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 known transition metal compound having an 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: It is 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 electron pair. 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, Lopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, adamantyl Den (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, cyclohexyl Den (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopentyl Ridene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, cyclohexylidene (Lopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, cyclopentylidene (cyclopentadiene) Enyl) (2,7-ditert-butylfluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, adamantylidene (cyclopentadiene) Enyl) (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, cyclopentylide (Cyclopentadienyl) (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 dichlor , Cycloheptylidene (cyclopentadienyl) (3,6-diphenyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-dibenzyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclo Pentadienyl) (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 , Cyclobut Den (cyclopentadienyl) (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, cyclobutylidene (cyclopentadienyl) (3,6-dibromo-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-dibromo-fluorenyl) zirconium dichloride, cyclohexylidene ( Cyclopentadi Nyl) (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 di Bromide, cyclopropylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium di Til, cyclobutylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cyclohexylidene (cyclopenta (Dienyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cycloheptylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cyclopropylidene (cyclopentadienyl) (3,6 -Di-tert-fluorenyl) hafnium dichloride,
Cyclobutylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) hafnium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) hafnium dichloride, cyclohexylidene (cyclopentadiene) (Dienyl) (3,6-ditert-fluorenyl) hafnium dichloride, cycloheptylidene (cyclopentadienyl) (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 Titanium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dichloride, cyclobutylidene, cyclodipropylene (cyclopentadienyl) (3,6-ditert-fluorenyl) (Cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (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 (Lopentadienyl) (2,7-ditert-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (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 (cyclohexane) Pentadienyl) (2,7-dicumyl-fluorenyl) Zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-dicumyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclo Butylidene (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 ( Cyclo Interdienyl) (2,7-diphenyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (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, cyclo Propyridene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7 Dibenzyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride, Cyclopropylidene (cyclopentadienyl) (2,7-difluoro-fluorenyl) zirconium dichloride, cyclobutylidene (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) -F Olenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-dibromo-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-dibromo-fluorenyl) zirconium dichloride, cyclopentylidene (Cyclopentadienyl) (2,7-dibromo-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (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, cycl Pentylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dibromide, cyclohexylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dibromide, cycloheptylidene (cyclo Pentadienyl) (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- (Luolenyl) zirconium dimethyl, cyclopropylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) hafnium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) hafnium dichloride, cyclo Pentylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) Hafnium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) Hafnium dichloride, cycloheptylidene (cyclopentyl) (Dienyl) (2,7-ditert-fluorenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) titanium dichloride, cyclobutylidene (cyclopentadienyl) (2, 7-ditert-fluorenyl) titanium dichloride, cyclopentylidene (cyclopentadiene) ) (2,7-ditert-fluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) titanium dichloride, cycloheptylidene (cyclopentadienyl) (2, 7-ditert-fluorenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) ) Zirconium dichloride, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclo Ptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclobutylidene (cyclopentadiene) Enyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclohexylidene (cyclopentadienyl) (octa Methyloctahydrodibenzofluorenyl) zirconium dibromide, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclopropylidene ( (Clopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) ( Octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzo) Fluorenyl) zirconium dimethyl, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, cyclobutylidene (cyclopentadienyl) Tiloctahydrodibenzofluorenyl) hafnium dichloride, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Nyl) hafnium dichloride, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, Cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzo (Luolenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, Di-n-butylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene ( Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di-n-butylmethylene (Cyclopentadienyl) (ben Zofluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di-n- Butylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclohexane) Pentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride,
Diisobutylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (dibenzofluorene) Nyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, dibenzylmethylene ( Cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium Um dichloride, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadi) (Enyl) (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-butylfluorene) Nyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, diphenethylmethylene (cyclohexane) Pentadienyl) (dibenzofluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluoro Olenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclope Tadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopenta Dienyl) (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) zirconi Um dichloride, di (cumyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (3,6-ditert-butyl) Fluorenyl) zirconium dichloride, 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 (cyclo Pentadienyl) (octamethyltetrahydrodicyclopen Fluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) ) (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) (octahydrodibenzofluoreni ) Zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (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 (cyclopentadienyl) (dibenzofluoride) Olenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl ) Zirconium dichloride di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorene) Nyl) zirconium dichloride, di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) ) ( Kutamethyloctahydrodibenzofluorenyl) 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) zirconium dichloride, di (Cyclopentylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopenta Dienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (1-cycl Pentyl-ethyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di ( 1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzo Fluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (dibenzofluorene) Nyl) zirconium dichloride, di (1- Cyclopentyl-ethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride Di (naphthylmethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (3,6-ditert-butyl Fluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) Zirconium dichloride, (Naphthylmethyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, 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 ( Cyclopen Dienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (dibenzo Fluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentaful Orenyl) zirconium dichloride, (benzyl) (phenethyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (benzyl) (phenethyl) methylene (cyclopentadienyl) (2,7-ditert- Tylfluorenyl) zirconium dichloride, (benzyl) (phenethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (phenethyl) methylene (cyclopentadienyl) (octamethyl) Octahydrodibenzofluorenyl) 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-butyl Fluorenyl) 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-butylfluorenyl) zirconium dichloride, (benzyl) (cyclohexylmethyl) methylene (Cyclopentadienyl) (3,6-ditert-butylfluorene ) Zirconium dichloride, (benzyl) (cyclohexylmethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-ditert-butyl) Fluorenyl) Titanium dichloride, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) Titanium dichloride, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) ) Titanium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Hafnium dichloride, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) ) Hafnium dichloride, dibenzylmethylene (cyclopente Tadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dibromide, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dibromide, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, dibenzylmethylene (cyclopentadienyl) ( 2,7-ditert-butylfluorenyl) zirconium dimethyl, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dimethyl, dibenzylmethylene (cyclopentadienyl) ( Octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, Methylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dimethyl, dimethylmethylene (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (benzofluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dimethyl, dimethylmethylene (cycline) Pentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3,6-ditert-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) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, dimethylsilylene (cyclopenta Dienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, dimethylsilylene ( Cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) 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, dimethylsilylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dimethyl, dimethylsilylene ( Cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) (2, 7-di-tert-butyl Fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorene) Nyl) zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorene) Nyl) 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-butyl (Luolenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-ditert-butylfluorene) Nyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (3,6-ditert-butylfullyl) Oleenyl) 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-butylphenyl) (Luolenyl) zirconium dichloride, diethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) ) Hafnium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Hafnium dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) ) Hafnium dichloride, monophenyl monomethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Hafnium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) ) Hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) ha Nium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Hafnium dichloride, diethylmethylene (cyclopentadienyl) (2,7-ditert-butylfullyl) Olenyl) hafnium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfullyl) Olenyl) Titanium dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Titanium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (2,7-ditert-butyl) Fluorenyl) Titanium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride Lido, Diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Titanium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorene) Nyl) titanium dichloride, diethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, isopropylidene (3,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropyl Riden (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-cyclo) Pentadienyl) (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) (octamethyloctahydrodibenzofluorenyl) 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-butylfluorenyl) zirconium dichloride, isopropylidene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (octamethyl) Octahydrodibenzofluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-ethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-ethyl-cyclopentadi) Enyl) (2,7-ditert-butylphenyl) Olenyl) 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-butyl-2,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride,
Isopropylidene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-2,5-dimethyl) -Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorene) Nyl) zirconium dichloride, diphenylmethylene (3,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluore Nyl) zirconium dichloride, diphenylmethylene (3,5-dimethyl) Cyclopentadienyl) (3,6-ditert-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-butylfur Olenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5 -Methyl-cyclopentadieny ) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (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-methyl-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-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (octamethyl) Octahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-2,5-dimethyl) -Cyclopentadie ) (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-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p -Tolyl) methylene (3,5-dimethyl-cyclopentadienyl) (3,6-ditert-butyl Fluorenyl) 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-butylfluore Nyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) Methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethy Octahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (3 -(2-adamantyl) -5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3- (2-adamantyl) -5- Methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (octa Methyloctahydrodibenzofluorenyl) 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-butylfluore Nyl) 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-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-2,5-dimethyl- Cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-ter t-butyl-2,5-dimethyl-cyclopentadienyl) (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) (octamethyl) Octahydrodibenzofluorenyl) 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 dichrome 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-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (P-tert-butylphenyl) methylene (3-tert-butyl-5-methyl) Ru-cyclopentadienyl) (3,6-ditert-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-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (3,6- tert-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 dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) ) (3,6-ditert-butylfluorenyl) zirconi Um 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-cyclo) Pentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (3 , 6-Ditert-butylfluorenyl) zirconium dichloride, di (p-ter -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) (o Kutamethyloctahydrodibenzofluorenyl) 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, dibe Jirumechiren (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-cyclo Pentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium Dichloride, fluorenylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, fluorenylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert- Butylfluorenyl) zirconium dichloride, fluo Renylidene (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-butyl-5-methyl-) Cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dimethyl, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorene) Nyl) 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-) 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-butylfluore Nyl) hafnium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (3-tert-butyl-5- Methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride and the like can be mentioned, but the transition metal compound used in the present invention is not 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) A compound that reacts with a transition metal compound to form an ion pair (B-3) A compound that reacts with a transition metal compound (A) to form an ion pair (hereinafter, “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 following two steps ([Step 1] and [Step 2]) are continuously performed using a polymerization apparatus in which two or more, preferably two, reactors are connected in series. It is obtained by carrying out.

[Step 1] comprises (co) polymerization of propylene and, if necessary, one or more olefins selected from ethylene and α-olefins having 4 or more carbon atoms, to produce a moiety soluble in n-decane (D ′ _sol ) is a step for producing a (co) polymer having a concentration of 1.0 wt% or less. 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, as ethylene having 2 carbon atoms and α-olefin having 4 or more carbon atoms. Olefins such as 1-butene, 2-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-eicose and the like. 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, hydroxystyrene, 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 1] The concentration of the portion soluble in room temperature n-decane (D ′ _sol ) of the polymer after completion of the step is 2.0 wt% or less, preferably 1.0 wt% or less.

[Step 2] is a copolymerization of propylene and one or more olefins selected from ethylene and α-olefins having 4 or more carbon atoms, and the portion insoluble in room temperature n-decane (D ′ _insol ) is 1.0 wt% or less. This is a process for producing a (co) polymer. As the one or more olefins selected from ethylene and the α-olefin having 4 or more carbon atoms used in combination with ethylene 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.

In the present invention, the molar concentration of the skeleton derived from the olefin in D _sol is 10 to 60 mol%, preferably 20 to 60 mol%.

  The propylene-based polymer of the present invention thus obtained is a sheet or film for retort that is excellent in balance between low-temperature impact resistance and heat sealability, in particular, alone or in the form of a blend with another elastomeric resin. Is preferably used.

  EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to this Example. The measuring method of the physical property in an Example is as follows.

(I) n -decane soluble part (D _sol ) and n-decane insoluble part (D _insol )
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

(Ii) Intrinsic viscosity measurement 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 adding 5 ml of decalin solvent to the decalin solution for dilution, 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)

(Iii) GPC molecular weight distribution (Mw / Mn) [weight average molecular weight (Mw), number average molecular weight (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 .

(Iv) About 0.3 g of IR measurement sample was heated and dissolved at 270 ° C. for 7 minutes to prepare a press sheet having a thickness of 0.2 mm at a pressure of 250 kg / cm ² , and this was used as a test piece for measuring an infrared absorption spectrum. .

Absorbances at 720 cm ⁻¹ and 730 cm ⁻¹ were measured using an infrared spectrophotometer FT / IR-410 manufactured by JASCO Corporation.

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 prepolymerized catalyst 202 g of the solid catalyst component prepared in 2) above, 109 mL of triethylaluminum, and 100 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 L, and the internal temperature was maintained at 15 to 20 ° C., and 2020 g of ethylene was inserted. , Reacted for 180 minutes with stirring. 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 polymerizer having an internal volume of 58 L is 3.1 g / hour and 1.7 g / hour of triethylaluminum as solid catalyst components. The polymer 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 0.16 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 vessel, propylene 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 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 0.16 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 copolymer. The resulting propylene copolymer was vacuum dried at 80 ° C. The analysis results of the propylene-based polymer thus obtained are shown in Table 1.

[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) Preparation 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. The inner temperature was kept 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 It sent to the vessel polymerizer with an internal capacity of 1000L with a stirrer, and the propylene was supplied to 133 kg / hour and hydrogen was supplied so that the hydrogen concentration of a gaseous phase part might be 7.9 mol%. The catalyst slurry produced in 2) of Comparative Example 1 was continuously fed as a solid catalyst component at 0.9 g / hour, triethylaluminum 19.2 g / hour, and dicyclopentyldimethoxysilane 2.6 mL / hour, with a polymerization temperature of 72 ° C. Polymerization was performed at a pressure of 3.5 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 5.3 mol%. Polymerization was carried out at a polymerization temperature of 72 ° C. and a pressure of 3.4 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 20 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 4.0 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and 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 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 62 ° C. and a pressure of 3.2 MPa / G.

 After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene copolymer. The resulting propylene copolymer was vacuum dried at 80 ° C. The analysis results of the propylene-based polymer thus obtained are shown in Table 1.

  The propylene polymer of the present invention is a polypropylene polymer having few ethylene chains in the rubber component and excellent physical properties.

Claims (3)

Propylene polymer particles composed of a part soluble in room temperature n-decane (D _sol ) and a part insoluble in room temperature n-decane (D _insol ) and simultaneously satisfy the following requirements (1) to (4).
1) The GPC molecular weight distribution (Mw / Mn) of D _sol and D _insol must both be 4.0 or less.
2) The ratio of the peak height P (E5) of 720 cm ^{-1 to} the peak height P (E3) of 730 cm ^-1 in the IR measurement of polymer particles satisfies P (E3) / P (E5) ≧ 0.9 .
3) D _sol / (D _sol + D _insol ) × 100 ≧ 5%.
4) The intrinsic viscosity ([η] (dl / g)) of D _sol is 1.5 or more. The propylene polymer particles according to claim 1, wherein D _sol is a polymer obtained from propylene and ethylene.   2. A retort material obtained from the polypropylene polymer particles according to claim 1.