JP4389071B2 - Propylene polymer - Google Patents

Description

  The present invention relates to a propylene-based polymer, more specifically to a propylene-based copolymer, and more particularly to a propylene-based copolymer with a small amount of solvent-insoluble components by-produced during propylene-α-olefin 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 polymerization or copolymerization of propylene and ethylene is performed 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, in the block copolymerization step, a copolymer of propylene and ethylene soluble in a solvent such as n-decane or paraxylene, a copolymer of propylene and ethylene insoluble in these solvents, polyethylene, or polypropylene are used. Generate.

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

  The problem to be solved by the present invention is to provide a propylene-based copolymer which is produced in a polypropylene block copolymerization stage and does not produce a solvent-insoluble component which causes a decrease in physical properties.

The propylene-based copolymer of the present invention has a portion soluble in normal decane at room temperature (hereinafter sometimes referred to as “room temperature n-decane”) (D _sol ) and a portion insoluble in room temperature n-decane. (D _insol ), a polymer obtained from propylene (M _P ) and one or more olefins (M _X ) selected from ethylene and α-olefins having 4 or more carbon atoms, and having the following requirements (1 ) To (4) are satisfied at the same time.
(1) Both D _sol and D _insol have a GPC molecular weight distribution (Mw / Mn) of 4.0 or less.
(2) The molar concentration of the skeleton derived from the olefin (M _X ) in D _sol is 10 to 60 mol%.
(3) The weight concentration of the skeleton derived from olefin (M _X ) in D _insol is 2.0 wt% or less.
(4) The intrinsic viscosity ([η] (dl / g)) of D _sol is 1.5 or more.

In addition, a preferred embodiment of the propylene polymer of the present invention is characterized in that one or more olefins (M _X ) selected from ethylene and an α-olefin having 4 or more carbon atoms are ethylene.

The propylene-based copolymer of the present invention comprises a polymerization apparatus in which two or more reactors are connected in series , diphenylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7-di-t -Butylfluorenyl) It is characterized by being obtained by carrying out the following two steps ([Step 1] and [Step 2]) successively using a catalyst containing zirconium dichloride .

[Step 1] Propylene (M _P ) and, if necessary, one or more olefins (M _X ) selected from ethylene and α-olefins having 4 or more carbon atoms are (co) polymerized into room temperature n-decane. A step of producing a (co) polymer having a soluble part (D ′ _sol ) concentration of 2.0 wt% or less.

[Step 2] Propylene (M _P ) and one or more olefins (M _X ) selected from ethylene and α-olefins having 4 or more carbon atoms are copolymerized to form a portion insoluble in room temperature n-decane (D ' _insol ) Is a step of producing a (co) polymer having 2.0 wt% or less.

In the above production method, the olefin used in [Step 1] is a kind of propylene (M _P ), and the olefin used in [Step 2] is a mixed olefin of propylene (M _P ) and ethylene. This is one of the preferred embodiments.

The propylene-based copolymer of the present invention is a propylene-based copolymer excellent in physical properties such as an elastic modulus and having few room temperature n-decane insoluble components produced in [Step 2], that is, a block copolymerization step.

Propylene copolymer of the present invention is composed of the portion soluble (D _sol) and insoluble portion at room temperature n- decane (D _insol) to room temperature n- decane, propylene (M _P) and ethylene and carbon A propylene-based polymer characterized in that it is a polymer obtained from one or more olefins (M _X ) selected from α-olefins of at least 4 and satisfying the following requirements (1) to (4) simultaneously: is there.
(1) The GPC molecular weight distribution (Mw / Mn) of D _sol and D _insol is 4.0 or less, respectively.
(2) The molar concentration of the skeleton derived from the olefin (M _X ) in D _sol is 10 to 60 mol%.
(3) The weight concentration of the skeleton derived from olefin (M _X ) in D _insol is 2.0 wt% or less.
(4) The intrinsic viscosity ([η] (dl / g)) of D _sol in the propylene-based polymer is 1.5 or more.

  The present invention will be described in detail below.

-Propylene-based copolymer-
The propylene-based copolymer of the present invention has a portion soluble in normal decane at room temperature (hereinafter sometimes referred to as “room temperature n-decane”) (D _sol ) and a portion insoluble in room temperature n-decane. It is a polymer composed of (D _insol ) and obtained from propylene (M _P ) and one or more olefins (M _X ) selected from ethylene and α-olefins having 4 or more carbon atoms. The α-olefin having 4 or more carbon atoms (M _X ) used in the propylene-based copolymer of the present invention is an olefin described in detail in the “polymerization method” described later, and among these, ethylene is preferably used. Is done. That is, the preferred propylene 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 molecular weight distribution (Mw / Mn) measured by GPC of the part soluble in room temperature n-decane (D _sol ) and the part insoluble in room temperature n-decane (D _insol ) is 4.0 or less. A preferable molecular weight distribution of D _sol is 3.8 or less, and a more preferable molecular weight distribution is 3.5 or less. On the other hand, the preferred molecular weight distribution of D _insol is 3.5 or less, and the more preferred molecular weight distribution is 3.0 or less. In addition, Mw is a weight average molecular weight and Mn is a number average molecular weight.
(2) The molar concentration of the skeleton derived from one or more olefins (M _X ) selected from ethylene and α-olefins having 4 or more carbon atoms in the portion soluble in room temperature n-decane (D _sol ) is 10 to 60 mol%. The amount is preferably 20 to 60 mol%, particularly preferably 25 to 50 mol%.
(3) The weight concentration of the skeleton derived from one or more olefins (M _X ) selected from ethylene and α-olefins having 4 or more carbon atoms in the insoluble portion (D _insol ) at room temperature n-decane is 2.0 wt% Hereinafter, it is preferably 1.0 wt% or less.
(4) The intrinsic viscosity ([η] (dl / g)) of the part soluble in n-decane at room temperature (D _sol ) is 1.5 or more, preferably 1.8 or more.

-Polymerization catalyst-
The propylene homopolymer and the copolymer obtained from propylene and the olefin (M _X ) constituting the propylene-based copolymer of the present invention are all 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,
A polymerization catalyst comprising as an essential component at least one compound selected from
The

Hereinafter, these catalyst components will be described in detail.
(A) Transition metal compound The transition metal compound used in the present invention is not particularly limited as long as it is a transition metal compound having a known olefin polymerization ability, but is preferably a transition metal compound of Groups 4 to 6 in the periodic table. Examples thereof include 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 a 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 (wherein 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. , A hydrocarbon group and a silicon-containing group, 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 on Y are preferably a hydrocarbon group having 1 to 20 carbon atoms. These may be the same as 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 a 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 Tadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (4-biphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, ( 4-biphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, (4-biphenyl) (phenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Clopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, Adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Cyclohexylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Cyclopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, cyclohexylidene ( Clopentadienyl) (2,7-ditert-butylfluorenyl) Hafnium dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Hafnium dichloride, cyclopentylidene ( (Cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, adamantylidene ( Cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) ) (3,6-Dimethyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-dimethyl) -Fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dichloride, cyclo Propyridene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadiene) Enyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3, 6-ditert-fluorenyl) zirconium dichloride, cyclopro Liden (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, cyclopentyl Den (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 Lido, 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 , Cyclob Liden (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 ( Cyclopenta Enyl) (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 Methyl, 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, cyclobutyryl
Den (cyclopentadienyl) (3,6-ditert-fluorenyl) hafnium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) hafnium dichloride, cyclohexylidene (cyclopentadienyl) ) (3,6-ditert-fluorenyl) hafnium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (3,6 -Di-tert-fluorenyl) titanium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) titanium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) Titanium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-di tert-fluorenyl) Titanium dichloride Lido, cycloheptylidene (cyclopentadienyl) (3,6-di tert-fluorenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dichloride, cyclobutylidene ( 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 (cyclopentadiene Nyl) (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, cyclobuty Ridene (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 Pentadieni ) (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, cyclopropyl Liden (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, cyclopropyl Liden (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-fluorenyl) ) Luconium 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, cyclopentylide (Cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dibromide, cyclohexylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dibromide, cycloheptylidene (cyclopentadiene) Dienyl) (2,7-ditert-fluorenyl) zirconium dibromide, cyclopropylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dimethyl, cyclobutylidene (cyclopentadienyl) (2, 7-dimethyl-fluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dimethyl , Cycloheptylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) Luconium dimethyl, cyclopropylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) hafnium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) hafnium dichloride, cyclopentyl Lidene (cyclopentadienyl) (2,7-ditert-fluorenyl) Hafnium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) Hafnium dichloride, cycloheptylidene (cyclopentadiene) Enyl) (2,7-ditert-fluorenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) titanium dichloride, cyclobutylidene (cyclopentadienyl) (2,7 -Di-tert-fluorenyl) titanium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-dite rt-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, cycloheptylidene ( (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclobutylidene (cyclopentadienyl) (Octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclohexylidene (cyclopentadienyl) (octamethyloctayl Hydrodibenzofluorenyl) zirconium dibromide, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclopropylidene (cyclopenta Enyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) (octamethylocta Hydrodibenzofluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) ) Zirconium dimethyl, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, cyclobutylidene (cyclopentadienyl) (octamethyloctahyd Drodibenzofluorenyl) hafnium dichloride, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Hafnium dichloride, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Titanium dichloride, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Titanium dichloride, cyclobutyl Liden (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Titanium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, di-n -Butylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopenta Dienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di-n-butylmethylene (cyclo Pentadienyl) (benzofluorenyl) ) 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, diisobuty
Lumethylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di
Isobutylmethylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclo Pentafluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (benzofluorenyl) zirconium Chloride, dibenzylmethylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) ( Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (3, 6-ditert-butylfluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (benzofluorenyl) ) Zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadiene) Enyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclo Pentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (benzhi Ryl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) ( Octahydrodibenzofluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (fluorenyl) zirconium Dichloride, di (cumyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (3,6-ditert-butylfull Oleenyl) zirconium di Loride, di (cumyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (cumyl) Methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) ( Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl- Ethyl) methylene (cyclopentadiene) Nyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (1- Phenyl-ethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (1-phenyl- Ethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (Cyclohexylmethyl) methylene (cyclo Pentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (cyclohexylmethyl) ) Methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclo Pentadienyl) (dibenzofluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadiene) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) ) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di ( 1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, Di (1-cyclohexyl-) Til) 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 Mudichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (Cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) ) Methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride Di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (octa Methyloctahydrodibenzofluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (Dibenzofluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (Octamethyltetrahydro Cyclopentafluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) ( 3,6-ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadi) Enyl) (benzofluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorene Nyl) zirconium dichlorine , Di (naphthylmethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (biphenylmethyl) Methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride Di (biphenylmethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (biphenyl) Methyl) Tylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, (benzyl) (phenethyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (benzyl) (phenethyl) methylene (cyclopentadienyl) (2, 7-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (phenethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (phenethyl) methylene ( Cyclopenta Dienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (benzyl) (n-butyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (benzyl) (n-butyl) methylene (cyclopentadienyl) ) (2,7-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (n-butyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl ) (N-butyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorene) Nyl) zirconium dichloride, (benzyl) (cumyl) methylene (cyclopentadiene) Nyl) (3,6-ditert-
Butylfluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene (cycl
Lopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride (benzyl) (cyclohexylmethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (cyclohexylmethyl) ) Methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (cyclohexylmethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride Dibenzylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) titanium dichloride Dibenzylmethylene (cyclo Tantadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, dibenzylmethylene (cyclopentadienyl) ( 3,6-ditert-butylfluorenyl) hafnium dichloride, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7 -Ditert-butylfluorenyl) zirconium dibromide, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dibromide, dibenzylmethylene (cyclopentadienyl) (octa Methyloctahydrodibenzofluorenyl) Zirconium dibromi Dibenzylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dimethyl, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dimethyl Dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dimethyl, dimethylmethylene ( Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (Benzofluorenyl) zirconium dimethyl, dimethylme Len (cyclopentadienyl) (dibenzofluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopenta Fluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorene) Nyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, dimethylmethylene (cyclohexane) Ntadienyl) (dibenzofluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium Dichloride, dimethylsilylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Dimethylsilylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, dimethylsilylene (cyclopenta Enyl) (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) (diben) Fluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dimethyl, cyclopentylidene ( (Cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, adamantylidene ( Cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dimethylmethylene ( Cyclopentadienyl) (2,7-di tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2, 7-ditert-butylfluorenyl) zirconium dichloride, diethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6 -Ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (3,6 -Di-tert-butylfluorenyl) zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (3,6-di-t ert-butylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diethylmethylene (cyclopentadienyl) (3,6- Ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, cyclohexylidene (cyclopentadienyl) (2,7- Di-tert-butylfluorenyl) hafnium dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Nyl) hafnium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorene) Nyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert- Butylfluorenyl) Hafnium dichloride, diethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Hafnium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-ditert-butyl) Fluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium Um dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) ) Titanium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Titanium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Titanium Dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Titanium dichloride, diethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorene) Nyl) titanium dichloride, isopropylidene (3,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride Lido, isopropylidene (3,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (3,5-dimethyl-cyclopentadienyl) (3,6 -Di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5- Methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, isopropylidene ( 3-tert-butyl-5-methyl-cyclope Ntadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, isopropyl Riden (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (2,7- Di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, isopropylidene ( 3- (2-adamantyl) -5-methyl-cyclope Tadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-ethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5- Ethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-ethyl-cyclopentadienyl) (3,6-ditert-butyl) Fluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-ethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-2,5 -Dimethyl-cyclope Ntadienyl) (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) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (3,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, dipheni
Lumethylene (3,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfur
Oleenyl) 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-cyclo) Pentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) ) Zirconium dichloride, di Enylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (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) (octa Methyloctahydrodibenzofluorenyl) zirconi Um 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) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium Dichloride, gif Nilmethylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-2,5-dimethyl- Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) ) Zirconium dichloride, di (p-tolyl) methylene (3,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (3,5-dimethyl-cyclopentadienyl) (2 , 7-Ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) me Len (3,5-dimethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3,5-dimethyl-cyclopentadienyl) (octa Methyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (3- tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-methyl-cyclopentadi) Enyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene ( 3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (3- (2-adamantyl) -5-methyl-cyclopenta Dienyl) (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) (octamethyloctahydrodibenzofluorenyl) Luconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-ethyl) -Cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (3,6- Ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p -Tolyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (fluoro Lenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-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) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3,5-dimethyl-cyclopentadienyl) (fluorenyl) Zirconium dichloride, di (p-tert-butylphenyl) methylene (3,5-dimethyl-cyclopenta) Enyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3,5-dimethyl-cyclopentadienyl) (3,6-ditert-butylfullyl) Olenyl) 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 ( -Tert-butylphenyl) methylene (3-tert-butyl-5-methyl-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-butylfur Oleenyl) zirconium dichloride, di (p-tert-butylphenyl) methyle (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3- (2- Adamantyl) -5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) ) (Fluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (P-tert-butylphenyl) methylene (3-tert-butyl-5-ethyl- Clopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (octamethyl) Octahydrodibenzofluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tert- Butylphenyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3 -Tert-butyl-2,5-dimethyl-cyclopentadienyl) (3,6-dit rt-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride (Methyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopenta) Dienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, (methyl) (phenyl) Tylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (p-tolyl) (phenyl) methylene (3-tert-butyl-5-methyl- Cyclopentadienyl) (fluorenyl) zirconium dichloride, (p-tolyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium Dichloride, (p-tolyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (phenyl ) Methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octame L-octahydrodibenzofluorenyl) zirconium dichloride, dibenzylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, dibenzylmethylene (3-tert-butyl-5-methyl-) Cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylful) Oleenyl) zirconium dichloride, dibenzylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, fluorenylidene (3-tert-butyl-5-methyl-) Cyclopentadienyl) Oreniru) zirconium dichloride, fluorenylidene (3
tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, fluorenylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6 -Ditert-butylfluorenyl) zirconium dichloride, fluorenylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl) -5-methyl-cyclopentadienyl) (fluorenyl) zirconium dimethyl, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dimethyl, Diphenylmethylene (3-tert- Butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dimethyl, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydro Dibenzofluorenyl) 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- Til-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (3-tert) -Butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6 -Ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, and the like. Transition metal compounds used in It is not intended to be limited to the above exemplified compounds.

(B-1) Organometallic compound As the (B-1) organometallic compound used in the present invention, specifically, the groups 1, 2 and 12 as shown in (B-1a) to (B-1c) , Group 13 organometallic compounds are used.
(B-1a) General formula: R ^a _m Al (OR ^b ) _n H _p X _q
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0 < m ≦ 3, n is 0 ≦ n <3, p is 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 or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, 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), an organoaluminum compound is preferable. 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, ceric 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 suspension of the hydrocarbon.
[2] A method in which water, ice or water vapor directly acts 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, etc., 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 precipitating agent may 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 other large and bulky ions using the ion-exchange property. . Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the 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. Among 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. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

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 above olefin polymerization catalyst, the component (A) is usually 10 ⁻⁸ to 10 ⁻² mol, preferably 10 ⁻⁷ to 10 ⁻³ , per liter of 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) polymerizing propylene (M _P ) and, if necessary, one or more olefins (M _X ) selected from ethylene and α-olefins having 4 or more carbon atoms, to produce n-decane This is a step for producing a (co) polymer in which the concentration of the soluble part (D ′ _sol ) is 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 step of copolymerizing propylene (M _P ) and one or more olefins (M _X ) selected from ethylene and α-olefins having 4 or more carbon atoms to form a portion insoluble in room temperature n-decane (D _Insol ) is a step for producing a (co) polymer having 2.0 wt% or less, preferably 1.0 wt% or less. [Second Step] ethylene and one or more olefins selected from C4 or more [α- olefin carbon used in (M _X), the olefin exemplified above in the first step] (M _X) can be used as it is . Further, the olefin (M _X ) used in the [second step] may be the same as or different from the olefin (M _X ) 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.

  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 )
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) The amount of α-olefin-derived skeleton contained in the n-decane insoluble part (D _insol )
After drying the n-decane insoluble part fractionated in (i), the skeleton derived from α-olefin in the n-decane insoluble part was measured by carbon nuclear magnetic resonance analysis ( ¹³ C-NMR).

  Carbon nuclear magnetic resonance analysis was performed after dissolving 20-30 mg of sample in 0.6 ml of 1,2,4-trichlorobenzene / heavy benzene (2: 1) solution.

Propylene, ethylene, and α-olefin were quantitatively determined from the dyad chain distribution. For example, in the case of propylene-ethylene copolymer,
PP = Sαα, EP = Sαγ + Sαβ, EE = 1/2 (Sβδ + Sδδ) + 1 / 4Sγδ
Was obtained from the following calculation formula.

In addition, with regard to the assignment with α-olefins, reference was made to published reports such as Macromolecules 1982, 15, 1150, Macromolecules 1991, 24, 4813, J. Appl. Polym. Sci 1991, 42, 399, etc.

(Iii) Carbon nuclear magnetic resonance analysis of the n-decane soluble part separated by the amount of skeleton derived from α-olefin (i) contained in the n-decane soluble part (D _sol ) as in (ii) The amount of skeleton derived from α-olefin contained in the n-decane soluble part was measured by ( ¹³ C-NMR). Propylene, ethylene, and α-olefin were quantified in the same manner as in (ii). For example, in the case of a propylene-ethylene copolymer, it was determined from the following calculation formula.

(Iv) n-decane soluble part (D ' _sol )
After completion of the first step, the amount of the n-decane soluble part (D ′ _sol ) was determined for the collected sample by the same method as in (i).

(V) n-decane insoluble part (D ' _insol )
After completion of the second step, the amount of n-decane soluble part (X) was determined for the collected sample in the same manner as in (i), and calculated according to the following formula.

X: 第2工程完了サンプルのn-デカン可溶部量（wt%）
Y: 第2工程の重合量比率（ｗｔ％）
また、 第1工程にてD’_solが存在する場合は、以下の式により算出した。

X: The amount of n-decane soluble part (wt%) of the sample completed in the second step
Y: Ratio of polymerization amount in the second step (wt%)
When D ′ _sol was present in the first step, the calculation was performed according to the following formula.

X: 第2工程完了サンプルのn-デカン可溶部量（wt%）
Y: 第2工程の重合量比率（ｗｔ％）
Z: 第1工程の重合量比率（ｗｔ％）
但し、Y＋Z = 100

X: The amount of n-decane soluble part (wt%) of the sample completed in the second step
Y: Ratio of polymerization amount in the second step (wt%)
Z: Polymerization ratio in the first step (wt%)
However, Y + Z = 100

(Vi) Intrinsic viscosity measurement It was measured at 135 ° C. using a decalin solvent. About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After 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)

(Vii) GPC molecular weight distribution (Mw / Mn) [weight average molecular weight (Mw), number average molecular weight (Mn)]
It measured as follows using GPC-150C Plus by Waters. The separation columns are TSKgel GMH6-HT and TSKgel GMH6-HTL, the column size is 7.5 mm in inner diameter and the length is 600 mm, the column temperature is 140 ° C., and the mobile phase is o-dichlorobenzene (Wako Pure Chemicals). 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 .

1) Production of solid catalyst carrier 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-t-butyl-5-methylcyclopentadienyl) (2,7- di- t-butylfluorenyl) zirconium dichloride / MAO / SiO2 / toluene slurry was 99 in n-heptane. % Substitution was performed and the final slurry volume was 4.5 liters. This operation was performed at room temperature.

3) Preparation 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 with an internal volume of 200 L with a stirrer, 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 In a tubular polymerization vessel having an internal volume of 58 L, propylene is 50 kg / hour, hydrogen is 5 NL / hour, and the catalyst slurry produced in 3) is used as a solid catalyst component of 3.1 g / hour and triethylaluminum 1.7 g / hour. 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 polymerization was performed in the same manner as in Example 1 except that the polymerization method was changed as follows.
1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 L, propylene is 50 kg / hour, hydrogen is 5 NL / hour, the catalyst slurry produced in 3) of Example 1 is used as a solid catalyst component, 3.1 g / hour, triethylaluminum 1. 7 g / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization vessel, propylene was supplied at 50 kg / hour, ethylene was supplied at 0.3 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.18 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.
The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization reactor, propylene was supplied at 12 kg / hour, ethylene was supplied at 0.2 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.18 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 reactor, propylene was supplied at 10 kg / hour, ethylene was supplied at 0.1 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.18 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 polymerization was performed in the same manner as in Example 1 except that the polymerization method was changed as follows.
1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 L, propylene is 50 kg / hour, hydrogen is 5 NL / hour, the catalyst slurry produced in 3) of Example 1 is used as a solid catalyst component, 3.1 g / hour, triethylaluminum 1. 7 g / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. 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. Propylene was supplied to the polymerization vessel at 10 kg / hour, hexene-1 was supplied at 5 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 66 ° 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.

[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 further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

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

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

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

2) Production of prepolymerization catalyst 56 g of transition metal catalyst component, 20.7 mL of triethylaluminum, 7.0 mL of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, and 80 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 L. 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 obtained 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 supplied as a solid catalyst component at 0.9 g / hour, triethylaluminum 19.2 g / hour, and dicyclopentyldimethoxysilane 2.6 mL / hour, and 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.

[Comparative Example 2]
The polymerization was carried out in the same manner as in Comparative Example 1 except that the polymerization method was changed as follows.
1) Main polymerization It was sent to a vessel polymerization vessel with a stirrer having an internal volume of 1000 L, and propylene was supplied at 133 kg / hour, ethylene was supplied at 0.3 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 10.3 mol%. . The catalyst slurry produced in 2) of Comparative Example 1 was continuously supplied as a solid catalyst component at 0.8 g / hour, triethylaluminum 19.2 g / hour, and dicyclopentyldimethoxysilane 2.3 mL / hour, and a polymerization temperature of 70 ° 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 25 kg / hour, ethylene was supplied at 0.2 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 6.9 mol%. Polymerization was carried out at a polymerization temperature of 70 ° 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. Propylene was supplied to the polymerization vessel at 20 kg / hour, ethylene was supplied at 0.1 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 5.2 mol%. Polymerization was performed at a polymerization temperature of 70 ° 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 polymerization was performed in the same manner as in Example 1 except that the polymerization method was changed as follows.
1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 L, propylene is 50 kg / hour, hydrogen is 5 NL / hour, the catalyst slurry produced in 3) of Example 1 is used as a solid catalyst component, 3.1 g / hour, triethylaluminum 1. 7 g / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.3 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, ethylene was supplied at 0.9 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.21 mol%. Polymerization was carried out at a polymerization temperature of 72 ° C. and a pressure of 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 12 kg / hour, ethylene was supplied at 0.6 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 0.21 mol%. Polymerization was performed at a polymerization temperature of 71 ° 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 10 kg / hour, ethylene was supplied at 0.3 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.21 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.0 MPa / G. Part of the powder was sampled, and the powder of the first step completed was analyzed.

  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 polymerization was performed in the same manner as in Example 1 except that the polymerization method was changed as follows.
1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 L, propylene is 50 kg / hour, hydrogen is 5 NL / hour, the catalyst slurry produced in 3) of Example 1 is used as a solid catalyst component, 3.1 g / hour, triethylaluminum 1. 7 g / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.3 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, ethylene was supplied at 0.9 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.21 mol%. Polymerization was carried out at a polymerization temperature of 72 ° C. and a pressure of 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 12 kg / hour, ethylene was supplied at 0.6 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 0.21 mol%. Polymerization was performed at a polymerization temperature of 71 ° 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 10 kg / hour, ethylene was supplied at 0.3 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.21 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.0 MPa / G. Part of the powder was sampled, and the powder of the first step completed was analyzed.

  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 reactor, propylene was supplied at 10 kg / hour, butene-1 was supplied at 5 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 65 ° 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 polymerization was performed in the same manner as in Example 1 except that the polymerization method was changed as follows.
1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 L, propylene is 50 kg / hour, hydrogen is 5 NL / hour, the catalyst slurry produced in 3) of Example 1 is used as a solid catalyst component, 3.1 g / hour, triethylaluminum 1. 7 g / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. 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. Propylene was supplied to the polymerization vessel at 10 kg / hour, hexene-1 was supplied at 5 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 66 ° 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 polymerization was performed in the same manner as in Example 1 except that the polymerization method was changed as follows.
1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 L, propylene is 15 kg / hour, hydrogen is 1.5 NL / hour, the catalyst slurry produced in 3) of Example 1 is used as a solid catalyst component, 0.8 g / hour, triethylaluminum. 0.4 g / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 100 L, and further polymerized. Hydrogen was supplied to the polymerization vessel so that propylene was 10 kg / hour and 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. Part of the powder was sampled, and the powder of the first step completed was analyzed.

  The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 L, gasified and subjected to gas-solid separation, and then a polypropylene homopolymer powder was sent to a 480 L gas phase polymerization vessel, where both ethylene / propylene blocks were mixed. Polymerization was performed. Propylene, ethylene, hydrogen so that the gas composition in the gas phase polymerizer is ethylene / (ethylene + propylene) = 0.5 (molar ratio), hydrogen / (ethylene + propylene) = 0.003 (molar ratio) Was fed continuously. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.3 MPa / G. The resulting propylene copolymer was vacuum dried at 80 ° C.

[Comparative Example 3]
The polymerization was carried out in the same manner as in Comparative Example 1 except that the polymerization method was changed as follows.
1) Main polymerization It was sent to a vessel polymerization vessel with an internal volume of 1000 L and equipped with a stirrer, and propylene was supplied at 133 kg / hour, ethylene at 0.9 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 15.8 mol% . The catalyst slurry produced in 2) of Comparative Example 1 was continuously fed as a solid catalyst component at 0.7 g / hour, triethylaluminum 19.2 g / hour, and dicyclopentyldimethoxysilane 2.0 mL / hour, and a polymerization temperature of 64 ° 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. To the polymerization reactor, propylene was supplied at 25 kg / hour, ethylene was supplied at 0.6 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 10.6 mol%. Polymerization was performed at a polymerization temperature of 66 ° 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, ethylene was supplied at 0.3 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 8.0 mol%. Polymerization was performed at a polymerization temperature of 67 ° C. and a pressure of 3.3 MPa / G. Part of the powder was sampled, and the powder of the first step completed was analyzed.

  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 propylene polymer of the present invention is a polypropylene polymer with few n-decane insoluble components and excellent physical properties.

Claims (3)

A polymerization apparatus in which two or more reactors are connected in series, and diphenylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride are included. With catalyst,
A portion (D) soluble in room temperature n-decane by (co) polymerizing propylene (Mp) and optionally one or more olefins (Mx) selected from ethylene and α-olefins having 4 or more carbon atoms (D) the concentration of _'sol) is not more than 2.0 wt% and (step of producing a co) polymer ([step 1]),
Propylene (Mp) and one or more olefins (Mx) selected from ethylene and α-olefins having 4 or more carbon atoms are copolymerized, and a portion insoluble in room temperature n-decane (D ′ _insol ) is 2.0 wt%. Obtained by continuously carrying out the following step ([Step 2]) for producing a copolymer,
One kind selected from propylene (Mp) and ethylene and an α-olefin having 4 or more carbon atoms, comprising a part soluble in room temperature n-decane (D _sol ) and a part insoluble in room temperature n-decane (D _insol ) more obtained from olefin (Mx), propylene-based polymer characterized by satisfying the following requirements (1) to (4) simultaneously.
(1) Both _Gsol molecular weight distribution (Mw / Mn) of D _sol and D _insol are 4.0 or less.
(2) The molar concentration of the skeleton derived from the olefin (Mx) in D _sol is 25 to 39 mol%.
(3) The weight concentration of the skeleton derived from the olefin (Mx) in D _insol is 2.0 wt% or less.
(4) Intrinsic viscosity _{D sol ([η] (dl} / g)) is Ru der 1.5 or more.   The propylene-based polymer according to claim 1, wherein the one or more olefins (Mx) selected from ethylene and an α-olefin having 4 or more carbon atoms are one kind of ethylene. The olefin used in the [Step 1] is only one propylene (Mp), and the olefin used in the [Step 2] is a mixed olefin of propylene (Mp) and ethylene. Item 2. The propylene polymer according to Item 1 .