JP2010047629A - Manufacturing method for high melting point olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for an olefin polymer using a polymerization catalyst capable of performing polymerization at a high temperature, being excellent in polymerization activity and indicating a high melting point and a high molecular weight by the obtained polymer. <P>SOLUTION: In the manufacturing method for the olefin polymer, 2C or more α-olefin is polymerized in the presence of the catalyst containing a crosslinked metallocene compound (A) represented by general formula [1]: and one kind or more of the compound (B) selected from an organic aluminumoxy compound (b-1), etc. (wherein M is Ti, Zr or Hf). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing an olefin polymer using an olefin polymerization catalyst containing a crosslinked metallocene compound having a specific structure.

  As a homogeneous catalyst for olefin polymerization, a so-called metallocene compound is well known. The method of polymerizing olefins using metallocene compounds, especially the method of stereoregularly polymerizing α-olefins, has been reported since W. Kaminsky et al. Reported isotactic polymerization and further improved polymerization activity and stereoregularity. Many improvement studies have been conducted from the viewpoint of improvement (Non-patent Document 1).

  As part of such research, propylene polymerization in the presence of a catalyst composed of a metallocene compound having a ligand obtained by crosslinking cyclopentadienyl and fluorenyl with isopropylidene and an aluminoxane resulted in a syndiotactic pentad fraction. It has been reported by JA Ewen that a polypropylene having a high tacticity exceeding 0.7 can be obtained (Non-patent Document 2).

  As an improvement of this metallocene compound, an attempt has been made to improve stereoregularity by changing the fluorenyl group to a 2,7-di-tert-butylfluorenyl group (Patent Document 1). In addition, an attempt to improve stereoregularity by changing the fluorenyl group to 3,6-di-tert-butylfluorenyl group (Patent Document 2), or by combining the cyclopentadienyl group and the fluorenyl group Attempts to convert existing cross-linked parts have been reported (Patent Documents 3 and 4). Compared with dimethylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylmethylene (3-tert-butyl-5-5-) introduced a methyl group at the 5-position of the cyclopentadienyl ring. It is also disclosed that methylcyclopentadienyl) (fluorenyl) zirconium dichloride can obtain a higher molecular weight isotactic polypropylene (Patent Document 5).

  From attempts to improve these metallocene compounds, a relatively high melting point, which is an indicator of the stereoregularity of the polymer, can be obtained. However, the polymerization performance for synthesizing a polymer having a sufficiently high molecular weight with high activity is still not sufficient, and therefore, efficient production of a polymer having a high melting point and a high molecular weight has been desired.

  Furthermore, in order to enable industrial production of these olefin polymers, it is desired that olefin polymers having the above characteristics can be produced at a temperature higher than room temperature, preferably higher than room temperature. Until now, there has been no polymerization catalyst capable of.

As a result of intensive studies in view of such circumstances, the present inventors have found that when olefin such as propylene is polymerized using an olefin polymerization catalyst containing a transition metal complex having a specific structure, only at room temperature. It has been found that an olefin polymer having a sufficiently high melting point can be obtained with excellent polymerization activity even in high temperature polymerization that can be industrialized, and the present invention has been completed.
JP-A-4-69394 JP 2000-212194 A JP 2004-189666 A JP 2004-189667 A Special table 2001-526730 gazette Angew. Chem. Int. Ed. Engl. , 24, 507 (1985) J. et al. Am. Chem. Soc. , 1988, 110, 6255

  The problem to be solved by the present invention is that, when an olefin such as propylene is polymerized, an olefin polymer which gives an olefin polymer having a sufficiently high melting point with excellent polymerization activity not only at room temperature but also at a high temperature. It is to provide a manufacturing method.

The method for producing an olefin polymer of the present invention comprises:
The bridged metallocene compound (A) represented by the following general formula [1], and the compound (B) selected from the following components (b-1), (b-2) and (b-3)
(b-1) an organoaluminum oxy compound,
(b-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair,
(b-3) A method for producing an olefin polymer, wherein one or more monomers selected from α-olefins having 2 or more carbon atoms are polymerized in the presence of an olefin polymerization catalyst comprising an organoaluminum compound;

(In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁴ > shows a hydrogen atom.
R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ²⁰ are selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group, and each may be the same or different, and in one or more adjacent group combinations The adjacent groups may be bonded to each other to form a ring.

R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹⁵ , R ¹⁶ , R ¹⁸ and R ^{19 each} represent a hydrogen atom. R ⁸ and R ¹⁷ are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, or a hydrocarbon group containing a halogen atom, and may be the same or different, but at least of R ⁸ and R ¹⁷ One is selected from a halogen atom or a hydrocarbon group containing a halogen atom. R ²¹ and R ²² are a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms or a silicon-containing group having 1 to 40 carbon atoms, which may be the same as or different from each other, and are bonded to each other to form a ring. Also good.
M is Ti, Zr or Hf, Y is a silicon atom or a carbon atom,
Q is selected from a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair in the same or different combination, and j is an integer of 1 to 4. In the production method of the present invention,
In the general formula [1], R ⁸ and R ¹⁷ are preferably a halogen atom or a hydrocarbon group containing a halogen atom.

  In the production method of the present invention, it is also a preferred embodiment that the olefin polymerization catalyst further contains a carrier (C).

  When olefin polymerization such as propylene is carried out using the olefin polymer production method of the present invention, olefin weight having a good activity and a sufficiently high molecular weight not only at low polymerization temperature conditions but also at high polymerization temperature conditions. Copolymers can be obtained, and the olefin polymers obtained there have a higher melting point than when using existing production methods.

The method for producing an olefin polymer of the present invention comprises:
(A) a bridged metallocene compound represented by the general formula [1], and (B) (b-1) an organoaluminum oxy compound,
(b-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair, and
(b-3) A method for producing an olefin polymer, wherein one or more monomers selected from α-olefins having 2 or more carbon atoms are polymerized in the presence of one or more olefin polymerization catalysts comprising an organoaluminum compound. .

  BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the invention will be sequentially described with respect to a crosslinked metallocene compound related to an olefin polymerization catalyst of the present invention, an olefin polymerization catalyst containing the crosslinked metallocene compound, and a method of polymerizing in the presence of the olefin polymerization catalyst. .

◆ Bridged metallocene compound (A)
(A) is a bridged metallocene compound represented by the general formula [1].
In the general formula [1], R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹⁵ , R ¹⁶ , R ¹⁸ and R ¹⁹ represent hydrogen atoms.

R ⁸ and R ¹⁷ are a hydrogen atom, a hydrocarbon group (F), silicon-containing group (S), is selected from a hydrocarbon group containing a halogen atom or a halogen atom, but each may be the same or different, R ⁸ And at least one of R ¹⁷ is selected from a halogen atom or a hydrocarbon group containing a halogen atom.

R ⁸ and R ¹⁷ are preferably a halogen atom or a hydrocarbon group containing a halogen atom.

  Examples of the halogen atom include fluoro, chloro, bromo and iodo, and examples of the hydrocarbon group containing a halogen atom include a trifluoromethyl group.

  The number of carbon atoms of the hydrocarbon group (F) is not particularly limited. For example, methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl Group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and other linear hydrocarbon groups; iso-propyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1 , 1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1 -Branched hydrocarbon groups such as isopropyl-2-methylpropyl group; cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; phenyl group, naphthyl group, biphenyl Group, phenanthryl group, anthracenyl group Mention may be made of any cyclic unsaturated hydrocarbon group and their nuclear alkyl substituents; saturated hydrocarbon groups substituted with aryl groups such as benzyl and cumyl groups.

  The number of carbon atoms and the number of silicon atoms in the silicon-containing group (S) is not particularly limited, but specifically, it is an alkylsilyl group or an arylsilyl group, such as a trimethylsilyl group, a triethylsilyl group, or a triphenylsilyl group. Can do.

  As a hydrocarbon group (F), a C1-C40 hydrocarbon group (f) is preferable, Among these, a C1-C20 alkyl group (f1-1), a C6-C20 aralkyl group, Particularly preferred are a nuclear-substituted aralkyl group (f1-2) and a group (f) selected from an aryl group having 6 to 20 carbon atoms and a nuclear-substituted aryl group (f1-3).

  Examples of the alkyl group having 1 to 20 carbon atoms (f1-1) include methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n- Linear hydrocarbon groups such as heptyl, n-octyl, n-nonyl, n-decanyl; iso-propyl, tert-butyl, amyl, 3-methylpentyl, 1,1-diethyl Propyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2 -Branched hydrocarbon groups such as methylpropyl group; cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group and adamantyl group.

  As the aralkyl group having 6 to 20 carbon atoms and the nucleus-substituted aralkyl group (f1-2), an aralkyl group such as a benzyl group, an α-phenethyl group, a β-phenethyl group, a diphenylmethyl group, a naphthylmethyl group, or a neophyll group; -Methylbenzyl group, m-methylbenzyl group, p-methylbenzyl group, ethylbenzyl group, n-propylbenzyl group, iso-propylbenzyl group, n-butylbenzyl group, sec-butylbenzyl group, tert-butylbenzyl group Alkyl aralkyl groups such as o-chlorobenzyl group, m-chlorobenzyl group, p-chlorobenzyl group, chlorophenethyl group, etc .; o-bromobenzyl group, m-bromobenzyl group, p-bromobenzyl group Bromoaralkyl group such as bromophenethyl group; o-iodobenzyl group, m-iodobenzyl group, p-iodobenzyl group, iodo Such as iodo aralkyl group such Enechiru group can be exemplified.

  Examples of the aryl group having 6 to 20 carbon atoms and the nuclear-substituted aryl group (f1-3) include aryl groups such as phenyl group and naphthyl group; o-tolyl group, m-tolyl group, p-tolyl group, ethylphenyl group, alkylaryl groups such as n-propylphenyl group, iso-propylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, xylyl group; o-chlorophenyl group, m-chlorophenyl group, p- Chloroaryl groups such as chlorophenyl group and chloronaphthyl group; bromoaryl groups such as o-bromophenyl group, m-bromophenyl group, p-bromophenyl group and bromonaphthyl group; bromomethylphenyl group and dibromomethylphenyl group Bromoalkylaryl group; o-iodophenyl group, m-iodophenyl group, p-iodomophenyl group, iodonaphthyl group, etc. Doariru group; iodo-methylphenyl group, and the like can be exemplified iodine alkylaryl group, such as di-iodo-methylphenyl group.

R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ²⁰ are preferably selected from a hydrogen atom and an alkyl group having 1 to 40 carbon atoms, and R ⁵ , R ¹² , R ¹³ , and R ²⁰ are hydrogen. It is an atom, and R ¹¹ and R ¹⁴ are more preferably an alkyl group having 1 to 20 carbon atoms and the same group. In addition, as a C1-C40 alkyl group, the group similar to above-mentioned group (f1-1) can be illustrated.
R ²¹ and R ²² are a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms or a silicon-containing group having 1 to 40 carbon atoms, which may be the same as or different from each other, and are bonded to each other to form a ring. Also good.

  Examples of the hydrocarbon group having 1 to 40 carbon atoms include the above-described alkyl group (f1-1) having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, and 1 to 40 carbon atoms, preferably 6 to 6 carbon atoms. A group selected from 20 aralkyl groups and nuclear-substituted aralkyl groups (f1-2), and aryl groups and nuclear-substituted aryl groups (f1-3) having 6 to 40 carbon atoms, preferably 6 to 20 carbon atoms described above. It can be used without limitation.

A preferred group as R ²¹ and R ²² is a hydrocarbon group having 1 to 20 carbon atoms, more preferably a phenyl group, a tolyl group, a chlorophenyl group, a bromophenyl group, an iodophenyl group, a benzyl group, a methylbenzyl group, An ethylbenzyl group, a propylbenzyl group, a butylbenzyl group, a chlorobenzyl group, a bromobenzyl group, or an iodobenzyl group.

M is Ti, Zr or Hf, preferably Zr or Hf, and Zr is particularly preferred. Y is a silicon atom or a carbon atom, preferably a carbon atom. Q is an atom or group selected from a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair in the same or different combination. Specific examples of the halogen are fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group are methyl, ethyl, n-propyl, iso-propyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, Examples include 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like. Neutral having 10 or less carbon atoms, and specific examples of the conjugated or non-conjugated dienes, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ⁴ - 1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4- Dibenzyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s -Trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. A preferred embodiment of Q is a halogen atom or an alkyl group having 1 to 5 carbon atoms.
j is an integer of 1 to 4, preferably 2.

  The effect of the present invention described above can be achieved by using a polymerization catalyst composed of the bridged metallocene compound (A) satisfying such conditions.

◆ Preferred Bridged Metallocene Compound and Examples thereof Specific examples of the bridged metallocene compound represented by the general formula [1] are shown below, but the scope of the present invention is not particularly limited by this.

  Dimethylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride, diethylmethylene (cyclopentadienyl) (3,6-ditert- Butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride, di-n-propylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluoride Olenyl) zirconium dichloride, di-iso-propylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride, di-n-butylmethylene (Cyclopentadienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride, di-iso-butylmethylene (cyclopentadienyl) (3,6-di- tert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium Dichloride, di-sec-butylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride, di-tert-butylmethylene (cyclopentadiene) Enyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride, di-n-octylmethylene (cyclopentadienyl) (3,6-ditert-butyl- 2,7-di-p-chlorophenylfluorenyl) zirconium dichloride, di-n-triacontylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluoride) Oleenyl) zirconium dichloride, phenylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2 , 7-Di-p-chlorophenyl-3,6-ditert-butylfur Olenyl) zirconium dichloride, di-p-tolyl-methylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (Cyclopentadienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride, di (p-trifluoromethylphenyl) methylene (cyclopentadienyl) (3 , 6-Ditert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (3,6-ditert-butyl-2,7 -Di-p-chlorophenylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride, di ( p-Chlorobenzyl) methylene (cyclopen Dienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride, di (p-methylbenzyl) methylene (cyclopentadienyl) (3,6-ditert- Butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride, cyclohexyl (cyclopentadienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride Dibenzylmethylene (cyclopentadienyl) (2,7-di-p-chlorophenyl-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di-p-chlorophenyl-3,6- Ditrimethylsilylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di-p-chlorophenyl-3,6-dicumylfluorenyl) zirconium dichloride, dibenzylmethylene Ntadienyl) (2,7-di-p-chlorophenyl-3,6-adamantylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6 -Ditert-butylfluorenyl) zirconium dichloride, diethylmethylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di -n-propylmethylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di-iso-propylmethylene (cyclopentadi Enyl) (2,7-di-p-trifluoromethylphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-di- p-trifluoromethylphenyl-3,6-dite rt-Butylfluorenyl) zirconium dichloride, di-iso-butylmethylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride Di-sec-butylmethylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di-tert-butylmethylene (cyclo Pentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-octylmethylene (cyclopentadienyl) (2,7- Di-p-trifluoromethylphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-triacontylmethylene (cyclopentadienyl) (2,7-di-p-trifluoromethyl Phenyl-3,6-ditert-butylfluorenyl) zirconi Um dichloride, phenylmethylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2 , 7-Di-p-trifluoromethylphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di-p-tolyl-methylene (cyclopentadienyl) (2,7-di-p-trifluoro Methylphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-di tert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-ditert-butylfluorene Nyl) zirconium dichloride, Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) ) (2,7-di-p-trifluoromethylphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorobenzyl) methylene (cyclopentadienyl) (2,7-di -p-trifluoromethylphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-methylbenzyl) methylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl -3,6-ditert-butylfluorenyl) zirconium dichloride, cyclohexyl (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, dibenzylmethylene (cyclope Tadienyl) (2,7-di-p-trifluoromethylphenyl-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-ditrimethylsilyl) Fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di-p-trifluoromethylphenyl-3,6-dicumylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) ) (2,7-di-p-trifluoromethylphenyl-3,6-adamantylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di-p-bromophenyl-3,6 -Ditrimethylsilylfluorenyl) zirconium dichloride, dibenzyl (cyclopentadienyl) (2,7-di-p-iodophenyl-3,6-ditrimethylsilylfluorenyl) Zirconium dichloride and the like can be mentioned.

  Similarly, the compounds described in the above-mentioned compounds in which “zirconium” is changed to “hafnium” or “titanium”, or metallocene compounds in which “dichloride” is changed to “dimethyl” or “methylethyl” are also related to the olefin polymerization catalyst of the present invention. It is a metallocene compound.

  The bridged metallocene compound [1] according to the present invention can be produced by a known method, and the production method is not particularly limited. Known production methods include, for example, WO2001 / 27124 pamphlet and WO2004 / 087775 pamphlet by the present applicant.

< Olefin polymerization catalyst > Next, a preferred embodiment when the above-described crosslinked metallocene compound (A) is used as a polymerization catalyst in the olefin polymerization method of the present invention will be described.

  When the crosslinked metallocene compound of the present invention is used as an olefin polymerization catalyst, the components constituting the catalyst are (A) a crosslinked metallocene compound, and (B) (b-1) an organoaluminum oxy compound, (b-2) the component ( A compound which reacts with A) to form an ion pair, and (b-3) one or more compounds selected from organoaluminum compounds. Furthermore, it is comprised from the (C) particulate carrier as needed. Hereinafter, each component will be specifically described.

(b-1) Organoaluminum Oxy Compound As the (b-1) organoaluminum oxy compound used in the present invention, a conventionally known aluminoxane can be used as it is. Specifically, the following general formula [2]

および／または一般式[３]

And / or general formula [3]

(In the above general formulas [2] and [3], R is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.) In particular, R is methyl. A methylaluminoxane group having n of 3 or more, preferably 10 or more is used. These aluminoxanes may be mixed with some organoaluminum compounds. A characteristic property in the high temperature solution polymerization of the present invention is that a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 can also be applied. In addition, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more kinds of alkyl groups described in JP-A-2-24701, and JP-A-3-103407, etc. It can be suitably used. The “benzene-insoluble” organoaluminum oxy compound used in the high-temperature solution polymerization of the present invention means that the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 5% or less. Is 2% or less, and is insoluble or hardly soluble in benzene.

  Examples of the organoaluminum oxy compound used in the present invention include modified methylaluminoxane as shown in [4] below.

(Here, R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n represent an integer of 2 or more.)
This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such a compound [4] is generally called MMAO. Such MMAO can be prepared by the methods listed in US4960878 and US5041584. In addition, Tosoh Finechem Co., Ltd., etc., which are prepared using trimethylaluminum and triisobutylaluminum and whose R is an isobutyl group, are commercially produced under the names MMAO and TMAO. Such MMAO is an aluminoxane with improved solubility in various solvents and storage stability. Specifically, it is different from those insoluble or hardly soluble in benzene such as [2] and [3] above. It is soluble in aliphatic hydrocarbons and alicyclic hydrocarbons.

  Furthermore, as an organoaluminum oxy compound used in the present invention, an organoaluminum oxy compound containing boron represented by the following general formula [5] can be exemplified.

(In the formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same or different and each represents a hydrogen atom, a halogen atom or a hydrocarbon having 1 to 10 carbon atoms. Group.)

(b-2) Compound that reacts with component (A) to form an ion pair Compound (b-2) that reacts with component (A) to form an ion pair (hereinafter referred to as "ionic compound") As an example). JP-A-1-501950, JP-A-1-502036, JP-A-3-17905, JP-A-3-179006, JP-A-3-207703 And Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-207704, USP5321106 and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

  In the present invention, the ionic compound preferably employed is a compound represented by the following general formula [6].

In the formula, R ^{e +} includes H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. R ^{f to} R ⁱ may be the same as or different from each other, and are organic groups, preferably aryl groups.

  Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.

  Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation. N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, N, N-dialkylanilinium cation, diisopropylammonium cation, dicyclohexyl And dialkyl ammonium cations such as ammonium cations.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

Among the above, Re ⁺ is preferably a carbenium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbenium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

  Specific examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methyl And phenyl) carbenium tetrakis (pentafluorophenyl) borate and tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

  Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and the like.

  Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis ( o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,4 -Dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (4- Trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, Dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate Dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecylmethylammonium Mo tetrakis (3,5-ditrifluoromethylphenyl) borate, such as dioctadecyl methyl ammonium.

  Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis ( 3,5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5- Ditrifluoromethylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, etc. .

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

In addition, ionic compounds disclosed by the present applicant (Japanese Patent Laid-Open No. 2004-51676) can also be used without limitation.
The ionic compound (b-2) as described above can be used as a mixture of two or more.

(b-3) Organoaluminum Compound Forming an Olefin Polymerization Catalyst (b-3) The organoaluminum compound is, for example, an organoaluminum compound represented by the following general formula [7], represented by the following general formula [8] A complex alkylated product of a Group 1 metal and aluminum can be used.

R ^a _m Al (OR ^b ) _n H _p X _q ... [7]
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is a number of 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3). Specific examples of such compounds include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, Tri-branched alkylaluminums such as tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triphenyl Triarylaluminum such as aluminum and tolylylaluminum; diisopropylaluminum hydride, diisobutyl Dialkylaluminum hydrides such as aluminum hydride; formula _{(iC 4 H 9) x Al} y (C 5 H 10) z (. Wherein, x, y, z are each a positive number, and z ≦ 2x), etc. Alkenyl aluminum alkoxides such as isoprenyl aluminum represented by: Alkyl aluminum alkoxides such as isobutyl aluminum methoxide and isobutyl aluminum ethoxide; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide and dibutyl aluminum butoxide; Alkyl aluminum sesquialkoxides such as butylaluminum sesquibutoxide; partially alkoxylated alkylaluminums having an average composition represented by the general formula Ra2.5Al (ORb) 0.5; diethyl Alkyl aluminum aryloxides such as luminium phenoxide and diethylaluminum (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, etc. Dialkylaluminum halides; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride; diethylaluminum hydride; Dialkylaluminum hydrides such as dibutylaluminum hydride; Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as tilaluminum dihydride, propylaluminum dihydride; partially alkoxylated such as ethylaluminum ethoxychloride, butylaluminum butoxycycloride, ethylaluminum ethoxybromide and Examples thereof include halogenated alkylaluminum.

M ² AlR ^a ₄ ... [8]
(Wherein M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). Alkylate complex of aluminum and aluminum. Examples of such a compound include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

A compound similar to the compound represented by the general formula [8] can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ⁵ ) Al (C ₂ H ₅ ) ₂ .

  From the viewpoint of availability, trimethylaluminum and triisobutylaluminum are preferably used as the (b-3) organoaluminum compound.

  In the olefin polymerization catalyst according to the present invention, the catalyst component includes (A) a bridged metallocene compound represented by the general formula [1], and (B) (b-1) an organoaluminum oxy compound, (b- 2) A carrier (C) may be used as needed together with a compound that reacts with the bridged metallocene compound (A) to form an ion pair and a compound selected from (b-3) an organoaluminum compound.

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

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or the like, or a composite or mixture containing these is used. For example, natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, etc. Can be used. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred. Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m. ² / g, preferably in the range of 100 to 700 m ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

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

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

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

  Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers produced by the main component, and their modified products. In the olefin polymerization catalyst according to the present invention, the catalyst component includes (A) a bridged metallocene compound represented by the general formula [1], and (B) (b-1) an organoaluminum oxy compound, (b- 2) A compound that reacts with the bridged metallocene compound (A) to form an ion pair, and a compound selected from (b-3) an organoaluminum compound, and a carrier (C) if necessary, and will be described later if necessary. Such specific organic compound component (D) can also be included.

(D) In the organic compound component present invention, (D) an organic compound component is optionally used for the purpose of improving the physical properties of the polymerization performance and the produced polymer. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates. In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding the component (A) alone to the polymerization vessel.
(2) A method in which component (A) and component (B) are added to the polymerization vessel in any order.
(3) A method in which the catalyst component having component (A) supported on carrier (C) and component (B) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having component (B) supported on carrier (C) and component (A) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which component (A) and component (B) are supported on a carrier (C) is added to a polymerization vessel.

  In each of the above methods (2) to (5), at least two or more of the catalyst components may be contacted in advance.

  In each of the above methods (4) and (5) in which the component (B) is supported, the unsupported component (B) may be added in any order as necessary. In this case, the components (B) may be the same or different.

  The solid catalyst component in which the component (A) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) are prepolymerized with olefin. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.

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

  In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and other aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof, and the olefin itself is used as a solvent. You can also

When the olefin polymerization is carried out using the above olefin polymerization catalyst, the component (A) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² , per liter of the reaction volume. It is used in such an amount that it becomes a mole.

  Component (b-1) has a molar ratio [(b-1) / M] of component (b-1) and all transition metal atoms (M) in component (A) of usually 0.01 to 5000, Preferably it is used in such an amount that it is 0.05-2000. Component (b-2) has a molar ratio [(b-2) / M] of component (b-2) to transition metal atom (M) in component (A) of usually 1 to 10, preferably It is used in such an amount as to be 1-5. Component (b-3) has a molar ratio [(b-3) / M] of the aluminum atoms in component (b-3) to the total transition metals (M) in component (A) usually 10 to 10. The amount used is 5000, preferably 20-2000.

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

  Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is usually -50 to + 200 ° C, preferably 0 to 170 ° C. More preferably, it is 40-170 degreeC, More preferably, it is 50-150 degreeC. Particularly preferred is an industrializable temperature. 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. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the component (B) to be used. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

  According to the present invention, for example, a propylene polymer having a high melting point, a high molecular weight, and a narrow molecular weight distribution can be obtained even under a polymerization temperature of 40 ° C. or higher.

  In the present invention, the olefin supplied to the polymerization reaction is at least one monomer selected from ethylene and α-olefin. As the α-olefin, a linear or branched α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as propylene, 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-octene Eikosen etc. In the polymerization method of the present invention, a cyclic olefin having 3 to 30, preferably 3 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, Α, β-unsaturated carboxylic acids such as itaconic anhydride and bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, and sodium, potassium, lithium and zinc salts thereof Metal salts such as magnesium salt and calcium salt; methyl acrylate, n-butyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate Α, β-unsaturation such as chill, 2-n-butylhexyl acrylate, methyl methacrylate, n-butyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Carboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate And unsaturated glycidyl. Vinylcyclohexane, diene or polyene; aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, on-butylstyrene, mn-butylstyrene, pn -Functional groups such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene Polymerization can also proceed by allowing a styrene derivative; and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene, and the like to coexist in the reaction system.

〔Example〕
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

  First, a method for measuring physical properties and properties of a polymer obtained by olefin polymerization in the presence of a catalyst containing the transition metal compound of the present invention will be described.

* Intrinsic viscosity ([η])
It is a value measured at 135 ° C. using a decalin solvent. That is, about 20 mg of granulated pellets are dissolved in 15 ml of decalin, and the specific viscosity ηsp is measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity ηsp is measured in the same manner. This dilution operation is further repeated twice, and the value of ηsp / C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity.
[Η] = lim (ηsp / C) (C → 0)

* Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)
The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were measured using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters as follows. The separation columns are two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C, and the mobile phase is o- Use dichlorobenzene (Wako Pure Chemical Industries) and 0.025 wt% BHT (Takeda Pharmaceutical) as an antioxidant, move at 1.0 ml / min, sample concentration 15 mg / 10 ml, and sample injection volume 500 microliters 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 . The molecular weight distribution and various average molecular weights were calculated as polypropylene molecular weights according to the general calibration procedure.

* Melting point ( _Tm ), heat of fusion (ΔH)
Using a DSC Pyris1 or DSC7 manufactured by PerkinElmer, a nitrogen atmosphere (20 ml / min) and a sample of about 5 mg were heated to 200 ° C. and held for 10 minutes, and then cooled to 30 ° C. at 10 ° C./min. After maintaining at 30 ° C. for 5 minutes, the melting point was calculated from the peak of the crystal melting peak when the temperature was raised to 200 ° C. at 10 ° C./min, and the heat of fusion was calculated from the integrated value of the peaks.

In the propylene-based polymer described in the examples of the present application, when two peaks are observed, T _m2 is the melting point (T _m ) when T _{m1 is the} low temperature side peak and T _m2 is the high temperature side peak. It was defined as

* Stereoregularity (rrrr)
Stereoregularity (rrrr) was calculated from ¹³ C-NMR spectrum measurement. The solvent polymerization solvent types used in Examples and Comparative Examples of the present invention to be described later are as follows.
· Cyclohexane · n-heptane · solvent A; n-hexane (60 to 65% by volume), isohexane (10 to 19% by volume), methylcyclopentane (18 to 22% by volume) and other aliphatic hydrocarbon components (0 to 3% by volume).

Catalysts (a) to (c) were synthesized by the method described in the following patent. JP2000-212194, JP2004-168744, JP2004-189666, JP2004-1619575, JP2007-302854, JP2007-302853, WO01 / 027124 brochure.
Catalyst (a): Dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride catalyst (b): Dibenzylmethylene (cyclopentadi) Enyl) (3,6-ditert-butyl-2,7-diphenylfluorenyl) zirconium dichloride
Catalyst (c): Dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride

[Synthesis Example 1]
Catalyst (a): Synthesis of dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluorenyl) zirconium dichloride (i) 2,7-dibromo-3 Synthesis of 1,6-di-tertbutylfluorene Under a nitrogen stream, 170 mL of propylene carbonate was added to 15.22 g (54.7 mmol) of 3,6-di-tertbutylfluorene and stirred. To this solution, N-bromosuccinimide 20.52 g (115 mmol) was added. Stirring was performed at 80 ° C. for 5 hours. After allowing to cool naturally, the reaction solution was added to 800 mL of water. The mixture was stirred at room temperature for 15 minutes and filtered using a Kiriyama funnel. The resulting white yellow powder was washed 5 times with 10 mL of ethanol. A mixed solution of hexane and a small amount of dichloromethane was added to the white yellow powder, and heated to 60 ° C. to completely dissolve it. Allowed to stand overnight at -20 ° C. The precipitated crystals were washed 3 times with 5 mL of hexane to obtain the desired product as a white yellow powder. Yield 21.16 g, 76% yield. ¹ H NMR (270 MHz, CDCl ₃ ): δ / ppm 1.60 (18H), 3.75 (2H), 7.73 (2H), 7.81 (2H). MS (FD): M / z 436 (M ⁺ ).

(Ii) Synthesis of 3,6-ditert-butyl-2,7-di-p-chlorophenylfluorene 2,7-dibromo-3,6-ditert-butylfluorene 4.36 g (10.0 mmol), Pd 60 mL of anhydrous dimethoxyethane was added to 0.58 g (0.50 mmol) of (PPh ₃ ) _{4 and the} mixture was stirred at room temperature for 20 minutes. To this solution, 4.99 g (31.9 mmol) of p-chlorophenylboronic acid dissolved in 30 mL of ethanol was added. After stirring at room temperature for 20 minutes, 25 mL (50.0 mmol) of a 2.0 mol / L aqueous sodium carbonate solution was added. Heating under reflux was performed for 24 hours. After naturally cooling, the reaction was terminated with 1N hydrochloric acid in an ice bath. Ethyl acetate was added for liquid separation, and the aqueous layer was extracted twice with ethyl acetate and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and once with a saturated saline solution, and dried over magnesium sulfate. The solvent was distilled off and separation by silica gel chromatography was performed. A mixed solution of hexane and a small amount of dichloromethane was added to the obtained white yellow powder, and heated to 60 ° C. to completely dissolve the powder. After leaving still at room temperature for 1 hour, it left still at -20 degreeC overnight. The precipitated crystals were washed 3 times with 10 mL of hexane to obtain the desired product as a white powder. Yield 2.65 g, 53% yield.
¹ H NMR (270 MHz, CDCl ₃ ): δ / ppm 1.29 (18H), 3.78 (2H), 7.11 (2H), 7.24-7.28 (10H), 7.96 (2H).

(Iii) Synthesis of 6,6-dibenzylfulvene
Under a nitrogen atmosphere, 8.0 g (121.0 mmol) of cyclopentadiene and 100 mL of dehydrated THF were added to a 500 mL three-necked flask and stirred. This mixed solution was cooled in an ice bath, and 80 mL (125.6 mmol) of a hexane solution of n-butyllithium having a concentration of 1.57 mol / L was added. Thereafter, the mixture was stirred at room temperature for 3 hours, and the resulting white slurry was cooled in an ice bath. Then, a solution of 25.0 g (118.0 mmol) of 1,3-diphenyl-2-propanone in 50 ml of dehydrated THF was added. The mixture was then stirred at room temperature for 12 hours, and the resulting yellow solution was quenched with saturated aqueous NH ₄ Cl. 100 mL of hexane was added to extract soluble components, and the organic phase was washed with water and saturated brine, and then dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to obtain the desired product as a yellow solid. Yield 3.7 g, 12% yield. ¹ H NMR (270 MHz, CDCl ₃ ): δ / ppm 3.69 (4H), 6.60-6.72 (4H), 7.13-7.32 (10H).

(Iv) Synthesis of dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-di-p-chlorophenylfluorene)
Under a nitrogen stream, 30 mL of anhydrous THF was added to 1.00 g (2.00 mmol) of 3,6-ditert-butyl-2,7-di-p-chlorophenylfluorene and stirred. The solution was cooled to −78 ° C. in a dry ice / methanol bath, and 1.39 mL (2.20 mmol) of a 1.58 M n-butyllithium hexane solution was added. The mixture was stirred for 2 hours while gradually raising the temperature to -30 ° C. The obtained red solution was cooled to −78 ° C. in a dry ice / methanol bath, and 13 mL of a THF solution of 0.57 g (2.20 mmol) of 6,6-dibenzylfulvene was added dropwise over 30 minutes. After stirring for 2 hours while gradually raising the temperature, 1N hydrochloric acid was added in an ice bath to terminate the reaction. Dichloromethane was added for liquid separation, and the aqueous layer was extracted twice with dichloromethane and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and once with a saturated saline solution, and dried over magnesium sulfate. The solvent was distilled off and the residue was separated by silica gel chromatography to obtain the desired product as a pale yellow powder. Yield 0.89g, yield 59%. ¹ H NMR (270 MHz, CDCl ₃ ): δ / ppm 1.25 (18H), 2.66 (2H), 3.21 (4H), 4.40 (1H), 5.87-6.47 (3H), 6.86-7.30 (20H), 7.64 ( 2H). MS (FD): M / z 756 (M ⁺ ).

(V) Synthesis of dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-dip-chlorophenylfluorenyl) zirconium dichloride 100 mL branched gildar flask under nitrogen atmosphere Dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butyl-2,7-dip-chlorophenylfluorene) 0.83 g (1.09 mmol) and anhydrous diethyl ether 50 mL were added and stirred. This mixed slurry solution is cooled to −78 ° C. in a dry ice / methanol bath, 1.52 mL (2.40 mmol) of a hexane solution of n-butyllithium having a concentration of 1.58 mol / L is added, and the temperature is gradually raised to room temperature. The mixture was stirred for 20 hours. The red reaction solution was cooled to −78 ° C. in a dry ice / methanol bath, and 0.303 g (1.30 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred for 22 hours while gradually warming to room temperature to obtain a red-orange suspension.

The solvent was dried under reduced pressure, dissolved in hexane in a glove box, washed with hexane through a glass filter packed with celite, and the orange powder not dissolved in hexane was extracted with dichloromethane. The solvent in the dichloromethane-dissolved part was distilled off, washed with hexane, and dried to obtain the desired product as an orange powder. Yield 602 mg, 60% yield. ¹ H NMR (270 MHz, CDCl ₃ ): δ / ppm 1.30 (18H), 3.81 (2H), 3.92 (2H), 5.80 (2H), 6.47 (2H), 6.87-7.33 (22H), 8.32 (2H) MS (FD): M / z 916 (M ⁺ ).

400 ml of heptane was charged into a glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen, and propylene was circulated in an amount of 150 liters / hour and kept at 50 ° C. for 10 minutes. On the other hand, a magnetic stirrer was placed in a 30 ml branch flask with a sufficient nitrogen substitution, and a toluene solution of methylaluminoxane (Al concentration = 1.53 mol / L) was converted to aluminum atoms so that it became 5.00 mmol. In addition, catalyst (a) 5.0 μmol of toluene solution was added and stirred for 15 minutes. This solution was added to heptane in a glass autoclave in which propylene had been circulated to initiate polymerization. Propylene gas was continuously supplied at a rate of 150 liter / hour, polymerization was carried out at 50 ° C. for 45 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 7.35 g of a polymer was obtained. The polymerization activity was 3.92 kg-PP / mmol-Zr · hr, Mw = 223000, Mw / Mn = 2.02, [η] = 1.77 dl / g, and Tm = 157.9 ° C.

[Comparative Example 1]
A catalyst solution was prepared and polymerized in the same manner as in Example 1 except that the catalyst (a) was changed to the catalyst (b) and the polymerization time was changed to 31 minutes in Example 1. As a result, 19.6 g of a polymer was obtained. The polymerization activity was 7.59 kg-PP / mmol-Zr · hr, and the obtained polymer [η] was 1.72 dl / g and Tm = 154.8 ° C.

[Comparative Example 2]
A catalyst solution was prepared and polymerized in the same manner as in Example 1 except that the catalyst (a) was changed to catalyst (c), the solvent was changed to toluene and the polymerization time was changed to 50 minutes. As a result, 8.23 g of polymer was obtained. The polymerization activity was 6.58 kg-PP / mmol-Zr · hr, and the obtained polymer [η] was 1.23 dl / g, Tm = 142.1 ° C.

A stainless steel autoclave with an internal volume of 1 L sufficiently purged with nitrogen was charged with 150 mL of cyclohexane and 150 mL of solvent A, and propylene was circulated in an amount of 30 L / hr and kept at 50 ° C. for 20 minutes. On the other hand, a magnetic stirrer was placed in a 30 mL branch flask with an internal volume sufficiently purged with nitrogen. mol / L) was added at 250.0 μmol, and then solvent A was added and stirred for 1 hour. This solution was added to a mixed solvent of cyclohexane and solvent A (volume ratio = 1: 1) in a stainless steel autoclave in which propylene had been circulated to initiate polymerization. Thereafter, only propylene was continuously supplied to maintain the total pressure at 0.5 MPa-G, and polymerization was carried out at 50 ° C. for 1 hour. Since it was easy to control the heat generation during the polymerization, it was expected to be uniform during the polymerization. After completion of the polymerization, the pressure was released while maintaining the temperature at 50 ° C., and a normal pressure was obtained. Thereafter, unreacted propylene was purged while maintaining 50 ° C. The homogeneity of the polymer solution was confirmed by opening the top plate of the autoclave and visually observing the polymer solution in the autoclave. The obtained polymer solution in a uniform state was poured into a large excess of methanol to precipitate a polymer, followed by drying under reduced pressure at 80 ° C. for 12 hours. As a result, 17.73 g of a polymer was obtained. The polymerization activity of polypropylene is 35.50 kg / mmol-Zr · hr, and the intrinsic viscosity [η] of the obtained polymer is 1.57 dl / g, MFR = 4.30 g / 10min, Tm ₁ = 156 ° C., Tm ₂ = 162 ° C. Met.

  About the above result, the result of Examples 1-2 regarding propylene polymerization and the comparative examples 1-2 was put together in Table 1.

  The merit given to the olefin polymerization industry by the production method of the high melting point olefin polymer is great. When an olefin polymerization catalyst comprising a crosslinked metallocene compound according to the present invention is used, for example, if propylene is used as a monomer, the resulting propylene polymer has a high molecular weight and a high melting point, and is excellent in processability. In addition, high melting point polypropylene can be produced even under high temperature polymerization conditions. Further, when a monomer other than propylene is used, a polymer having a melting point equivalent to or higher than that when a known metallocene compound is used can be obtained.

Claims (3)

The bridged metallocene compound (A) represented by the following general formula [1], and the compound (B) selected from the following components (b-1), (b-2) and (b-3)
(b-1) an organoaluminum oxy compound,
(b-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair,
(b-3) A method for producing an olefin polymer, wherein one or more monomers selected from α-olefins having 2 or more carbon atoms are polymerized in the presence of an olefin polymerization catalyst comprising an organoaluminum compound;

(In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁴ > shows a hydrogen atom.
R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ²⁰ are selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group, and each may be the same or different, and in one or more adjacent group combinations The adjacent groups may be bonded to each other to form a ring.
R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹⁵ , R ¹⁶ , R ¹⁸ and R ^{19 each} represent a hydrogen atom. R ⁸ and R ¹⁷ are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, or a hydrocarbon group containing a halogen atom, and may be the same or different, but at least of R ⁸ and R ¹⁷ One is selected from a halogen atom or a hydrocarbon group containing a halogen atom.
R ²¹ and R ²² are a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms or a silicon-containing group having 1 to 40 carbon atoms, which may be the same as or different from each other, and are bonded to each other to form a ring. Also good.
M is Ti, Zr or Hf, Y is a silicon atom or a carbon atom,
Q is selected from a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair in the same or different combination, and j is an integer of 1 to 4. ) In the said General formula [1], R < ⁸ > and R < ¹⁷ > is the hydrocarbon group containing a halogen atom or a halogen atom, The manufacturing method of the olefin polymer of Claim 1 characterized by the above-mentioned.   The method for producing an olefin polymer according to claim 1 or 2, wherein the olefin polymerization catalyst further contains a carrier (C).