WO2013022108A1

WO2013022108A1 - Olefin polymerization catalyst and method for producing olefin polymer

Info

Publication number: WO2013022108A1
Application number: PCT/JP2012/070574
Authority: WO
Inventors: 正人 ▲高▼野; 高沖　和夫; 健二十河; 伊藤　和幸
Original assignee: 住友化学株式会社
Priority date: 2011-08-11
Filing date: 2012-08-10
Publication date: 2013-02-14
Also published as: JP2014198744A

Abstract

An olefin polymerization catalyst is obtained by causing a complex represented by general formula (1-1) or (1-2), an activating co-catalyst component, and a carrier to contact one another.

Description

Olefin polymerization catalyst and process for producing olefin polymer

The present invention relates to a catalyst for olefin polymerization using a titanium, zirconium or hafnium complex and a method for producing an olefin polymer.

There is known a method for producing an olefin polymer in which olefins are polymerized or copolymerized in the presence of a catalyst obtained by contacting a carrier such as an inorganic compound or a particulate polymer, a transition metal complex, and a promoter component for activation. From the viewpoints of polymer structure such as molecular weight and molecular weight distribution, particle properties of the polymer, and operational stability during polymerization, this is an advantageous production method. However, not all transition metal compounds capable of polymerizing olefins are suitable for this production method.

On the other hand, the development of metallocene catalysts is one of the topics in recent years in the chemistry of olefin polymerization that has been greatly developed by Ziegler-Natta type magnesium-supported highly active titanium catalysts. Further, recently, development of so-called post metallocene catalysts has attracted attention as a catalyst for constructing a more precise polymerization process.

Patent Document 1 reports propylene polymerization using a diphenoxy titanium complex, a zirconium complex or a hafnium complex derived from ethane-1,2-dithiol.

In addition, diphenoxy titanium complex, zirconium complex and hafnium complex derived from trans-cyclooctane-1,2-dithiol have been reported (Non-patent Document 1). Furthermore, of these complexes, 1-hexene polymerization using a zirconium complex as a catalyst has been reported (Non-patent Document 2).

International publication: WO2007 / 075299 (publication date: July 5, 2007)

The problems to be solved by the present invention include an olefin polymerization catalyst capable of producing an olefin polymer with high activity in the presence of a catalyst obtained by contacting a transition metal complex, an activation promoter component and a support, and An object of the present invention is to provide a method for producing an olefin polymer in which an olefin is polymerized in the presence of an olefin polymerization catalyst.

That is, the present invention relates to an olefin polymerization catalyst obtained by contacting a complex represented by the general formula (1-1) or (1-2), an activation promoter component and a carrier.

(Wherein n is 1 or 2,
M represents a zirconium atom or a hafnium atom.
R ¹ and R ⁵ are each independently
Hydrogen atom,
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An alkenyl group having 2 to 20 carbon atoms,
An alkynyl group having 2 to 20 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aralkyloxy group having 7 to 30 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms or a substituted silyl group is represented.
R ² to R ⁴ and R ⁶ to R ¹⁰ are each independently
Hydrogen atom,
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An alkenyl group having 2 to 20 carbon atoms,
An alkynyl group having 2 to 20 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aralkyloxy group having 7 to 30 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms,
It represents a substituted silyl group or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring.
The alkyl group, the cycloalkyl group, the alkenyl group, the alkynyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the heterocyclic compound in R ¹ to R ¹⁰ Each residue may have a substituent.
Regardless of the definition of R ¹ to R ¹⁰ above, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ² And R ⁹ and R ⁶ and R ¹⁰ may be independently connected to each other to form a ring, and these rings may have a substituent.
Each X is independently
Hydrogen atom,
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An alkenyl group having 2 to 20 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aralkyloxy group having 7 to 30 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms,
Substituted silyl groups,
A substituted amino group,
It represents a substituted thiolate group or a carboxylate group having 1 to 20 carbon atoms.
The alkyl group, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the carboxylate group in X each have a substituent. Also good.
Adjacent Xs may be connected to each other to form a ring.
L represents a neutral Lewis base. When there are a plurality of L, the plurality of L may be the same or different. l is 0, 1, or 2. )

The present invention also relates to a method for producing an olefin polymer in which an olefin is polymerized in the presence of the catalyst.

Furthermore, the present invention relates to an ethylene-α having a polymer particle content of not more than 2% by volume, a 50% volume particle size of not less than 500 μm, and a particle bulk density of not less than 400 kg / m ^3. -Relating to olefin copolymer particles.

According to the present invention, an olefin polymer can be produced with high productivity. In the polymerization of α-olefin, an α-olefin polymer having high stereoregularity can be produced with high productivity.

It is a figure which shows the SEM image of the polymer particle obtained in one Example.

[Olefin polymerization catalyst]
The olefin polymerization catalyst according to the present invention is obtained by contacting a complex represented by the following general formula (1-1) or (1-2), an activation promoter component and a carrier.
(Complex)
The complexes represented by the following general formulas (1-1) and (1-2) will be described.

M represents a zirconium atom or a hafnium atom. From the viewpoint of producing a high molecular weight polyolefin, hafnium atoms are preferred.

N is 1 or 2, preferably 2.

R ¹ and R ⁵ are each independently
Hydrogen atom,
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An alkenyl group having 2 to 20 carbon atoms,
An alkynyl group having 2 to 20 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aralkyloxy group having 7 to 30 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms or a substituted silyl group is represented.
R ¹ and R ⁵ are preferably each independently
Hydrogen atom,
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aralkyloxy group having 7 to 30 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms, or a substituted silyl group,
More preferably, each independently
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms, or a substituted silyl group,
R ¹ and R ⁵ are particularly preferably when R ¹ and R ⁵ are the same,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms or a substituted silyl group.

R ⁹ and R ¹⁰ are each independently
Hydrogen atom,
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An alkenyl group having 2 to 20 carbon atoms,
An alkynyl group having 2 to 20 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aralkyloxy group having 7 to 30 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms,
It represents a substituted silyl group or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring.
R ⁹ and R ¹⁰ are preferably each independently
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms,
A substituted silyl group, or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring,
More preferably, each independently an alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms,
Or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring,
R ⁹ and R ¹⁰ are particularly preferably R ⁹ and R ¹⁰ are the same,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
It is an aryl group having 6 to 30 carbon atoms, or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring.

R ² to R ⁴ and R ⁶ to R ⁸ are each independently
Hydrogen atom,
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An alkenyl group having 2 to 20 carbon atoms,
An alkynyl group having 2 to 20 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aralkyloxy group having 7 to 30 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms,
It represents a substituted silyl group or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring.
R ² to R ⁴ and R ⁶ to R ⁸ are preferably each independently
Hydrogen atom,
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms, or a substituted silyl group,
More preferably, each independently
Hydrogen atom,
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms or a substituted silyl group.
R ² , R ⁴ , R ⁶ and R ⁸ are more preferably a hydrogen atom.
More preferably, R ³ and R ⁷ are each independently
A halogen atom,
A cycloalkyl group having 3 to 10 carbon atoms constituting an alkyl group ring having 1 to 20 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms or a substituted silyl group.
As R ³ and R ⁷ , particularly preferably, R ³ and R ⁷ are the same,
A cycloalkyl group having 3 to 10 carbon atoms constituting an alkyl group ring having 1 to 20 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms, or a substituted silyl group,
Most preferably,
An alkyl group having 1 to 20 carbon atoms.

The alkyl group, the cycloalkyl group, the alkenyl group, the alkynyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the heterocyclic group in R ¹ to R ¹⁰ Each compound residue may have a substituent.

Examples of the halogen atom in R ¹ to R ¹⁰ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in R ¹ to R ¹⁰ include a perfluoromethyl group, a perfluoroethyl group, a perfluoro-n-propyl group, a perfluoroisopropyl group, and a perfluoro group. -N-butyl, perfluoro-sec-butyl, perfluoroisobutyl, perfluoro-tert-butyl, perfluoro-n-pentyl, perfluoroisopentyl, perfluoro-tert-pentyl, perfluoro Fluoroneopentyl group, perfluoro-n-hexyl group, perfluoro-n-heptyl group, perfluoro-n-octyl group, perfluoro-n-decyl group, perfluoro-n-dodecyl group, perfluoro-n- Pentadecyl group, perfluoro-n-eicosyl group, methyl group, ethyl group, -Propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, n-hexyl group, texyl group, neohexyl Group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group and n-eicosyl group.

The substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in R ¹ , R ⁵ , R ⁹ and R ¹⁰ is preferably an n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n- Alkyl groups having 4 to 10 carbon atoms such as pentyl group, isopentyl group, tert-pentyl group, neopentyl group, n-hexyl group, texyl group, neohexyl group, n-heptyl group, n-octyl group and n-decyl group And
More preferably, it is a tertiary alkyl group having 4 to 10 carbon atoms such as a tert-butyl group, a tert-pentyl group, or a texyl group,
Most preferred is a tertiary alkyl group having 5 to 10 carbon atoms, such as a tert-pentyl group or a texyl group.

The substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in R ² to R ⁴ and R ⁶ to R ⁸ is preferably a perfluoromethyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, n-hexyl group, texyl group, neohexyl group, n-heptyl group, n An alkyl group having 4 to 10 carbon atoms such as an octyl group or an n-decyl group,
More preferably, it is an alkyl group having 1 to 8 carbon atoms such as perfluoromethyl group, methyl group, isopropyl group, isobutyl group, tert-butyl group, isopentyl group, tert-pentyl group, neopentyl group, texyl group,
More preferred are alkyl groups having 1 to 4 carbon atoms such as perfluoromethyl group, methyl group, isopropyl group, isobutyl group and tert-butyl group.

Examples of the substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms constituting the ring in R ¹ to R ¹⁰ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Group, 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-phenylcyclohexyl group, 1-indanyl group, 2-indanyl group, norbornyl group, bornyl group, menthyl group, 1-adamantyl group, 2-adamantyl group, 3 , 5-dimethyladamantyl group, 3,5,7-trimethyladamantyl group, 3,5-diethyladamantyl group, 3,5,7-triethyladamantyl group, 3,5-diisopropyladamantyl group, 3,5,7-tri Isopropyl adamantyl group, 3,5-diisobutyl adamant Group, 3,5,7-triisobutyladamantyl group, 3,5-diphenyladamantyl group, 3,5,7-triphenyladamantyl group, 3,5-di (p-toluyl) adamantyl group, 7-tri (p-toluyl) adamantyl group, 3,5-di (3,5-xylyl) adamantyl group, 3,5,7-tri (3,5-xylyl) adamantyl group,
Preferably, a cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-indanyl group, 2-indanyl group, norbornyl group, bornyl group, menthyl group, 1- Adamantyl group, 2-adamantyl group, 3,5-dimethyladamantyl group, 3,5-diethyladamantyl group, 3,5-diphenyladamantyl group, 3,5-di (p-toluyl) adamantyl group, 3,5-di (3,5-xylyl) adamantyl group and the like, which is a cycloalkyl group having 5 to 26 carbon atoms (including carbon atoms other than carbon atoms constituting the ring) of 5 to 26,
More preferably, the number of carbon atoms such as cyclohexyl group, 1-methylcyclohexyl group, norbornyl group, bornyl group, 1-adamantyl group, 2-adamantyl group, 3,5-dimethyladamantyl group, 3,5-diethyladamantyl group ( A number of carbon atoms other than the carbon atoms constituting the ring) 6 to 14 cycloalkyl groups.

Examples of the substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms in R ¹ to R ¹⁰ include a vinyl group, an allyl group, a propenyl group, a 2-methyl-2-propenyl group, a homoallyl group, a pentenyl group, and a hexenyl. Group, heptenyl group, octenyl group, nonenyl group, decenyl group, etc.,
An alkenyl group having 3 to 6 carbon atoms is preferable, and an allyl group or a homoallyl group is more preferable.

Examples of the substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms in R ¹ to R ¹⁰ include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, and 3-methyl-1-butynyl. Group, 3,3-dimethyl-1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 4-methyl-1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl Group, 4-methyl-1-pentenyl group, 1-hexynyl group, 1-octynyl group, phenylethynyl group,
Preferably, it is an alkynyl group having 3 to 8 carbon atoms, more preferably a 3-methyl-1-butynyl group, a 3,3-dimethyl-1-butynyl group, a 4-methyl-1-pentenyl group or a phenylethynyl group. is there.

Examples of the substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms in R ¹ to R ¹⁰ include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methyl Phenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, ( 3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2, 3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-te Lamethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) ) Methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (isobutylphenyl) ) Methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl Group, anthracenylmethyl group, dimethyl (phenyl) methyl group, dimethyl (4-methylphenyl) Methyl group, dimethyl (1-naphthyl) methyl, dimethyl (2-naphthyl) methyl group, methyl (diphenyl) methyl, methyl bis (4-methylphenyl) methyl group, and a triphenylmethyl group,
Preferably, benzyl group, naphthylmethyl group, anthracenylmethyl group, dimethyl (phenyl) methyl group, dimethyl (4-methylphenyl) methyl group, dimethyl (1-naphthyl) methyl group, dimethyl (2-naphthyl) methyl group Methyl (diphenyl) methyl group, methylbis (4-methylphenyl) methyl group, triphenylmethyl group,
More preferably, dimethyl (phenyl) methyl group, dimethyl (4-methylphenyl) methyl group, dimethyl (1-naphthyl) methyl group, dimethyl (2-naphthyl) methyl group, methyl (diphenyl) methyl group, methylbis (4- A tertiary aralkyl group having 9 to 20 carbon atoms, such as a methylphenyl) methyl group or a triphenylmethyl group;

Examples of the substituted or unsubstituted aryl group having 6 to 30 carbon atoms in R ² to R ⁴ and R ⁶ to R ¹⁰ include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, 2 , 3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetra Methylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n - Ruphenyl group, sec-butylphenyl group, tert-butylphenyl group, isobutylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n- Dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group, 3,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, 3,5-ditert-butylphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, pentafluorophenyl group, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 2,3-difluorophenyl group, 2 , 4-difluorophenyl group, 2,5- Fluorophenyl group, 2,6-difluorophenyl group, 2-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2,3-dibromophenyl group, 2,4-dibromophenyl group, 2,5-dibromophenyl group, and the like.
Preferably, phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3 , 4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethyl Phenyl group, 3,4,5-trimethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, 3,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, 3,5-ditert- A phenyl group having 6 to 20 carbon atoms such as butylphenyl group; 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, pentafluorophenyl group, 2, -Fluorinated phenyl groups such as difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group; 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group , A fluorinated alkylphenyl group such as 4-trifluoromethylphenyl group,
More preferably, phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,6-xylyl group, 3,5-xylyl group, 2,4,6-trimethylphenyl group, 3,5- Diisopropylphenyl group, 2,6-diisopropylphenyl group, 3,5-ditert-butylphenyl group, 2-fluorophenyl group, pentafluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 2,4,6-trifluorophenyl group.

Examples of the substituted silyl group in R ¹ to R ¹⁰ include a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a tri-n-butylsilyl group, a triisobutylsilyl group, and a tert-butyldimethyl group. Examples include silyl group, methyldiphenylsilyl group, dimethyl (phenyl) silyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, methylbis (trimethylsilyl) silyl group, dimethyl (trimethylsilyl) silyl group, and tris (trimethylsilyl) silyl group. ,
Preferably, a trialkylsilyl group having 3 to 20 carbon atoms such as trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group; methylbis (trimethylsilyl) silyl group, dimethyl group A silyl group having a hydrocarbylsilyl group having 3 to 20 carbon atoms as a substituent, such as (trimethylsilyl) silyl group and tris (trimethylsilyl) silyl group.

Examples of the substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms in R ¹ to R ¹⁰ include, for example, a perfluoromethoxy group, a perfluoroethoxy group, a perfluoro-n-propoxy group, a perfluoroisopropoxy group, a perfluoro group, Fluoro-n-butoxy group, perfluoro-sec-butoxy group, perfluoroisobutoxy group, perfluoro-n-pentyloxy group, perfluoronepentyloxy group, perfluoro-n-hexyloxy group, perfluoro-n -Heptyloxy group, perfluoro-n-octyloxy group, perfluoro-n-decyloxy group, perfluoro-n-dodecyloxy group, perfluoro-n-pentadecyloxy group, perfluoro-n-eicosyloxy group Methoxy group, ethoxy group, n-propoxy group, isop Poxy group, n-butoxy group, sec-butoxy group, isobutoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, n-pentadecyloxy group, n-eicosyloxy group, and the like.
An alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butoxy group are more preferable.

Examples of the aryloxy group having 6 to 30 carbon atoms in R ¹ to R ¹⁰ include, for example, phenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6- Trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, 2,6-diisopropylphenoxy group, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, pentafluorophenoxy group, 2 -Trifluoromethylphenoxy group, 3-trifluoromethylphenoxy group, 4-trifluoromethylphenoxy group Group, 2,3-difluorophenoxy group, 2,4-fluorophenoxy group, 2,5-difluorophenoxy group, 2-chlorophenoxy group, 2,3-dichlorophenoxy group, 2,4-dichlorophenoxy group, 2, 5-dichlorophenoxy group, 2-bromophenoxy group, 3-bromophenoxy group, 4-bromophenoxy group, 2,3-dibromophenoxy group, 2,4-dibromophenoxy group, or 2,5-dibromophenoxy group And
Preferably, it is an aryloxy group having 6 to 14 carbon atoms, more preferably 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,6-diisopropylphenoxy group, pentafluorophenoxy group. It is.

Examples of the substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms in R ¹ to R ¹⁰ include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4 -Methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, 2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) Nyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n- (Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group , (N-tetradecylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group It is,
Preferred is an aralkyloxy group having 7 to 12 carbon atoms, and more preferred is a benzyloxy group.

Examples of the substituted or unsubstituted heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring in R ² to R ⁴ and R ⁶ to R ¹⁰ include a thienyl group, a furyl group, and a 1-pyrrolyl group. 1-imidazolyl group, 1-pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, 2-isoindolyl group, 1-indolyl group, quinolyl group, dibenzo-1H-pyrrol-1-yl group, N-carbazolyl Groups,
Preferred are thienyl group, furyl group, 1-pyrrolyl group, pyridyl group, pyrimidinyl group, 2-isoindolyl group, 1-indolyl group, quinolyl group, dibenzo-1H-pyrrol-1-yl group, or N-carbazolyl group. .

Regardless of the definition of R ¹ to R ¹⁰ above, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ² And R ⁹ and R ⁶ and R ¹⁰ may be independently connected to each other to form a ring, and these rings may have a substituent, preferably 2 on the benzene ring. It is a 4- to 10-membered hydrocarbyl ring or heterocyclic ring containing one carbon atom, and the ring may have a substituent.

Specific examples of the ring include cyclobutene ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring, benzene ring or naphthalene ring, furan ring, 2,5-dimethylfuran ring, thiophene ring, 2, 5-dimethylthiophene ring, pyridine ring and the like can be mentioned, and preferably a cyclopentene ring, cyclopentadiene ring, cyclohexene ring, benzene ring or naphthalene ring, more preferably R ¹ and R ² , R ⁵ and R ⁶ , A cyclopentene ring, a cyclohexene ring, a benzene ring or a naphthalene ring in which R ² and R ⁹ and / or R ⁶ and R ¹⁰ are linked.

Each X is independently
Hydrogen atom,
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An alkenyl group having 2 to 20 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aralkyloxy group having 7 to 30 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms,
Substituted silyl groups,
A substituted amino group,
It represents a substituted thiolate group or a carboxylate group having 1 to 20 carbon atoms.
The alkyl group, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the carboxylate group in X each have a substituent. Also good.
Adjacent Xs may be connected to each other to form a ring, and the ring may have a substituent.
A halogen atom in X, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, an alkenyl group having 2 to 20 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms An aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyloxy group having 7 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and a substituted silyl group, , R ² to R ⁴ and R ⁶ to R ⁸ are the same as described above.

Examples of the substituted amino group in X include, for example, a dimethylamino group, a diethylamino group, a di-n-butylamino group, a di-n-propylamino group, a diisopropylamino group, a dibenzylamino group, or a diphenylamino group. 14 hydrocarbylamino groups,
A dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group or a dibenzylamino group is preferable.

Examples of the substituted thiolate group in X include a thiophenoxy group, 2,3,4-trimethylthiophenoxy group, 2,3,5-trimethylthiophenoxy group, 2,3,6-trimethylthiophenoxy group, 2,4 , 6-trimethylthiophenoxy group, 3,4,5-trimethylthiophenoxy group, 2,3,4,5-tetramethylthiophenoxy group, 2,3,4,6-tetramethylthiophenoxy group, 2,3,5 , 6-tetramethylphenoxy group, pentamethylphenoxy group, 2-fluorothiophenoxy group, 3-fluorothiophenoxy group, 4-fluorophenoxy group, pentafluorothiophenoxy group, 2-trifluoromethylthiophenoxy group, 3-tri Fluoromethylthiophenoxy group, 4-trifluoromethylthiophenoxy group, 2,3 Difluorothiophenoxy group, 2,4-fluorothiophenoxy group, 2,5-difluorothiophenoxy group, 2-chlorothiophenoxy group, 2,3-dichlorothiophenoxy group, 2,4-dichlorothiophenoxy group, 2, 5-dichlorothiophenoxy group, 2-bromothiophenoxy group, 3-bromothiophenoxy group, 4-bromothiophenoxy group, 2,3-dibromothiophenoxy group, 2,4-dibromothiophenoxy group, and 2,5 -Hydrocarbyl thiolate groups having 6 to 12 carbon atoms such as dibromothiophenoxy groups,
Preferably, thiophenoxy group, 2,4,6-trimethylthiophenoxy group, 3,4,5-trimethylthiophenoxy group, 2,3,4,5-tetramethylthiophenoxy group, 2,3,4,6-tetra A methylthiophenoxy group, a 2,3,5,6-tetramethylthiophenoxy group, a pentamethylthiophenoxy group or a pentafluorothiophenoxy group;

Examples of the substituted or unsubstituted carboxylate group having 1 to 20 carbon atoms in X include an acetate group, propionate group, butyrate group, pentanate group, hexanoate group, 2-ethylhexanoate group or trifluoroacetate group. Named,
A hydrocarbyl carboxylate group having 2 to 10 carbon atoms is preferred, and an acetate group, propionate group, 2-ethylhexanoate group or trifluoroacetate group is more preferred.

X is preferably a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyloxy group having 7 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, or a substituted amino group, more preferably a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. , An alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a hydrocarbylamino group having 1 to 20 carbon atoms, and more preferably a chlorine atom, a bromine atom, or a carbon atom An alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a carbon atom A hydrocarbylamino group of 2 to 10, more preferably a chlorine atom, a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, a benzyl group, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, a phenoxy group, a dimethylamino group, or a diethylamino group, particularly preferably a chlorine atom, a methyl group, a benzyl group, an isopropoxy group, a phenoxy group, or a dimethylamino group, most preferably chlorine An atom or a benzyl group.

L represents a neutral Lewis base. Examples of L include ethers, amines or thioethers, and specific examples include tetrahydrofuran, diethyl ether, 1,4-dioxane, and pyridine. L is preferably tetrahydrofuran.
l is 0, 1, or 2, preferably 0 or 1, and more preferably 0. When there are a plurality of L, the plurality of L may be the same or different.

The alkyl group, the cycloalkyl group, the alkenyl group, the alkynyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the heterocyclic compound in R ¹ to R ¹⁰ Substituents that the residue may have, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ² and R ⁹ or a ring formed by connecting R ⁶ and R ¹⁰ may have a substituent, the alkyl group in X, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the above The alkoxy group, the aralkyloxy group, the aryloxy group, the substituent that the carboxylate group may have, and the ring formed by linking X to each other. As also substituent, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a silicon atom, a nitrogen atom, and a substituted group containing a phosphorus atom or a sulfur atom.

Specific examples of the complex represented by the formula (1-1) include the following compounds, but are not intended to be limited to these compounds.

In addition to these, two benzyl groups directly bonded to the zirconium atom of each of the above compounds can be replaced with a chlorine atom, a methyl group, a dimethylamino group, an isopropoxy group, a tert-butoxy group, or a phenoxy group. Also included are modified compounds.

Furthermore, compounds in which the zirconium atom in each of the above compounds is changed to a hafnium atom are also included.

Further, in each of the above compounds, the group corresponding to R ³ and R ⁷ in the general formula (1-1) is changed to a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group. The compound which was made is also mentioned.

Furthermore, compounds obtained by substituting the cyclooctane ring that bridges the sulfur atom of each of the above compounds with a cycloheptane ring are also included.

Preferred examples of the complex represented by the formula (1-1) include the following compounds.

In addition to these, compounds in which the two benzyl groups directly bonded to the zirconium atom of each of the above compounds are changed to chlorine atoms or methyl groups are also included.

More preferable examples of the complex represented by the formula (1-1) include the following compounds.

In addition to these, compounds in which the two benzyl groups directly bonded to the zirconium atom of each of the above compounds are changed to chlorine atoms can also be mentioned.

Furthermore, compounds in which the groups corresponding to R ³ and R ⁷ in the general formula (1-1) in each of the above compounds are changed to methyl groups are also included.

Most preferred examples of the complex represented by the formula (1-1) include the following compounds.

Specific examples of the complex represented by the formula (1-2) include the following compounds, but are not intended to be limited to these compounds.

In addition to these, two benzyl groups directly bonded to the titanium atom of each of the above compounds can be replaced with a chlorine atom, a methyl group, a dimethylamino group, an isopropoxy group, a tert-butoxy group, or a phenoxy group. Also included are modified compounds.

Further, in each of the above compounds, the group corresponding to R ³ and R ⁷ in the general formula (1-2) is changed to a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group. Also included are the compounds.

Preferred examples of the complex represented by the formula (1-2) include the following compounds.

In addition to these, compounds in which the two benzyl groups directly bonded to the titanium atom of each of the above compounds are changed to chlorine atoms or methyl groups are also included.

More preferable examples of the complex represented by the formula (1-2) include the following compounds.

In addition to these, compounds in which the two benzyl groups directly bonded to the titanium atom of each of the above compounds are changed to chlorine atoms can also be mentioned.

Furthermore, compounds in which the groups corresponding to R ³ and R ⁷ in the above general formula (1-2) in each of the above compounds are changed to methyl groups are also included.

Particularly preferable examples of the complex represented by the formula (1-2) include the following compounds.

In addition to these, compounds in which the benzyl group directly bonded to the titanium atom of each of the above compounds is changed to a chlorine atom can also be mentioned.

The complex represented by the general formula (1-1) and the complex represented by the general formula (1-2) (hereinafter collectively referred to as “complex (1)”) are described in, for example, the method described in Non-Patent Document 2. Can be synthesized. Specifically, the compound represented by the following general formula (2-1) or (2-2) (hereinafter collectively referred to as “compound (2)”) and the following general formula (3-1) or (3 -2) (hereinafter collectively referred to as “compound (3)”) can be produced by the following scheme 1 as a starting material. However, it should not be limited to this method.

^R 1 ~ ^{R 8} and n in the general formula (2-1) is the same as the ^R 1 ~ ^{R 8} and n in the general formula (1-1) in. ^R 2 ^~ R ⁴ in the general formula ^{(2-2), R 6 ~ R} 10 and n are the same as the general formula (1-2) in the ^{^{^{R 2 ~ R 4, R 6}}} ~ R 10 and n is there.

M and X in the general formula (3-1) are the same as M and X in the general formula (1-1). MX ₄ includes, for example, Zr (CH ₂ Ph) ₄ , ZrCl ₂ (CH ₂ Ph) ₂ , Zr (CH ₂ SiMe ₃ ) ₄ , ZrF ₄ , ZrCl ₄ , ZrBr ₄ , ZrI ₄ , Zr (OMe) ₄ , Zr (OEt) ₄ , Zr (Oi-Pr) ₄ , ZrCl ₂ (Oi-Pr) ₂ , Zr (On-Bu) ₄ , Zr (Oi-Bu) ₄ , Zr ( Ot-Bu) ₄ , Zr (OPh) ₄ , Zr (NMe ₂ ) ₄ , ZrCl ₂ (NMe ₂ ) ₂ , Zr (NEt ₂ ) ₄ , Hf (CH ₂ Ph) ₄ , HfCl ₂ (CH ₂ Ph _{_{) 2, Hf (CH 2 SiMe}} 3) 4, HfF 4, HfCl 4, HfBr 4, HfI 4, Hf (OMe) 4, Hf (OEt) 4, Hf (O-i-Pr) 4, HfCl 2 (O -I-Pr) ₂ , Hf (On-Bu) ₄ , Hf (Oi-Bu) ₄ , Hf (Ot- Bu) ₄ , Hf (OPh) ₄ , Hf (NMe ₂ ) ₄ , HfCl ₂ (NMe ₂ ) ₂ , and Hf (NEt ₂ ) ₄ . Preferably, Zr (CH ₂ Ph) ₄ , ZrCl ₂ (CH ₂ Ph) ₂ , Zr (CH ₂ SiMe ₃ ) ₄ , ZrCl ₄ , ZrBr ₄ , Zr (OMe) ₄ , Zr (OEt) ₄ , Zr (O _{-i-Pr) 4, Zr (} O-i-Bu) 4, Zr (O-t-Bu) 4, Zr (OPh) 4, Zr (NMe 2) 4, ZrCl 2 (NMe 2) 2, Zr ( _{_{_{NEt 2) 4, Hf (CH}}} 2 Ph) 4, HfCl 2 (CH 2 Ph) 2, Hf (CH 2 SiMe 3) 4, HfCl 4, HfBr 4, Hf (OMe) 4, Hf (OEt) 4, Hf _{(O-i-Pr) 4} , Hf (O-i-Bu) 4, Hf (O-t-Bu) 4, Hf (OPh) 4, Hf (NMe 2) 4, HfCl 2 (NMe 2) 2, Or Hf (NEt ₂ ) ₄ .

X in the general formula (3-2) is the same as X in the general formula (1-2). Examples of TiX ₄ include Ti (CH ₂ Ph) ₄ , TiCl ₂ (CH ₂ Ph) ₂ , Ti (CH ₂ SiMe ₃ ) ₄ , TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , and Ti (OMe) _4. , Ti (OEt) ₄ , Ti (Oi-Pr) ₄ , TiCl ₂ (Oi-Pr) ₂ , Ti (On-Bu) ₄ , Ti (Oi-Bu) ₄ , Ti ( _{O-t-Bu) 4,} Ti (OPh) 4, Ti (NMe 2) 4, TiCl 2 (NMe 2) 2, Ti (NEt 2) 4 and the like. Preferably, Ti (CH ₂ Ph) ₄ , TiCl ₂ (CH ₂ Ph) ₂ , Ti (CH ₂ SiMe ₃ ) ₄ , TiCl ₄ , TiBr ₄ , Ti (OMe) ₄ , Ti (OEt) ₄ , Ti (O _{-i-Pr) 4, Ti (} O-i-Bu) 4, Ti (O-t-Bu) 4, Ti (OPh) 4, Ti (NMe 2) 4, TiCl 2 (NMe 2) 2 or Ti, (NEt ₂ ) ₄

The complex (1) may be formed by reacting the compound (2) and the compound (3) as they are. If necessary, the compound (2) is reacted with a base and then the compound (3) is reacted. It may be formed. These reactions are usually performed in a solvent. Examples of the base to be used include organic lithium reagents, Grignard reagents and metal hydrides. Specifically, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, lithium hexamethyldisilazane, Potassium hexamethyldisilazane, sodium hydride or potassium hydride can be mentioned, and preferably n-butyllithium, lithium diisopropylamide, potassium hexamethyldisilazane, sodium hydride or potassium hydride.

Since the compound obtained by reacting the compound (2) with a base, the complex (1) and the compound (3) are usually unstable to air and moisture, the reaction is preferably carried out under dehydration and deoxygenation. Specifically, it is under dry nitrogen or dry argon.

The amount of compound (2) used may be 1 molar equivalent or more with respect to compound (3), and is preferably in the range of 1.0 to 1.5 molar equivalents. Moreover, when the compound (2) remains in the course of the reaction, the compound (3) may be added during the reaction.

The temperature at which compound (2) and compound (3) are reacted is in the range of −100 ° C. to 150 ° C., preferably in the range of −80 ° C. to 50 ° C. However, it is not intended to be limited to this range.

The reaction of the compound (2) and the compound (3) may be carried out until the time when the yield of the product becomes the highest, preferably 5 minutes to 48 hours, more preferably 10 minutes to 24 hours.

The temperature at which the compound (2) reacts with the base is in the range of −100 ° C. to 150 ° C., preferably in the range of −80 ° C. to 50 ° C. However, it is not intended to be limited to this range.

The reaction time of the compound (2) and the base may be performed until the product yield becomes the highest, for example, 5 minutes to 24 hours, preferably 10 minutes to 12 hours, more preferably 30 minutes. ~ 3 hours.

The temperature at which the compound (2) and the compound produced by reacting the base and the compound (3) are reacted is in the range of −100 ° C. to 150 ° C., preferably in the range of −80 ° C. to 50 ° C. However, it is not intended to be limited to this range.

The reaction time of the compound produced by reacting the compound (2) with the base and the compound (3) may be up to the time when the yield of the product is the highest, for example, 5 minutes to 48 hours. It is preferably 10 minutes to 24 hours.

The solvent to be used is not particularly limited as long as it is a solvent generally used in similar reactions, and examples thereof include a hydrocarbon solvent or an ether solvent. Preferred is toluene, benzene, o-xylene, m-xylene, p-xylene, hexane, pentane, heptane, cyclohexane, diethyl ether or tetrahydrofuran, and more preferred is diethyl ether, toluene, tetrahydrofuran, hexane, pentane, heptane. Or cyclohexane.

Compound (2) can be synthesized, for example, according to the method described in Reference: Journal of American Chemical Society, 2009, Volume 131, 13566-13567. Specifically, although it can manufacture by the following scheme 2, it should not be limited to this method. Hereinafter, each process will be described in detail. A compound represented by the following general formula (4), (5-1), (5-2), (6-1), (6-2), (7-1), or (7-2) Are represented by “compound (4)”, “compound (5-1)”, “compound (5-2)”, “compound (6-1)”, “compound (6-2)”, “compound (7- 1) "or" Compound (7-2) ". Further, “compound (5-1)” and “compound (5-2)” are collectively referred to as “compound (5)”, and “compound (6-1)” and “compound (6-2)” are referred to as “compound (6-1)”. These are collectively referred to as “compound (6)”, and “compound (7-1)” and “compound (7-2)” are collectively referred to as “compound (7)”.

^R 1 ^{~ R 10} and n in each compound in scheme2 the general formula (1-1) and (1-2) is the same as ^R 1 ^{~ R 10} and n in.

X ′ represents an anionic leaving group such as a halogen atom, acetate group, trifluoroacetate group, benzoate group, CF ₃ SO ₃ group, CH ₃ SO ₃ group, 4-MeC ₆ H ₄ SO ₃ group or PhSO ₃ groups, etc. are mentioned, and preferred are a chlorine atom, a bromine atom, an iodine atom, a CF ₃ SO ₃ group, a CH ₃ SO ₃ group, a 4-MeC ₆ H ₄ SO ₃ group or a PhSO ₃ group.

[Step 1]
Compound (6) can be synthesized by reacting compound (4) with 1.0 to 4.0 equivalents, preferably 1.0 to 1.5 equivalents of compound (5) in the presence of a base.

The base is not particularly limited, but includes inorganic bases such as potassium carbonate, calcium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and calcium hydrogen carbonate, and amine bases such as triethylamine and triisobutylamine. Preferably, it is an amine base.

This reaction can be performed in an atmosphere of air, helium, argon, or nitrogen. Preferably, it is under a helium, argon or nitrogen atmosphere, more preferably under a nitrogen or argon atmosphere.

After completion of the reaction, the compound (6) may be purified as necessary. As a purification method, for example, an ammonium chloride aqueous solution, a hydrochloric acid aqueous solution or a sodium chloride aqueous solution is added to the reaction solution, followed by addition of ethyl acetate or diethyl ether, and an extraction operation is performed to remove excess base or salt. Can be mentioned. Furthermore, the purity of the compound (6) can be increased by purification operations such as distillation, recrystallization or silica gel chromatography.

[Step 2]
Compound (2) can be synthesized by reacting compound (6) with 1.0 to 4.0 equivalents, preferably 1.0 to 1.5 equivalents of compound (7) in the presence of a base.

Examples of the base include inorganic bases such as potassium carbonate, calcium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and calcium hydrogen carbonate, and amine bases such as triethylamine and triisobutylamine, with amine bases being preferred.

After completion of the reaction, the compound (2) may be purified as necessary. As a purification method, for example, an ammonium chloride aqueous solution, a hydrochloric acid aqueous solution or a sodium chloride aqueous solution is added to the reaction solution, followed by addition of ethyl acetate or diethyl ether, and an extraction operation is performed to remove excess base or salt. Can be mentioned. Furthermore, the purity of the compound (2) can be increased by purification operations such as distillation, recrystallization or silica gel chromatography.

The compound (2) can also be obtained by reacting the compound (6) and the compound (7) produced in the reactor by controlling the reaction conditions of [step 1].

When R ¹ is the same as R ⁵ (or R ⁹ is R ¹⁰ ), R ² is the same as R ⁶ , R ³ is the same as R ⁷ and R ⁴ is the same as R ⁸ , The compound (5) and the compound (7) are combined, and the compound (4) is reacted with 2.0 to 8.0 equivalents, preferably 2.0 to 4.0 equivalents in the presence of a base. (2) can also be synthesized.

Specific examples of the compound (2-1) include the following compounds, but are not intended to be limited to these compounds.

In addition to these, the groups corresponding to R ³ and R ⁷ in the general formula (2-1) in each of the above compounds are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, Or the compound substituted with the methyl group is also mentioned.

Specific examples of the compound (2-2) include, in addition to the specific examples of the compound (2-1), the following compounds and R ³ and R ^{7 in the} general formula (2-2) in these compounds. And a compound in which a group corresponding to is substituted with a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group.

Specific examples of the compound (5-1) and the compound (7-1) include the following compounds, but are not intended to be limited to these compounds.

In addition to these, a group corresponding to R ³ or R ⁷ in each of the above compounds, the general formula (5-1) or (7-1) is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom. , An iodine atom, or a compound substituted with a methyl group.

Specific examples of the compound (5-2) and the compound (7-2) include, in addition to the specific examples of the compound (5-1) and the compound (7-1), the following compounds and the above compounds in these compounds. And compounds in which the groups corresponding to R ³ and R ⁷ in formula (5-2) or (7-2) are substituted with a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group. .

The complex (1) described above is used as a polymerization catalyst component in the production of a polymer by homopolymerization of olefins or copolymerization of two or more polymerizable olefins. Preferably, the catalyst component for homopolymerization is used. It is.

As the polymerization catalyst, a polymerization catalyst obtained by bringing the complex (1), the activation promoter component and the carrier into contact with each other is used.

(Activation promoter component)
Examples of the activation co-catalyst component include an activation co-catalyst component containing a Group 13 element of the periodic table. For example, an organoaluminum compound (A), a boron compound (B), and boron described below are used. The at least 1 sort (s) of compound chosen from the group which consists of a compound (C) can be mentioned. The organoaluminum compound (A), the boron compound (B), and the boron compound (C) are respectively referred to as “activation promoter component (A)”, “activation promoter component (B)”, and “ Hereinafter, it may be referred to as “activation promoter component (C)”.

<Organic aluminum compound (A)>
As the organoaluminum compound (A) in the present invention, a known organoaluminum compound can be used. Preferably, any one of the following compounds (A-1), (A-2), and (A-3), or a mixture of 2 to 3 thereof can be exemplified.
(A-1): Organoaluminum compound represented by general formula E ¹ _a AlY ¹ _3-a (A-2): General formula {-Al (E ² ) —O—} having a structure represented by _b Cyclic aluminoxane (A-3): linear aluminoxane having a structure represented by the general formula E ³ {—Al (E ³ ) —O—} _c AlE ³ _{2 wherein} E ¹ has 1 to E ² and E ³ each independently represents a hydrocarbyl group having 1 to 8 carbon atoms, an alkoxy group containing an electron withdrawing group or an electron withdrawing group. An aryloxy group to be contained is represented. A plurality of E ^{1 s} , E ^{2 s,} and E ^{3 s} may be the same or different. Y ¹ represents a hydrogen atom or a halogen atom, and a plurality of Y ¹ may be the same or different. a represents an integer of 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.

Examples of the hydrocarbyl group having 1 to 8 carbon atoms in E ¹ to E ³ of the compounds (A-1) to (A-3) include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, and a normal butyl group. Group, isobutyl group, normal pentyl group, and neopentyl group.

E ² and E ³ of the compounds (A-2) and (A-3) may be an alkoxy group containing an electron withdrawing group or an aryloxy group containing an electron withdrawing group. As an index of attracting property, Hammett's rule substituent constant σ and the like are known, and a functional group having positive σ can be cited as an electron withdrawing group.

Specific examples of the electron withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group, and a phenyl group.

Examples of the alkoxy group containing an electron withdrawing group in E ² and E ³ include a fluoromethoxy group, a chloromethoxy group, a bromomethoxy group, an iodomethoxy group, a difluoromethoxy group, a dichloromethoxy group, a dibromomethoxy group, Iodomethoxy group, trifluoromethoxy group, trichloromethoxy group, tribromomethoxy group, triiodomethoxy group, 2,2,2-trifluoroethoxy group, 2,2,2-trichloroethoxy group, 2,2,2- Tribromoethoxy group, 2,2,2-triiodoethoxy group, pentafluoroethoxy group, pentachloroethoxy group, pentabromoethoxy group, pentaiodoethoxy group, 2,2,3,3,3-pentafluoropropoxy group 2,2,3,3,3-pentachloropropoxy group, 2,2,3,3 3-pentabromopropoxy group, 2,2,3,3,3-pentaiodopropoxy group, heptafluoropropoxy group, heptachloropropoxy group, heptabromopropoxy group, heptaiodopropoxy group, 2,2,2-trifluoro 1-trifluoromethylethoxy group, 2,2,2-trichloro 1-trichloromethylethoxy group, 2,2,2-tribromo-1-tribromomethylethoxy group, 2,2,2-triiodo-1-tri Iodomethylethoxy group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethoxy group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethoxy group, 1,1 -Bis (tribromomethyl) -2,2,2-tribromoethoxy group, 1,1-bis (triiodomethyl) -2,2,2-tri Examples thereof include an iodoethoxy group, 1H, 1H-perfluorobutoxy group, 1H, 1H-perfluoropentoxy group, 1H, 1H-perfluorohexano group, and 1H, 1H-perfluorooctanoxy group. 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethoxy group is preferred.

Examples of the aryloxy group containing an electron withdrawing group in E ² and E ³ include, for example, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, 2,3-difluorophenoxy group, 2, 4-difluorophenoxy group, 2,5-difluorophenoxy group, 2,6-difluorophenoxy group, 3,4-difluorophenoxy group, 3,5-difluorophenoxy group, 2,3,4-trifluorophenoxy group, 2 , 3,5-trifluorophenoxy group, 2,3,6-trifluorophenoxy group, 2,4,5-trifluorophenoxy group, 2,4,6-trifluorophenoxy group, 3,4,5-tri Fluorophenoxy group, 2,3,4,5-tetrafluorophenoxy group, 2,3,4,6-tetrafluorophenoxy group, , 3,5,6-tetrafluorophenoxy group, 2,3,4,5,6-pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenoxy group, 2-chlorophenoxy Group, 3-chlorophenoxy group, 4-chlorophenoxy group, 2,3-dichlorophenoxy group, 2,4-dichlorophenoxy group, 2,5-dichlorophenoxy group, 2,6-dichlorophenoxy group, 3,4- Dichlorophenoxy group, 3,5-dichlorophenoxy group, 2,3,4-trichlorophenoxy group, 2,3,5-trichlorophenoxy group, 2,3,6-trichlorophenoxy group, 2,4,5-trichlorophenoxy group Group, 2,4,6-trichlorophenoxy group, 3,4,5-trichlorophenoxy group, 2,3,4,5-tetrachlorophenoxy group 2,3,4,6-tetrachlorophenoxy group, 2,3,5,6-tetrachlorophenoxy group, 2,3,4,5,6-pentachlorophenoxy group, 2,3,5,6- Tetrachloro 4-trichloromethylphenoxy group, 2-bromophenoxy group, 3-bromophenoxy group, 4-bromophenoxy group, 2,3-dibromophenoxy group, 2,4-dibromophenoxy group, 2,5-dibromophenoxy group 2,6-dibromophenoxy group, 3,4-dibromophenoxy group, 3,5-dibromophenoxy group, 2,3,4-tribromophenoxy group, 2,3,5-tribromophenoxy group, 2,3 , 6-tribromophenoxy group, 2,4,5-tribromophenoxy group, 2,4,6-tribromophenoxy group, 3,4,5-tribromophenoxy group, 2, , 4,5-tetrabromophenoxy group, 2,3,4,6-tetrabromophenoxy group, 2,3,5,6-tetrabromophenoxy group, 2,3,4,5,6-pentabromophenoxy group 2,3,5,6-tetrabromo-4-tribromomethylphenoxy group, 2-iodophenoxy group, 3-iodophenoxy group, 4-iodophenoxy group, 2,3-diiodophenoxy group, 2,4-di Iodophenoxy group, 2,5-diiodophenoxy group, 2,6-diiodophenoxy group, 3,4-diiodophenoxy group, 3,5-diiodophenoxy group, 2,3,4-triiodophenoxy group 2,3,5-triiodophenoxy group, 2,3,6-triiodophenoxy group, 2,4,5-triiodophenoxy group, 2,4,6-triiodophenoxy group, 3, , 5-triiodophenoxy group, 2,3,4,5-tetraiodophenoxy group, 2,3,4,6-tetraiodophenoxy group, 2,3,5,6-tetraiodophenoxy group, 2,3 4,5,6-pentaiodophenoxy group, 2,3,5,6-tetraiodo 4-triiodomethylphenoxy group. A 3,4,5-trifluorophenoxy group or a 2,3,4,5,6-pentafluorophenoxy group is preferable.

Specific examples of the organoaluminum compound (A-1) represented by the general formula E ¹ _a AlY ¹ _3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum. Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkyls such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride Aluminum dichloride; Dimethyla Mini um hydride, diethylaluminum hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, dialkylaluminum hydride such as dihexyl aluminum hydride; and the like. Trialkylaluminum is preferable, and triethylaluminum or triisobutylaluminum is more preferable.

A cyclic aluminoxane (A-2) having a structure represented by the general formula {—Al (E ² ) —O—} _b , and a general formula E ³ {—Al (E ³ ) —O—} _c AlE ³ ₂ Specific examples of E ² and E ^{3 in} the linear aluminoxane (A-3) having the structure represented by the formula: methyl group, ethyl group, n-propyl group, isopropyl group, normal butyl group, isobutyl group, Alkoxy groups containing electron-withdrawing groups such as alkyl groups such as n-pentyl group and neopentyl group, trifluoromethoxy groups, and 1,1-bis (trifluoro) methyl-2,2,2-trifluoroethoxy groups An aryloxy group containing an electron withdrawing group such as 4-fluorophenoxy group, 3,4,5-trifluorophenoxy group, 2,3,4,5,6-pentafluorophenoxy group; It is below. Preferably, E ² and E ³ are methyl groups or isobutyl groups, b is 2 to 40, and c is 1 to 40.

The above aluminoxane can be made by various methods. There is no restriction | limiting in particular about the method, What is necessary is just to make according to a well-known method. For example, a method in which a solution of trialkylaluminum (eg, trimethylaluminum) dissolved in an appropriate organic solvent (benzene, toluene, aliphatic hydrocarbon, etc.) is contacted with water to make aluminoxane, trialkylaluminum (eg, trimethylaluminum) Examples thereof include a method of making an aluminoxane by contacting a metal salt containing water of crystallization (for example, copper sulfate hydrate) and a method of making an aluminoxane using benzoic acid or the like.

In addition, the compound (A-2) and the compound (A-3) obtained by the above method may be used after removing volatile components by distillation, if necessary. Further, the compound obtained by distilling off the volatile components and drying may be washed with an appropriate organic solvent (benzene, toluene, aliphatic hydrocarbon, etc.) and dried again.

<Boron compound (B)>
Examples of the boron compound (B) in the present invention include use of any of the following compounds (B-1), (B-2), and (B-3).
(B-1): Boron compound represented by the general formula BR ¹¹ R ¹² R ¹³ (B-2): Boron compound represented by the general formula U ⁺ (BR ¹¹ R ¹² R ¹³ R ¹⁴ ) ^— 3): Boron compound represented by the general formula (TH) ⁺ (BR ¹¹ R ¹² R ¹³ R ¹⁴ ) ^{— wherein} R ¹¹ to R ¹⁴ each independently represents a halogen atom or a carbon atom number of 1 A hydrocarbyl group having 1 to 20 carbon atoms, a halogenated hydrocarbyl group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 2 to 20 carbon atoms Represents a disubstituted amino group. R ¹¹ to R ¹⁴ may be the same as or different from each other. R ¹¹ to R ¹⁴ are preferably each independently a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, or a halogenated hydrocarbyl group having 1 to 20 carbon atoms.
B is a boron atom in a trivalent valence state. U ⁺ is an inorganic or organic cation. T is a neutral Lewis base and (TH) ⁺ is a Bronsted acid.

Examples of U ⁺ that is an inorganic cation include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation. Examples of U ⁺ that is an organic cation include a triphenylcarbenium cation.

Specific examples of the borate represented by (BR ¹¹ R ¹² R ¹³ R ¹⁴ ) ^— include, for example, tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis ( 2,3,4,5-tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate -To, tetrakis (3,5-bistrifluoromethylphenyl) borate and the like.

Examples of (TH) ⁺ that is a Bronsted acid include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, and triarylphosphonium.

Specific examples of the boron compound (B-1) include triphenylborane, tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4,5). -Tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, and the like. Is triphenylborane or tris (pentafluorophenyl) borane.

Specific examples of the boron compound (B-2) include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Examples include triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-bistrifluoromethylphenyl) borate, and most preferred is triphenylcarbenium tetrakis (pentafluorophenyl) borate. .

Specific examples of the boron compound (B-3) include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, (N-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N , N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) , Diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethyl) Phenyl) phosphonium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate and the like, and most preferably triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (Pentafluorophenyl) borate or N, N-dimethylanily Umutetorakisu (pentafluorophenyl) borate.

<Boron compound (C)>
Examples of the boron compound (C) in the present invention include use of any of the following compounds (C-1) and (C-2).
(C-1): Boron compound represented by the general formula U ⁺ (BR ¹⁵ R ¹⁶ R ¹⁷ R ¹⁸ ) ⁻ (C-2): General formula (TH) ⁺ (BR ¹⁵ R ¹⁶ R ¹⁷ R ¹⁸ ) ^- boron in the compound ^formulas, R 15 ^{~ R 18} represented by each independently, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a halogenated hydrocarbyl of 1 to 20 carbon atoms Group, a substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a disubstituted amino group having 2 to 20 carbon atoms. R ¹⁵ to R ¹⁸ may be the same or different from each other, but at least one of R ¹⁵ to R ¹⁸ has the general formula (ZH) (wherein Z represents O, S, NR or PR; R represents a hydrocarbyl group, a trihydrocarbylsilyl group, a trihydrocarbylgermyl group, or hydrogen.
B is a boron atom in a trivalent valence state. U ⁺ is an inorganic or organic cation. T is a neutral Lewis base and (TH) ⁺ is a Bronsted acid.

U ⁺ and (TH) ⁺ are the same as those described for the boron compound (B).

Specific examples of the borate represented by (BR ¹⁵ R ¹⁶ R ¹⁷ R ¹⁸ ) ^— include triphenyl (hydroxyphenyl) borate, diphenyl di (hydroxyphenyl) borate, triphenyl (2,4-dihydroxyphenyl) borate, Tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (4-hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) (Hydroxyphenyl) borate, tris (3,5-bis (trifluoromethyl) phenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxy The Borate, tris (pentafluorophenyl) (2-hydroxycyclohexyl) borate, tris (pentafluorophenyl) (4- (4′-hydroxyphenyl) phenyl) borate, tris (pentafluorophenyl) (6-hydroxy-2) -Naphthyl) borate and the like, and tris (pentafluorophenyl) (4-hydroxyphenyl) borate is preferable. Other preferred borates include borates in which the hydroxyl group in the borate is substituted with an amino group NHR. However, R is preferably a methyl group, an ethyl group or a butyl group.

Specific examples of the boron compound (C-1) include ferrocenium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, silver tris (pentafluorophenyl) (4-hydroxyphenyl) borate, triphenylcarbenium tris. (Pentafluorophenyl) (4-hydroxyphenyl) borate and the like.

Specific examples of the boron compound (C-2) include triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, tripropylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, tri (n- Butyl) ammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, tri (n-butyl) ammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, N, N-dimethylanilinium tris (pentafluorophenyl) ) (4-hydroxyphenyl) borate, N, N-diethylanilinium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, N, N-2,4,6-pentamethylanilinium tris Tafluorophenyl) (4-hydroxyphenyl) borate, N, N-dimethylanilinium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, diisopropylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, dicyclohexyl Ammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, triphenylphosphonium tris (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tris (pentafluorophenyl) (4-hydroxyphenyl) Examples thereof include borate and tri (dimethylphenyl) phosphonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate.

(Carrier)
As the carrier, a porous material is preferably used, an inorganic material or an organic polymer is preferable, and an inorganic material is more preferable.

Examples of the inorganic substance include inorganic oxides, magnesium compounds, clays, clay minerals, and combinations thereof. Among these, inorganic oxides are preferable.

Examples of the inorganic _{_{_{oxide, SiO 2, Al 2 O 3}}} , MgO, ZrO 2, TiO 2, B 2 O 3, CaO, ZnO, BaO, ThO 2, V 2 O 5, Cr 2 O 3 , and mixtures thereof (For example, 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 , and SiO ₂ —TiO ₂ —MgO). . Of these, SiO ₂ and / or Al ₂ O ₃ are preferable, and SiO ₂ is particularly preferable. The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) _2. Carbonates, sulfates, nitrates or oxides such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O may be included.

Examples of the magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, and octoxy magnesium chloride. Alkoxymagnesium halides; allyloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, and 2-ethylhexoxymagnesium; phenoxymagnesium And allilo such as dimethylphenoxymagnesium Shi magnesium; and carboxylic acid salts of magnesium such as magnesium laurate and magnesium stearate. Among them, preferred is magnesium halide or alkoxymagnesium, and more preferred is magnesium chloride or butoxymagnesium.

Examples of the clay or the clay mineral include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, bayophilite, talc, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, Dickite, and halloysite. Among them, preferred is smectite, montmorillonite, hectorite, laponite or saponite, and more preferred is montmorillonite or hectorite.

The inorganic substance is preferably dried to substantially remove moisture, and is preferably dried by heat treatment. The heat treatment is usually carried out at a temperature of 100 to 1,500 ° C., preferably 100 to 1,000 ° C., more preferably 200 to 800 ° C. for inorganic substances whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the drying method include a method of circulating an inert gas (for example, nitrogen or argon) dried under heating at a constant flow rate, and a method of depressurizing under heating.

The average particle size of the inorganic substance is preferably 5 to 1000 μm, more preferably 10 to 500 μm, and still more preferably 10 to 100 μm. The pore volume of the inorganic substance is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area of the inorganic substance is preferably 10 to 1000 m ² / g, more preferably 100 to 500 m ² / g.

As the organic polymer for the carrier, a polymer having a functional group having active hydrogen or a non-proton donating Lewis basic functional group is preferred.

Examples of the functional group having active hydrogen include primary amino group, secondary amino group, imino group, amide group, hydrazide group, amidino group, hydroxy group, hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid Groups, sulfinic acid groups, sulfenic acid groups, thiol groups, thioformyl groups, pyrrolyl groups, imidazolyl groups, piperidyl groups, indazolyl groups, and carbazolyl groups. Among them, preferably a primary amino group, a secondary amino group, an imino group, an amide group, an imide group, a hydroxy group, a formyl group, a carboxyl group, a sulfonic acid group or a thiol group, particularly preferably a primary amino group, Secondary amino group, amide group or hydroxy group. These functional groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.

Examples of the non-proton-donating Lewis basic functional group include pyridyl group, N-substituted imidazolyl group, N-substituted indazolyl group, nitrile group, azide group, N-substituted imino group, N, N-substituted amino group, N , N-substituted aminooxy group, N, N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group, furyl group, carbonyl group, thiocarbonyl group, alkoxy group, alkyloxycarbonyl group, N, N-substituted Examples include a carbamoyl group, a thioalkoxy group, a substituted sulfinyl group, a substituted sulfonyl group, and a substituted sulfonic acid group. Among them, preferred is a heterocyclic group, more preferred is an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring, and particularly preferred are a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group. And most preferably a pyridyl group. These functional groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.

The amount of the functional group having active hydrogen or the non-proton-donating Lewis basic functional group is preferably 0.01 to 50 mmol / g as the molar amount of the functional group per gram of polymer unit, more preferably 0.8. 1 to 20 mmol / g.

As a method for producing the polymer having the functional group, a method of homopolymerizing a monomer having a functional group having active hydrogen or a non-proton donating Lewis basic functional group and one or more polymerizable unsaturated groups, And a method of copolymerizing the monomer and another monomer having a polymerizable unsaturated group. The monomer is preferably combined with a crosslinking polymerizable monomer having two or more polymerizable unsaturated groups. Examples of the monomer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and one or more polymerizable unsaturated groups include (1) a functional group having active hydrogen and one or more polymerizations. And a monomer having an unsaturated proton group and (2) a monomer having a non-proton-donating Lewis basic functional group and one or more polymerizable unsaturated groups.

Monomers having a functional group having active hydrogen and one or more polymerizable unsaturated groups include vinyl group-containing primary amines, vinyl group-containing secondary amines, vinyl group-containing amide compounds, and vinyl group-containing hydroxy compounds. Can be mentioned. Specific examples include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, N- (2-propenyl) -N-methylamine, 1- And ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, and 3-buten-1-ol. It is done. Monomers having a non-proton donating Lewis basic functional group and one or more polymerizable unsaturated groups include vinyl pyridine, vinyl (N-substituted) imidazole, and vinyl (N-substituted) indazole.

Examples of the other monomer having a polymerizable unsaturated group include ethylene, α-olefin, and aromatic vinyl compounds. Specific examples include ethylene, propylene, 1-butene, 1-hexene, 4- And methyl-1-pentene, styrene, and combinations of two or more thereof. Among these, ethylene or styrene is preferable. Examples of the crosslinkable monomer having two or more polymerizable unsaturated groups include divinylbenzene.

The average particle size of the organic polymer is preferably 5 to 1000 μm, more preferably 10 to 500 μm. The pore volume of the organic polymer is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area of the organic polymer is preferably 10 to 1000 m ² / g, more preferably 50 to 500 m ² / g.

The organic polymer is preferably dried to substantially remove moisture, and is preferably dried by heat treatment. The heat treatment is usually carried out at a temperature of 30 to 400 ° C., preferably 50 to 200 ° C., more preferably 70 to 150 ° C. for an organic polymer whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 30 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the drying method include a method of circulating an inert gas (for example, nitrogen or argon) dried under heating at a constant flow rate, and a method of depressurizing under heating.

The volume standard geometric standard deviation of the particle size of the support is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.7 or less, from the viewpoint of the particle size distribution of the obtained polymer.

The carrier, inorganic material is preferred, the inorganic oxide is more preferably, SiO ₂ is more preferred.

(Method for producing olefin polymerization catalyst)
The olefin polymerization catalyst of the present invention can be obtained by contacting the complex represented by the general formula (1-1) or (1-2), the co-catalyst component for activation, and the support. The activation promoter component is at least one compound selected from the group consisting of an organoaluminum compound (A), a boron compound (B), or a boron compound (C). Further, as the activation promoter component (A), a plurality of components among the organoaluminum compounds (A-1) to (A-3) may be used.

The following method is mentioned as a manufacturing method of the catalyst for olefin polymerization, Preferably it is method 2. In addition, the order of charging in each contact of each method is not particularly limited, and some or all of these contacts may be performed in a polymerization tank or a reactor.
Method 1: A method in which a support is brought into contact with a contact product obtained by bringing the complex (1) into contact with an activation promoter component.
Method 2: A method in which the complex (1) is brought into contact with a contact product obtained by bringing the support into contact with the activating cocatalyst component.
Method 3: A method of bringing an activating co-catalyst component into contact with a contact product obtained by bringing the carrier into contact with the complex (1).
Method 4: A method in which the complex (1), the activating co-catalyst component and the support are simultaneously contacted.

In any of the above methods, the complex (1) may be an isolated one, or may be used as it is by contacting the compound (2) with the compound (3).

From the viewpoint of the particle properties of the resulting olefin polymer, the contact product in contact with the support and the activation promoter component is brought into contact with the contact product in contact with the complex (1) and the activation promoter component. The method is preferred.

In the contact in the above method, it is preferable to carry out the reaction in the presence of a solvent. Examples of the solvent include aromatic hydrocarbyl solvents such as benzene, toluene and xylene, aliphatic hydrocarbyl solvents such as hexane, heptane and octane, and halogenated hydrocarbyl solvents such as dichloromethane. The solvent which does not dissolve is preferable, and the solvent which dissolves the complex (1) and the promoter component for activation is more preferable.

The temperature and time for contact are not particularly limited. The temperature is usually -100 ° C to 200 ° C, preferably -50 ° C to 150 ° C, more preferably -20 ° C to 120 ° C. In particular, in the initial stage of contact, it is preferable to contact at a low temperature in order to suppress heat generation due to the reaction. The contact time is usually about 30 minutes to 12 hours, preferably about 30 minutes to 8 hours, more preferably about 30 minutes to 6 hours.

The ratio of each component when contacting the carrier, the complex (1) and the activating cocatalyst component (A) is 0.05 to 20 parts by weight of the complex (1) per 1 part by weight of the carrier. Component (A) is 10 to 300 parts by weight, preferably 0.1 to 10 parts by weight of complex (1) and 20 to 200 parts by weight of activation promoter component (A) per part by weight of the support.

The ratio of each component when contacting the carrier, the complex (1) and the activating co-catalyst component (B) is 0.05 to 20 parts by weight of the complex (1) per 1 part by weight of the carrier. Component (B) is 0.1 to 60 parts by weight, preferably 0.1 to 10 parts by weight of complex (1) and 0.2 to 30 parts by weight of activation promoter component (B) per part by weight of the support. It is.

The olefin polymerization catalyst of the present invention can also be obtained by bringing the complex (1), the carrier and the activation promoter component (C) into contact with each other, but the activation promoter component (A) can be used in combination. preferable. These contact methods are not particularly limited, and a plurality of components among the compounds (A-1) to (A-3) may be used as the activation promoter component (A).

The order of contacting the support, the complex (1) and the activating cocatalyst components (C) and (A) is not particularly limited, and examples thereof include the following methods. Preferably, it is Method 6, Method 7 or Method 8, and more preferably Method 6 or Method 8. In addition, the order of charging in each contact of each method is not particularly limited, and some or all of these contacts may be performed in a polymerization tank or a reactor.
Method 5: A method of bringing the co-catalyst component for activation (C) into contact with the contact product obtained by bringing the co-catalyst component for activation (A) into contact with the carrier, and further bringing the complex (1) into contact therewith.
Method 6: A method in which the support is brought into contact with the contact product obtained by bringing the activating cocatalyst component (A) and the activating cocatalyst component (C) into contact, and the complex (1) is further brought into contact.
Method 7: A method in which the complex (1) is brought into contact with the contact product obtained by bringing the activating cocatalyst component (A) and the carrier into contact, and the activating cocatalyst component (C) is further brought into contact.
Method 8: A method of bringing the co-catalyst component for activation (C) into contact with the contact product obtained by bringing the co-catalyst component for activation (A) into contact with the carrier, and further bringing the complex (1) into contact therewith.

The ratio of each component when contacting the support, the complex (1), the activating co-catalyst component (A) and the activating co-catalyst component (C) is 0.05% of complex (1) per 1 part by weight of the support. To 20 parts by weight, 10 to 300 parts by weight of the activating cocatalyst component (A), 1 to 30 parts by weight of the activating cocatalyst component (C), preferably 1 part by weight of the complex (1) 0 1 to 10 parts by weight, 20 to 200 parts by weight of the activation promoter component (A), and 2 to 15 parts by weight of the activation promoter component (C).

The catalyst according to the present invention produced by the above-described method can be used for homopolymerization of olefins or for copolymerization of two or more olefins. The catalyst according to the present invention can be particularly preferably used for homopolymerization of olefins having 2 to 6 carbon atoms or copolymerization of two or more olefins having 2 to 6 carbon atoms.

[Olefin polymer production method]
The method for producing an olefin polymer in the present invention is a method including polymerizing an olefin alone in the presence of the catalyst or copolymerizing two or more olefins.

The olefin can be a monoolefin or a diolefin.
Examples of the monoolefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, vinylcyclohexane, etc. 1-alkene having 3 to 10 carbon atoms (which may be branched), or cyclopentene, cyclohexene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene , Tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene , 5-Met Sicarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclo Examples thereof include cyclic alkenes such as dodecene.

Examples of the diolefin include 1,5-hexadiene, 1,4-hexadiene, 1,6-heptadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4 -Methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5 -Methyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, 1,3-hexadiene, 1,3-octadiene, 1,3 -Cyclooctadiene, 1,3-cyclohexadiene, butadiene and the like.

Preferred monoolefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, vinylcyclohexane, and the like. Olefin having 2 to 10 carbon atoms, more preferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, vinylcyclohexane and the like. An olefin having 2 to 8 carbon atoms, more preferably an olefin having 2 to 5 carbon atoms such as ethylene, propylene, 1-butene and 1-pentene.

When a olefin having 3 or more carbon atoms is polymerized using the catalyst of the present invention, a polyolefin having high stereoregularity is obtained.

As a measure of stereoregularity, isotactic pentad fraction [mmmm] (%) is used. The isotactic pentad fraction referred to here is A.I. Isotactic linkage at the pentad unit in a crystalline polypropylene molecular chain measured using the method published by Macrobells, 1973, No. 6, pp. 925-926, ie, using ¹³ C-NMR. In other words, it is the fraction of propylene monomer units at the center of a chain in which five propylene monomer units are continuously meso-bonded.

As the diolefin, 1,5-hexadiene, 1,6-heptadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, norbornadiene, 5- Methylene-2-norbornene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene, or butadiene, more preferably 1,5-hexadiene, 1,6-heptadiene, 1,3-cyclohexadiene or butadiene.

Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and 1-butene, ethylene and 1-pentene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and 1-decene, ethylene and 4 -Methyl-1-pentene, ethylene and vinylcyclohexane, ethylene and 4-methyl-1-pentene, ethylene and butadiene, ethylene and 1,5-hexadiene.
Preferably, ethylene and carbon such as ethylene and propylene, ethylene and 1-butene, ethylene and 1-pentene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and vinylcyclohexane, ethylene and 4-methyl-1-pentene Copolymerization with olefins having 3 to 10 atoms, more preferably ethylene and carbon atoms such as ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and vinylcyclohexane, etc. Copolymerization with olefins of 3 to 8.

In the present invention, the particle property is very high by the method of bringing the contact product in contact with the support and the activation promoter component into contact with the contact product in contact with the complex (1) and the activation promoter component. The following ethylene-α-olefin copolymer excellent in the above can be obtained. The following copolymer particles are not particles obtained by granulating copolymer particles obtained by copolymerization of ethylene and α-olefin, but directly by copolymerizing ethylene and α-olefin in a polymerization reactor. Means the resulting particles.
The ethylene-α-olefin copolymer having a volume particle size of 300 μm or less and a polymer particle content of 2% by volume or less, a 50% volume reference particle size (D50) of 500 μm or more, and a particle bulk density of 400 kg / m ³ or more. Polymer particles.

In the ethylene-α-olefin copolymer particles, the amount of particles having a volume standard particle size of 300 μm or less is preferably smaller from the viewpoint of operational stability, preferably 2% by volume or less, more preferably 1% by volume or less, More preferably, it is 0.5 volume% or less.

The ethylene-α-olefin copolymer particles have a 50% volume standard particle diameter (D50) of 500 μm or more, and are preferably higher from the viewpoint of productivity, preferably 750 μm or more, more preferably 1000 μm or more. From the viewpoint of the fluidity of the particles, it is preferably not too large, preferably 4000 μm or less, more preferably 3500 μm or less, and still more preferably 3000 μm or less.

The ethylene-α-olefin copolymer particles have a particle bulk density of 400 kg / m ³ or more, and preferably have a high particle bulk density from the viewpoint of enhancing production, preferably 425 kg / m ³ or more, and more preferably Is 450 kg / m ³ or more. The particle bulk density (BD) can be determined by filling a 10 cc graduated cylinder from 10 cm above the powder and dividing the mass of the powder by the volume including the voids between the particles.

The particle size measurement on the volume basis of the polymer particles can be calculated, for example, by measuring the particle size distribution by dispersing the polymer particles in a dry state using a laser diffraction particle size distribution analyzer HELOS & RODOS system manufactured by SYMPATEC. Can do.

The content derived from α-olefin in the ethylene-α-olefin copolymer particles obtained by the production method of the present invention is preferably smaller from the viewpoint of the tackiness of the copolymer, and the number of short chain branches (N _SCB ) Is less than 30 / 1000C, more preferably less than 25 / 1000C, and even more preferably less than 20 / 1000C.

The melt flow rate (MFR) of the ethylene-α-olefin copolymer obtained by the production method of the present invention is the method defined in JIS K7210-1995 under the conditions of a temperature of 190 ° C. and a load of 21.18 N. Is a value measured by.
The MFR of the ethylene-α-olefin copolymer obtained by the production method of the present invention is 0.1 to 100 g / 10 min. The MFR is preferably 0.2 g / 10 min or more from the viewpoint of improving molding processability, particularly from the viewpoint of reducing the extrusion load. Further, from the viewpoint of increasing the melt tension and the mechanical strength of the resulting molded article, it is preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, and further preferably 20 g / 10 min or less.

H-MFR is a value of MFR measured under the conditions of a load of 211.82 N and a temperature of 190 ° C. in the method defined in JIS K7210-1995.
The MFRR is a value obtained by dividing H-MFR by the MFR measured under the conditions of a load of 21.18 N and a temperature of 190 ° C. in the method specified in JIS K7210-1995. is there.
The MFRR of the ethylene-α-olefin copolymer obtained by the production method of the present invention is preferably 70 or more, more preferably 100 or more, and still more preferably, from the viewpoint of further reducing the extrusion load during the molding process. Is 130 or more, particularly preferably 170 or more. Moreover, from a viewpoint which raises the mechanical strength of the molded object obtained more, Preferably it is 300 or less, More preferably, it is 250 or less.

The density of the ethylene-α-olefin copolymer obtained by the production method of the present invention is 850 to 940 kg / m ³ , and preferably 930 kg / m ³ from the viewpoint of increasing the impact strength of the mechanical strength of the obtained molded product. ³ or less. From the viewpoint of enhancing among tensile strength of mechanical strength of the resulting molded product, it is preferably 870 kg / ^{m 3} or more, more preferably 880 kg / ^{m 3} or more, more preferably 890 kg / ^{m 3} or more, particularly preferably Is 900 kg / m ³ or more

The weight average molecular chain length (hereinafter sometimes referred to as “Aw”) and the number average molecular chain length (hereinafter referred to as “An”) of the ethylene-α-olefin copolymer obtained by the production method of the present invention. The ratio (hereinafter sometimes referred to as “Aw / An”) is 2 to 10. If Aw / An is too small, the extrusion load at the time of molding may increase. Aw / An is preferably 2.5 or more. When Aw / An is too large, the mechanical strength of the obtained molded product may be lowered. Aw / An is preferably 6.5 or less, more preferably 6 or less, and even more preferably 5 or less.

N _LCB has a carbon atom number of 5 or more, with the total area of all peaks observed at 5 to 50 ppm as 1000 from the ¹³ C-NMR spectrum measured by the carbon nuclear magnetic resonance ( ¹³ C-NMR) method. It is obtained by determining the area of the peak derived from the methine carbon to which the branch is bonded. The peak derived from methine carbon to which a branch having 5 or more carbon atoms is bonded is around 38.2 ppm (Reference: Scientific literature “Macromolecules”, (USA), American Chemical Society, 1999, Vol. 32, p.3817-3818) ). Since the position of the peak derived from methine carbon to which a branch having 5 or more carbon atoms is bonded may vary depending on the measuring device and the measuring conditions, the standard is usually measured for each measuring device and measuring conditions. decide. In the spectrum analysis, it is preferable to use a negative exponential function as the window function.
The N _LCB of the ethylene-α-olefin copolymer obtained by the production method of the present invention is preferably at least 0.05, more preferably at least 0.10, per 1000 carbons from the viewpoint of processability. Especially preferably, it is 0.15 or more. From the viewpoint of the mechanical strength of the obtained polymer, it is preferably not too much, preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less.

The olefin polymer obtained by the method for producing an olefin polymer of the present invention has an extrusion load at the time of molding, bubble stability at the time of forming an inflation film, neck-in at the time of T-die film molding, and a shape retention of the parison at the time of hollow molding. Excellent moldability such as properties, and excellent mechanical strength. Moreover, the transparency of the molded product is also excellent.

The olefin polymer is molded by a known molding method, for example, an extrusion molding method such as an inflation film molding method and a T-die film molding method, a hollow molding method, an injection molding method, a compression molding method, or the like. As the molding method, an extrusion molding method and a hollow molding method are preferably used, and an inflation film molding method, a T-die film molding method, and a hollow molding method are particularly preferably used.

The olefin polymer is used after being molded into various forms. Although the form of a molded article is not specifically limited, it is used for a film, a sheet, a container (tray, bottle, etc.), etc. The molded article is also suitably used for applications such as food packaging materials; pharmaceutical packaging materials; electronic component packaging materials used for packaging semiconductor products, etc .; surface protection materials.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. The measured value of each item in an Example was measured with the following method.

(1) Melting point Thermal analyzer The measurement was performed by the following method using a differential scanning calorimeter (manufactured by Diamond DSC Perkin Elmer).
<Polyethylene measurement conditions>
1) Hold about 10 mg of sample in a nitrogen atmosphere at 150 ° C. for 5 minutes 2) Cooling 150 ° C. to 20 ° C. (5 ° C./minute) Hold for 2 minutes 3) Measurement 20 ° C. to 150 ° C. (5 ° C./minute)
<Polypropylene measurement conditions>
1) Hold about 10 mg of sample under nitrogen atmosphere at 220 ° C. for 5 minutes 2) Cooling 220 ° C. to 20 ° C. (5 ° C./minute) Hold for 2 minutes 3) Measurement 20 ° C. to 220 ° C. (5 ° C./minute)

(2) Molecular weight and molecular weight distribution The polystyrene equivalent weight average molecular chain length (Aw) and polystyrene equivalent number average molecular chain length (An) of each polymer were calculated by gel permeation chromatography (GPC) under the following conditions. A calibration curve was prepared using standard polystyrene. 41.3 was used as the Q factor of polystyrene.
<Measurement conditions>
Equipment: TSK HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Column: TSKgel GMHHR-H (20) 2 Measurement temperature: 152 ° C
Solvent: o-dichlorobenzene (0.05% BHT added)
Solvent flow rate: 1 ml / min
Sample concentration: 0.05%
Sample for column / equipment calibration: TSK standard polystyrene F-2000 to A-1000 (manufactured by Tosoh)

The weight average molecular weight (Mw) and number average molecular weight (Mn) of each polymer are based on the weight average molecular chain length (Aw) in terms of polystyrene and the number average molecular chain length (An) in terms of polystyrene. Factors were calculated from the following formulas with 17.7 and 26.4, respectively.
Molecular weight (Mw, Mn) = molecular chain length (Aw, An) × Q factor

(3) Isotactic pentad fraction of polypropylene ([mmmm] (%))
The [mmmm] fraction of polypropylene is 21.64 to 22.22 relative to the peak area (I (CH ₃ )) attributed to 19.4 to 22.2 ppm of methyl carbon in the ¹³ C-NMR spectrum measured under the following conditions. The peak area (I (mmmm)) attributed to methyl carbon of 02 ppm mmmm pentad was determined.
<Measurement conditions>
Apparatus: Bruker AVANCE 600 10 mm cryoprobe measurement solvent: 1,2-dichlorobenzene / 1,2-dichlorobenzene-d ₄ = 75/25 (volume ratio) mixture measurement temperature: 130 ° C.
Measuring method: Proton decoupling method Pulse width: 45 degrees Pulse repetition time: 4 seconds Chemical shift value Criteria: Tetramethylsilane

(4) Intrinsic viscosity ([η], unit: dl / g)
Using an Ubbelohde viscometer, tetralin was used as a solvent at a measurement temperature of 135 ° C.

(5) Density (d, unit: Kg / m ³ )
Measured according to the method defined in Method A of JIS K7112-1980. The sample was annealed according to JIS K6760-1995.

(6) Number of short chain branches (N _SCB , unit: 1 / 1000C)
Using an infrared spectrophotometer (FT-IR7300, manufactured by JASCO Corporation), the number of short chain branches (N _SCB ) per 1000 carbon atoms was determined using a calibration curve from the characteristic absorption of ethylene and α-olefin. This N _SCB value represents the content of monomer units derived from α-olefin in a copolymer of ethylene and α-olefin.

(7) Melt flow rate (MFR, unit: g / 10 min)
In the method defined in JIS K7210-1995, measurement was performed by the method A under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(8) Melt flow rate ratio (H-MFR)
In the method defined in JIS K7210-1995, the measurement was performed at a melt flow rate measured under conditions of a test load of 211.82 N and a measurement temperature of 190 ° C.

(9) Swell ratio (SR)
In the measurement of the melt flow rate in (7), an ethylene-α-olefin copolymer strand extruded at a length of about 15 to 20 mm from an orifice under the conditions of a temperature of 190 ° C. and a load of 21.18 N Cooled to obtain a solid strand. Next, the diameter D (unit: mm) of the strand at a position of about 5 mm from the upstream end of extrusion of the strand was measured, and the value obtained by dividing the diameter D by the orifice diameter 2.095 mm (D ₀ ) (D / D ₀ ) was calculated and used as the swell ratio.

(10) Particle bulk density (BD)
The particle bulk density (BD) is a value obtained by dividing the mass of the powder by the volume including 10 cm of powder in a 10 cc graduated cylinder and including the voids between the particles.

(11) Elemental analysis Aluminum and hafnium: A metal component was extracted by irradiating an ultrasonic wave after throwing the sample into a sulfuric acid aqueous solution (1M). The obtained liquid portion was quantified by ICP emission spectrometry.
A combustion gas generated by burning a sample in a flask filled with fluorine: oxygen was absorbed in an aqueous sodium hydroxide solution (10%), and the obtained aqueous solution was quantified using an ion electrode method.

(12) Particle size measurement based on volume of polymer particles The particle size distribution was measured by dispersing polymer particles in a dry state under the following measurement conditions using a laser diffraction particle size distribution analyzer HELOS & RODOS system manufactured by SYMPATEC. A 10% volume reference particle size (D10), a 50% volume reference particle size (D50), and a 90% volume reference particle size (D90) were calculated.

(Measurement condition)
Range: 18-3500μm
Trigger condition: Reference duration 2 seconds: Time base 100 ms: Start channel 15 ≧ 0.5%
: Stop 2s, channel 15 ≦ 0.5%, 10s real time Dispersion condition: RODOS (dry airflow type dispersion unit) direct throwing type: Feeder VIBRI
: Feed 50%
: Injector 4mm
: Dispersion pressure 1.5bar

Content of Particles whose Volume-Based Particle Size is 300 μm or Less From the particle size distribution measured above, the amount of particles whose particle size is 300 μm or less was calculated in terms of volume.

(Reference Example 1)
Synthesis of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclohexane 1.08 g (7.3 mmol) of trans-cyclohexane-1,2-dithiol and bromide 3 under argon atmosphere Then, 4.58 g (15.3 mmol) of 5-di-t-butyl-2-hydroxybenzyl was dissolved in 90 mL of tetrahydrofuran and cooled to 0 ° C. Triethylamine 2.13mL (15.3mmol) was added there, and it stirred at 0 degreeC for 15 hours. The formed precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure. Ether and dilute hydrochloric acid were added to the resulting residue, the ether layer was washed with water and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent hexane-dichloromethane 1: 1) to obtain 3.86 g (yield 90%) of the title compound as colorless crystals.
Melting point: 104-106 ℃ Decomposition (recrystallization from ethanol)
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.19-1.43 (m, 44 H), 2.09-2.15 (m, 2 H), 2.58-2.61 (m, 2 H), 3.79 (s, 4 H), 6.75 (s, 2 H), 6.93 (d, J = 2 Hz, 2 H), 7.25 (d, J = 2 Hz, 2 H).
¹³ C-NMR (100.7 MHz, δ, CDCl ₃ )
24.7, 29.7, 31.6, 32.6, 33.9, 34.2, 35.0, 48.1, 121.6, 123.7, 125.2, 137.3, 142.2, 152.0.
Elemental analysis: calculated (C ₃₆ H ₅₆ O ₂ S ₂ ) C, 73.92%; H, 9.34%.
Found: C, 74.17%; H, 9.31%.

(Reference Example 2)
Synthesis of [cyclohexanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium The following experiment was performed in a glove box under an argon atmosphere. In a 50 mL Schlenk tube, 300 mg (0.513 mmol) of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclohexane was dissolved in 5 mL of toluene, and this solution was dissolved at room temperature. 5 mL of a toluene solution of 234 mg (0.513 mmol) of tetrabenzylzirconium was added dropwise, and the mixture was further stirred for 2 hours. Toluene was distilled off under reduced pressure, and the residue was washed with 2 mL of pentane and dried to obtain 176 mg (yield 40%) of the title compound as colorless crystals.
¹ H-NMR (500 MHz, δ, ppm, C ₆ D ₆ )
0.42-1.08 (m, 8 H, major, minor), 1.22 (s, 18 H, major), 1.24 (s, 18 H, minor), 1.57-1.61 (m, 2 H, major), 1.77 (s, 18 H, major), 1.80 (s, 18 H, minor), 1.84 (d, J = 9 Hz, 2 H, major), 1.96-2.02 (m, 2 H, minor), 2.16 (d, J = 10 Hz, 2 H, minor), 2.64 (d, J = 9 Hz, 2 H, major), 2.79 (d, J = 10 Hz, 2 H, minor), 2.94 (d, J = 12 Hz, 2 H, major), 3.22 (d, J = 15 Hz, 2 H, major), 3.23 (d, J = 15 Hz, 2 H, minor), 3.52 (d, J = 15 Hz, 2 H, minor), 6.57 ( d, J = 2 Hz, 2 H, major), 6.63 (d, J = 2 Hz, 2 H, minor), 6.90-7.27 (m, 10 H, major, minor), 7.42 (d, J = 2 Hz , 2 H, major), 7.52 (d, J = 2 Hz, 2 H, minor).

(Reference Example 3)
Synthesis of [cyclohexanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium The following experiment was conducted in a glove box under an argon atmosphere. In a 100 mL Schlenk tube, 200.0 mg (0.342 mmol) of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclohexane is dissolved in 10 mL of toluene, and tetrabenzyl is dissolved in this solution at room temperature. 10 mL of a toluene solution of 185.7 mg (0.342 mmol) of hafnium was added dropwise, and the mixture was further stirred for 1 hour. Toluene was distilled off under reduced pressure, and the residue was washed 3 times with 2 mL of hexane and dried to obtain 201.3 mg (yield 62%) as a diastereomeric mixture of the title compound as colorless crystals. The diastereomeric ratio was 64/36.
Major: ¹ H-NMR (400 MHz, δ, ppm, CD ₃ C ₆ D ₅ )
1.06-1.92 (m, 44H), 2.55 (d, J = 12 Hz, 2H), 2.84 (d, J = 12 Hz, 2H), 3.21 (d, J = 14 Hz, 2H), 3.37 (d, J = 14 Hz, 2H), 6.62 (d, J = 2 Hz, 2H), 6.74-6.81 (m, 2H), 7.04-7.12 (m, 6H), 7.25 (d, J = 8 Hz, 4H), 7.54 (d, J = 2 Hz, 2H).
Minor: ¹ H-NMR (400 MHz, δ, ppm, CD ₃ C ₆ D ₅ )
1.06-1.92 (m, 44H), 2.38 (d, J = 12 Hz, 2H), 2.85 (d, J = 14 Hz, 2H), 2.94 (d, J = 12 Hz, 2H), 3.18 (d, J = 14 Hz, 2H), 6.59 (d, J = 2 Hz, 2H), 6.74-6.81 (m, 2H), 7.04-7.12 (m, 6H), 7.31 (d, J = 8 Hz, 4H), 7.47 (d, J = 2 Hz, 2H).

(Reference Example 4)
Synthesis of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane 2.18 g (12.4 mmol) of trans-cyclooctane-1,2-dithiol and odor under argon atmosphere 7.55 g (25.1 mmol) of 3,5-di-t-butyl-2-hydroxybenzyl was dissolved in 80 mL of tetrahydrofuran and cooled to 0 ° C. Triethylamine 3.5mL (24.9mmol) was added there, and it stirred at 0 degreeC for 1 hour and room temperature all night. The formed precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure. Ether and saturated aqueous ammonium chloride solution were added to the resulting residue, and the ether layer was washed with water and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent hexane-dichloromethane 1: 1) to obtain 6.74 g (yield 89%) of the title compound as colorless crystals.
Melting point: 122-123 ° C (recrystallized from hexane)
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.12-1.94 (m, 48 H), 2.63-2.65 (m, 2 H), 3.81 (d, J = 13 Hz, 2 H), 3.90 (d, J = 13 Hz, 2 H), 6.92 (d, J = 2 Hz, 2 H), 6.95 (s, 2 H), 7.26 (d, J = 2 Hz, 2 H).
¹³ C-NMR (100.7 MHz, δ, CDCl ₃ )
25.7, 25.8, 29.8, 31.2, 31.6, 34.2, 35.0, 35.4, 49.6, 121.6, 123.7, 125.4, 137.4, 142.0, 152.2.
Elemental analysis: calculated (C ₃₈ H ₆₀ O ₂ S ₂ ) C, 74.45%; H, 9.87%.
Found: C, 74.39%; H, 10.09%.

(Reference Example 5)
Synthesis of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium The following experiment was performed in a glove box under an argon atmosphere. In a 50 mL Schlenk tube, 207 mg (0.336 mmol) of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane was dissolved in 10 mL of toluene, and this solution was dissolved at room temperature. 10 mL of a toluene solution of tetrabenzylzirconium 153 mg (0.336 mmol) was added dropwise, and the mixture was further stirred for 1 hour. Toluene was distilled off under reduced pressure, and the residue was washed with 2 mL of hexane and dried to obtain 216 mg (yield 76%) of the title compound as colorless crystals.
Melting point: 181-183 ° C decomposition
¹ H-NMR (400 MHz, δ, ppm, C ₆ D ₆ )
1.16-1.80 (m, 48H), 2.16 (d, J = 10 Hz, 2H), 2.42 (m, 2H), 2.78 (d, J = 10 Hz, 2H), 3.16 (d, J = 14 Hz, 2H ), 3.50 (d, J = 14 Hz, 2H), 6.61 (d, J = 2 Hz, 2H), 6.90 (t, J = 8 Hz, 2H), 7.09 (t, J = 8 Hz, 4H), 7.25 (t, J = 8 Hz, 4H), 7.52 (d, J = 2 Hz, 2H).
¹³ C-NMR (100.4 MHz, δ, ppm, C ₆ D ₆ )
25.2, 26.1, 28.6, 30.6, 31.7, 34.2, 34.8, 35.7, 48.7, 64.0, 122.0, 123.1, 124.3, 126.2, 128.5, 128.7, 129.6, 140.9, 145.8, 158.0.
Elemental analysis: calculated (C ₅₂ H ₇₂ O ₂ S ₂ Zr) C, 70.61%; H, 8.21%.
Found: C, 70.54%; H, 8.31%.

(Reference Example 6)
Synthesis of trans-1,2-bis (5-tert-butyl-3-cumyl-2-hydroxybenzylsulfanyl) cyclooctane (1) Synthesis of 4-tert-butyl-2-cumylphenol 200 mL 4-Tert-butylphenol 12.7 g (84.6 mmol), α-methylstyrene 5.5 mL (42 mmol) and cyclohexane 100 mL were added to the neck flask, and the temperature was raised to 50 ° C. To this, 73 mg (0.42 mmol) of p-toluenesulfonic acid was added and stirred for 4 hours. After the reaction solution was cooled to room temperature, water and dichloromethane were added. The organic layer was dried over anhydrous magnesium sulfate, and the volatile component was distilled off under reduced pressure. The resulting colorless oil is purified by silica gel column chromatography (developing solvent: dichloromethane: heptane = 1: 3) to give 8.06 g (yield 71%) of 4-tert-butyl-2-cumylphenol as a colorless oil. It was.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.35 (s, 9H), 1.69 (s, 6H), 4.17 (s, 1H), 6.68 (d, J = 8 Hz, 1H), 7.19 (dd, J = 2 Hz, 8 Hz, 1H), 7.2 ~ 7.3 (5H), 7.48 (d, J = 2 Hz, 1H).
¹³ C { ¹ H} -NMR (100.4 MHz, δ, ppm, CDCl ₃ )
29.6, 31.6, 34.3, 41.8, 117.1, 123.1, 124.7, 126.0, 126.9, 129.1, 134.5, 143.1, 148.5, 151.4
(2) Synthesis of 4-tert-butyl-6-cumyl-2-hydroxymethylphenol In a 200 mL two-necked flask purged with nitrogen, 7.25 g (23.3 mmol, purity 86.3%) of 4-tert-butyl-2-cumylphenol, Magnesium chloride 4.44 g (46.6 mmol), paraformaldehyde 3.50 g (117 mmol) and tetrahydrofuran 145 mL were added. Triethylamine 6.5 mL (47 mmol) was added here, and it heated and refluxed for 3 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After evaporating volatile components from the filtrate under reduced pressure, ethyl acetate and water were added to the residue. The organic layer was washed with 1 M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 8.05 g of a mixture containing 5-tert-butyl-3-cumylsalicylaldehyde (purity 79.9%, yield 93%).
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.42 (s, 9H), 1.74 (s, 6H), 7.1 to 7.4 (5H), 7.39 (d, J = 2 Hz, 1H), 7.74 (d, J = 2 Hz, 1H), 9.81 (s, 1H ), 11.2 (s, 1H)
To a 100 mL flask purged with nitrogen, 8.05 g of the above mixture, 40 mL of tetrahydrofuran and 40 mL of methanol were added, and the mixture was ice-cooled. Sodium borohydride 340 mg (8.97 mmol) was slowly added here, and it heated up to room temperature, and stirred for 7 hours. After distilling off volatile components from the reaction solution under reduced pressure, water and ethyl acetate were added. The organic layer was washed with 1 M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The obtained colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 15 to 1: 5) to give 4.88 g of 4-tert-butyl-6-cumyl-2-hydroxymethylphenol ( Yield 75%) was obtained as a colorless oil.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.34 (s, 9H), 1.70 (s, 6H), 2.16 (t, J = 6 Hz, 1H), 4.65 (d, J = 6 Hz, 2H), 5.56 (s, 1H), 7.09 (d, J = 2 Hz, 1H), 7.2 to 7.4 (5H), 7.45 (d, J = 2 Hz, 1H).
(3) Synthesis of 5-tert-butyl-3-cumyl-2-hydroxybenzyl bromide Nitrogen-substituted 50 mL Schlenk was charged with 4.88 g (16.4 mmol) of 4-tert-butyl-6-cumyl-2-hydroxymethylphenol. Dichloromethane 24 mL was added. To this, 8.2 mL of phosphorus tribromide (1.0 M dichloromethane solution, 8.2 mmol) was added and stirred at room temperature for 1.5 hours. Water was added to the reaction solution, and the organic layer was further washed twice with water and then with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and volatile components were distilled off under reduced pressure to obtain 5.76 g (98% yield) of 5-tert-butyl-3-cumyl-2-hydroxybenzyl bromide as a colorless oil. It was.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.35 (s, 9H), 1.69 (s, 6H), 4.47 (s, 2H), 7.24 (d, J = 2 Hz, 1H), 7.2 to 7.4 (5H), 7.48 (d, J = 2 Hz, 1H ).
(4) Synthesis of trans-1,2-bis (5-tert-butyl-3-cumyl-2-hydroxybenzylsulfanyl) cyclooctane 5-tert-butyl-3-bromide bromide in a nitrogen-substituted 100 mL two-necked flask Cumyl-2-hydroxybenzyl 2.85 g (7.89 mmol), trans-cyclooctane-1,2-dithiol 7.6 mL (0.5 M tetrahydrofuran solution, 3.8 mmol) and tetrahydrofuran 21 mL were added, and the mixture was ice-cooled. Triethylamine 1.1 mL (7.9 mmol) was added here, and it stirred at 0 degreeC for 1 hour, and 2 hours at room temperature. After the volatile components were distilled off from the reaction solution under reduced pressure, ethyl acetate and an aqueous ammonium chloride solution were added. The organic layer was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (developing solvent: dichloromethane: hexane = 1: 1) to obtain trans-1,2-bis (5-tert-butyl-3-cumyl-2 There was obtained 2.26 g of a 2: 1 mixture of -hydroxybenzylsulfanyl) cyclooctane and trans-1- (5-tert-butyl-3-cumyl-2-hydroxybenzylsulfanyl) -2-sulfanylcyclooctane. This mixture was dissolved in 4 mL of tetrahydrofuran, and 0.42 g (1.2 mmol) of 5-tert-butyl-3-cumyl-2-hydroxybenzyl bromide and 0.2 mL (1.4 mmol) of triethylamine were added at room temperature. After stirring for 2 hours, volatile components were distilled off under reduced pressure. Ethyl acetate and aqueous ammonium chloride solution were added to the obtained reaction mixture, and the organic layer was further washed with water and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (developing solvent: dichloromethane: hexane = 1: 1) to obtain trans-1,2-bis (5-tert-butyl-3-cumyl-2-hydroxybenzylsulfanyl) ) 2.30 g (89% yield) of cyclooctane was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.35 (s, 18H), 1.68 (s, 6H), 1.69 (s, 6H), 1.13 to 1.79 (m, 12H), 2.55 (m, 2H), 3.64 (d, J = 14 Hz, 2H), 3.68 (d, J = 14 Hz, 2H), 5.77 (s, 2H), 7.03 (d, J = 2 Hz, 2H), 7.13 to 7.26 (10H), 7.39 (d, J = 2 Hz, 2H).
¹³ C { ¹ H} -NMR (100.4 MHz, δ, ppm, CDCl ₃ )
25.8, 25.9, 29.4, 30.0, 31.0, 31.6, 34.0, 34.3, 42.1, 49.9, 123.1, 123.4, 125.67, 125.74, 126.0, 128.2, 136.1, 142.1, 150.2, 150.8.

(Reference Example 7)
Synthesis of [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium Trans in a 50 mL Schlenk tube in a glove box under nitrogen atmosphere To a solution of 1,2-bis (5-tert-butyl-3-cumyl-2-hydroxybenzylsulfanyl) cyclooctane 200 mg (0.27 mmol) in toluene (5 mL), tetrabenzylzirconium 124 mg (0.27 mmol) A toluene (5 mL) solution was added dropwise at room temperature. After 1 hour, the reaction solution was filtered, and volatile components were removed from the filtrate under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to give [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzyl Zirconium (121 mg, yield 44%) was obtained as a yellow powder.
¹ H-NMR (400 MHz, δ, ppm, toluene-d ₈ )
0.79-1.8 (m, 12H), 1.23 (s, 18H), 1.84 (s, 6H), 1.99 (s, 6H), 2.03 (d, J = 10 HZ), 2.29 (m, 2H), 3.11 (d , J = 14 Hz, 2H), 3.41 (d, J = 14 Hz, 2H), 6.49 (d, J = 8 Hz, 4H), 6.63 (d, J = 2 Hz, 2H), 6.85 (t, J = 8 Hz, 2H), 7.0-7.1 (4H), 7.16 (t, J = 8 Hz, 2H), 7.25 (t, J = 8 Hz, 4H), 7.34 (d, J = 8 Hz, 4H), 7.44 (d, J = 2 Hz, 2H).

(Reference Example 8)
Synthesis of [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylhafnium trans in 50 mL Schlenk tube in a glove box under nitrogen To a solution of 1,2-bis (5-tert-butyl-3-cumyl-2-hydroxybenzylsulfanyl) cyclooctane 200 mg (0.27 mmol) in toluene (5 mL), tetrabenzylhafnium 147 mg (0.27 mmol) was added. A toluene (5 mL) solution was added dropwise at room temperature. After 1 hour, the reaction solution was filtered, and volatile components were removed from the filtrate under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to obtain [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzyl Hafnium 215 mg (yield 72%) was obtained as a white powder.
¹ H-NMR (400 MHz, δ, ppm, toluene-d ₈ )
0.86 to 1.4 (m, 12H), 1.20 (s, 18H), 1.44 (d, J = 12 Hz, 2H), 1.85 (d, J = 12 Hz, 2H), 1.92 (s, 6H), 1.94 (s , 6H), 2.21 (m, 2H), 3.04 (d, J = 14 Hz, 2H), 3.13 (d, J = 14 Hz, 2H), 6.62 (d, J = 8 Hz, 2H), 6.74 (t , J = 8 Hz, 2H), 6.89 (d, J = 8 Hz, 4H), 7.05-7.16 (4H), 7.25 (t, J = 8 Hz, 4H), 7.40 (d, J = 8 Hz, 4H ), 7.52 (d, J = 2 Hz, 2H).

(Reference Example 9)
Synthesis of MAO / SiO ₂ Silica (Sypolol 948 manufactured by Devison Corp .; average particle size = 55 μm; pore volume = silica) heat-treated at 300 ° C. under nitrogen flow as a solid support in a 50-liter reactor equipped with a nitrogen-substituted stirrer 1.67 ml / g; specific surface area = 325 m ² / g) 9.68 kg was added. After adding 100 liters of toluene, it was cooled to 2 ° C. To this, 26.3 liters of a toluene solution of methylalumoxane (manufactured by Tosoh Finechem) (2.9M) was added dropwise over 1 hour. After stirring at 5 ° C. for 30 minutes, the mixture was heated to 95 ° C. over 90 minutes and stirred for 4 hours. After cooling to 40 ° C., the mixture was allowed to stand for 40 minutes to allow the solid component to settle, and the upper slurry portion was removed. As a washing operation, 100 liters of toluene was added thereto, and the mixture was stirred for 10 minutes. Then, the stirring was stopped and the mixture was allowed to stand to settle the solid component. Similarly, the upper slurry portion was removed. The above washing operation was repeated 3 times in total. Furthermore, after adding 100 liters of toluene and stirring, it filtered simultaneously with stopping stirring. After repeating this operation once more, 110 liters of hexane was added, followed by filtration in the same manner. This operation was repeated once more. Then, to obtain a MAO / _SiO 2 12.6 kg was dried for 7 hours in a nitrogen flow under 70 ° C.. As a result of elemental analysis, it was Al = 4.4 mmol / g.

(Reference Example 10)
Synthesis of [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl)] dichlorohafnium 50 mL Schlenk tube in a glove box under nitrogen atmosphere Trans-1,2-bis (5-tert-butyl-2-hydroxy-3- (triphenylmethyl) benzylsulfanyl) cyclooctane in a solution of 0.40 g (0.41 mmol) in toluene (4 mL) with dichlorodibenzylhafnium -A solution of 0.21 g (0.41 mmol) of diethyl ether complex in toluene (4 mL) was added dropwise at room temperature. After 6 hours, the reaction solution was filtered, and volatile components were removed from the filtrate under reduced pressure. The obtained residue was washed with hexane and then dissolved in a mixed solvent of diethyl ether / hexane. After concentration under reduced pressure, hexane was added and the mixture was allowed to stand at room temperature for 3 days. The precipitated solid was collected and dried under reduced pressure to obtain [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl)] dichlorohafnium 0.31 g (62% yield) was obtained as a white powder.
¹ H NMR (500 MHz, δ, ppm, CDCl ₃ )
0.50-1.6 (m, 30H), 1.83 (brs, 2H), 3.44 (d, J = 14 Hz, 2H), 3.98 (d, J = 14 Hz, 2H), 6.7-7.4 (m, 34H).

(Reference Example 11)
Synthesis of trans-1,2-bis (5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl) cyclooctane (1) 4-tert-butyl-2- ( Synthesis of 3,5-dimethyl-1-adamantyl) phenol Nitrogen-substituted 50 mL Schlenk with 4-tert-butylphenol 3.3 g (22 mmol), 3,5-dimethyl-1-adamantanol 4.0 g (22 mmol) and dichloromethane 20 mL was added and cooled to 0 ° C. in an ice bath. Sulfuric acid 1.2 mL (22 mmol) was added here, and it stirred at room temperature for 1 hour. The reaction solution was poured into an aqueous sodium bicarbonate solution. The organic layer was dried over anhydrous magnesium sulfate, and the volatile component was distilled off under reduced pressure. The obtained white solid was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10) to give 4.0 g of 4-tert-butyl-2- (3,5-dimethyl-1-adamantyl) phenol ( Yield 59%) was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.874 (s, 6H), 1.20 (s, 2H), 1.29 (s, 9H), 1.35 to 1.45 (m, 4H), 1.70 to 1.78 (m, 4H), 1.95 (m, 2H), 2.17 (m, 1H), 4.56 (s, 1H), 6.56 (d, J = 8 Hz, 1H), 7.06 (dd, J = 2 Hz, 8 Hz, 1H), 7.2 to 7.3 (1H), 7.24 (d, J = (2 Hz, 1H).
(2) Synthesis of 4-tert-butyl-6- (3,5-dimethyl-1-adamantyl) -2-hydroxymethylphenol 4-tert-butyl-2- (3, 5 -Dimethyl-1-adamantyl) phenol 4.0 g (13 mmol), magnesium chloride 4.8 g (50 mmol), paraformaldehyde 2.1 g (70 mmol) and tetrahydrofuran 50 mL were added. Triethylamine 6.7 mL (48 mmol) was added here, and it heated and refluxed for 3 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After evaporating volatile components from the filtrate under reduced pressure, ethyl acetate and water were added to the residue. The organic layer was washed with 1 M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 4.2 g of a mixture containing 5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) salicylaldehyde (yield 96%).
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.874 (s, 6H), 1.2-2.2 (m, 22H), 7.32 (d, J = 2 Hz, 1H), 7.53 (d, J = 2 Hz, 1H), 9.85 (s, 1H), 11.7 (s , 1H).
4.2 g of the above mixture, 20 mL of tetrahydrofuran and 20 mL of methanol were added to a 100 mL flask purged with nitrogen, and the mixture was ice-cooled. 490 mg (13 mmol) of sodium borohydride was slowly added here, and it heated up to room temperature, and stirred for 1 hour. After distilling off volatile components from the reaction solution under reduced pressure, water and ethyl acetate were added. The organic layer was washed with 1 M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The resulting colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10-1: 5) to give 4-tert-butyl-6- (3,5-dimethyl-1-adamantyl) ) -2-hydroxymethylphenol (3.4 g, yield 81%) was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.875 (s, 6H), 1.2-2.2 (m, 23H), 4.85 (d, J = 5 Hz, 2H), 6.88 (d, J = 2 Hz, 1H), 7.22 (d, J = 2 Hz, 1H ), 7.55 (s, 1H).
(3) Synthesis of 5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzyl bromide In a 200 mL flask purged with nitrogen, 4-tert-butyl-6- (3, 5 -Dimethyl-1-adamantyl) -2-hydroxymethylphenol 3.4 g (9.9 mmol) and dichloromethane 20 mL were added. To this was added 6.6 mL of phosphorus tribromide (1.0 M dichloromethane solution, 6.6 mmol), and the mixture was stirred at room temperature for 1 hour. Water was added to the reaction solution, and the organic layer was further washed twice with water and then with saturated brine. After drying the organic layer over anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure to give 3.95 g of 5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzyl bromide ( Yield 98%) as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.882 (s, 6H), 1.22 (s, 2H), 1.28 (s, 9H), 1.35 to 1.45 (m, 4H), 1.70 to 1.78 (m, 4H), 1.96 (m, 2H), 2.19 (m, 1H), 4.57 (s, 1H), 7.08 (d, J = 2 Hz, 1H), 7.27 (d, J = 2 Hz, 1H).
(4) Synthesis of trans-1,2-bis (5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl) cyclooctane bromide into nitrogen-substituted 50 mL Schlenk 5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzyl 1.0 g (2.5 mmol), trans-cyclooctane-1,2-dithiol 0.18 g (1.0 mmol) and tetrahydrofuran 7 mL was added and ice-cooled. Triethylamine 0.7 mL (5.0 mmol) was added here, and it stirred at 0 degreeC for 1 hour, and 2 hours at room temperature. Further, 0.05 g (0.013 mmol) of 5-tert-butyl-2-hydroxy-3- (3,5-dimethyl-1-adamantyl) benzyl bromide was added, and the mixture was stirred at room temperature for 1 hour. After the volatile components were distilled off from the reaction solution under reduced pressure, ethyl acetate and an aqueous ammonium chloride solution were added. The organic layer was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10) to obtain trans-1,2-bis (5-tert-butyl-3- (3 , 5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl) cyclooctane (1.0 g, yield> 99%) was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.88 (s, 12H), 1.2-2.2 (m, 56H), 2.59 (m, 2H), 3.77 (d, J = 14 Hz, 2H), 3.87 (d, J = 14 Hz, 2H), 6.89 (d , J = 2 Hz, 2H), 7.19 (d, J = 2 Hz, 2H).

(Reference Example 12)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-oxoylbenzylsulfanyl]} dichlorohafnium Globe under nitrogen atmosphere In a box, in a 50 mL Schlenk tube, trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] cyclooctane 83 mg (0.10 mmol) A toluene (1 mL) solution of 51 mg (0.10 mmol) of dichloro {1,1′-oxybis [ethane] [bis (phenylmethyl) hafnium]} in a toluene (1 mL) solution at room temperature was added dropwise. After 1.5 hours, volatile components were distilled off under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to obtain {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) − 2-Oxoylbenzylsulfanyl]} dichlorohafnium 55 mg (51% yield) was obtained as a white powder.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.901 (s, 12H), 1.0-2.4 (m, 56H), 2.58 (brs, 2H), 3.88 (d, J = 14 Hz, 2H), 4.54 (d, J = 14 Hz, 2H), 6.85 (d , J = 2 Hz, 2H), 7.37 (d, J = 2 Hz, 2H).

(Reference Example 13)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-oxoylbenzylsulfanyl]} dichlorozirconium Globe under nitrogen atmosphere In a box, in a 50 mL Schlenk tube, trans-1,2-bis (5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl) cyclooctane 83 mg (0.10 mmol) Toluene (1 mL) solution of tetrachlorozirconium 23 mg (0.10 mmol) in toluene (1 mL) was added dropwise at room temperature. After 1.5 hours, volatile components were distilled off under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to obtain {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) − 2-Oxoylbenzylsulfanyl]} dichlorozirconium 51 mg (52% yield) was obtained as a white powder.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.903 (s, 12H), 1.0-2.4 (m, 56H), 2.55 (brs, 2H), 3.84 (d, J = 14 Hz, 2H), 4.52 (d, J = 14 Hz, 2H), 6.85 (d , J = 2 Hz, 2H), 7.34 (d, J = 2 Hz, 2H).

(Reference Example 14)
Synthesis of trans-1,2-bis {5-tert-butyl-3- [1- (3,5-dimethylphenyl) -1-methylethyl] -2-hydroxybenzylsulfanyl} cyclooctane (1) 1- ( Synthesis of 3,5-dimethylphenyl) -1-methylethanol To a nitrogen-substituted 200 mL four-necked flask, 60 mL of THF and 40 mL of 3,5-dimethylphenylmagnesium bromide (0.50 M THF solution, 20 mmmol) were added. After cooling to -65 ° C, 5.2 mL (71 mmol) of acetone was added dropwise. The mixture was warmed to room temperature, stirred for 2.5 hours, and poured into 60 g of ice water. 1 M HCl, diethyl ether was added. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. After drying over anhydrous magnesium sulfate, volatile components were distilled off under reduced pressure. The obtained pale yellow oil was purified by silica gel column chromatography (developing solvent, ethyl acetate: hexane = 1: 10 to 1: 4), and then purified again by silica gel column chromatography (developing solvent, ethyl acetate: hexane = 1: 9). Purification gave 1.7 g (yield 50%) of 1- (3,5-dimethylphenyl) -1-methylethanol as a pale yellow oil.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.56 (s, 6H), 1.76 (s, 1H), 2.33 (s, 6H), 6.89 (s, 1H), 7.10 (s, 2H).
(2) Synthesis of 4-tert-butyl-2- [1- (3,5-dimethylphenyl) -1-methylethyl] phenol In a 100 mL flask purged with nitrogen, 1- (3,5-dimethylphenyl) -1 -1.7 g (10 mmol) of methyl ethanol, 3.0 g (20 mmol) of 4-tert-butylphenol and 40 mL of heptane were added. 40 mg (0.23 mmol) of p-toluenesulfonic acid was added thereto, the temperature was raised to 100 ° C., and the mixture was stirred for 16 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate, and then the volatile component was distilled off under reduced pressure. The obtained light orange solid was purified by silica gel column chromatography (developing solvent, ethyl acetate: hexane = 1: 20), and then purified again by silica gel column chromatography (developing solvent, ethyl acetate: hexane = 1: 50). 1.9 g (66% yield) of 4-tert-butyl-2- (1- (3,5-dimethylphenyl) -1-methylethyl) phenol was obtained as a colorless oil.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.36 (s, 9H), 1.65 (s, 6H), 2.28 (s, 6H), 4.38 (s, 1H), 6.68 (d, J = 8 Hz, 1H), 6.89 (s, 1H), 6.94 (s , 2H), 7.18 (dd, J = 2 Hz, 8 Hz, 1H), 7.46 (d, J = 2 Hz, 1H).
(3) Synthesis of 4-tert-butyl-6- [1- (3,5-dimethylphenyl) -1-methylethyl] -2-hydroxymethylphenol 4-tert-butyl-into a nitrogen-substituted 100 mL four-necked flask 2- [1- (3,5-dimethylphenyl) -1-methylethyl] phenol 1.9 g (6.5 mmol), magnesium chloride 1.3 g (13 mmol), paraformaldehyde 0.98 g (33 mmol) and tetrahydrofuran 38 mL. added. Triethylamine 1.8 mL (13 mmol) was added here, and it heated and refluxed for 100 minutes. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After evaporating volatile components from the filtrate under reduced pressure, ethyl acetate and 2% HCl were added to the residue. The organic layer was washed with water and saturated brine in that order and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 2.2 g of a mixture containing 5-tert-butyl-3- [1- (3,5-dimethylphenyl) -1-methylethyl] salicylaldehyde (yield> 99%). Obtained.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.37 (s, 9H), 1.71 (s, 6H), 2.26 (s, 6H), 6.79 (s, 2H), 6.81 (s, 1H), 7.39 (s, 1H), 7.72 (s, 1H), 9.83 (s, 1H), 11.2 (s, 1H).
To a 200 mL four-necked flask purged with nitrogen, 2.5 g of the above mixture, 40 mL of tetrahydrofuran and 20 mL of methanol were added and cooled on ice. To this, 180 mg (4.8 mmol) of sodium borohydride was slowly added, and the mixture was warmed to room temperature and stirred for 15 hours. After evaporating volatile components from the reaction solution under reduced pressure, 2 M HCl and ethyl acetate were added. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate. The resulting colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 6 to 1: 4) to give 4-tert-butyl-6- [1- (3,5-dimethylphenyl) ) -1-methylethyl] -2-hydroxymethylphenol (2.2 g, yield 86%) was obtained as a colorless oil.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.35 (s, 9H), 1.66 (s, 6H), 2.24 (t, J = 6 Hz, 1H), 2.28 (s, 6H), 4.62 (d, J = 6 Hz, 2H), 5.26 (s, 1H ), 6.89 (s, 1H), 6.93 (s, 2H), 7.12 (s, J = 2 Hz, 1H), 7.43 (s, J = 2 Hz, 1H).
(3) Synthesis of 5-tert-butyl-3- [1- (3,5-dimethylphenyl) -1-methylethyl] -2-hydroxybenzyl bromide 4-nitro-substituted 4-tert- Butyl-6- [1- (3,5-dimethylphenyl) -1-methylethyl] -2-hydroxymethylphenol 2.2 g (6.8 mmol) and dichloromethane 30 mL were added. A mixed solution (4.1 mmol) of 2 mL of dichloromethane and 0.43 mL of phosphorus tribromide was added thereto, and the mixture was stirred at room temperature for 3 hours. The reaction solution was added to ice water, and the organic layer was washed twice with saturated brine. The organic layer is dried over anhydrous magnesium sulfate, and the volatile components are distilled off under reduced pressure to give 5-tert-butyl-3- [1- (3,5-dimethylphenyl) -1-methylethyl] -2 2.8 g (yield> 99%) of -hydroxybenzyl were obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.35 (s, 9H), 1.65 (s, 6H), 2.28 (s, 6H), 4.48 (s, 2H), 6.91 (s, 1H), 6.94 (s, 2H), 7.23 (s, J = 2 Hz , 1H), 7.46 (s, J = 2 Hz, 1H).
(4) Synthesis of trans-1,2-bis {5-tert-butyl-3- [1- (3,5-dimethylphenyl) -1-methylethyl] -2-hydroxybenzylsulfanyl} cyclooctane In a 100 mL four-necked flask, 1.8 g (4.7 mmol) of 5-tert-butyl-3- [1- (3,5-dimethylphenyl) -1-methylethyl] -2-hydroxybenzyl bromide, trans-cyclooctane 1,2-Dithiol 0.42 g (2.4 mmol) and tetrahydrofuran 30 mL were added, and the mixture was ice-cooled. Triethylamine 1.0 mL (7.2 mmol) was added here, and it stirred at room temperature for 15.5 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 40-1: 20) to obtain trans-1,2-bis {5-tert-butyl 2-hydroxy-3- [1- (3,5-dimethylphenyl) -1-methylethyl] benzylsulfanyl} cyclooctane and trans-1- {5-tert-butyl-2-hydroxy-3- [1- 1.7 g of a 7: 3 mixture with (3,5-dimethylphenyl) -1-methylethyl] benzylsulfanyl} -2-sulfanylcyclooctane was obtained. This mixture and 5-tert-butyl-3- [1- (3,5-dimethylphenyl) -1-methylethyl] -2-hydroxybenzyl bromide 0.50 g (1.3 mmol) were dissolved in 20 mL of tetrahydrofuran, and iced. Chilled. Triethylamine 0.25 mL (1.8 mmol) was added here, and it stirred for 21.5 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and an aqueous ammonium chloride solution were added to the obtained residue, and the organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 40), whereby trans-1,2-bis {5-tert-butyl-3- [1- (3, 1.8 g (yield 94%) of 5-dimethylphenyl) -1-methylethyl] -2-hydroxybenzylsulfanyl} cyclooctane was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.2 to 2.0 (m, 42H), 2.25 (s, 12H), 2.64 (brs, 2H), 3.67 (s, 4H), 5.56 (s, 2H), 6.82 (s, 2H), 6.86 (s, 4H) , 7.09 (d, J = 2 Hz, 2H), 7.36 (d, J = 2 Hz, 2H).

(Reference Example 15)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1- (3,5-dimethylphenyl) -1-methylethyl) benzylsulfanyl]} dichlorohafnium Trans-1,2-bis {5-tert-butyl-3- [1- (3,5-dimethylphenyl) -1-methylethyl] -2-hydroxy in a 100 mL Schlenk tube in a glove box under nitrogen atmosphere To a solution of benzylsulfanyl} cyclooctane 1.0 g (1.3 mmol) in toluene (5 mL), dichloro {1,1′-oxybis [ethane] [bis (phenylmethyl) hafnium]} 640 mg (1.3 mmol) in toluene (5 mL) The solution was added dropwise at room temperature. After stirring for 1 hour, volatile components were distilled off under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to give {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1- (3, 5 -Dimethylphenyl) -1-methylethyl) benzylsulfanyl]} dichlorohafnium 1.1 g (81% yield) was obtained as a white powder.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.73 to 1.7 (m, 36H), 1.96 (s, 6H), 2.08 (brs, 2H), 2.21 (s, 12H), 3.53 (d, J = 14 Hz, 4H), 4.05 (d, J = 14 Hz , 4H), 6.72 (s, 2H), 6.83 (d, J = 2 Hz, 2H), 6.90 (s, 4H), 7.51 (d, J = 2 Hz, 2H).

(Reference Example 16)
Synthesis of carrier A Silica heat-treated at 300 ° C. under a nitrogen flow as a solid carrier (Sypolol 948 manufactured by Devison; average particle size = 55 μm; pore volume = 1.67 ml / g; specific surface area = 325 m ² / g) 9 .68 kg was added. After adding 100 L of toluene, it was cooled to 2 ° C. To this was added dropwise 23.3 kg (75.9 mol) of methylalumoxane in toluene (PMAO-S) (manufactured by Tosoh Finechem) over 1 hour. After stirring at 5 ° C. for 30 minutes, the mixture was heated to 95 ° C. over 90 minutes and stirred for 4 hours. After cooling to 40 ° C., the mixture was allowed to stand for 40 minutes to allow the solid component to settle, and toluene was removed with a dip tube. As a washing operation, 100 L of toluene was added thereto and stirred, and then stirring was stopped and the mixture was allowed to stand for 40 minutes to precipitate a solid component, and toluene was similarly removed. The above washing operation was repeated 5 times in total. Further, 110 L of hexane was added and stirred, followed by filtration. This operation was repeated once more. Thereafter, it was dried at 70 ° C. under reduced pressure for 7 hours to obtain 12.6 kg of carrier A. As a result of elemental analysis, it was Al = 4.4 mmol / g.

(Reference Example 17)
Synthesis of carrier B Silica heated at 300 ° C. under nitrogen flow as a solid carrier in a nitrogen-substituted 100 ml four-necked flask (Sypolol 948 manufactured by Devison; average particle size = 55 μm; pore volume = 1.67 ml / g; ratio (Surface area = 325 m ^{2 /} g) 5.03 g was added. After adding 50 ml of toluene, it was cooled to 5 ° C. To this was added dropwise 11.9 ml of a toluene solution of methylalumoxane (TMAO-211) (manufactured by Tosoh Finechem) (3.2M) over 1 hour. After stirring at 5 ° C. for 30 minutes, the mixture was heated to 95 ° C. over 90 minutes and stirred for 4 hours. After cooling to 30 ° C., the mixture was allowed to stand for 10 minutes to precipitate the solid components, and toluene was removed with a glass filter of G3 grade (maximum pore size (20-30 μm)). As a washing operation, 50 ml of toluene was added thereto, and the mixture was stirred for 2 minutes. Then, the stirring was stopped and the mixture was allowed to stand to precipitate a solid component, and toluene was similarly removed. The above washing operation was repeated 3 times in total. Further, 50 ml of hexane was added and stirred, followed by filtration in the same manner. This operation was repeated once more. Then, it dried at 70 degreeC under pressure reduction for 2 hours, and obtained the support B 6.51g. As a result of elemental analysis, it was Al = 3.2 mmol / g.

(Reference Example 18)
Synthesis of carrier C 10.42 g of carrier A and 180 ml of toluene were introduced into a nitrogen-substituted 300 ml four-necked flask. A toluene solution of 9.89 g of 3,4,5-trifluorophenol was added at room temperature and stirred for 3 hours. Filtration was performed using a 3G glass filter, and the resultant was washed with 180 ml of toluene four times and hexane 180 ml once and dried under reduced pressure to obtain 14.43 g of carrier C.
As a result of elemental analysis, Al = 2.9 mmol / g and F = 6.3 mmol / g.

(Reference Example 19)
Complex supported catalyst 1
2.00 g of carrier A and 10 ml of toluene were introduced into a 4-necked 100 ml flask that had been purged with nitrogen. After mixing 89.7 mg of [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dichlorozirconium and 3.5 ml of toluene in another flask. TMAO-212 (3.1 mmol-Al / ml manufactured by Tosoh Finechem) was added and stirred for 1 hour and added to a 100 ml flask. The mixture was reacted at 50 ° C. for 4 hours, and the solvent was removed using a 3G grade glass filter. After adding 20 ml of hexane and washing the carrier, the solvent was removed again using a glass filter. The above operation was repeated once, followed by drying at room temperature under reduced pressure.
As a result, 1.90 g of a carrier carrying the complex was obtained.
As a result of elemental analysis, Al = 5.2 mmol / g and Zr = 13 μmol / g.

(Reference Example 20)
Complex supported catalyst 2
2.01 g of carrier A and 10 ml of toluene were introduced into a 4-neck 100 ml flask that had been purged with nitrogen. In a separate flask, [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl)] dichlorohafnium 123.2 mg and toluene 3.5 ml. After mixing, 6.5 ml of TMAO-212 (3.1 mmol-Al / ml manufactured by Tosoh Finechem) was added, and the solution stirred for 1 hour was added to a 100 ml flask. The mixture was reacted at 50 ° C. for 4 hours, and the solvent was removed using a 3G grade glass filter. After adding 20 ml of hexane and washing the carrier, the solvent was removed again using a glass filter. The above operation was repeated once, followed by drying at room temperature under reduced pressure.
As a result, 2.06 g of a carrier carrying the complex was obtained.
As a result of elemental analysis, Al = 5.2 mmol / g and Hf = 13 μmol / g.

(Reference Example 21)
Complex supported catalyst 3
2.02 g of carrier A and 10 ml of toluene were introduced into a 4-necked 100 ml flask that had been purged with nitrogen. In another flask, {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-oxoylbenzylsulfanyl]} dichlorohafnium107. After mixing 2 mg and 3.5 ml of toluene, 6.5 ml of TMAO-212 (3.1 mmol-Al / ml manufactured by Tosoh Finechem) was added, and the solution stirred for 1 hour was added to a 100 ml flask. The mixture was reacted at 50 ° C. for 4 hours, and the solvent was removed using a 3G grade glass filter. After adding 20 ml of hexane and washing the carrier, the solvent was removed again using a glass filter. The above operation was repeated once, followed by drying at room temperature under reduced pressure.
As a result, 2.03 g of a carrier carrying the complex was obtained.
As a result of elemental analysis, Al = 5.2 mmol / g and Hf = 15 μmol / g.

(Reference Example 22)
Complex supported catalyst 4
2.00 g of carrier A and 10 ml of toluene were introduced into a 4-necked 100 ml flask that had been purged with nitrogen. In another flask, {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-oxoylbenzylsulfanyl]} dichlorozirconium 98. After mixing 5 mg and 3.5 ml of toluene, 6.5 ml of TMAO-212 (3.1 mmol-Al / ml manufactured by Tosoh Finechem) was added, and the solution stirred for 1 hour was added to a 100 ml flask. The mixture was reacted at 50 ° C. for 4 hours, and the solvent was removed using a 3G grade glass filter. After adding 20 ml of hexane and washing the carrier, the solvent was removed again using a glass filter. The above operation was repeated once, followed by drying at room temperature under reduced pressure.
As a result, 1.96 g of a carrier carrying the complex was obtained.
As a result of elemental analysis, Al = 4.8 mmol / g and Zr = 15 μmol / g.

(Reference Example 23)
Complex supported catalyst 5
2.00 g of carrier B and 10 ml of toluene were introduced into a 4-neck 100 ml flask that had been purged with nitrogen. In a separate flask, [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl)] dichlorohafnium 123.2 mg and toluene 3.5 ml. After mixing, 6.5 ml of TMAO-212 (3.1 mmol-Al / ml manufactured by Tosoh Finechem) was added, and the solution stirred for 1 hour was added to a 100 ml flask. The mixture was reacted at 50 ° C. for 4 hours, and the solvent was removed using a 3G grade glass filter. After adding 20 ml of hexane and washing the carrier, the solvent was removed again using a glass filter. The above operation was repeated once, followed by drying at room temperature under reduced pressure.
As a result, 1.96 g of a carrier carrying the complex was obtained.

(Reference Example 24)
Complex supported catalyst 6
2.01 g of carrier C and 10 ml of toluene were introduced into a 4-neck 100 ml flask that had been purged with nitrogen. In a separate flask, [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl)] dichlorohafnium 123.2 mg and toluene 3.5 ml. After mixing, 6.5 ml of TMAO-212 (3.1 mmol-Al / ml manufactured by Tosoh Finechem) was added, and the solution stirred for 1 hour was added to a 100 ml flask. The mixture was reacted at 50 ° C. for 4 hours, and the solvent was removed using a 3G grade glass filter. After adding 20 ml of hexane and washing the carrier, the solvent was removed again using a glass filter. The above operation was repeated once, followed by drying at room temperature under reduced pressure.
As a result, 2.02 g of a carrier carrying the complex was obtained.

(Reference Example 25)
Complex supported catalyst 7
2.00 g of carrier A and 10 ml of toluene were introduced into a 4-necked 100 ml flask that had been purged with nitrogen. In another flask [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-2-oxoyl-3- (dimethyl-3,5-dimethylphenyl-methyl) benzylsulfanyl)] dichlorohafnium 104. After mixing 1 mg and 3.5 ml of toluene, 6.5 ml of TMAO-212 (3.1 mmol-Al / ml manufactured by Tosoh Finechem) was added, and the solution stirred for 1 hour was added to a 100 ml flask. The mixture was reacted at 50 ° C. for 4 hours, and the solvent was removed using a 3G grade glass filter. After adding 20 ml of hexane and washing the carrier, the solvent was removed again using a glass filter. The above operation was repeated once, followed by drying at room temperature under reduced pressure.
As a result, 1.92 g of a carrier carrying the complex was obtained.

(Reference Example 26)
Complex supported catalyst 8
2.00 g of carrier A and 10 ml of toluene were introduced into a 4-necked 100 ml flask that had been purged with nitrogen. In another flask, 123.2 mg of [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl)] dichlorohafnium and 10 ml of toluene were mixed. The solution was added to a 100 ml flask. The mixture was reacted at 50 ° C. for 4 hours, and the solvent was removed using a 3G grade glass filter. After adding 20 ml of hexane and washing the carrier, the solvent was removed again using a glass filter. The above operation was repeated once, followed by drying at room temperature under reduced pressure.
As a result, 1.72 g of a carrier carrying the complex was obtained.

(Reference Example 27)
Complex supported catalyst 9
2.00 g of carrier A and 10 ml of toluene were introduced into a 4-necked 100 ml flask that had been purged with nitrogen. In a separate flask, [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl)] dichlorohafnium 123.2 mg and toluene 9 ml, A solution mixed with 1 ml (1 mmol / ml) of triisobutylaluminum solution was added to a 100 ml flask. The mixture was reacted at 50 ° C. for 4 hours, and the solvent was removed using a 3G grade glass filter. After adding 20 ml of hexane and washing the carrier, the solvent was removed again using a glass filter. The above operation was repeated once, followed by drying at room temperature under reduced pressure.
As a result, 1.89 g of a carrier carrying the complex was obtained.

<Ethylene polymerization>
(Example 1)
The autoclave with a stirrer with an internal volume of 400 mL was vacuum-dried and replaced with argon, 200 mL of hexane was charged as a solvent, and the reactor was heated to 70 ° C. After the temperature rise, the ethylene pressure was adjusted to 0.6 MPa and then fed, and 0.5 mL (0.5 mmol) of triisobutylaluminum (1.0 mol / L, toluene solution) was synthesized in Reference Example 7 [cyclooctane. Diyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium (1.0 mmol / L, toluene solution) 1.0 mL (1.0 μmol) Subsequently, 14.5 mg of MAO / SiO ₂ was added to initiate polymerization. Polymerization was performed for 60 minutes while maintaining the temperature at 70 ° C. The results are shown in Table 1.

(Comparative Example 1)
[Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] [cyclohexanediyl-trans-1 synthesized in Reference Example 2 instead of dibenzylzirconium , 2-Bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium and the amount of MAO / SiO ₂ charged was 12.8 mg, the same as in Example 1. Carried out. The results are shown in Table 1.

(Example 2)
[Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] synthesized in Reference Example 8 instead of dibenzylzirconium Example 1, except that 1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylhafnium was used and the amount of MAO / SiO ₂ was 17.1 mg. It carried out similarly. The results are shown in Table 1.

(Comparative Example 2)
[Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] [cyclohexanediyl-trans-1 synthesized in Reference Example 3 instead of dibenzylzirconium , 2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium (1.0 mmol / L, toluene solution) 2.0 mL (2.0 μmol) The same operation as in Example 1 was carried out except that the amount of SiO ₂ input was 19.5 mg. The results are shown in Table 1.

(Example 3)
An autoclave with a stirrer having an internal volume of 400 mL was vacuum-dried and replaced with argon, 185 mL of hexane was charged as a solvent, 15 mL of 1-hexene was charged as a comonomer, and the reactor was heated to 70 ° C. After raising the temperature, the ethylene pressure was adjusted to 0.6 MPa and then fed, and triisobutylaluminum (1.0 mol / L, toluene solution) 0.5 mL (0.5 mmol) was synthesized in Reference Example 5 [cyclooctanediyl. -Trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (1.0 μmol / mL, toluene solution) 1.0 mL (1.0 μmol) followed by Polymerization was initiated by charging 21.1 mg of MAO / SiO ₂ . Polymerization was performed for 60 minutes while maintaining the temperature at 70 ° C. The results are shown in Table 1.

The polymerization results obtained in Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 1.

<Propylene polymerization>
(Example 4)
An autoclave with a stirrer having an internal volume of 400 mL was vacuum dried and replaced with argon, and then 40 mL of hexane as a solvent and 80 g of propylene as a monomer were charged, and the temperature of the reactor was raised to 70 ° C. After raising the temperature, 0.5 mL (0.5 mmol) of triisobutylaluminum (1.0 mol / L, toluene solution) was synthesized in Reference Example 7 [cyclooctanediyl-trans-1,2-bis (5-tert- Butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium (1.0 mmol / L, toluene solution) 2.0 mL (2.0 μmol) followed by MAO / SiO ₂ 17.0 mg for polymerization Started. Polymerization was performed for 60 minutes while maintaining the temperature at 70 ° C. The results are shown in Table 2.

(Comparative Example 3)
[Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] [cyclohexanediyl-trans-1 synthesized in Reference Example 2 instead of dibenzylzirconium , 2-Bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (1.0 mmol / L, toluene solution) 0.5 mL (0.5 μmol) This was carried out in the same manner as in Example 4 except that the amount of / SiO ₂ input was 13.1 mg. The results are shown in Table 2.

(Example 5)
[Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] synthesized in Reference Example 8 instead of dibenzylzirconium 1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylhafnium (1.0 mmol / L, toluene solution) 0.2 mL (0.2 μmol) was used, The same operation as in Example 4 was carried out except that the amount of MAO / SiO ₂ input was 20.4 mg. The results are shown in Table 2.

(Comparative Example 4)
[Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] [cyclohexanediyl-trans-1 synthesized in Reference Example 3 instead of dibenzylzirconium , 2-Bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium (1.0 mmol / L, toluene solution) 0.5 mL (0.5 μmol) The same operation as in Example 4 was carried out except that the input amount of SiO ₂ was 18.8 mg. The results are shown in Table 2.

Table 2 shows the polymerization results obtained in Examples 4 and 5 and Comparative Examples 3 and 4.

(Examples 6 to 32)
In Examples 6 to 19, the complex-supported catalyst 2 was used to examine ethylene-butene or ethylene-hexene copolymerization. During the polymerization, the temperature was kept constant, and the pressure was kept constant with ethylene gas to carry out the polymerization. The polymerization conditions and results are summarized in Tables 3 and 4.

In Examples 20 to 28, the ethylene-butene or ethylene-hexene copolymerization was examined using the complex-supported catalysts 1, 3 to 9. During the polymerization, the temperature was kept constant, and the pressure was kept constant with ethylene gas to carry out the polymerization. The polymerization conditions and results are summarized in Table 5.
In Examples 29 to 32, propylene was polymerized using complex-supported catalysts 1 to 4. The polymerization conditions and results are summarized in Table 6.

For Examples 7, 8, 13, 23, and 24, the particle size and particle size bulk density are summarized in Table 7.

The polymer particles obtained in Example 13 were observed with a scanning microscope (manufactured by KEYENCE, VE-8800). An SEM photograph taken at that time is shown in FIG. In addition, (a) and (b) of FIG. 1 image | photographs the separate visual field in the same sample. As shown in FIG. 1, the shape of the polymer particles was almost spherical.

The present invention is useful in the field relating to the production of polyolefins.

Claims

A catalyst for olefin polymerization comprising contacting a complex represented by the general formula (1-1) or (1-2), an activation promoter component and a carrier.

(Wherein n is 1 or 2,
M represents a zirconium atom or a hafnium atom.
R 1 and R 5 are each independently
Hydrogen atom,
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An alkenyl group having 2 to 20 carbon atoms,
An alkynyl group having 2 to 20 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aralkyloxy group having 7 to 30 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms or a substituted silyl group is represented.
R 2 to R 4 and R 6 to R 10 are each independently
Hydrogen atom,
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An alkenyl group having 2 to 20 carbon atoms,
An alkynyl group having 2 to 20 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aralkyloxy group having 7 to 30 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms,
It represents a substituted silyl group or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring.
The alkyl group, the cycloalkyl group, the alkenyl group, the alkynyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the heterocyclic compound in R 1 to R 10 Each residue may have a substituent.
Regardless of the definition of R 1 to R 10 above, R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 2 And R 9 and R 6 and R 10 may be independently connected to each other to form a ring, and these rings may have a substituent.
Each X is independently
Hydrogen atom,
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An alkenyl group having 2 to 20 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aralkyloxy group having 7 to 30 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms,
Substituted silyl groups,
A substituted amino group,
It represents a substituted thiolate group or a carboxylate group having 1 to 20 carbon atoms.
The alkyl group, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the carboxylate group in X each have a substituent. Also good.
Adjacent Xs may be connected to each other to form a ring.
L represents a neutral Lewis base. When there are a plurality of L, the plurality of L may be the same or different. l is 0, 1, or 2. )
The catalyst according to claim 1, wherein the activation promoter component is at least one of a boron compound and an organoaluminum compound.
R 1 and R 5 are each independently
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
The catalyst according to claim 1 or 2, which is an aralkyl group having 7 to 30 carbon atoms or a substituted silyl group, and the alkyl group, the cycloalkyl group and the aralkyl group may have a substituent.
R 9 and R 10 are each independently
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms,
A substituted silyl group or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring, the alkyl group, the cycloalkyl group, the aralkyl group, the aryl group, and the heterocyclic compound residue The catalyst according to any one of claims 1 to 3, wherein each may have a substituent.
The alkyl group of R 1 , R 5 , R 9 and R 10 is an alkyl group having 4 to 10 carbon atoms, and the alkyl group may have a substituent. 2. The catalyst according to item 1.
R 2 to R 4 and R 6 to R 8 are each independently
Hydrogen atom,
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
6. An aryl group having 6 to 30 carbon atoms or a substituted silyl group, wherein the alkyl group, the cycloalkyl group, the aralkyl group, and the aryl group each may have a substituent. The catalyst of any one of these.
R 3 and R 7 are each independently
A halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms or a substituted silyl group, wherein the alkyl group, the cycloalkyl group, the aralkyl group and the aryl group each may have a substituent. The catalyst of any one of these.
The catalyst according to any one of claims 1 to 7, wherein R 2 , R 4 , R 6 and R 8 are hydrogen atoms.
X is a halogen atom,
An alkyl group having 1 to 20 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aralkyloxy group having 7 to 30 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms, or a substituted amino group, and the alkyl group, the aralkyl group, the alkoxy group, the aralkyloxy group, and the aryloxy group each may have a substituent. The catalyst according to any one of claims 1 to 8.
The catalyst according to any one of claims 1 to 9, wherein n is 2.
The catalyst according to any one of claims 1 to 10, which is used for homopolymerization of an olefin having 2 to 6 carbon atoms or copolymerization of two or more olefins having 2 to 6 carbon atoms.
A process for producing an olefin polymer, wherein an olefin is polymerized in the presence of the catalyst according to any one of claims 1 to 11.
Ethylene-α-olefin copolymer particles having a volume particle size of 300 μm or less and a polymer particle content of 2% by volume or less, a 50% volume reference particle size of 500 μm or more, and a particle bulk density of 400 kg / m 3 or more .