JP4828172B2 - Olefin polymer particles and process for producing olefin polymer particles - Google Patents

Description

  The present invention relates to olefin polymer particles and a method for producing the same. Specifically, the present invention relates to olefin copolymer particles having a high melting point, high stereoregularity, and high molecular weight, and a method for producing the same.

A highly crystalline polyolefin obtained by polymerizing olefins in the presence of a polymerization catalyst containing a metallocene compound (hereinafter sometimes referred to as “metallocene catalyst”) is excellent in rigidity and heat resistance as a thermoplastic resin. Widely used as a material. On the other hand, in the conventional process using silica as a carrier, it is impossible to obtain a highly stereoregular polymer due to distortion in the metallocene complex. It was done. This is also the case with copolymerization, and it was difficult to regularly introduce long-chain branches of C ₆ or more. In addition, due to the use of silica, it has been difficult to reduce the amount of ash in the final product. Therefore, all kinds of olefin polymerization are possible, high stereoregularity, a process for producing olefin polymer particles having a low ash content, and the appearance of a polymer have been awaited.

  An object of the present invention is to provide an olefin polymer particle having a high stereoregularity, a high melting point, a high molecular weight and a low ash content, and a method for producing the polymer particle.

The olefin polymer particles of the present invention are characterized by satisfying the following requirements (1) to (5) simultaneously.
(1) The molecular weight distribution (Mw / Mn) measured by GPC is 4.0 or less,
(2) The minimum particle size of the polymer particles is 3 μm or more, the average particle size is 20 μm or more, (3) the ash content of the polymer particles is 2000 ppm by weight or less,
(4) The Si content of the polymer particles is 10 ppm by weight or less,
(5) The polymer particles contain a contact product of an aluminoxane and a diol compound represented by the following general formula [I].

^{H-O-R 1 -O-} H ... [I]
(In the above general formula [I], R ¹ is an alkylene group having 1 to 20 carbon atoms, and at least one hydrogen atom bonded to carbon is an aryl group, a halogen atom, a halogen-containing hydrocarbon group or an acyl group. May be substituted.)
The olefin polymer particles of the present invention are polymer particles obtained from propylene, and the n-decane soluble component at room temperature is preferably 2 wt% or less.

The method for producing olefin polymer particles of the present invention is characterized by including the following step 1.
[Step 1]: Transition metal compound (A) and
A contact product of an aluminoxane (B) and a diol compound (C) represented by the following general formula [I],
A step of polymerizing at least one olefin selected from ethylene and an α-olefin having 3 or more carbon atoms in the presence of an olefin polymerization catalyst.

^{H-O-R 1 -O-} H ... [I]
(In the above general formula [I], R ¹ is an alkylene group having 1 to 20 carbon atoms, and at least one hydrogen atom bonded to carbon is an aryl group, a halogen atom, a halogen-containing hydrocarbon group or an acyl group. May be substituted.)
In the method for producing olefin polymer particles of the present invention, the following step 2 is carried out after step 1 described above.
And step 3 are preferably performed sequentially.
[Step 2]: a step of contacting a polyoxyalkylene compound having one alcoholic hydroxyl group in the molecule represented by the following general formula [II]:
_{H-O- [CH 2 -CH (} R 1) -O] m -R 2 ... (II)
(In the above general formula [II], R ¹ and R ² are selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. (M represents the average number of repeating units and is in the range of 1 to 100.)
[Step 3]: A step of recovering the olefin polymer particle part by removing the liquid phase part after contacting the aliphatic hydrocarbon having 5 to 10 carbon atoms.

In the method for producing olefin polymer particles of the present invention, it is also preferable that the following step 2 ′ and step 3 ′ are sequentially performed after the step 1.
[Step 2 ′]: Step of dissolving in an aliphatic hydrocarbon having 5 to 10 carbon atoms,
[Step 3 ']: A step of contacting the acidic alcohol to precipitate a polymer and recovering the olefin polymer particle part.

  According to the present invention, it is possible to provide an olefin polymer particle having a high stereoregularity, a high melting point, a high molecular weight and a low ash content, and a method for producing the polymer particle.

Hereinafter, the olefin polymer particles of the present invention and the method for producing the olefin polymer particles will be specifically described.
Olefin polymer particles The olefin polymer particles of the present invention satisfy the following requirements (1) to (5) simultaneously.
(1) The molecular weight distribution (Mw / Mn) measured by GPC is 4.0 or less. The molecular weight distribution (Mw / Mn) is preferably 3.5 or less, more preferably 3.0 or less. The molecular weight distribution is
Olefin polymer particles in this range exhibit the property of monodispersion.
(2) The minimum particle size of the polymer particles is 3 μm or more, and the average particle size is 20 μm or more. Preferably, the minimum particle size of the polymer particles is 5 μm or more, and the average particle size is 50 μm or more. Polymer particles satisfying this particle size range are preferably used industrially from the viewpoint of transport.
(3) The ash content of the polymer particles is 2000 ppm by weight or less. Preferably, the ash content of the polymer particles is 1500 ppm by weight or less. An ash content within this range is preferable in terms of processing characteristics.
(4) The Si content of the polymer particles is 10 ppm by weight or less. Preferably, the Si content of the polymer particles is 1 ppm by weight or less, more preferably 0.1 ppm by weight or less. Polymer particles having an Si content in this range are preferred from the viewpoint of processing characteristics.
(5) The polymer particles contain a contact product of an aluminoxane and a diol compound represented by the following general formula [I].

^{H-O-R 1 -O-} H ... [I]
(In the above general formula [I], R ¹ is an alkylene group having 1 to 20 carbon atoms, and at least one hydrogen atom bonded to carbon is an aryl group, a halogen atom, a halogen-containing hydrocarbon group or an acyl group. May be substituted.)
Such diol compounds include ethylene glycol, 1,2-propanediol, 1,
3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10 -Decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc. can be exemplified, but from the viewpoint of solubility in aliphatic hydrocarbons and aromatic hydrocarbons, 1,9-nonanediol, 1 1,10-decanediol is preferably used.

  The olefin polymer particles of the present invention are usually composed of a polymer produced by polymerization of olefin, the above contact product, and a metallocene compound described later, but the coexistence of other optional components within a range not impairing the present invention. Permissible.

As the aluminoxane used in the present invention, specifically, the following general formula [III]
And / or a compound represented by [IV].

(In the general formula [III] or [IV], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.)
Among these, in the above general formula [III] or [IV], R is a methyl group, and n is 3 or more,
Preferably, 10 or more methylaluminoxanes are preferably used. These aluminoxanes may be mixed with some organoaluminum compounds. The aluminoxane used in the present invention may be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687, or an organoaluminum described in JP-A-2-167305. Oxy compounds, aluminoxanes having two or more kinds of alkyl groups described in JP-A-2-24701 and JP-A-3-103407 can also be suitably used.

Among the olefin polymer particles of the present invention, a highly industrially useful form is a polymer obtained from propylene, and the n-decane soluble component at room temperature is 2 wt% or less, preferably 0.01 wt%. The propylene polymer particles are as follows. Such propylene polymer particles include not only homopropylene particles but also polymers obtained from propylene (P) and olefin (X) different from propylene. (Here, X (mol) / (X (mol) + P (mol)) is 0.2 to 1.0, preferably 0.1 to 1.0.)
Process for producing olefin polymer particles
The method for producing olefin polymer particles of the present invention includes the following step 1.
[Step 1]: Transition metal compound (A) and
A contact product of an aluminoxane (B) and a diol compound (C) represented by the following general formula [I],
A step of polymerizing one or more olefins selected from ethylene and an α-olefin having 3 or more carbon atoms in the presence of an olefin polymerization catalyst comprising:

^{H-O-R 1 -O-} H ... [I]
(In the above general formula [I], R ¹ is an alkylene group having 1 to 20 carbon atoms, and at least one hydrogen atom bonded to carbon is an aryl group, a halogen atom, a halogen-containing hydrocarbon group or an acyl group. May be substituted.)
In the method for producing olefin polymer particles of the present invention, the following step 2 is carried out after step 1 described above.
And step 3 are preferably performed sequentially.
[Step 2]: a step of contacting a polyoxyalkylene compound having one alcoholic hydroxyl group in the molecule represented by the following general formula [II]:
_{H-O- [CH 2 -CH (} R 1) -O] m -R 2 ... (II)
(In the above general formula [II], R ¹ and R ² are selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. (M represents the average number of repeating units and is in the range of 1 to 100.)
[Step 3]: A step of recovering the olefin polymer particle part by removing the liquid phase part after contacting the aliphatic hydrocarbon having 5 to 10 carbon atoms.

In the method for producing olefin polymer particles of the present invention, it is also preferable that the following step 2 ′ and step 3 ′ are sequentially performed after the step 1.
[Step 2 ′]: Step of dissolving in an aliphatic hydrocarbon having 5 to 10 carbon atoms,
[Step 3 ']: A step of contacting the acidic alcohol to precipitate a polymer and recovering the olefin polymer particle part.

According to such a method for producing olefin polymer particles of the present invention, the above-described olefin polymer particles of the present invention can be suitably produced.
Below, each process is demonstrated in detail.
Process 1
Step 1 is an olefin polymerization catalyst comprising a transition metal compound (A) and a contact product (hereinafter also referred to as contact product I) of the aluminoxane (B) and the diol compound (C) represented by the general formula [I]. Is a step of polymerizing one or more olefins selected from ethylene and an α-olefin having 3 or more carbon atoms.

^{H-O-R 1 -O-} H ... [I]
(In the above general formula [I], R ¹ is an alkylene group having 1 to 20 carbon atoms, and at least one hydrogen atom bonded to carbon is an aryl group, a halogen atom, a halogen-containing hydrocarbon group or an acyl group. May be substituted.)
The transition metal compound (A), which is an essential component of the olefin polymerization catalyst 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 preferably is a group 4 to 6 in the periodic table. Transition metal compounds such as transition metal halides, transition metal alkylates, transition metal alkoxylates, non-crosslinkable or crosslinkable metallocene compounds of Groups 4-6 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.

Preferred transition metal compounds (A) include non-crosslinkable or crosslinkable metallocene compounds, which are transition metal compounds of Group 4 of the periodic table having a cyclopentadienyl skeleton. The compounds represented can be exemplified.

ML _x ... [V]
In the formula [V], M represents one transition metal atom selected from Group 4 of the periodic table, preferably zirconium, titanium or hafnium. x is the valence of the transition metal and represents the number of L. L represents a ligand or group coordinated to the transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and other than the ligand having the cyclopentadienyl skeleton. L is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO ₃ R (where R is a carbon which may have a substituent such as halogen) A hydrocarbon group having 1 to 8 atoms), a halogen atom, and one kind of 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 [V] includes two or more ligands having a cyclopentadienyl skeleton, among the ligands having two cyclopentadienyl skeletons, 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-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1 -(2,7-dimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, rac-dimethylsilylene -Bis {1- (2,7-dimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride, rac-diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium Dichloride, rac-di (i-propyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (n-butyl) silyle -Bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (cyclohexyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl) )} Zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,7-dimethyl) -4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7-
Dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1 -(2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride Rac-di (p-chlorophenyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-ethylindenyl)} zirconium dibromide, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4 -Ethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2 , 3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-butylindenyl)} zirconium dichloride, rac -Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-sec-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-t -Butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2 , 3,7-trimethyl-4-n-pentylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-hexylindenyl)} zirconium dichloride, rac -Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-methylcyclohexylindene) Nyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2,3,7-trimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-phenyl) Dichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-diethylsilylene-bis {1- (2 , 3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl) } Zirconium Dichlor Rac-di (n-butyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (cyclohexyl) silylene-bis {1- ( 2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride Rac-methylphenylsilylene-bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-trimethyl- 4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1 -(2,3,7-trimethyl-4-ethylindenyl)} zirconium Chloride, 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-bis (methanesulfonate), rac-dimethyl Silylene-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)} titanium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-i -Propyl-7-methylindenyl)} hafnium dichloride and the like.

  Furthermore, as the transition metal compound (A), a crosslinkable metallocene compound represented by the general formula [VI] is also preferably used.

In the general formula [VI], 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 and adamantyl group; cyclic unsaturated carbonized groups such as phenyl group, tolyl group, naphthyl group, biphenyl group, phenanthryl group and anthracenyl group A hydrogen group; Saturated hydrocarbon group substituted with cyclic unsaturated hydrocarbon group such as benzyl group, cumyl group, 1,1-diphenylethyl group, triphenylmethyl group; methoxy group, ethoxy group, phenoxy group, furyl group, N-methylamino A heteroatom-containing hydrocarbon group such as a 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. Further, 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 [VI], 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 hydrocarbon groups described above. More preferably, R ³ is a hydrocarbon group having 1 to 20 carbon atoms.

In the general formula [VI], 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 hydrocarbon groups described above. The adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring.

In the general formula [VI], Y that bridges the cyclopentadienyl ring and the fluorenyl ring is preferably a group 14 element, more preferably carbon, silicon, or germanium, and further preferably a carbon atom. R ¹³ and R ¹⁴ substituted for Y are preferably a hydrocarbon group having 1 to 20 carbon atoms. These may be the same 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 hydrocarbon groups described above. 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, 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 [VI], M is preferably a Group 4 transition metal, more preferably Ti, Zr, Hf and the like. Q is selected from the same or different combinations from halogen, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other. Specific examples of the halogen include fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group include those described above.

Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by lone pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy. And ethers such as ethane. At least one Q is preferably a halogen or an alkyl group.

The crosslinkable metallocene compound represented by the general formula [IV] is specifically described as follows: 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 (pn-butylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butyl Fluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-tri ) Methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

(p-Tolyl) (phenyl) methylene (cyclopentadienyl) (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (cyclo Pentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tert-butylphenyl)
Methylene (cyclopentadienyl) (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (cyclopentadienyl) (octamethyloctahydro Dibenzofluorenyl) zirconium dimethyl, (p-tolyl) (phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopenta Dienyl) (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) ( Eniru) methylene (cyclopentadienyl) (3,6-di-tert- butyl fluorenyl) 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 (cyclopentadienyl) (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-dimethylfluoride) Oleenyl) 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-dimethylfluoro) Olenyl) zirconium dichloride, (p-n-ethylphenyl) (phenyl) methylene (cyclopentadienyl) (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,

Cyclopentylidene (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 (cyclopentadienyl) (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, cycl Butylidene (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, cyclopropylidene (cyclopentadienyl) (3,6-ditert-
Fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclohexyl Silidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride,

Cyclopropylidene (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, Si Lopentylidene (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 dichloride, cycloheptylidene (cyclopentadienyl) (3,6-diphenyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-dibenzyl-fluorenyl) zirconium dichloride, cyclobutyl Liden (cyclopentadienyl) (3,6-dibenzyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-dibenzyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) ( 3,6-dibenzyl-
Fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-dibenzyl-fluorenyl) zirconium dichloride,

Cyclopropylidene (cyclopentadienyl) (3,6-difluoro-fluorenyl) zirconium dichloride, cyclobutylidene (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, cyclopentyl Reden (Clopentadienyl) (3,6-dibromo-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-dibromo-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3 , 6-Dibromo-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dibromide, cyclobutylidene (cyclopentadienyl) (3,6-ditert- Fluorenyl) zirconium dibromide, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dibromide, cyclohexylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium di Bromide, cycloheptylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) Zirconium dibromide, cyclopropylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cyclobutylidene
(Cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentadienyl) (3 , 6-Dimethyl-fluorenyl) zirconium dimethyl, cycloheptylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cyclopropylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) ) Hafnium dichloride,

Cyclobutylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) hafnium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) hafnium dichloride, cyclohexylidene (cyclopenta Dienyl) (3,6-ditert
-Fluorenyl) hafnium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) titanium dichloride , Cyclobutylidene (
(Cyclopentadienyl) (3,6-ditert-fluorenyl) titanium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) ( 3,6-ditert-fluorenyl) titanium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-ditert-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, cyclohexyl Den (cyclopentadienyl) (2,7-dimethyl-fluoreni ) Zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dichloride, cyclo Butylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadiene) Enyl) (2,7-ditert-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dichloride,
Cyclopropylidene (cyclopentadienyl) (2,7-dicumyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-dicumyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) ) (2,7-dicumyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-dicumyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-dicumyl) -Fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-di (trimethylsilyl) -fluorenyl ) Zirconium dichloride, Si Lopentylidene (cyclopentadienyl) (2,7-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cycloheptylidene (Cyclopentadienyl) (2,7-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-diphenyl-fluorenyl) zirconium dichloride, cyclobutylidene (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,

Cyclopropylidene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) ) (2,7-dibenzyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-dibenzyl) -Fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-difluoro-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-difluoro-fluorenyl) zirconium dichloride, cyclopentylide (Cyclopentadienyl) (2,7-difluoro-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-difluoro-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) ( 2,7-difluoro-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-dibromo-fluorenyl) 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, cyclopentylidene ( Cyclopentadienyl) (2,7-ditert-
Fluorenyl) zirconium dibromide, cyclohexylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dibromide, cycloheptylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium Dibromide, cyclopropylidene
(Cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dimethyl, cyclobutylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) (2 , 7-dimethyl-fluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dimethyl, cycloheptylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) Zirconium dimethyl, cyclopropylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) hafnium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) hafnium dichloride, cyclopentylidene (Cyclopentadienyl) (2,7-ditert-fluorenyl) Hough Um dichloride, cyclohexylidene (cyclopentadienyl) (2,7-di tert-fluorenyl) hafnium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-di tert-fluorenyl) titanium dichloride, cyclopropyl Liden (cyclopentadienyl) (2,7-ditert-fluorenyl) Titanium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-ditert
-Fluorenyl) titanium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) titanium dichloride, Cycloheptylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) titanium dichloride,

Cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclopentylidene (cyclopenta Dienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (octa Methyloctahydrodibenzofluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclobuty Liden (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclohexylidene (cyclopenta (Dienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide,
Cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadiene) (Dienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cycloheptylidene (cyclopentadienyl) (octa Methyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, cyclobutylidene (cyclopentylene) Tadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctayl) Hydrodibenzofluorenyl)
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 ( Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di-n-butylmethylene (Cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (octahydrodibenzo Fluorenyl)
Zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium Dichloride, diisobutylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diisobutylmethylene ( Cyclopentadienyl) (benzofluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (octahydro Benzofluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (octamethyl-tetrahydrodicyclopentadiene fluorenyl) zirconium dichloride,

Dibenzylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) ( Dibenzofluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride Lido,

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 (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) di Conium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium Dichloride, di (benzhydryl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (benzhydryl) methyle (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-butylfluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) ) Zirconium dichloride, di (
Cumyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) ( Octahydrodibenzofluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl)
Zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) ( Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (
Cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene ( Cyclopentadienyl)
(Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,

Di (cyclohexylmethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (3,6-ditert-butylful Olenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium Dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (cyclo Xylmethyl) methylene (cyclopentadienyl) (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-butylfluorene) Nil)
Zirconium dichloride, di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (benzofluorene) Nyl) zirconium dichloride, di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (1-cyclohexyl-ethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorene Nyl) 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-butylfull Olenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium Dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (cyclo Nethylmethyl) 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-butylfluoride) Oleenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (1-cyclopentyl-ethyl) methylene (cyclopentadienyl) ( Benzofluorenyl) zirco Um 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) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,

Di (naphthylmethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfull Olenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium Dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (
Naphthylmethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclo Pentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di ( Biphenylmethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene ( Cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) ( (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,

(Benzyl) (phenethyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (benzyl) (phenethyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (benzyl ) (Phenethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (phenethyl) methylene (cyclopentadienyl) (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-butylfluorenyl) zirconium dichloride,

(Benzyl) (cumyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorene Nyl) 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-butylfluoreni ) Titanium dichloride, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) Titanium dichloride, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Titanium dichloride Dibenzylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride Dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-ditert-
Butylfluorenyl) zirconium dibromide, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) Zirconium dibromide, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzo Fluorenyl) Zirconium dibromide, dibenzylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Zirconium dimethyl, dibenzylmethylene (cyclopentadienyl) (3,6-ditert- Butyl fluorenyl) 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, dimethylmethylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dimethyl, dimethylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dimethyl, dimethylmethylene (cycline) (Lopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, dimethylmethylene ( Cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,

Dimethylsilylene (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 (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, dimethyl Silylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dimethyl, dimethylsilylene ( Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (benzofluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (dibenzofluorenyl) zirconium Dimethyl, dimethylsilylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dimethyl,

Cyclopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, Adamantylidene (cyclopentadienyl) (2,7
-Di-tert-butylfluorenyl) zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (2,7 -Ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) ( 2,7-ditert-butylfluorenyl) zirconium dichloride, diethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3 , 6-Ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6 Ditert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (3,6 -Di-tert-butylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-di) tert-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- tert-butylfluorenyl) hafnium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, adamantylidene (cyclopentadienyl) (2,7-di tert-butylfluorenyl) hafnium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-di) tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2, 7-ditert-butylfluorenyl) hafnium dichloride, diethylmethylene (cyclopentadienyl) (2,7-ditert-butyl (Luolenyl) hafnium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorene) Nyl) titanium dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (2,7-ditert-butylfullyl) Olenyl) titanium dichloride, dimethylmethylene (cyclopentadienyl)
(2,7-ditert-butylfluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, di (p-tolyl) methylene (cyclopenta Dienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, diethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride,

Isopropylidene (3,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, Isopropylidene (3,5-
Dimethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (3,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, Isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert- Butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-diter
t-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-
Butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, isopropylidene (3- (2-adamantyl) -5-
Methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, isopropyl Riden (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (3- (2-adamantyl) -5-methyl-
Cyclopentadienyl) (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-di-) tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-ethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl- 2,5-dimethyl Cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, isopropylidene ( 3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (3,6
-Di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-
tert-butyl-2,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

Diphenylmethylene (3,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, Diphenylmethylene (3,5-dimethyl-cyclopentadienyl) (3,6-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, diphenylmethylene (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-butylfull Olenyl) zirconium dichloride, diphenylmethylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3- (2- Adamantyl) -5-methyl-cyclopentadie ) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5- Ethyl-cyclopentadienyl) (2,7-diter
t-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert
-Butyl-5-ethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (octamethylocta Hydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-ter
t-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-di tert-butylfluorenyl) zirconium dichloride, di (p
-Tolyl) methylene (3,5-dimethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3,5-dimethyl-cyclopentadienyl) ) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-
Butyl-5-methyl-cyclopentadienyl) (3,6-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-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) Methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di p-tolyl) methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl- 5-ethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (2,7-dit
ert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3
-Tert-butyl-5-ethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-5-ethyl-cyclopenta) Dienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p -Tolyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-tert- Butyl-2,5-dimethyl-cyclopentadienyl) (3,6-dite)
rt-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (3-
tert-butyl-2,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

Di (p-tert-butylphenyl) methylene (3,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3,5-dimethyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3,5-dimethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) ) Zirconium dichloride, di (p-tert-butylphenyl) methylene (3,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene ( 3-tert-butyl-5-methyl-cyclopentadienyl) (fluoreni ) Zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p- te
rt-butylphenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (pt
ert-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-butylfluore Nyl) zirconium dichloride, di (p-te)
rt-butylphenyl) methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p
-Tert-butylphenyl) methylene (3- (2-adamantyl) -5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3 -Tert-butyl-5-ethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (2,7 -Ditert-butylfluorenyl) zirconium dichloride, di (p-te)
rt-butylphenyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (pt
ert-butylphenyl) methylene (3-tert-butyl-5-ethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert- Butyl-2,5-dimethyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (2, 7-ditert-butylfluorenyl) zirconium dichloride, di (p-te)
rt-butylphenyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p
-Tert-butylphenyl) methylene (3-tert-butyl-2,5-dimethyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

(Methyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadiene) Enyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3-ter
t-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadi) Enyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (p-tolyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride,
(P-tolyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (p-
Tolyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (phenyl) methylene (3- tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Dibenzylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, dibenzylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-di tert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (3 -Tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, fluorenylidene (3-
tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, fluorenylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium Dichloride, 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) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, diphenylmethylene (3-ter
t-butyl-5-methyl-cyclopentadienyl) (fluorenyl) titanium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) Titanium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) titanium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-) Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (3-ter
t-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. The transition metal compound (A) used in the present invention is not limited to the above exemplified compounds.

The olefin polymerization catalyst used in Step 1 includes a contact product I which is a contact product of an aluminoxane (B) and a diol compound (C) represented by the following general formula [I].
^{H-O-R 1 -O-} H ... [I]
(In the above general formula [I], R ¹ is an alkylene group having 1 to 20 carbon atoms, and at least one hydrogen atom bonded to carbon is an aryl group, a halogen atom, a halogen-containing hydrocarbon group or an acyl group. May be substituted.)
As the aluminoxane (B), the compound represented by the general formula [III] or [IV] described above in the olefin polymer particles, a benzene-insoluble organoaluminum oxy compound, an aluminoxane having two or more kinds of alkyl groups, and the like are used. be able to. As the diol compound (C), any of the compounds represented by the above general formula [I] can be used. Preferably, in the above general formula [I], R 1 is an alkylene group having 2 to 15 carbon atoms. Can be used. Examples of the diol compound (C) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, Examples include 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and the like. From the viewpoint of solubility in hydrocarbons and aromatic hydrocarbons, 1,9-nonanediol and 1,10-decanediol are preferably used.

Contact between the aluminoxane (B) represented by the general formula [III] or [IV] and the diol compound (C) represented by the general formula [I] is usually performed in an inert gas atmosphere in a hydrocarbon solvent. It is carried out under heating and stirring. When contacting, the ratio of the number of moles of aluminum atoms (α) contained in the aluminoxane (B) to the number of moles (β) of the diol compound (C), that is, (α / β) is usually 1/5000 to 2 / 1. Contact is preferably made to be 1/2000 to 1/5. When contacting, it is also possible to use the aluminoxane (B) and the diol compound (C) after dissolving them in a hydrocarbon solvent used at the time of contact. The hydrocarbon solvent has a boiling point of 40 to 150 ° C at normal pressure.
And a solvent excellent in dissolving power between the aluminoxane (B) and the diol compound (C) is preferably used. Usually, aromatic hydrocarbons such as toluene are preferably used. As the contact order, a method of slowly adding the diol compound (C) to the aluminoxane (B) is usually used. The contact temperature is usually 40 to 150 ° C., preferably 50 to 120 ° C., and the contact time is usually 1 minute to 600 minutes, preferably 30 minutes to 300 minutes. After the contact, the contact material I dissolved in the hydrocarbon solvent is usually used without separating and removing the hydrocarbon solvent.

The olefin polymerization catalyst used in Step 1 may contain, as an optional component, for example, an organic compound component (D) such as alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates disclosed in WO2004 / 29062. it can. The olefin polymerization catalyst may contain an organometallic compound (E) as disclosed in WO2004 / 29062. Specific examples of such an organometallic compound (E) include the following (Ea), (
Organometallic compounds of Groups 1 and 2 and Groups 12 and 13 of the periodic table, such as Eb) and (Ec), are used.

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

(Eb): General formula M ² AlR ^a ₄
(Wherein M ² represents Li, Na or K, and Ra represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) Complex alkylated product with aluminum. Examples of such a compound include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

(Ec): 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. .) Periodic table 2nd
A dialkyl compound of a Group 12 or Group 12 metal.

  When the organometallic compound (E) is used in combination, an organoaluminum compound is preferable. Moreover, such an organometallic compound (E) may be used individually by 1 type, and may be used in combination of 2 or more type.

In step 1, olefin polymerization is carried out in the presence of an olefin polymerization catalyst containing the transition metal compound (A), the contact material I described above, and optional components used as necessary.
When performing olefin polymerization using the olefin polymerization catalyst as described above, the transition metal compound (A) is usually 10 ⁻⁸ to 10 ⁻² mol, preferably 10 ⁻⁷ to 10 ⁻ , per liter of reaction volume. It is used in such an amount that it becomes ³ mol. The amount of contact I used between the aluminoxane (B) and the diol compound (C) represented by the above general formula [I] is determined by the number of moles (γ) of aluminum atoms in the contact I and the transition metal compound ( It is used in such an amount that the molar ratio (γ / δ) to the number of moles (δ) of the transition metal atom in A) is usually 10 to 5,000, preferably 20 to 2,000.

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. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

In the present invention, when the polyolefin is produced using the above-mentioned olefin polymerization catalyst, preliminary polymerization 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, allyltoluene Olefins having a branched structure such as allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes, and the like may be used, and these may be copolymerized. Of these, ethylene and propylene are particularly preferably used.

  The prepolymerization is carried out by adding the prepolymerized olefin and the above catalyst components to an inert hydrocarbon medium such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene and other aliphatic hydrocarbons. Preferably it is done.

The olefin monomer supplied to the olefin polymerization reaction in the present invention will be described in detail. One or more olefins selected from propylene, ethylene and an α-olefin having 4 or more carbon atoms are (co) polymerized to produce a (co) polymer. The α-olefin having 4 or more carbon atoms is a linear or branched α-olefin having 4 to 50 carbon atoms, preferably 4 to 10 carbon atoms, 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-eicosene and the like can be mentioned. Furthermore, the polymerization of metal alcoholates of these monomers is also possible. Also, a cyclic olefin having 4 to 30, 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) α, β-unsaturated carboxylic acids such as 5-heptene-2,3-dicarboxylic anhydride, and 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, 2-ethylhexyl acrylate, meta Α, β-unsaturated carboxylic acid esters such as methyl laurate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; vinyl acetate, vinyl propionate, vinyl caproate, Examples include vinyl esters such as vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; unsaturated glycidyl such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate. Also, 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; functional groups such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene Polymerization can also be carried out in the reaction system by containing a styrene derivative containing; and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like.
As the polymerization method, processes such as gas, bulk, and slurry can be used.

As described above, among the olefin polymers of the present invention, the industrially valuable form is a polymer obtained from propylene. Such propylene polymer particles include not only homopropylene particles but also polymers obtained from propylene (P) and olefin (X) different from propylene. [Where X (mol) / [X (mol) + P (mol)] is 0.2 to 1.0, preferably 0.1 to 1.0. ]
In the olefin polymerization according to the present invention, it is possible to use a polymerization machine composed of two or more polymerization stages.

In the first preferred embodiment of the method for producing olefin polymer particles according to the present invention, Step 2 and Step 3 are sequentially performed after Step 1 above.
Process 2
In step 2, a polyoxyalkylene compound having one alcoholic hydroxyl group in the molecule represented by the following general formula [II] is applied to the olefin polymer after completion of step 1 (in the following description,
Sometimes simply referred to as “polyoxyalkylene compound”. ). In addition, the contact thing obtained by this contact is also called "contact thing II" in the following description.

_{H-O- [CH 2 -CH (} R 1) -O] m -R 2 ... (II)
(In the above general formula [II], R ¹ and R ² are selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. (M represents the average number of repeating units and is in the range of 1 to 100.)
Specific examples of such polyoxyalkylene compounds include polyoxyethylene isopropyl ether (also known as “polyethylene glycol monoisopropyl ether”), polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyalkylene lauryl ether, polyoxyethylene. Isodecyl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene styrenated phenyl ether,
Polyoxyethylene oleate, polyoxyethylene distearate, polyoxyalkylene glycol, sorbitan sesquioleate, sorbitan monooleate, sorbitan monostearate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester, polyoxyethylene alkylamine ether, polyethylene glycol alkyl ether, polyethylene glycol monolaurate, polyethylene glycol monostearate , Polyethylene glycol monooleate, polyethylene glycol sol Tan monolaurate, polyethylene glycol sorbitan monooleate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol isopropyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol isopropyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether And triethylene glycol isopropyl ether. These polyalkylene compounds can be used alone or in combination of two or more.

In the nomenclature of the exemplified compounds described above, “poly” means m = 1 in the above general formula [II].
The compounds corresponding to ˜100 are collectively used. For example, when R ¹ = hydrogen atom and R ² = methyl group are fixed, m = 1 is monoethylene glycol methyl ether and m = 2 is diethylene glycol methyl ether.

The polyoxyalkylene compound used in step 2 is 1.0 to 20, preferably 1.2 to 10 times the moles of aluminum atoms (γ) in the contact product I used in the olefin polymerization step of step 1. A quantity is used. The contact is usually carried out under an inert gas atmosphere such as nitrogen, heating and stirring after removing unreacted olefin and hydrogen gas used for molecular weight adjustment as needed from the polymerization vessel after completion of Step 1. The The contact temperature is usually 40 to 150 ° C., preferably 50 to 120 ° C., and the contact time is usually 1 minute to 300 minutes, preferably 30 minutes to 240 minutes. At the time of contact, the same hydrocarbon solvent as that used in Step 1 can be used as necessary. After completion of the contact, it may be used as it is as a raw material for the next step 3, or may be used as a raw material for the next step 3 after separating the solvents by separation operations frequently used in normal chemical engineering such as filtration .
Process 3
Step 3 is a step of further recovering the olefin polymer particle part by removing the liquid phase part after further contacting the aliphatic hydrocarbon having 5 to 10 carbon atoms with the contact material II obtained in Step 2. is there. Examples of the aliphatic hydrocarbon having 5 to 10 carbon atoms include n-pentane, isopentane, n-hexane, n-heptane, n-octane, and n-decane. The aliphatic hydrocarbons include cyclohexane, methylcyclohexane, and cyclic hydrocarbons such as dimethylcyclohexane. The aliphatic hydrocarbon having 5 to 10 carbon atoms is usually 100 times the weight, preferably 10 times the weight of the solid equivalent weight of the contact material II obtained in step 2. Here, as the aliphatic hydrocarbon, it is also possible to add the polyoxyalkylene compound used in Step 2.

Contact temperature is 0 to 100 ° C, preferably room temperature to 80 ° C, contact time is usually 1 to 300 minutes, preferably
10 to 180 minutes. Contact is usually performed under stirring. As a stirring method, a stirring method employed in a normal chemical industry can be used without limitation. After completion of the contact, the liquid phase portion is removed by filtration, and the olefin polymer particles according to the present invention can be obtained by vacuum drying at 50 to 100 ° C. as necessary.

Moreover, in the 2nd preferable aspect of the manufacturing method of the olefin polymer particle which concerns on this invention, after the said process 1, process 2 'and process 3' are implemented sequentially.
Process 2 '
Step 2 ′ is a step of dissolving the olefin polymer after completion of Step 1 in an aliphatic hydrocarbon having 5 to 10 carbon atoms.

As the aliphatic hydrocarbon having 5 to 10 carbon atoms used in Step 2 ′, the aliphatic hydrocarbon having 5 to 10 carbon atoms used in Step 3 described above can be used without limitation. In step 2 ′, after completion of the olefin polymerization reaction in step 1, unreacted monomers and molecular weight modifier hydrogen gas are removed as necessary, and then an aliphatic gas having 5 to 10 carbon atoms in an inert gas atmosphere. Group hydrocarbons are added. The amount of the aliphatic hydrocarbon having 5 to 10 carbon atoms is usually the minimum amount that can achieve complete homogenization at a temperature of room temperature to 50 ° C. When the olefin polymerization in step 1 is carried out in the presence of an aliphatic hydrocarbon solvent having 5 to 10 carbon atoms, it is not necessary to replace the solvent, and therefore step 2 ′ can be omitted.
Step 3 '
Step 3 ′ is a step of bringing the solution containing the olefin polymer obtained in Step 2 ′ into contact with an acidic alcohol to precipitate a polymer and recovering the olefin polymer particle part.

The acidic alcohol used in step 3 ′ refers to a mixed solution in which a mineral acid aqueous solution such as hydrogen chloride, sulfuric acid, nitric acid or the like is mixed with an aliphatic alcohol having 1 to 5 carbon atoms. Usually, a mixed solution in which 1 to 20 parts by volume of 0.1 to 5N hydrochloric acid is mixed with 100 parts by volume of water-soluble methanol is used. The olefin polymer particles of the present invention are precipitated by adding the acidic alcohol to the solution obtained in step 2 ′ under stirring. The precipitate is isolated by conventional chemical engineering separation means such as filtration and drying.

  According to such a method for producing olefin polymer particles of the present invention, the olefin polymer particles of the present invention that satisfy the above-mentioned requirements (1) to (5) at the same time can be suitably produced.

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

The measuring method of the physical property in an Example is as follows.
(i) n-decane soluble part amount 200 ml of n-decane was added to 5 g of a sample of an olefin polymer 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 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) was filtered off 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 (wt%) = [precipitate (A) weight / sample weight] × 100
(ii) GPC molecular weight distribution (Mw / Mn)
Measurement was performed as follows using GPC-150C Plus manufactured by Waters. The separation columns are TSK gel GNH6-HT and TSK gel GMH6-HTL, and the column size is 7.5 mm in inner diameter and 600 mm in length, respectively.
The column temperature is 140 ° C., o-dichlorobenzene (Wako Pure Chemical Industries) is used as the mobile phase and 0.025% by weight of BHT (Wako Pure Chemical Industries) is used as the antioxidant, and the column is moved at 1.0 ml / min. The sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. The 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 .

(iii) Melting point (Tm) measurement method [DSC measurement]
The measurement was performed using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). Here, the endothermic peak in the third step was defined as the melting point (Tm).

First step: After holding at 30 ° C. for 0.5 min, heat up to 240 ° C. at 30 ° C./min and hold for 10 min.
Second step: The temperature is lowered to 30 ° C. at 10 ° C./min and held for 2 min.

Third step: The temperature is raised to 200 ° C. at 10 ° C./min.
(iv) Method for measuring ash content A sample is placed in a magnetic crucible having a constant weight, the polymer is burned and removed to some extent with an electric heater, and then the residue is completely ashed in an electric furnace at 750 ° C for 30 minutes. Next, after 5 minutes of air cooling, let it cool in a desiccator for 60 minutes. Finally, weighed to determine the ash content.

(v) Measurement method of polymer average particle size [Laser particle size distribution measurement]
A large lump was removed from a 10 g sample using a 42-mesh sieve, and the particle size distribution was determined by measuring with a laser particle size distribution measuring device (manufactured by HORIBA). The average particle diameter is the median diameter value.

[1] Modification of aluminoxane with diol compound Under a nitrogen atmosphere, 272.2 mg of 1,10-decanediol was weighed in a 50 ml Schlenk flask, 36.2 ml of toluene was added, and the mixture was heated to 60 ° C. to dissolve. Next, in a 200 ml four-necked flask, 56.5 ml of toluene 50 ml and methylaluminoxane (hereinafter referred to as MAO) -toluene solution (Albemarle 10 wt% solution) was added and stirred while heating to 60 ° C. 1 , 10-decanediol-toluene solution (10 ml, 1,10-decanediol 75.1 mg) was gradually added and contacted at 60 ° C. for 2 hours.
[2] Preparation of olefin polymerization catalyst In a glove box, isopropylidene (3-t-butyl-5-methylcyclopentadienyl) (3,6 di-t-butylfluorenyl) zirconium dichloride was placed in a 50 ml Schlenk flask. 8.7 mg was weighed. Next, 2.0 ml of toluene was added to dissolve, 24.9 ml of 1,10-decanediol-modified MAO-toluene solution (amount in which Al is 1000 times mol with respect to Zr) was added, and the mixture was stirred at room temperature for 15 minutes.
[3] Propylene polymerization reaction 2.0-liter autoclave with n-heptane (contact with silica gel overnight or longer,
1.0 liter of dissolved gas substitution with nitrogen) was added and nitrogen substitution was performed. Next, the gas phase portion and the liquid phase portion were thoroughly replaced with propylene, and all the polymerization catalyst solutions prepared in [2] were transferred from the handhole using a Teflon (registered trademark) tube. Subsequently, 100 ml of hydrogen was charged, propylene was intermittently supplied at a pressure of 0.2 MPa / G, and a polymerization reaction was carried out at an autoclave internal temperature of 25 ° C. for 1 hour.
[4] Treatment with polyoxyalkylene compound and deashing treatment After completion of the polymerization in [3] above, propylene was depressurized and the inside of the autoclave system was replaced with a nitrogen atmosphere. Next, diethylene glycol monoisopropyl ether (Al in MAO as a quencher)
4.8 ml), and contact treatment was performed for 1 hour at an autoclave internal temperature of 60 ° C. Next, the polymer heptane slurry was taken out and the polymer was recovered by filtration. The polymer was washed by adding 1.0 liter of heptane and then vacuum-dried at 80 ° C.

  Table 1 shows the property values, polymerization activity, and the like of the obtained olefin polymer particles.

[1] Modification of aluminoxane with diol compound In the same manner as in Example 1, a modification of aluminoxane with a diol compound was performed.
[2] Preparation of Olefin Polymerization Catalyst In a glove box, 6.0 mg of dibenzylmethylene (cyclopentadienyl) (3,6di-t-butylfluorenyl) zirconium dichloride was weighed in a 50 ml Schlenk flask. Next, 6.0 ml of toluene was added and dissolved by stirring for 5 minutes. Next, 17.2 ml of 1,10-decanediol-modified MAO-toluene solution (amount in which Al is 1000 times mol of Zr) was added and stirred at room temperature for 15 minutes.
[3] Polymerization reaction of 4-methyl-1-pentene In an autoclave with an internal volume of 2.0 liters, add 1.0 liter of n-heptane (contacted with silica gel overnight and displace the dissolved gas with nitrogen), and purge with nitrogen. did. Next, transfer all of the olefin polymerization catalyst solution prepared in [2] from the handhole using a Teflon (registered trademark) tube, and then add 100 ml (66 g) of 4-methyl-1-pentene, The polymerization reaction was carried out at a temperature of 25 ° C. for 5 hours.
[4] Contact with acidic alcohol and deashing treatment After completion of the polymerization in [3] above, the pressure was released and the inside of the autoclave system was replaced with a nitrogen atmosphere. The polymer heptane solution was then removed and concentrated to 300 ml with an evaporator. To the concentrate, 1500 ml of a 5-fold volume of methanol (containing 10 vol% of 1N-HCl aqueous solution) was added to precipitate only the polymer, which was collected by filtration.

Table 1 shows the property values, polymerization activity, and the like of the obtained olefin polymer particles.
[Comparative Example 1]
[1] Synthesis of solid catalyst support
300 g of SiO ₂ (manufactured by Dokai Chemical Co., Ltd.) was sampled in a 1 liter branch flask, and 800 ml of toluene was put into a slurry. Next, the solution was transferred to a 5-liter four-necked flask, and 260 ml of toluene was added. Methylaluminoxane (MAO) -toluene solution (Albemarle 10wt%
2830 ml of solution) was introduced. The mixture was stirred at room temperature for 30 minutes. 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] Synthesis of solid catalyst (support of metal catalyst component on support)
In a glove box, add a isopropylidene (3-t-butyl-5-
18.0 mg of methylcyclopentadienyl) (3,6di-t-butylfluorenyl) zirconium dichloride was weighed. The flask was taken out, 4.1 ml of toluene and 3.4 ml of MAO / SiO ₂ / toluene slurry prepared in [1] (0.6 g as MAO / SiO ₂ ) were added under nitrogen, and the mixture was stirred for 30 minutes to carry. The resulting isopropylidene (3-t-butyl-5-methylcyclopentadienyl) (3,6 di-t-butylfluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99 in n-heptane. % Substitution was performed and the final slurry volume was 12.5 ml. This operation was performed at room temperature.
[3] Pre-polymerization of solid catalyst (pre-contact treatment of solid catalyst and alkylaluminum)
13.0 ml of triisobutylaluminum / heptane solution (0.1345 g / ml heptane solution) was added to the solid catalyst prepared in [2] under a nitrogen atmosphere (amount in which Al is 300 times mol with respect to Zr in the solid catalyst). The mixture was stirred for 15 minutes and used for polymerization.
[4] Propylene polymerization reaction An autoclave with an internal volume of 2.0 liters was charged with 1.0 liters of n-heptane (contacted with silica gel for one night or more and subjected to replacement of dissolved gas with nitrogen), and the atmosphere was replaced with nitrogen. Next, the gas phase portion and the liquid phase portion were well substituted with propylene. Next, the entire amount of the solid catalyst slurry prepared in [3] was put in an autoclave, and propylene was intermittently supplied at an internal temperature of 25 ° C. so that the internal pressure was 0.20 MPa / G, and a polymerization reaction was performed for 2 hours.
[5] Treatment with polyoxyalkylene compound and decalcification treatment Deactivation and decalcification treatment were carried out in the same manner as in Example 1.

Table 1 shows the property values, polymerization activity, and the like of the obtained olefin polymer particles.
[Comparative Example 2]
[1] Synthesis of solid catalyst carrier A solid catalyst carrier was synthesized in the same manner as in Comparative Example 1.
[2] Synthesis of solid catalyst (support of metal catalyst component on support)
In a glove box, 17.4 mg of dibenzylmethylene (cyclopentadienyl) (3,6 di-t-butylfluorenyl) zirconium dichloride was weighed in a 200 ml four-necked flask. The flask was taken out, 4.0 ml of toluene and 11.4 ml of MAO / SiO ₂ / toluene slurry prepared in [1] (1.74 g as MAO / SiO ₂ ) were added under nitrogen and stirred for 30 minutes to carry. The resulting dibenzylmethylene (cyclopentadienyl) (3,6 di-t-butylfluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99% substituted with n-heptane and the final The amount of slurry was 30.0 ml. This operation was performed at room temperature.
[3] Pre-polymerization of catalyst (pre-contact treatment of solid catalyst and alkylaluminum)
10.3 ml of solid catalyst / heptane slurry synthesized in [2] (606 mg as a solid catalyst) was placed in a 50 ml Schlenk flask under a nitrogen atmosphere, and 2.0 ml of triethylaluminum / heptane solution (20 wt% heptane solution) in a solid catalyst. The amount of Al was 300 times mol with respect to Zr), and the mixture was stirred for 15 minutes and used for polymerization.
[4] Polymerization reaction of 4-methyl-1-pentene 2.0-liter autoclave with n-heptane (silica gel contacted overnight or longer,
1.0 liter of dissolved gas substitution with nitrogen) was added and nitrogen substitution was performed. Next, all of the solid catalyst / heptane slurry prepared in advance in [3] above from the handhole was transferred using a Teflon tube, and then 100 ml (66 g) of 4-methyl-1-pentene was transferred. In addition, the polymerization reaction was carried out at an autoclave internal temperature of 25 ° C. for 5 hours.
[5] Treatment with polyoxyalkylene compound and decalcification treatment Deactivation and decalcification treatment were carried out in the same manner as in Example 1.

Table 1 shows the property values, polymerization activity, and the like of the obtained olefin polymer particles.
[Comparative Example 3]
Methanol was used instead of diethylene glycol monoisopropyl ether. The other conditions were the same as in Example 1 except that propylene was polymerized and treated.

  Table 1 shows the property values, polymerization activity, and the like of the obtained olefin polymer particles.

The olefin polymer particles of the present invention are olefin polymers having high stereoregularity and low ash content. It can be applied in many fields from hard to soft.

Claims (1)

An olefin-based polymer comprising the following steps 1 , 2 and 3 , which are sequentially performed to produce olefin-based polymer particles that simultaneously satisfy the following requirements (1) to (5): Production method of polymer particles;
[Step 1]: Transition metal compound (A) and
A contact product of an aluminoxane (B) and a diol compound (C) represented by the following general formula [I],
A step of polymerizing at least one olefin selected from ethylene and an α-olefin having 3 or more carbon atoms in the presence of an olefin polymerization catalyst.
H—O—R ¹ —O—H [I]
(In the above general formula [I], R ¹ is an alkylene group having 1 to 20 carbon atoms, and at least one hydrogen atom bonded to carbon is an aryl group, a halogen atom, a halogen-containing hydrocarbon group or an acyl group. May be substituted.)
[Step 2]: a step of contacting a polyoxyalkylene compound having one alcoholic hydroxyl group in the molecule represented by the following general formula [II]:
_{H-O- [CH 2 -CH (} R 1) -O] m -R 2 ... (II)
(In the above general formula [II], R ¹ and R ² are selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. (M represents the average number of repeating units and is in the range of 1 to 100.)
[Step 3]: A step of contacting the aliphatic hydrocarbon having 5 to 10 carbon atoms and then removing the liquid phase portion to recover the olefin polymer particle portion;
Requirements (1) to (5) for olefin polymer particles:
(1) The molecular weight distribution (Mw / Mn) measured by GPC is 4.0 or less,
(2) The minimum particle size of the polymer particles is 3 μm or more, and the average particle size is 20 μm or more,
(3) The ash content of the polymer particles is 2000 ppm by weight or less,
(4) The Si content of the polymer particles is 10 ppm by weight or less,
(5) The polymer particles contain a contact product of an aluminoxane and a diol compound represented by the following general formula [III].
H—O—R ¹ —O—H [III]
(In the above general formula [III], R ¹ is an alkylene group having 1 to 20 carbon atoms, and one or more hydrogen atoms bonded to carbon are an aryl group, a halogen atom, a halogen-containing hydrocarbon group or an acyl group. May be substituted).