WO2012111780A1

WO2012111780A1 - Catalyst for olefin polymerization and method for producing olefin polymer

Info

Publication number: WO2012111780A1
Application number: PCT/JP2012/053731
Authority: WO
Inventors: 正人 ▲高▼野; 伊藤　和幸; 昭彦石井; 憲男中田; 智之戸田; 啓太伊久間; 史彦河内
Original assignee: 住友化学株式会社; 国立大学法人埼玉大学
Priority date: 2011-02-18
Filing date: 2012-02-16
Publication date: 2012-08-23

Abstract

Provided is a catalyst for olefin polymerization with which it is possible to produce a high-molecular-weight olefin polymer. Also provided is a method for producing an olefin polymer using the catalyst for olefin polymerization. The invention is a catalyst for olefin polymerization comprising a complex represented by general formula (1) and a method for producing an olefin homopolymer or an olefin copolymer whereby olefin is subjected to homopolymerization or copolymerization using the catalyst.

Description

Olefin polymerization catalyst and process for producing olefin polymer

The present invention relates to an olefin polymerization catalyst using a titanium complex, a method for producing an olefin polymer, a titanium complex for the polymerization catalyst, and a ligand thereof.

In recent years, the development of metallocene catalysts has been one of the topics 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 diphenoxytitanium complex, a zirconium complex or a hafnium complex derived from ethane-1,2-dithiol, but the resulting polymer has a low molecular weight, such as rigidity. There is room for improvement in terms of mechanical strength.

On the other hand, diphenoxytitanium complexes, zirconium complexes and hafnium complexes derived from trans-cyclooctane-1,2-dithiol have been reported (Non-Patent Document 1), but there are no reports of titanium complexes as polymerization catalysts. .

WO2007 / 075299

The problem to be solved by the present invention is to provide an olefin polymerization catalyst capable of producing a high molecular weight olefin polymer, and a method for producing an olefin polymer using the olefin polymerization catalyst.

The present inventor has found that the above-mentioned problems can be solved by intensive studies.

That is, the present invention relates to an olefin polymerization catalyst obtained by bringing a complex represented by the following general formula (1) into contact with an activation promoter component.

(Wherein n is 1 or 2,
R ¹ to R ¹² 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,
Substituted silyl groups,
Alternatively, it represents 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 ¹² The residue may have a substituent.
Regardless of the definition of R ¹ to R ¹² 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 ⁹ And R ¹⁰ , and R ¹¹ and R ¹² may be independently connected to each other to form a ring, and these rings may have a substituent.
X is independently a 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 may have a substituent. 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 homopolymer or copolymer using the polymerization catalyst.

Furthermore, the present invention relates to a complex represented by the following general formula (1 ').

(Wherein n ′ is 1 or 2,
R ¹ ′ to R ¹² ′ 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,
Substituted silyl groups,
Alternatively, it represents a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring. However, R ¹ ′ and R ⁵ ′ are not simultaneously a tert-butyl group.
R ¹ ′ to R ¹² ′ 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 ring The formula compound residue may have a substituent.
Regardless of the definition of R ¹ ′ to R ¹² ′, 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 ⁹ ′ and R ¹⁰ ′, and R ¹¹ ′ and R ¹² ′ may be independently connected to each other to form a ring. May have a substituent.
X ′ each independently represents a 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 ′ have a substituent. Also good.
Adjacent X ′ 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. )
Furthermore, the present invention relates to a compound represented by the following general formula (2 ′).

(Wherein n ′ is 1 or 2,
R ¹ ′ to R ¹² ′ 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,
Substituted silyl groups,
Alternatively, it represents a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring. However, R ¹ ′ and R ⁵ ′ are not simultaneously a tert-butyl group.
R ¹ ′ to R ¹² ′ 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 ring The formula compound residue may have a substituent.
Despite the definition of the ^{^{R 1 '~ R 12',}} R 1 ' and ^{^{R 2',} R 2} 'and ^{^{R 3',} R 3} 'and ^{R 4',} 'a ^{^R 6' R} ^5, and ^{R 6} ' R ⁷ ′, R ⁷ ′ and R ⁸ ′, R ⁹ ′ and R ¹⁰ ′, and R ¹¹ ′ and R ¹² ′ may be independently connected to each other to form a ring. May have a substituent. )

According to the present invention, a high molecular weight olefin polymer can be produced.

The complex represented by formula (1) will be described.

N is 1 or 2, preferably 2.

R ¹ and R ⁵ 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,
Substituted silyl groups,
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,
More preferably, each independently an alkyl group having 5 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,
Alternatively, it is a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring.
Particularly preferred forms of R ¹ and ^{R 5,} ^{R 1} and ^{R 5} are the same,
An alkyl group having 5 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,
Alternatively, it is 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 a 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,
A substituted silyl group,
More preferably, each independently a hydrogen 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 it is a substituted silyl group.
R ² , R ⁴ , R ⁶ and R ⁸ are more preferably a hydrogen atom, and more preferably R ³ and R ⁷ .
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 it is a substituted silyl group.
Particularly preferred form as R ³ and ^{R 7,} ^{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.
R ⁹ to R ¹² are preferably each independently a hydrogen 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,
A substituted silyl group,
More preferably, each independently a hydrogen 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,
More preferably, each independently a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
Most preferably,
It is a hydrogen atom.

The alkyl group, cycloalkyl group, aralkyl group, aryl group, alkoxy group, aryloxy group and heterocyclic compound residue described above may have a substituent.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in R ¹ to R ¹² 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.

As the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in R ¹ or R ⁵ , an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, Alkyl groups having 4 to 10 carbon atoms such as tert-pentyl group, neopentyl group, n-hexyl group, texyl group, neohexyl group, n-heptyl group, n-octyl group, n-decyl group, etc., more preferably An alkyl group having 4 to 8 carbon atoms such as n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, texyl group, etc. More preferably, a tertiary amine having 4 to 8 carbon atoms such as a tert-butyl group, a tert-pentyl group, or a texyl group. A kill group. Most preferably, it is a tertiary alkyl group having 5 to 8 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 ¹² 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 and an n-decyl group, more preferably a perfluoromethyl group, a methyl group, an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a tert- An alkyl group having 1 to 8 carbon atoms, such as a pentyl group, neopentyl group, and texyl group; , Perfluoromethyl group, a methyl group, an isopropyl group, an isobutyl group, tert- butyl group such as an alkyl group having 1 to 4 carbon atoms.

Examples of the substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms constituting the ring in R ¹ to R ¹² 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, Examples thereof include 7-tri (p-toluyl) adamantyl group, 3,5-di (3,5-xylyl) adamantyl group, and 3,5,7-tri (3,5-xylyl) adamantyl group, preferably 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-diphenyladaman Number of carbon atoms such as ruthel group, 3,5-di (p-toluyl) adamantyl group, 3,5-di (3,5-xylyl) adamantyl group (including carbon atoms other than carbon atoms constituting the ring) ) 5-26 cycloalkyl group, more preferably cyclohexyl group, 1-methylcyclohexyl group, norbornyl group, bornyl group, 1-adamantyl group, 2-adamantyl group, 3,5-dimethyladamantyl group, 3, A cycloalkyl group having 6 to 14 carbon atoms (number including carbon atoms other than carbon atoms constituting the ring) such as 5-diethyladamantyl group;

Examples of the substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms in R ¹ to R ¹² include vinyl group, allyl group, propenyl group, 2-methyl-2-propenyl group, homoallyl group, pentenyl group, hexenyl group, A heptenyl group, an octenyl group, a nonenyl group, a decenyl group and the like can be mentioned. An alkenyl group having 3 to 6 carbon atoms is preferable, and an allyl group and a homoallyl group are more preferable.

Examples of the substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms in R ¹ to R ¹² include, for example, 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 and phenylethynyl group, preferably an alkynyl group having 3 to 8 carbon atoms, more preferably 3-methyl-1- A butynyl group, a 3,3-dimethyl-1-butynyl group, a 4-methyl-1-pentenyl group or a phenylethynyl group;

Examples of the substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms in R ¹ to R ¹² 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 group, dimethyl (2-naphthyl) methyl group, methyl (ethyl) (phenyl) methyl group, methyl (diphenyl) methyl group, methylbis (4-methylphenyl) methyl group, triphenyl Methyl 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 (ethyl) (phenyl) 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) C) Number of carbon atoms such as methyl, dimethyl (2-naphthyl) methyl, methyl (ethyl) (phenyl) methyl, methyl (diphenyl) methyl, methylbis (4-methylphenyl) methyl, triphenylmethyl 9 to 20 tertiary aralkyl groups.

Examples of the substituted or unsubstituted aryl group having 6 to 30 carbon atoms in R ¹ to R ¹² include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 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-tetramethylphenyl group, 2, 3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, s c-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-fluoro Phenyl 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-difluorophenyl 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-bromo A phenyl group, a 2,3-dibromophenyl group, a 2,4-dibromophenyl group, or a 2,5-dibromophenyl group, preferably a phenyl group, a 2-tolyl group, a 3-tolyl group, and a 4-tolyl group. 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, ethyl Phenyl groups having 6 to 20 carbon atoms such as ruphenyl group, n-propylphenyl group, isopropylphenyl 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, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2, Fluorinated phenyl groups such as 6-difluorophenyl group; fluorinated alkylphenyl groups such as 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, more preferably phenyl Group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,6-alkyl Ryl group, 3,5-xylyl group, 2,4,6-trimethylphenyl group, 3,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, 3,5-ditert-butylphenyl group, 2-fluoro Phenyl group, pentafluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 2,4,6-trifluorophenyl group It is.

Examples of the substituted silyl group in R ¹ to R ¹² include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, triisobutylsilyl group, 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; Methylsilyl) silyl group, dimethyl (trimethylsilyl) silyl group, and a silyl group having as a substituent a hydrocarbyl silyl group having 3 to 20 carbon atoms, such as tris (trimethylsilyl) silyl group.

Examples of the substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms in R ¹ to R ¹² include 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, An n-dodecyloxy group, an n-pentadecyloxy group, and an n-eicosyloxy group are exemplified, preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group, an ethoxy group, and an n-propoxy group. , Isopropoxy group, n-butoxy group.

Examples of the substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms in R ¹ to R ¹² 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-tetra Methylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, 2,6-diisopropylphenoxy group, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, pentafluoro Phenoxy group, 2-trifluoromethylphenoxy group, 3-trifluoromethylphenoxy group, 4-trifluoro Methylphenoxy 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 Preferably an aryloxy group having 6 to 14 carbon atoms, more preferably a 2,4,6-trimethylphenoxy group, a 3,4,5-trimethylphenoxy group, a 2,6-diisopropylphenoxy group, It is a pentafluorophenoxy group.

Examples of the substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms in R ¹ to R ¹² include, for example, 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 Is preferably an aralkyloxy group having 7 to 12 carbon atoms, more preferably a benzyloxy group.

Examples of the substituted or unsubstituted heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring in R ¹ to R ¹² include thienyl group, furyl group, 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, and N-carbazolyl group are preferable. Are thienyl, furyl, 1-pyrrolyl, pyridyl, pyrimidinyl, 2-isoindolyl, 1-indolyl, quinolyl, dibenzo-1H-pyrrol-1-yl, N-carbazolyl.

Regardless of the definitions of R ¹ to R ⁸ 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 , and R ⁷ and R ⁸ are Each independently may be linked to each other to form a ring, and the ring may have a substituent, and is preferably a 4- to 10-membered hydrocyclic hydrocarbon containing two carbon atoms on the benzene ring. It is a carbyl ring or a heterocyclic ring, and this 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 preferred are cyclobutene ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, benzene ring or naphthalene ring, and more preferred are R ¹ and R ² and R ⁵ A cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring, a benzene ring, and a naphthalene ring in which at least one pair with R ⁶ is linked.

Regardless of the definitions of R ⁹ to R ¹² above, R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² may be independently connected to each other to form a ring, and the ring has a substituent. You may do it.

An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a carbon atom in X 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 are represented by R ¹ to R ^8. It is the same as the group described above.

Examples of the substituted amino group in X include 2 to 14 carbon atoms such as dimethylamino group, diethylamino group, di-n-butylamino group, di-n-propylamino group, diisopropylamino group, dibenzylamino group, or diphenylamino group. And a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, or a dibenzylamino group.

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, -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, or 2, Examples thereof include hydrocarbylthiolate groups having 6 to 12 carbon atoms such as 5-dibromothiophenoxy group, preferably thiophenoxy group, 2,4,6-trimethylthiophenoxy group, 3,4,5-trimethylthiophenoxy group. 2,3,4,5-tetramethylthiophenoxy group, 2,3,4,6-teto Methylthiophenoxy group, 2,3,5,6 methylthiophenoxy group, penta methylthiophenoxy group, a pentafluoro thio phenoxy 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. Preferred are hydrocarbyl carboxylate groups having 2 to 10 carbon atoms, and more preferred are acetate groups, propionate groups, 2-ethylhexanoate groups or trifluoroacetate groups.

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

R ¹ to R ¹² and X may each independently have a substituent containing a halogen atom, an oxygen atom, a silicon atom, a nitrogen atom, a phosphorus atom, or a sulfur atom.

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.

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 preferably 1 or 0, more preferably 0.

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

In addition, compounds in which the benzyl group directly bonded to the titanium atom of these compounds is changed to a chlorine atom, a methyl group, a dimethylamino group, an isopropoxy group, a tert-butoxy group, or a phenoxy group are also included.

The compound which changed the group corresponding to R < ³ > and R < ⁷ > in each said compound into the hydrogen atom, the fluorine atom, the chlorine atom, the bromine atom, the iodine atom, or the methyl group can also be mentioned.

Included are compounds in which the cyclooctane ring that bridges the sulfur atom of each of the above compounds is substituted with a cycloheptane ring.

Examples thereof also include compounds in which the groups corresponding to R ⁹ to R ¹² in each of the above compounds are substituted with a methyl group or an ethyl group.

Preferred examples of the complex (1) include the following compounds.

Also, compounds in which the benzyl group directly bonded to the titanium atom of these compounds is changed to a chlorine atom or a methyl group can be mentioned.

There can also be mentioned compounds in which the groups corresponding to R ³ and R ⁷ in each of the above compounds are changed to hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, or methyl groups.

More preferable examples of the complex (1) include the following compounds.

Also, compounds in which the benzyl group directly bonded to the titanium atom of these compounds is changed to a chlorine atom can be mentioned.

There can also be mentioned compounds in which the groups corresponding to R ³ and R ⁷ in each of the above compounds are changed to methyl groups.

As the complex (1), the following compounds are particularly preferable.

Next, the complex represented by the general formula (1 ') will be described.

N ′ is 1 or 2, preferably 2.

R ¹ ′ and R ⁵ ′ are preferably each independently a 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,
Substituted silyl groups,
Or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring, wherein R ¹ ′ and R ⁵ ′ are not simultaneously a tert-butyl group,
More preferably, each independently an alkyl group having 5 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,
Alternatively, it is a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring.
A further preferred embodiment of R ¹ 'and ^{R 5'} are, ^{R 1} 'and ^{R 5'} are the same,
An alkyl group having 5 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,
Alternatively, it is 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 a 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,
A substituted silyl group,
More preferably, each independently a hydrogen 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 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 it is a substituted silyl group.
Particularly preferred form as R ³ 'and ^{R 7'} is, ^{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.
R ⁹ ′ to R ¹² ′ are preferably each independently a hydrogen 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,
A substituted silyl group,
More preferably, each independently a hydrogen 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,
More preferably, each independently a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
Most preferably,
It is a hydrogen atom.

These alkyl groups, cycloalkyl groups, aralkyl groups, aryl groups, alkoxy groups, aryloxy groups and heterocyclic compound residues may have a substituent.

An alkyl group having 1 to 20 carbon atoms in R ¹ ′ to R ¹² ′, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, an alkenyl group having 2 to 20 carbon atoms, and 2 to 20 carbon atoms An alkynyl 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, and 6 to 6 carbon atoms. The aryloxy group of 30, the substituted silyl group, or the heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring is the same as the group described above for R ¹ to R ¹² in the general formula (1). is there.

Regardless of the definition of R ¹ ′ to R ⁸ ′, 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 ′ and R ⁷ ′ and R ⁸ ′ may be independently connected to each other to form a ring, which ring may have a substituent, preferably on the benzene ring A 4- to 10-membered hydrocarbyl ring or heterocyclic ring containing two carbon atoms, 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 are mentioned, and preferred are cyclobutene ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, benzene ring or naphthalene ring, and more preferred are R ¹ ′, R ² ′ and R A cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring, a benzene ring, and a naphthalene ring in which at least one pair of ⁵ ′ and R ⁶ ′ is connected.

Regardless of the definitions of R ⁹ ′ to R ¹² ′, R ⁹ ′ and R ¹⁰ ′, and R ¹¹ ′ and R ¹² ′ may be independently connected to each other to form a ring, The ring may have a substituent.

An alkyl group having 1 to 20 carbon atoms in X ′, 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, carbon Aryl group having 6 to 30 atoms, alkoxy group having 1 to 20 carbon atoms, aralkyloxy group having 7 to 30 carbon atoms, aryloxy group having 6 to 30 carbon atoms, substituted silyl group, substituted amino group, substituted The thiolate group and the carboxylate group having 1 to 20 carbon atoms are the same as those described above for X in the general formula (1).

X ′ is preferably a fluorine atom, a chlorine atom, a bromine 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, or 6 to 6 carbon atoms. 30 aryloxy groups or hydrocarbylamino groups having 1 to 20 carbon atoms, more preferably chlorine atoms, bromine atoms, alkyl groups having 1 to 6 carbon atoms, and aralkyls having 7 to 10 carbon atoms. Group, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and a hydrocarbylamino group having 2 to 10 carbon atoms, and more preferably a chlorine atom, a methyl group, or an ethyl group N-butyl group, tert-butyl group, benzyl group, methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, phenoxy group dimethylamino group, die An arylamino group, particularly preferably a chlorine atom, a methyl group, a benzyl group, an isopropoxy group, a phenoxy group, a dimethylamino group, and most preferably, a chlorine atom, a benzyl group.

R ¹ ′ to R ¹² ′ and X ′ may each independently have a substituent containing a halogen atom, an oxygen atom, a silicon atom, a nitrogen atom, a phosphorus atom or a sulfur atom.

L ′ and l ′ are the same as L and l in the general formula (1).

Specific examples of the complex represented by the formula (1 ′) include the following compounds.

Examples thereof also include compounds in which the groups corresponding to R ³ ′ and R ⁷ ′ in each of the above compounds are changed to hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, or methyl groups.

Examples also include compounds in which the groups corresponding to R ⁹ ′ to R ¹² ′ in each of the above compounds are substituted with a methyl group or an ethyl group.

Preferred examples of the complex (1 ′) include the following compounds.

There may also be mentioned compounds in which the groups corresponding to R ³ ′ and R ⁷ ′ in each of the above compounds are changed to hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, or methyl groups.

More preferable examples of the complex (1 ′) include the following compounds.

A compound obtained by changing the group corresponding to R ³ ′ and R ⁷ ′ of each of the above compounds to a methyl group can also be mentioned.

The complex represented by the general formula (1) and the complex represented by the general formula (1 ′) are synthesized according to the method described in, for example, Journal of American Chemical Society, 2009, Volume131,13566-13567 Can do. For example, in the case of the complex (1), it can be produced by the following scheme 1 using the compound represented by the general formula (2) and the compound represented by the general formula (3) as starting materials, but should be limited to this method. It is not a thing.

X in the compound (3) is the same as in the general formula (1). 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 ( Ot-Bu) ₄ , Ti (OPh) ₄ , Ti (NMe ₂ ) ₄ , TiCl ₂ (NMe ₂ ) ₂ , and Ti (NEt ₂ ) ₄ . 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, Ti ( NEt ₂ ) ₄ .

In the complex (1), the compound (2) and the compound (3) may be reacted as they are, or the compound (3) may be reacted after reacting the compound (2) with a base as necessary. Examples of the base to be used include an organic lithium reagent, a Grignard reagent, and a metal hydride. Specifically, methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, lithium hexamethyl Examples thereof include disilazane, potassium hexamethyldisilazane, sodium hydride and potassium hydride, and preferably n-butyllithium, lithium diisopropylamide, potassium hexamethyldisilazane, sodium hydride or potassium hydride.

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

The amount of the compound (2) used may be 1 molar equivalent or more with respect to the compound (3), and preferably 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 temperature range of −100 ° C. to 150 ° C., preferably in the temperature 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 temperature range of −100 ° C. to 150 ° C., preferably in the temperature 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 carried out until the product yield becomes the highest, and is 5 minutes to 24 hours, preferably 10 minutes to 12 hours, more preferably 30 minutes to 3 hours.

The temperature at which the compound (2) is reacted with the base and the compound (3) is reacted in the temperature range of −100 ° C. to 150 ° C., preferably in the temperature range of −80 ° C. to 50 ° C. is there. 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 the time until the yield of the product becomes the highest, and is 5 minutes to 48 hours. Preferably, it is 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 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.

R ¹ to R ¹² and n in the compounds (4) to (7) are the same as in the complex (1).

Z represents an anionic leaving group, for example, 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 group Preferred are chlorine atom, bromine atom, iodine atom, CF ₃ SO ₃ group, CH ₃ SO ₃ group, 4-MeC ₆ H ₄ SO ₃ group or PhSO ₃ group.
[Step 1]
Trans-cyclooctane-1,2-dithiol (4) is reacted with 1.0 to 4.0 equivalents, preferably 1.0 to 1.5 equivalents of compound (5) in the presence of a base to give compound (6) Can be synthesized.

The base is not particularly limited, and examples thereof include inorganic bases such as potassium carbonate, calcium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and calcium 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 can be increased by a purification operation 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 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 can be increased by a purification operation 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].

R ¹ is the same as R ⁵ , R ² is the same as R ⁶ , R ³ is the same as R ⁷ , R ⁴ is the same as R ⁸ , and the combination of R ⁹ and R ¹⁰ is R ^When it is the same as the combination of ¹¹ and R ¹² , the compound (5) and the compound (7) are combined and 2.0 to 8.0 equivalents with respect to trans-cyclooctane-1,2-dithiol (4) The compound (2) can also be synthesized by reacting preferably 2.0 to 4.0 equivalents in the presence of a base.

Specific examples of the compound (2) include the following compounds.

Examples thereof also include compounds in which groups corresponding to R ³ and R ⁷ of these compounds are 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) and the compound (7) include the following compounds.

Examples thereof also include compounds in which a group corresponding to R ³ or R ⁷ of these compounds is substituted with a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group.

Next, the compound represented by the general formula (2 ') will be described.

Formula (2 ') and ^{^R 1'} ^~ ^R ¹² 'n' in is the same as in the general formula (1 ') n in' and ^{^R 1} ^'~ ^R ^12'.

Specific examples of the compound represented by the general formula (2 ') include the following compounds.

There can also be mentioned compounds in which groups corresponding to R ³ ′ and R ⁷ ′ of these compounds are substituted with a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group.

Preferred examples of the compound (2 ′) include the following compounds.

Moreover, the compound which changed the group corresponding to R < ³ '> and R < ⁷ >' of these compounds into the hydrogen atom, the fluorine atom, the chlorine atom, the bromine atom, the iodine atom, or the methyl group can also be mentioned.

More preferable examples of the compound (2 ′) include the following compounds.

Moreover, the compound which changed the group corresponding to R < ³ '> and R < ⁷ >' of these compounds into the methyl group can also be mentioned.

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

As the polymerization catalyst, a polymerization catalyst obtained by contacting the complex (1) and the promoter component (A) is used. Examples of such promoter components include activation promoter components containing Group 13 elements of the Periodic Table, such as
(A-1) Organoaluminum compound (A-2) There may be mentioned at least one compound selected from the group consisting of boron compounds.
[Organic aluminum compound (A-1)]
As the organoaluminum compound (A-1) used in the present invention, a known organoaluminum compound can be used. Preferably, (A-1-1) an organoaluminum compound represented by the general formula E ¹ a AlY ¹ _3-a , (A-1-2) a general formula {—Al (E ² ) —O—} _b A cyclic aluminoxane having a structure represented by: (A-1-3) a linear aluminoxane having a structure represented by the general formula E ³ {-Al (E ³ ) —O—} c AlE ³ ₂ (provided that , E ¹ , E ² , and E ³ are each a hydrocarbyl group having 1 to 8 carbon atoms, and all E ¹ , all E ^2, and all E ³ may be the same or different. Y ¹ represents a hydrogen atom or a halogen atom, and all Y ¹ may be the same or different, a is an integer of 0 <a ≦ 3, b is an integer of 2 or more, and c is 1 or more. Any one of them, or a mixture of 2 to 3 thereof.

Specific examples of the organoaluminum compound (A-1-1) represented by the general formula E ¹ _a AlY ¹ _3-a include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum and the like. Dialkylaluminum chlorides such as alkylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride, etc. Alkyl aluminum dichloride; dimethyl aluminum Um hydride, diethylaluminum hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, there can be mentioned dialkyl aluminum hydride such as dihexyl aluminum hydride. Trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are more preferable.

Cyclic aluminoxane (A-1-2) having a structure represented by the general formula {-Al (E ² ) —O—} _b , general formula E ³ {-Al (E ³ ) —O—} _c AlE ³ Specific examples of E ² and E ^{3 in} the linear aluminoxane (A-1-3) having the structure represented by ₂ are methyl group, ethyl group, n-propyl group, isopropyl group, normal butyl group, Examples thereof include alkyl groups such as isobutyl group, n-pentyl group and neopentyl group. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ² and E ³ are a methyl group and an isobutyl group, 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, an aluminoxane is prepared by bringing a solution obtained by dissolving a trialkylaluminum (for example, trimethylaluminum) in an appropriate organic solvent (benzene, toluene, aliphatic hydrocarbon, etc.) into contact with water. Moreover, the method of making aluminoxane by making trialkylaluminum (for example, trimethylaluminum etc.) contact the metal salt (for example, copper sulfate hydrate etc.) containing crystal water can be illustrated.

In addition, (A-1-2) the general formula {-Al (E ² ) -O—} _b obtained by the above method and a cyclic aluminoxane having a structure represented by the formula (A-1-3) The linear aluminoxane having a structure represented by E ³ {—Al (E ³ ) —O—} c AlE ³ ₂ may be used after distilling off the volatile components if necessary. Furthermore, 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 for use.
[Boron compound (A-2)]
In the present invention, the boron compound (A-2) includes (A-2-1) a boron compound represented by the general formula BR ¹³ R ¹⁴ R ¹⁵ , (A-2-2) a general formula W ⁺ (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ^— or a boron compound represented by (A-2-3) general formula (VH) ⁺ (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ^— Use.

In the boron compound (A-2-1) represented by the general formula BR ¹³ R ¹⁴ R ¹⁵ , B is a trivalent boron atom, R ¹³ to R ¹⁵ are halogen atoms, 1 to 20 Hydrocarbyl group containing 1 to 20 carbon atoms, halogenated hydrocarbyl group containing 1 to 20 carbon atoms, substituted silyl group containing 1 to 20 carbon atoms, alkoxy group containing 1 to 20 carbon atoms Or a disubstituted amino group containing 2 to 20 carbon atoms, which may be the same or different. Preferred R ¹³ to R ¹⁵ are a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, and a halogenated hydrocarbyl group containing 1 to 20 carbon atoms.

Specific examples of the boron compound (A-2-1) include triphenylborane, tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, 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. Most preferred are triphenylborane and tris (pentafluorophenyl) borane.

In the boron compound (A-2-2) represented by the general formula W ⁺ (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ⁻ , W ⁺ is an inorganic or organic cation, and B is a trivalent valence state. It is a boron atom, and R ¹³ to R ¹⁶ are the same as R ¹³ to R ¹⁵ in the boron compound (A-2-1). That is, R ¹³ to R ¹⁶ include a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, a halogenated hydrocarbyl group containing 1 to 20 carbon atoms, and 1 to 20 carbon atoms. A substituted silyl group, an alkoxy group containing 1 to 20 carbon atoms or a disubstituted amino group containing 2 to 20 carbon atoms, which may be the same or different. Preferred R ¹³ to R ¹⁶ are a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, and a halogenated hydrocarbyl group containing 1 to 20 carbon atoms.

Examples of W ⁺ that is an inorganic cation include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation. Examples of W ⁺ that is an organic cation include a triphenylcarbenium cation. (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ^— includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro). Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistri) Fluoromethylphenyl) borate and the like.

Specific examples of the compound represented by the general formula W ⁺ (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ^— include ferrocenium tetrakis (pentafluorophenyl) borate and 1,1′-dimethylferrocenium tetrakis (pentafluoro). Phenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-bistrifluoromethylphenyl) borate, etc. Triphenylcarbenium tetrakis (pentafluorophenyl) borate is preferable.

In the boron compound (A-2-3) represented by the general formula (VH) ⁺ (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ^— , V is a neutral Lewis base, H) ⁺ is a Bronsted acid, B is a boron atom in a trivalent valence state, and R ¹³ to R ¹⁶ are the same as R ¹³ to R ¹⁵ in the boron compound (A-2-3). is there. That is, R ¹³ to R ¹⁶ include a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, a halogenated hydrocarbyl group containing 1 to 20 carbon atoms, and 1 to 20 carbon atoms. A substituted silyl group, an alkoxy group containing 1 to 20 carbon atoms or a disubstituted amino group containing 2 to 20 carbon atoms, which may be the same or different. Preferred R ¹³ to R ¹⁶ are a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, and a halogenated hydrocarbyl group containing 1 to 20 carbon atoms.

Examples of (VH) ⁺ that is a Bronsted acid include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ⁻ Is the same as described above.

Specific examples of the compound represented by the general formula (VH) ⁺ (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ^— include triethylammonium tetrakis (pentafluorophenyl) borate and tripropylammonium tetrakis (pentafluorophenyl) borate. , Tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (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 teto Kis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium Examples include tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and most preferably triphenylcarbenium tetrakis. (Pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (pe Motor-fluorophenyl) borate, or, N, is N- dimethylanilinium tetrakis (pentafluorophenyl) borate.

In the production of an olefin polymerization catalyst obtained by bringing the complex (1) and the promoter component (A) into contact with each other in the present invention, the complex (1) and the promoter component (A) are in contact with each other. Can be formed by any means, for example, by diluting with a solvent in advance, or by mixing and contacting the complex (1) and the cocatalyst component (A) without diluting, or the complex (1) And the cocatalyst component (A) can be separately supplied to the polymerization tank and brought into contact with each other in the polymerization tank. Here, the co-catalyst component (A) may be used in combination of a plurality of types, but some of them may be mixed in advance or used separately by supplying them to the polymerization tank. May be.

As the complex (1), an isolated one may be used, or a compound obtained by contacting the compound (2) and the compound (3) may be used as it is.

The amount of each component used is usually such that the molar ratio of the organoaluminum compound (A-1) to the complex (1) is in the range of 0.01 to 10000, preferably in the range of 1 to 5000. It is desirable to use each component so that the molar ratio of the boron compound (A-2) to the complex represented by 1) is in the range of 0.01 to 100, preferably 1.0 to 50.

When the catalyst is produced before the polymerization reaction in the polymerization reactor, the concentration when each component is supplied in a solution state or suspended or slurried in a solvent is determined depending on the performance of the apparatus for supplying each component to the polymerization reactor, etc. In general, the complex represented by the general formula (1) is usually 0.0001 to 10000 mmol / L, more preferably 0.001 to 1000 mmol / L, and still more preferably, 0.01 to 100 mmol / L, the organoaluminum compound (A-1) is usually 0.01 to 10000 mmol / L, more preferably 0.05 to 5000 mmol / L, still more preferably 0, in terms of Al atom. The boron compound (A-2) is usually from 0.001 to 500 mmol / L, more preferably from 0.01 to 2000 mmol / L. 50 mmol / L, more preferably, it is desirable to use each component to be in the range of 0.05 ~ 100mmol / L.

The olefin polymerization catalyst is an olefin polymerization catalyst obtained by contacting the complex (1) with at least one of the organoaluminum compound (A-1) and the boron compound (A-2). However, when an olefin polymerization catalyst obtained by contacting the complex represented by the general formula (1) with the organoaluminum compound (A-1) is used, the organoaluminum compound (A-1) Cyclic aluminoxane (A-1-2) and / or linear aluminoxane (A-1-3) are preferred. Another preferred embodiment of the olefin polymerization catalyst is an olefin polymerization catalyst obtained by contacting the complex (1), the organoaluminum compound (A-1) and the boron compound (A-2). As the organoaluminum compound (A-1), the organoaluminum compound (A-1-1) can be easily used. As the boron compound (A-2), a boron compound (A-2-1) or boron Compound (A-2-2) is preferred.
[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 monoolefins 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-metoki Carbonyl norbornene, 5-ethoxycarbonyl norbornene, 5-methyl-5-methoxycarbonyl norbornene, 5-cyanonorbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclodone Examples thereof include cyclic alkenes such as decene. In addition, the monoolefin in the present specification includes styrene in which a part of hydrogen atoms of the monoolefin (for example, ethylene) is substituted with an aromatic group.

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 are ethylene, propylene, 1-butene, 1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene and vinylcyclohexane, more preferably , Propylene, 1-butene, 1-pentene, 1-octene, 1-decene, 4-methyl-1-pentene, vinylcyclohexane, and more preferably propylene, 1-butene, 1-pentene, 4-methyl- 1-pentene and vinylcyclohexane are most preferable, and ethylene and propylene are most preferable.

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, butadiene, more preferably 1,5-hexadiene, 1,6-heptadiene, 1 , 3-cyclohexadiene, 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, and 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 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, and more Preferred are ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and vinylcyclohexane, and more preferred are ethylene and propylene, ethylene and 1-butene, and ethylene and 1 -Hexene, ethylene and vinylcyclohexane.

The polymerization method is not particularly limited. For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbons such as benzene and toluene, or halogenated hydrocarbons such as methylene dichloride. Solvent polymerization using carbon as a solvent, slurry polymerization, or the like is possible, and either continuous polymerization or batch polymerization is possible.

The temperature and time of the polymerization reaction can be determined in consideration of the desired polymerization average molecular weight, and the activity and usage of the catalyst. The polymerization temperature can usually be in the range of −50 ° C. to 200 ° C., but the range of −20 ° C. to 100 ° C. is particularly preferable. The polymerization pressure is usually preferably from normal pressure to 50 MPa. In general, the polymerization time is appropriately determined depending on the kind of the target polymer and the reaction apparatus, but it can usually be in the range of 1 minute to 20 hours, preferably in the range of 5 minutes to 18 hours. However, it is not intended to be limited to these ranges. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.

When a solvent is used for the polymerization reaction, the concentration of each compound in the solvent is not particularly limited. The concentration of the titanium complex in the solvent can be selected, for example, in the range of 1 × 10 ⁻⁸ mmol / L to 10 mol / L, and the concentration of the promoter component is, for example, 1 × 10 ⁻⁸ mmol / L to 10 mol / L. A range can be selected. Further, the volume ratio of olefin: solvent can be selected from 100: 0 to 1: 1000. However, these ranges are examples and are not intended to be limited to them. Even when no solvent is used, the concentration can be appropriately set with reference to the above range.

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 A 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 / min) Hold for 2 minutes 3) Measurement 20 ° C to 150 ° C (5 ° C / min)
<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>
Apparatus: 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 determined based on the polystyrene-equivalent weight average molecular chain length (Aw) and the polystyrene-equivalent number average molecular chain length (An). 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

(Reference Example 1)
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. Thereto was added 3.5 mL (24.9 mmol) of triethylamine, and the mixture was stirred at 0 ° C. for 1 hour and further at room temperature overnight. 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 2)
Synthesis of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium The following experiment was conducted under an argon atmosphere. In a 100 ml Schlenk tube, 525 mg (0.856 mmol) of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane was dissolved in 20 ml of toluene. 30 mL of a toluene solution of 286 mg (0.856 mmol) of tetrachlorotitanium THF complex was added dropwise at room temperature, and the mixture was further stirred for 4 hours. Toluene was distilled off under reduced pressure, and the residue was washed with 2 mL of hexane and then dried. )
¹ H NMR (400 MHz, δ, ppm, C ₆ D ₆ )
0.58-1.92 (m, major + minor), 2.62 (br s, major), 2.66-2.70 (m, minor), 3.07 (d, J = 14 Hz, minor), 3.16 (d, J = 15 Hz, major ), 3.57 (d, J = 12 Hz, minor), 3.63-3.67 (m, minor), 4.35 (d, J = 14 Hz, minor), 4.57 (d, J = 15 Hz, major), 4.88 (
d, J = 12 Hz, minor), 6.59 (d, J = 2 Hz, major), 6.63 (d, J = 2 Hz, minor), 6.94 (d, J = 2 Hz, minor), 7.36 (d, J = 2 Hz, minor), 7.51 (d, J = 2 Hz, minor), 7.54 (d, J = 2 Hz, major). Elemental analysis: calculated (C ₃₈ H ₅₈ Cl ₂ O ₂ S ₂ Ti) : C, 62.54%; H, 8.01%. Found: C, 62.38%; H, 8.21%.

(Reference Example 3)
Synthesis of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium The following experiment was conducted 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. Then, 10 mL of a toluene solution of 153 mg (0.336 mmol) of tetrabenzylzirconium 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 4)
Synthesis of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclohexane Under an argon atmosphere, 1.08 g (7.3 mmol) of trans-cyclohexane-1,2-dithiol and bromide 3 , 5-di-t-butyl-2-hydroxybenzyl (4.58 g, 15.3 mmol) was dissolved in tetrahydrofuran (90 mL) 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 5)
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. After the organic layer was dried over anhydrous magnesium sulfate, 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- (hydroxymethyl) phenol 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 was added. %), 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 distilling off 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)
Next, 8.05 g of the above mixture, 40 mL of tetrahydrofuran and 40 mL of methanol were added to a 100 mL flask purged with nitrogen, and ice-cooled. To this, 340 mg (8.97 mmol) of sodium borohydride was slowly added and the temperature was raised to room temperature, followed by stirring 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. After distilling off the solvent under reduced pressure, the obtained colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 15 to 1: 5) to give 4-tert-butyl-6- 4.88 g (75% yield) of cumyl-2- (hydroxymethyl) phenol 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 To 50 mL Schlenk substituted with nitrogen, 4-tert-butyl-6-cumyl-2- (hydroxymethyl) phenol (4.88 g) (16.4 mmol) and 24 mL of dichloromethane were added. To this, 8.2 mL of phosphorus tribromide (1.0 M dichloromethane solution, 8.2 mmol) was added, and the mixture was 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. After drying the organic layer over anhydrous magnesium sulfate, the volatile component was 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. Got as.
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 In a nitrogen-substituted 100 mL two-necked flask, 5-tert-butyl-3 -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 also at room temperature for 2 hours. After distilling off volatile components 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 then saturated brine, 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- 2.26 g of a 2: 1 mixture of 2-hydroxybenzylsulfanyl) cyclooctane and trans-1- (5-tert-butyl-3-cumyl-2-hydroxybenzylsulfanyl) -2-sulfanylcyclooctane was obtained. 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 an 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 then 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 6)
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 distilled off 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 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 7)
Synthesis of trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl] cyclooctane (1) 6- (1-adamantyl) -2- (hydroxymethyl) -p- Synthesis of Cresol A nitrogen-substituted 1 L four-necked flask was charged with 20.9 g (86.1 mmol) of 2- (1-adamantyl) -p-cresol, 16.4 g (172 mmol) of magnesium chloride, 13.0 g (433 mmol) of paraformaldehyde and tetrahydrofuran. 400 mL was added. Triethylamine 24 mL (172 mmol) was added here, and it heated and refluxed for 2.5 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate was added to the residue, followed by washing with 1M HCl and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 19.2 g of a mixture containing 2- (1-adamantyl) -5-methylsalicylaldehyde.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.78 to 2.25 (15H), 2.32 (s, 3H), 6.98 (d, J = 2 Hz, 1H), 7.27 (d, J = 2 Hz, 1H), 9.82 (s, 1H), 11.64 (s, 1H ).
Next, 19.2 g of the above mixture, 135 mL of tetrahydrofuran and 80 mL of methanol were added to a 500 mL four-necked flask purged with nitrogen, and the mixture was ice-cooled. To this, 1.60 g (42.5 mmol) of sodium borohydride was slowly added, and the temperature was raised to room temperature, followed by stirring for 14.5 hours. After evaporating volatile components under reduced pressure, ethyl acetate was added, and the mixture was washed with 1 M HCl and saturated brine in this order. After drying the organic layer with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: chloroform: hexane = 1: 3 to 1: 0) to give 6- (1-adamantyl) -2- (hydroxymethyl) -p-cresol 8.80 g (38% yield) was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.78 (m, 6H), 2.01 (br, 1H), 2.07 (m, 3H), 2.15 (m, 6H), 2.25 (s, 3H), 4.81 (d, J = 4 Hz, 2H), 6.70 (d , J = 2 Hz, 1H), 6.99 (d, J = 2 Hz, 1H), 7.50 (s, 1H).
(2) Synthesis of 3- (1-adamantyl) -5-methyl-2-hydroxybenzyl bromide In a nitrogen-substituted 200 mL four-necked flask, 6- (1-adamantyl) -2- (hydroxymethyl) -p- Cresol 8.80 g (32.3 mmol) and dichloromethane 132 mL were added. To this, 15 mL of phosphorus tribromide (1.23 M dichloromethane solution, 18.5 mmol) was added, and the mixture was stirred at room temperature for 3.5 hours. The reaction solution was added to ice water, and the organic layer was washed with water and saturated brine. After drying the organic layer over anhydrous magnesium sulfate, the volatile components were distilled off under reduced pressure to obtain 11.1 g (crude yield 103%) of 3- (1-adamantyl) -5-methyl-2-hydroxybenzyl bromide. Obtained as a pale yellow solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.78 (m, 6H), 2.09 (m, 3H), 2.12 (m, 6H), 2.26 (s, 3H), 4.54 (s, 2H), 6.92 (d, J = 2 Hz, 1H), 7.04 (d , J = 2 Hz, 1H).
(3) Synthesis of trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl] cyclooctane In a nitrogen-substituted 200 mL four-necked flask, 3- (1- Adamantyl) -5-methyl-2-hydroxybenzyl 7.04 g (21.0 mmol), trans-cyclooctane-1,2-dithiol 1.83 g (10.4 mmol), and tetrahydrofuran 100 mL were added. Triethylamine 4.3 mL (31 mmol) was added here, and it stirred at room temperature for 21.5 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 the solvent was distilled off under reduced pressure, trans-1,2-bis (3- (1-adamantyl) -5 was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 20: 1). -Methyl-2-hydroxybenzylsulfanyl) cyclooctane and trans-1- (3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl) -2-sulfanylcyclooctane 6: 1 mixture 6.61 g Got. This mixture and 1.36 g (3.98 mmol) of 3- (1-adamantyl) -5-methyl-2-hydroxybenzyl bromide were dissolved in 100 mL of tetrahydrofuran and cooled on ice. Triethylamine 0.74 mL (5.31 mmol) was added here, and it stirred for 15.5 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 = 20: 1), and the resulting solid was further repulp washed with hexane at room temperature to obtain trans-1,2-bis 6.08 g (yield 85%) of [3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl] cyclooctane was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.2 to 2.0 (m, 12H), 1.77 (m, 12H), 2.05 (m, 6H), 2.13 (12H), 2.24 (s, 6H), 2.67 (m, 2H), 3.73 (d, J = 13 Hz , 2H), 3.82 (d, J = 13 Hz, 2H), 6.71 (d, J = 2Hz, 2H), 6.83 (s, 2H), 6.97 (d, J = 2 Hz, 2H).

(Reference Example 8)
Synthesis of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylzirconium 50 mL Schlenk tube in a glove box under nitrogen atmosphere In a solution of trans-1,2-bis (3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl) cyclooctane 200 mg (0.29 mmol) in toluene (6 mL), tetrabenzylzirconium 133 mg ( 0.29 mmol) in toluene (6 mL) was added dropwise at room temperature. After 1.5 hours, the reaction solution was filtered, and volatile components were distilled off 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 [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl] } 238 mg (yield 85%) of dibenzylzirconium was obtained as a yellow powder.
¹ H-NMR (400 MHz, δ, ppm, toluene-d ₈ )
0.7 to 1.4 (m, 12H), 1.85 (m, 6 H), 2.1 to 2.2 (16H), 2.17 (s, 6H), 2.42 (m, 12H), 2.75 (d, J = 10 Hz, 2H), 3.12 (d, J = 14 Hz, 2H), 3.65 (d, J = 14 Hz, 2H), 6.27 (d, J = 2Hz, 2H), 6.87 (t, J = 6 Hz, 2H), 7.1 to 7.2 (10H).

(Reference Example 9)
Synthesis of trans-1,2-bis [3- (N-carbazolyl) -2-hydroxy-5-methylbenzylsulfanyl] cyclooctane (1) Synthesis of 3- (N-carbazolyl) -4-methoxytoluene In a 200 mL two-neck flask, carbazole 25 g (149 mmol), 3-bromo-4-methoxytoluene 25 g (125 mmol), copper (I) iodide 1.13 g (6.0 mmol), potassium phosphate tribasic acid 44 g (207 mmol), trans-1,2-diaminocyclohexane 2.9 mL (42 mmol) and dioxane 80 mL were added, and the mixture was heated to reflux temperature and stirred for 44 hours. After cooling the reaction solution to room temperature, insolubles were filtered. Volatile components were distilled off under reduced pressure. The resulting black-green solid was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 9) to obtain 15.14 g (42% yield) of 3- (N-carbazolyl) -4-methoxytoluene. Obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
2.37 (s, 3H), 3.66 (s, 3H), 7.0 to 7.5 (9H), 8.12 (d, J = 8 Hz, 2H).
(2) Synthesis of 2- (N-carbazolyl) -4-methylphenol To a nitrogen-substituted 500 mL flask was added 15.14 g (53 mmol) of 3- (N-carbazolyl) -4-methoxytoluene and 75 mL of methylene chloride. And cooled to 0 ° C. To this, 75 mL of boron tribromide (1.0 M dichloromethane solution, 75 mmol) was added, and the mixture was warmed to room temperature and stirred for 3 hours. The reaction solution was introduced into 300 mL of ice water, and 150 mL of ethyl acetate was further added. The organic layer was washed twice with a saturated aqueous sodium hydrogen carbonate solution and then washed with saturated brine. The extract was dried over anhydrous sodium sulfate, and the volatile component was distilled off under reduced pressure. The obtained white solid was purified by silica gel column chromatography (developing solvent hexane: ethyl acetate = 85: 15) to obtain 14.45 g (yield> 99%) of 2- (N-carbazolyl) -4-methylphenol as white. Obtained as a solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
2.34 (s, 3H), 4.83 (s, 1H), 7.1-7.5 (9H), 8.16 (d, J = 0.8 Hz, 2H).
(3) Synthesis of 6- (N-carbazolyl) -2- (hydroxymethyl) -4-methylphenol In a 200 mL two-necked flask purged with nitrogen, 5.0 g (18.3 mmol) of 2- (N-carbazolyl) -4-methylphenol was added. ), Magnesium chloride 3.5 g (36.6 mmol), paraformaldehyde 3.50 g (117 mmol) and tetrahydrofuran 15 mL were added. Triethylamine 5.0 mL (49 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 distilling off 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 5.53 g of a mixture containing 3- (N-carbazolyl) -5-methylsalicylaldehyde (CG purity 91%, yield 91%).
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
2.43 (s, 3H), 7.15 (s, 6H), 7.1 to 7.4 (8H), 8.14 (d, J = 0.8 Hz, 2H), 9.99 (s, 1H), 11.1 (s, 1H).
Next, 2.0 g of the above mixture, 10 mL of tetrahydrofuran and 10 mL of methanol were added to a 100 mL flask purged with nitrogen, and the mixture was ice-cooled. To this, 260 mg (6.9 mmol) of sodium borohydride was slowly added, and the mixture was warmed to room temperature and stirred for 1 hour. After adding water to the reaction solution, volatile components were distilled off under reduced pressure, and then 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: 2) to give 2.18 g of 6- (N-carbazolyl) -2- (hydroxymethyl) -4-methylphenol ( Yield> 99%) as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
2.28 (s, 3H), 4.89 (d, J = 6 Hz, 2H), 5.96 (s, 1H), 7.1 to 7.5 (8H), 8.15 (d, J = 8 Hz, 2H).
(4) Synthesis of 3- (N-carbazolyl) -2-hydroxy-5-methylbenzyl bromide In a nitrogen-substituted 100 mL flask, 6- (N-carbazolyl) -4-methyl-2- (hydroxymethyl) phenol 2.18 g (7.2 mmol) and 10 mL of dichloromethane were added. To this, 4.5 mL of phosphorus tribromide (1.0 M dichloromethane solution, 4.5 mmol) was added, 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 components were distilled off under reduced pressure to obtain 2.45 g (93% yield) of 3- (N-carbazolyl) -2-hydroxy-5-methylbenzyl bromide. Obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
3.34 (s, 3H), 4.67 (s, 2H), 7.1 to 7.5 (8H), 8.16 (d, J = 8 Hz, 2H).
(5) Synthesis of trans-1,2-bis (3- (N-carbazolyl) -2-hydroxy-5-methylbenzylsulfanyl) cyclooctane In a nitrogen-substituted 50 mL flask, 3- (N-carbazolyl bromide) -2-hydroxy-5-methylbenzyl 0.84 g (2.28 mmol), trans-cyclooctane-1,2-dithiol 2.0 mL (0.5 M tetrahydrofuran solution, 1.0 mmol) and tetrahydrofuran 6 mL were added, and the mixture was ice-cooled. . Triethylamine 0.7 mL (5.0 mmol) was added here, and it stirred at 0 degreeC for 1 hour, and also at room temperature for 12 hours. To the reaction solution, 0.15 g (0.4 mmol) of 3- (N-carbazolyl) -2-hydroxy-5-methylbenzyl bromide was added at room temperature. After stirring for 12 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 saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (developing solvent: dichloromethane) to obtain trans-1,2-bis [3- (N-carbazolyl) -2-hydroxy-5-methylbenzylsulfanyl] cyclooctane 0.88 g (Yield> 99%) was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.13 to 1.79 (m, 12H), 2.24 (s, 6H), 2.97 (m, 2H), 3.91 (s, 4H), 5.90 (s, 2H), 7.0 to 7.35 (16H), 8.10 (d, J = (3 Hz, 4H).

(Reference Example 10)
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 was charged with 3.3 g (22 mmol) of 4-tert-butylphenol, 4.0 g (22 mmol) of 3,5-dimethyl-1-adamantanol and Dichloromethane (20 mL) was added, and the mixture was cooled to 0 ° C. with 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. After the organic layer was dried over anhydrous magnesium sulfate, 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), 7.24 (d, J = 2 Hz, 1H).
(2) Synthesis of 4-tert-butyl-6- (3,5-dimethyl-1-adamantyl) -2-hydroxymethylphenol Into a nitrogen-substituted 100 mL two-necked flask, 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 distilling off 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).
To a 100 mL flask purged with nitrogen, 4.2 g of the above mixture, 20 mL of tetrahydrofuran and 20 mL of methanol were added and cooled on ice. 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. After distilling off the solvent under reduced pressure, the resulting colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10 to 1: 5) to give 4-tert-butyl-6- 3.4 g (yield 81%) of (3,5-dimethyl-1-adamantyl) -2-hydroxymethylphenol 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, 3.4 g (9.9 mmol) of 5-dimethyl-1-adamantyl) -2-hydroxymethylphenol and 20 mL of dichloromethane were added. To this, 6.6 mL of phosphorus tribromide (1.0 M dichloromethane solution, 6.6 mmol) was added and 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 with anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure to give 5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzyl bromide 3.95 g (yield 98%) was obtained 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 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 stirred at room temperature for 1 hour. After distilling off volatile components 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 then saturated brine, 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: 10) to obtain trans-1,2-bis [5-tert-butyl-3- ( 1.0 g (yield> 99%) of 3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] cyclooctane 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 11)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl]} dichlorotitanium Glove box under nitrogen atmosphere 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) To a dichloromethane (1 mL) solution, a solution of dichlorodiisopropoxytitanium 24 mg (0.10 mmol) in dichloromethane (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-hydroxybenzylsulfanyl]} dichlorotitanium 50 mg (yield 53%) was obtained as a red powder.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.8 to 2.4 (m, 56H), 2.67 (brs, 2H), 3.80 (d, J = 14 Hz, 2H), 4.67 (d, J = 14 Hz, 2H), 6.86 (s, 2H), 7.35 (s , 2H).

(Reference Example 12)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl]} dichlorozirconium Glove box under nitrogen atmosphere 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 23 mg (0.10 mmol) of tetrachlorozirconium was added dropwise to a toluene (1 mL) solution 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-hydroxybenzylsulfanyl]} dichlorozirconium 51 mg (yield 52%) 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 13)
Synthesis of trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzylsulfanyl] cyclooctane (1) 4-tert-butyl-2- (2- Synthesis of phenyl-2-butyl) phenol To a nitrogen-substituted 50 mL Schlenk, 6.6 g (44 mmol) of 4-tert-butylphenol, 3.4 mL (22 mmol) of 2-phenyl-2-butanol and 20 mL of heptane were added. Heated to ° C. 73 mg (0.38 mmol) of p-toluenesulfonic acid monohydrate was added here, and it stirred at 100 degreeC for 11.5 hours. Water and ethyl acetate were added to the reaction solution. After the organic layer was dried over anhydrous magnesium sulfate, 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 4.4 g of 4-tert-butyl-2- (2-phenyl-2-butyl) phenol (yield) 71%) was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.683 (t, J = 7Hz, 3H), 1.35 (s, 9H), 1.61 (s, 3H), 2.02-2.26 (m, 2H), 4.18 (s, 1H), 6.66 (d, J = 8 Hz, 1H), 7.15-7.38 (m, 6H), 7.44 (d, J = 2 Hz, 1H).
(2) Synthesis of 4-tert-butyl-6- (2-phenyl-2-butyl) -2-hydroxymethylphenol Into a 500 mL flask purged with nitrogen, 4-tert-butyl-2- (2-phenyl-2-) was added. (Butyl) phenol 3.0 g (11 mmol), magnesium chloride 4.0 g (41 mmol), paraformaldehyde 1.8 g (60 mmol) and tetrahydrofuran 45 mL were added. Triethylamine 5.6 mL (41 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 distilling off 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 2.7 g of a mixture containing 5-tert-butyl-3- (2-phenyl-2-butyl) salicylaldehyde (yield 77%).
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.882 (t, J = 7 Hz, 3H), 1.34 to 1.55 (m, 11H), 1.83 (s, 6H), 7.2 to 7.9 (m, 7H), 9.82 (s, 1H), 11.2 (s, 1H) .
To a 200 mL flask purged with nitrogen, 2.7 g of the above mixture, 15 mL of tetrahydrofuran and 15 mL of methanol were added. Sodium borohydride 340 mg (8.9 mmol) 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. After distilling off the solvent under reduced pressure, the resulting colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10 to 1: 3) to give 4-tert-butyl-6- 2.1 g (yield 79%) of (2-phenyl-2-butyl) -2-hydroxymethylphenol was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.685 (t, J = 8 Hz, 3H), 1.34 (s, 9H), 1.62 (s, 6H), 2.0 to 2.4 (m, 3H), 4.62 (d, J = 6 Hz, 2H), 5.38 (s , 1H), 7.0-7.5 (m, 7H).
(3) Synthesis of 5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzyl bromide In a nitrogen-substituted 500 mL flask, 4-tert-butyl-6- (2-phenyl-2 -Butyl) -2-hydroxymethylphenol 2.1 g (6.7 mmol) and dichloromethane 15 mL were added. To this, 4.5 mL of phosphorus tribromide (1.0 M dichloromethane solution, 4.5 mmol) was added, 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 with anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure to give 2.5 g of 5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzyl bromide ( Yield> 99%) as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.669 (t, J = 8 Hz, 3H), 1.35 (s, 9H), 1.61 (s, 6H), 2.0 to 2.3 (m, 2H), 4.46 (m, 2H), 7.2 to 7.5 (m, 7H) .
(4) Synthesis of trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzylsulfanyl] cyclooctane Into a nitrogen-substituted 50 mL flask, bromide 5 -tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzyl 0.94 g (2.5 mmol), trans-cyclooctane-1,2-dithiol 90 mg (0.50 mmol) and tetrahydrofuran 7 mL were added. Chilled on ice. Triethylamine 0.70 mL (5.1 mmol) was added here, and it stirred at 0 degreeC for 1 hour, and room temperature for 1 hour. Further, 90 mg (0.50 mmol) of trans-cyclooctane-1,2-dithiol was added and stirred at room temperature for 1 hour. Volatile components were distilled off under reduced pressure, and ethyl acetate and an 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: 10) to obtain trans-1,2-bis [5-tert-butyl-3- ( 0.8 g (yield> 99%) of 2-phenyl-2-butyl) -2-hydroxybenzylsulfanyl] cyclooctane was obtained as a pale yellow solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.663 (t, J = 8 Hz, 3H), 1.1 to 2.6 (m, 48H), 3.65 (m, 4H), 5.60 to 5.71 (m, 2H), 7.0 to 7.4 (m, 14H).

(Reference Example 14)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzylsulfanyl]} dichlorotitanium in a glove box under a nitrogen atmosphere, In a 50 mL Schlenk tube, trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzylsulfanyl] cyclooctane 130 mg (0.17 mmol) in dichloromethane (1 mL ) A solution of dichlorodiisopropoxytitanium 40 mg (0.17 mmol) in dichloromethane (1 mL) was added dropwise to the solution 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- (2-phenyl-2-butyl) -2 -Hydroxybenzylsulfanyl]} dichlorotitanium 67 mg (yield 42%) was obtained as a red powder.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.5 to 2.8 (m, 47H), 3.1 to 4.8 (m, 5H), 6.3 to 7.5 (m, 14H).

(Reference Example 15)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzylsulfanyl]} dichlorozirconium in a glove box under a nitrogen atmosphere, In a 50 mL Schlenk tube, trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (2-phenyl-2-butyl) benzylsulfanyl] cyclooctane 150 mg (0.20 mmol) in toluene (1 mL ) A solution of tetrachlorozirconium 46 mg (0.20 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- (2-phenyl-2-butyl) -2 -Hydroxybenzylsulfanyl]} dichlorozirconium 110 mg (yield 58%) was obtained as a white powder.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.8 to 2.2 (m, 46H), 2.52 (m, 1H), 3.16 (m, 1H), 3.52 (m, 2H), 4.06 (m, 2H), 6.83 (s, 2H), 7.0 to 7.5 (m, 10H).

(Reference Example 16)
Synthesis of trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl] cyclooctane (1) 4-tert-butyl-2- (1 -Methyl-1-naphthylethyl) phenol synthesis Nitrogen-substituted 50 mL Schlenk was charged with 6.6 g (44 mmol) of 4-tert-butylphenol, 73 mg (0.38 mmol) of p-toluenesulfonic acid monohydrate and 20 mL of heptane. In addition, it was heated to 100 ° C. A solution prepared by dissolving 3.7 g (22 mmol) of isopropenylnaphthalene in 5 mL of heptane was added dropwise thereto and stirred at room temperature for 1 hour. The reaction solution was poured into an aqueous sodium bicarbonate solution. After the organic layer was dried over anhydrous magnesium sulfate, 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 3.0 g of 4-tert-butyl-2- (1-methyl-1-naphthylethyl) phenol. 43%) was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.38 (s, 9H), 1.79 (s, 6H), 4.34 (s, 1H), 6.66 (d, J = 8 Hz, 1H), 7.19-7.30 (m, 2H), 7.44-7.54 (m, 3H) , 7.75-7.92 (m, 4H).
(2) Synthesis of 4-tert-butyl-2-hydroxymethyl-6- (1-methyl-1-naphthylethyl) phenol Into a 500 mL flask purged with nitrogen, 4-tert-butyl-2- (1-methyl-1 -Naphthylethyl) phenol 1.7 g (5.4 mmol), magnesium chloride 2.0 g (20 mmol), paraformaldehyde 0.9 g (30 mmol) and tetrahydrofuran 20 mL were added. Triethylamine 2.8 mL (20 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 distilling off 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 4.0 g of a mixture containing 5-tert-butyl-3- (1-methyl-1-naphthylethyl) salicylaldehyde (yield 73%).
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.37 (s, 9H), 1.83 (s, 6H), 4.34 (s, 1H), 7.2 to 7.9 (m, 9H), 9.82 (s, 1H), 11.2 (s, 1H).
1.4 g of the above mixture, 10 mL of tetrahydrofuran and 10 mL of methanol were added to a 200 mL flask purged with nitrogen. Sodium borohydride 160 mg (4.2 mmol) 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. After distilling off the solvent under reduced pressure, the obtained colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10 to 1: 3) to give 4-tert-butyl-2- Hydroxymethyl-6- (1-methyl-1-naphthylethyl) phenol 1.3 g (91% yield) was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.37 (s, 9H), 1.80 (s, 6H), 2.08 (t, J = 6 Hz, 1H), 4.62 (d, J = 6 Hz, 2H), 5.60 (s, 1H), 7.1 to 7.9 (m , 9H).
(3) Synthesis of 5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzyl bromide In a nitrogen-substituted 500 mL flask, 4-tert-butyl-2-hydroxymethyl-6- 1.3 g (3.6 mmol) of (1-methyl-1-naphthylethyl) phenol and 10 mL of dichloromethane were added. To this was added 2.7 mL of phosphorus tribromide (1.0 M dichloromethane solution, 2.7 mmol), and the mixture was stirred at room temperature for 2 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 the volatile component was distilled off under reduced pressure to give 1.5 g of 5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzyl bromide. (Yield> 99%) was obtained as a pale yellow oil.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.30 (s, 9H), 1.79 (s, 6H), 4.43 (s, 2H), 7.2 to 8.0 (m, 9H).
(4) Synthesis of trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl] cyclooctane In a 50 mL flask purged with nitrogen, brominated 5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzyl 1.1 g (2.5 mmol), trans-cyclooctane-1,2-dithiol 0.18 g (1.0 mmol) and tetrahydrofuran 7 mL And cooled with ice. Triethylamine 0.70 mL (5.1 mmol) was added here, and it stirred at 0 degreeC for 1 hour, and 2 hours at room temperature. Volatile components were distilled off under reduced pressure, and ethyl acetate and an 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, trans-1,2-bis [5-tert-butyl-2-hydroxy was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10). 0.9 g (yield> 99%) of -3- (1-methyl-1-naphthylethyl) benzylsulfanyl] cyclooctane was obtained as a pale yellow solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.8 to 1.8 (m, 42H), 2.46 (m, 2H), 2.51 (m, 4H), 3.51 (m, 4H), 5.72 (s, 2H), 6.99 (d, J = 2 Hz, 2H), 7.20 ~ 7.23 (m, 2H), 7.35 ~ 7.44 (m, 6H), 7.60 ~ 7.89 (m, 8H).

(Reference Example 17)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl]} dichlorotitanium in a glove box under nitrogen atmosphere , Trans-1,2-bis (5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl) cyclooctane 170 mg (0.20 mmol) in dichloromethane (50 mL Schlenk tube) 1 mL), a solution of dichlorodiisopropoxytitanium 50 mg (0.17 mmol) in dichloromethane (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-2-hydroxy-3- (1-methyl-1- Naphthylethyl) benzylsulfanyl]} dichlorotitanium 95 mg (yield 50%) was obtained as a red powder.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.8 to 2.2 (m, 44H), 2.34 (d, J = 15 Hz, 2H), 3.41 (d, J = 15 Hz, 2H), 6.56 (s, 2H), 6.9 to 7.9 (m, 14H),. 18 (s, 2H).

(Reference Example 18)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl]} dichlorozirconium in a glove box under nitrogen atmosphere , Trans-1,2-bis (5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl) cyclooctane 170 mg (0.20 mmol) in toluene (50 mL Schlenk tube) To a 1 mL) solution, a solution of tetrachlorozirconium 46 mg (0.20 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-2-hydroxy-3- (1-methyl-1- Naphthylethyl) benzylsulfanyl]} dichlorozirconium 81 mg (yield 41%) was obtained as a white powder.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.8 to 2.2 (m, 44H), 2.49 (d, J = 15 Hz, 2H), 3.27 (d, J = 15 Hz, 2H), 6.59 (d, J = 2 Hz, 2H), 6.98 (dd, J = 2 Hz, 7 Hz, 2H), 7.3 to 8.2 (m, 14H).

(Reference Example 19)
Synthesis of trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl] cyclooctane (1) 4-tert-butyl-2- (1-methylcyclohexyl) Synthesis of Phenol To 50 mL Schlenk purged with nitrogen was added 3.3 g (22 mmol) of 4-tert-butylphenol, 2.7 mL (22 mmol) of 1-methylcyclohexanol and 20 mL of dichloromethane, and the mixture was 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 20 minutes. The reaction solution was poured into an aqueous sodium bicarbonate solution. After the organic layer was dried over anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure. The resulting white solid is purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10) to give 3.8 g of 4-tert-butyl-2- (1-methylcyclohexyl) phenol (yield 70%) Was obtained as a colorless oil.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.2 to 1.8 (m, 20H), 2.19 (m, 2H), 4.60 (s, 1H), 6.58 (d, J = 8 Hz, 1H), 7.06 (dd, J = 2 Hz, 8 Hz, 1H), 7.31 (d, J = 2 Hz, 1H).
(2) Synthesis of 4-tert-butyl-2-hydroxymethyl-6- (1-methylcyclohexyl) phenol In a 200 mL four-necked flask purged with nitrogen, 4-tert-butyl-2- (1-methylcyclohexyl) phenol 3.8 g (16 mmol), magnesium chloride 3.0 g (31 mmol), paraformaldehyde 2.3 g (78 mmol) and tetrahydrofuran 70 mL were added. Triethylamine 4.3 mL (31 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 distilling off 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 4.0 g of a mixture containing 5-tert-butyl-3- (1-methylcyclohexyl) salicylaldehyde (yield 91%).
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.2 to 1.8 (m, 20H), 2.20 (m, 2H), 7.33 (d, J = 2 Hz, 1H), 7.61 (d, J = 2 Hz, 1H), 9.86 (s, 1H), 11.7 (s , 1H).
To a 200 mL four-necked flask purged with nitrogen, 4.0 g of the above mixture, 40 mL of tetrahydrofuran and 20 mL of methanol were added and cooled on ice. Sodium borohydride 330 mg (8.7 mmol) was slowly added here, and it heated up to room temperature, and stirred for 15 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. After distilling off the solvent under reduced pressure, the obtained colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 9) to give 4-tert-butyl-2-hydroxymethyl-6 There was obtained 2.4 g (61% yield) of-(1-methylcyclohexyl) phenol as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.2 to 1.8 (m, 20H), 2.16 (brs, 1H), 2.19 (m, 2H), 4.84 (s, 2H), 6.88 (d, J = 2 Hz, 1H), 7.30 (d, J = 2 Hz , 1H), 7.52 (s, 1H).
(3) Synthesis of 5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzyl bromide To a nitrogen-substituted 200 mL four-necked flask, 4-tert-butyl-2-hydroxymethyl-6- (1 -Methylcyclohexyl) phenol 2.4 g (8.8 mmol) and dichloromethane 40 mL were added. To this, 5.3 mL of phosphorus tribromide (1.0 M dichloromethane solution, 5.3 mmol) was added, and the mixture was stirred at room temperature for 3.5 hours. 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 3.8 g of 5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzyl bromide (yield> 99%) was obtained as a pale yellow oil.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.2 to 1.8 (m, 20H), 2.18 (m, 2H), 4.58 (s, 2H), 7.08 (d, J = 2 Hz, 1H), 7.35 (d, J = 2 Hz, 1H).
(4) Synthesis of trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl] cyclooctane Into a nitrogen-substituted 50 mL four-necked flask, Add 1.5 g (4.3 mmol) of tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzyl, 0.38 g (2.1 mmol) of trans-cyclooctane-1,2-dithiol and 22 mL of tetrahydrofuran, and cool with ice. . Triethylamine 0.90 mL (6.5 mmol) was added here, and it stirred at room temperature for 22.5 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: 20) to obtain trans-1,2-bis [5-tert-butyl-2-hydroxy 7 of 3- (1-methylcyclohexyl) benzylsulfanyl] cyclooctane and trans-1- [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl] -2-sulfanylcyclooctane : 1.6 g of a mixture was obtained. This mixture and 0.18 g (0.53 mmol) of 5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzyl bromide were dissolved in 20 mL of tetrahydrofuran and ice-cooled. Triethylamine 0.10 mL (0.72 mmol) was added here, and it stirred for 22 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: 20), whereby trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1 1.6 g (yield> 99%) of -methylcyclohexyl) benzylsulfanyl] cyclooctane were obtained as a yellow oil.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
1.1 to 1.8 (m, 50H), 1.90 (m, 2H), 2.20 (m, 4H), 2.64 (m, 2H), 3.80 (d, J = 13 Hz, 2H), 3.89 (d, J = 13 Hz , 2H), 6.90 (d, J = 2 Hz, 2H), 7.27 (d, J = 2 Hz, 2H).

(Reference Example 20)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl]} dichlorotitanium 50 mL Schlenk in a glove box under nitrogen atmosphere In a tube, add trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl] cyclooctane 140 mg (0.20 mmol) in dichloromethane (1 mL) to dichlorodi A solution of isopropoxytitanium 50 mg (0.17 mmol) in dichloromethane (1 mL) was added dropwise at room temperature. After 1.5 hours, volatile components were distilled off under reduced pressure. The residue obtained was washed with pentane and dried under reduced pressure to give {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzyl Sulfanyl]} dichlorotitanium 100 mg (yield 60%) was obtained as a red powder.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.5 to 2.4 (m, 56H), 2.6 to 3.9 (m, 4H), 4.6 to 4.8 (m, 2H), 6.8 to 7.0 (m, 2H), 7.2 to 7.4 (m, 2H).

(Reference Example 21)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl]} dichlorozirconium 50 mL Schlenk in a glove box under nitrogen atmosphere In a tube, add trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl] cyclooctane 140 mg (0.20 mmol) in toluene (1 mL) to tetrachloro A solution of zirconium (46 mg, 0.20 mmol) in toluene (1 mL) was added dropwise at room temperature. After 1.5 hours, volatile components were distilled off under reduced pressure. The residue obtained was washed with pentane and dried under reduced pressure to give {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzyl Sulfanyl]} dichlorozirconium 80 mg (yield 47%) was obtained as a white powder.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.8 to 2.4 (m, 56H), 2.71 (brs, 2H), 3.83 (d, J = 14 Hz, 2H), 4.53 (d, J = 14 Hz, 2H), 6.86 (s 2H), 7.38 (s, 2H).

(Reference Example 22)
Synthesis of trans-1,2-bis (2-hydroxy-3-trimethylsilyl-5-methylbenzylsulfanyl) cyclooctane (1) Synthesis of 3-trimethylsilyl-5-methyl-2-hydroxybenzyl alcohol 2-Hydroxo-5- 9.57 g (45.9 mmol) of methyl-3- (trimethylsilyl) benzaldehyde was dissolved in 70 mL of diethyl ether and cooled to 0 ° C. Thereto was added 2.27 g (59.8 mmol) of lithium aluminum hydride, and the mixture was stirred at 0 ° C. for 2 hours. Dilute hydrochloric acid and diethyl ether were added, and the ether layer was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to give 9.57 g of 3-trimethylsilyl-5-methyl-2-hydroxybenzyl alcohol as colorless crystals. Rate 98%).
¹ H NMR (500 MHz, δ, ppm, CDCl ₃ )
0.30 (s, 9H), 2.03 (br s, 1H), 2.25 (s, 3H), 4.83 (br s, 1H), 6.84 (d, J = 2 Hz, 1H), 7.11 (d, J = 2 Hz , 1H), 7.39 (s, 1H).
(2) Synthesis of trans-1,2-bis (2-hydroxy-3-trimethylsilyl-5-methylbenzylsulfanyl) cyclooctane 1.03 g (4.87) of 3-trimethylsilyl-5-methyl-2-hydroxybenzyl alcohol under argon atmosphere mmol) was dissolved in 30 mL of diethyl ether and cooled to 0 ° C. 1,8-diazabicyclo [5.4.0] undec-7-ene 6.2 mL (44.5 mmol) was added thereto, and then phosphorus tribromide 0.35 mL (3.69 mmol) was added, followed by stirring at 25 ° C. for 2 hours. Thereto, a solution obtained by dissolving 289.2 mg (1.64 mmol) of trans-cyclooctane-1,2-dithiol (document known) in 20 mL of diethyl ether was transferred in a tube under an argon atmosphere and stirred for 13 hours under heating and reflux. A dilute aqueous ammonium chloride solution and diethyl ether were added, and the ether layer was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: dichloromethane), and trans-1,2-bis (2-hydroxy-3-trimethylsilyl-5-methylbenzylsulfanyl) cyclooctane 672.9 mg (yield as a colorless oil) 73%).
¹ H NMR (500 MHz, δ, ppm, CDCl ₃ )
0.29 (s, 18H), 1.15-1.96 (m, 12H), 2.25 (s, 6H), 2.65 (br s, 2H), 3.73-3.85 (m, 4H), 6.85 (d, J = 2 Hz, 2H ), 6.90 (s, 2H), 7.10 (d, J = 2 Hz, 2H).
¹³ C NMR (125.7 MHz, δ, ppm, CDCl ₃₎
-0.88, 20.5, 25.7, 26.0, 30.9, 34.5, 49.9, 120.8, 127.7, 129.1, 132.4, 135.2, 158.4.

(Reference Example 23)
Synthesis of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3-trimethylsilyl-5-methylbenzylsulfanyl)] dichlorozirconium The following experiment was conducted under an argon atmosphere. In a 50 mL Schlenk tube, 501.5 mg (0.894 mmol) of trans-1,2-bis (2-hydroxy-3-trimethylsilyl-5-methylbenzylsulfanyl) cyclooctane is dissolved in 20 mL of diethyl ether. Butyllithium 1.3 mL (1.65 mol / L, 2.15 mmol) was added, and the mixture was stirred at 0 ° C. for 3 hours. This solution was added dropwise to 10 mL of diethyl ether solution of 280 mg (1.20 mmol) of tetrachlorozirconium at −78 ° C., and further stirred overnight. The formed precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was washed with hexane, dried, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3-trimethylsilyl-5-methylbenzylsulfanyl)] dichlorozirconium 427 mg (yield 66) as colorless crystals. %).
¹ H NMR (500 MHz, δ, ppm, C ₆ D ₆ )
0.53-1.31 (m, 12H), 0.72 (s, 18H), 2.13 (s, 6H), 2.50 (br s, 2H), 3.14 (d, J = 14 Hz, 2H), 4.30 (d, J = 14 Hz, 2H), 6.36 (s, 2H), 7.34 (s, 2H).
¹³ C NMR (125.7 MHz, δ, ppm, C ₆ D ₆ )
-2.30, 18.5, 23.0, 24.0, 26.5, 33.2, 47.3, 117.7, 127.4, 127.5, 130.7, 135.0, 161.2.

(Reference Example 24)
Synthesis of trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl) cyclooctane (1) Synthesis of 2-tert-amyl-4-tert-butylphenol Nitrogen-substituted 50 To mL Schlenk, 3.3 g (22 mmol) of 4-tert-butylphenol, 2.4 mL (22 mmol) of tert-amyl alcohol and 20 mL of dichloromethane were 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 20 minutes. The reaction solution was poured into an aqueous sodium bicarbonate solution. After the organic layer was dried over anhydrous magnesium sulfate, 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 3.7 g of 2-tert-amyl-4-tert-butylphenol (yield 75%) as a colorless oil. Obtained.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.682 (t, J = 8 Hz, 3H), 1.29 (s, 9H), 1.37 (s, 6H), 1.84 (q, J = 8 Hz, 2H), 4.57 (s, 1H), 6.57 (d, J = 8 Hz, 1H), 7.06 (dd, J = 2 Hz, 8 Hz, 1H), 7.23 (d, J = 2 Hz, 1H).
(2) Synthesis of 6-tert-amyl-4-tert-butyl-2-hydroxymethylphenol In a 200 mL four-necked flask purged with nitrogen, 3.7 g (17 mmol) of 2-tert-amyl-4-tert-butylphenol, chloride Magnesium 3.2 g (33 mmol), paraformaldehyde 2.5 g (83 mmol) and tetrahydrofuran 75 mL were added. Triethylamine 4.6 mL (33 mmol) was added here, and it heated and refluxed for 1.5 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off 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 3.9 g of a mixture containing 3-tert-amyl-5-tert-butylsalicylaldehyde (yield 94%).
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.648 (t, J = 8 Hz, 3H), 1.28 (s, 9H), 1.37 (s, 6H), 1.90 (q, J = 8 Hz, 2H), 7.33 (d, J = 2 Hz, 1H), 7.54 (d, J = 2 Hz, 1H), 9.86 (s, 1H), 11.6 (s, 1H).
To a 200 mL four-necked flask purged with nitrogen, 3.9 g of the above mixture, 40 mL of tetrahydrofuran and 20 mL of methanol were added and ice-cooled. Sodium borohydride 360 mg (9.5 mmol) was slowly added here, and it heated up to room temperature, and stirred for 15 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. After evaporating the solvent under reduced pressure, the colorless oil obtained was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 20 to 1: 9) to give 6-tert-amyl-4- 2.4 g (61% yield) of tert-butyl-2-hydroxymethylphenol was obtained as a white solid.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.681 (t, J = 7 Hz, 3H), 1.28 (s, 9H), 1.38 (s, 6H), 1.90 (q, J = 7 Hz, 2H), 4.84 (s, 2H), 6.88 (d, J = 2 Hz, 1H), 7.21 (d, J = 2 Hz, 1H), 7.48 (s, 1H).
(3) Synthesis of 3-tert-amyl-5-tert-butyl-2-hydroxybenzyl bromide In a 200 mL four-necked flask purged with nitrogen, 6-tert-amyl-4-tert-butyl-2-hydroxymethylphenol 2.4 g (9.4 mmol) and 40 mL of dichloromethane were added. To this, 5.7 mL of phosphorus tribromide (1.0 M dichloromethane solution, 5.7 mmol) was added, and the mixture was stirred at room temperature for 3.5 hours. 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 components are distilled off under reduced pressure to give 3.2 g of 3-tert-amyl-5-tert-butyl-2-hydroxybenzyl bromide (yield> 99%) Was obtained as a pale yellow oil.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.676 (t, J = 8 Hz, 3H), 1.29 (s, 9H), 1.37 (s, 6H), 1.86 (q, J = 7 Hz, 2H), 4.58 (s, 2H), 7.09 (d, J = 2 Hz, 1H), 7.26 (d, J = 2 Hz, 1H).
(4) Synthesis of trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl) cyclooctane In a 50 mL four-necked flask purged with nitrogen, 3-tert-amyl bromide -5-tert-butyl-2-hydroxybenzyl 1.4 g (4.5 mmol), trans-cyclooctane-1,2-dithiol 0.40 g (2.2 mmol), and tetrahydrofuran 22 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 22.5 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: 20) to obtain trans-1,2-bis (3-tert-amyl-5-tert 1.5 g of a 6: 1 mixture of 2-butyl-2-hydroxybenzylsulfanyl) cyclooctane and trans-1- (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl) -2-sulfanylcyclooctane It was. This mixture and 0.20 g (0.64 mmol) of 3-tert-amyl-5-tert-butyl-2-hydroxybenzyl bromide were dissolved in 100 mL of tetrahydrofuran and ice-cooled. Triethylamine 0.12 mL (0.86 mmol) was added here, and it stirred for 22.5 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) to obtain trans-1,2-bis (3-tert-amyl-5-tert-butyl-2- Hydroxybenzylsulfanyl) cyclooctane 1.5 g (yield> 99%) was obtained as a yellow oil.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.649 (t, J = 8 Hz, 6H), 1.1 to 2.0 (m, 46H), 2.64 (m, 2H), 3.81 (d, J = 13 Hz, 2H), 3.90 (d, J = 13 Hz, 2H ), 6.90 (d, J = 2 Hz, 2H), 7.19 (d, J = 2 Hz, 2H).

(Reference Example 25)
Synthesis of [cyclooctanediyl-trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl)] dichlorotitanium in a 50 mL Schlenk tube in a glove box under nitrogen atmosphere -1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl) cyclooctane 130 mg (0.20 mmol) in dichloromethane (1 mL) was added to dichlorodiisopropoxytitanium 50 mg ( 0.17 mmol) in dichloromethane (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 (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl)] Dichlorotitanium 81 mg (54% yield) was obtained as a red powder.

(Reference Example 26)
Synthesis of [cyclooctanediyl-trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl)] dichlorozirconium in a 50 mL Schlenk tube in a glove box under nitrogen atmosphere To a solution of 1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl) cyclooctane 130 mg (0.20 mmol) in toluene (1 mL), tetrachlorozirconium 46 mg (0.20 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 (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl)] Dichlorozirconium 80 mg (yield 47%) was obtained as a white powder.
¹ H-NMR (400 MHz, δ, ppm, CDCl ₃ )
0.707 (t, J = 7 Hz, 6H), 1.1-2.3 (m, 46H), 2.57 (brs, 2H), 3.81 (d, J = 14 Hz, 2H), 4.46 (d, J = 14 Hz, 2H ), 6.86 (d, J = 2 Hz, 2H), 7.31 (d, J = 2 Hz, 1H).

(Reference Example 27)
(Preparation of d-MAO (dry methylaluminoxane))
A 200 mL two-necked flask containing a stirring bar equipped with a three-way cock was purged with nitrogen, and a PMAO-S toluene solution (aluminum content 6.1 wt%) manufactured by Tosoh Finechem Co. was measured with a 100 mL syringe and charged into the flask. The solution was depressurized to remove volatile components. The obtained white solid was redissolved in 100 mL of dehydrated toluene, and then volatile components were removed under reduced pressure. This operation was further repeated twice to obtain 14.1 g of white powder.

<Ethylene homopolymerization>
Example 1
The autoclave with a stirrer with an internal volume of 400 mL was vacuum-dried and replaced with argon, and then 200 mL of toluene was charged as a solvent, and the temperature of the reactor was raised to 40 ° C. After raising the temperature, the ethylene pressure was fed while adjusting the pressure to 0.6 MPa, 119 mg of d-MAO was added, and then synthesized in Reference Example 2 [cyclooctanediyl-trans-1,2-bis (2-oxoyl- 3,5-Di-tert-butylbenzylsulfanyl)] dichlorotitanium (0.5 mmol / L, toluene solution) was added in an amount of 0.10 mL (0.050 μmol) to initiate polymerization. Polymerization was carried out for 60 minutes while maintaining the temperature at 40 ° C. About the obtained polymer, melting | fusing point, molecular weight, and molecular weight distribution were measured. The results are shown in Table 1.

(Example 2)
The autoclave with a stirrer with an internal volume of 400 mL was vacuum-dried and replaced with argon, and then 200 mL of toluene was charged as a solvent, and the temperature of the reactor was raised to 40 ° C. After raising the temperature, the ethylene pressure was fed while adjusting the pressure to 0.6 MPa, 122 mg of d-MAO was added, and then trans-1,2-bis (2-hydroxy-3,5- Di-tert-butylbenzylsulfanyl) cyclooctane and TiBn ₄ 1: 1 reaction mixture (titanium concentration 1.0 mmol / L, toluene solution) 0.5 mL (titanium complex 0.50 μmol) was added to polymerize. Started. Polymerization was carried out for 60 minutes while maintaining the temperature at 40 ° C. About the obtained polymer, melting | fusing point, molecular weight, and molecular weight distribution were measured. The results are shown in Table 1.

(Example 3)
The amount of d-MAO input was 141 mg, and trans-1,2-synthesized in Reference Example 5 was used instead of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane. The same procedure as in Example 2 was performed except that bis (5-tert-butyl-3-cumyl-2-hydroxybenzylsulfanyl) cyclooctane was used. The results are shown in Table 1.

Example 4
The amount of d-MAO input was 149 mg, and trans-1,2-synthesized in Reference Example 7 was used instead of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane. The same procedure as in Example 2 was performed except that bis [3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl] cyclooctane was used. The results are shown in Table 1.

(Example 5)
The trans-1,2-synthesized in Reference Example 9 was used instead of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane, with a d-MAO input of 123 mg. Using bis [3- (N-carbazolyl) -2-hydroxy-5-methylbenzylsulfanyl] cyclooctane, the input amount of the reaction mixture (titanium concentration 2.0 mmol / L, toluene solution) was 0.5 mL (titanium amount 1 0.0 μmol), and the same procedure as in Example 2 was performed. The results are shown in Table 1.

(Example 6)
The amount of d-MAO charged was 124 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium (0.5 mmol / L, toluene solution) ) Synthesized in Reference Example 11 instead of 0.10 mL (0.050 μmol) {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl)] -2-hydroxybenzylsulfanyl]} dichlorotitanium (1.0 mmol / L, toluene solution) 1.0 mL (1.0 μmol) was used, and the same procedure as in Example 1 was performed. The results are shown in Table 1.

(Example 7)
The amount of d-MAO charged was 127 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium (0.5 mmol / L, toluene solution) ) {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2] synthesized in Reference Example 14 instead of 0.10 mL (0.050 μmol) -Hydroxybenzylsulfanyl]} dichlorotitanium (1.0 mmol / L, toluene solution), except that 1.0 mL (1.0 μmol) was used. The results are shown in Table 1.

(Example 8)
The amount of d-MAO charged was 136 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium (0.5 mmol / L, toluene solution) ) {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methyl-1-) synthesized in Reference Example 17 instead of 0.10 mL (0.050 μmol) Naphthylethyl) benzylsulfanyl]} dichlorotitanium (1.0 mmol / L, toluene solution) was used in the same manner as in Example 1 except that 1.0 mL (1.0 μmol) was used. The results are shown in Table 1.

Example 9
d-MAO input was 148 mg, [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium (0.5 mmol / L, toluene solution) ) {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzyl] synthesized in Reference Example 20 instead of 0.10 mL (0.050 μmol) Sulfanyl]} dichlorotitanium (1.0 mmol / L, toluene solution) was used in the same manner as in Example 1 except that 1.0 mL (1.0 μmol) was used. The results are shown in Table 1.

(Example 10)
d-MAO input was 111 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium (0.5 mmol / L, toluene solution) ) Synthesized in Reference Example 25 instead of 0.10 mL (0.050 μmol) [cyclooctanediyl-trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl)] The same procedure as in Example 1 was performed except that 1.0 mL (1.0 μmol) of dichlorotitanium (1.0 mmol / L, toluene solution) was used. The results are shown in Table 1.

(Comparative Example 1)
The amount of d-MAO input was 111 mg, and synthesized in Reference Example 3 instead of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium. The same procedure as in Example 1 was performed except that [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium was used. The results are shown in Table 1.

(Comparative Example 2)
The amount of d-MAO input was 119 mg, and trans-1,2-synthesized in Reference Example 4 was used instead of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane. Using bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclohexane, the input amount of the reaction mixture (titanium concentration 2.0 mmol / L, toluene solution) was 0.25 mL (titanium amount 0.5 μmol) The same procedure as in Example 2 was performed except that. The results are shown in Table 1.

(Comparative Example 3)
The amount of d-MAO input was 129 mg, and synthesized in Reference Example 6 instead of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium. Performed in the same manner as in Example 1 except that [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium was used. . The results are shown in Table 1.

(Comparative Example 4)
The amount of d-MAO input was 149 mg, and synthesized in Reference Example 8 instead of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium. {Cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl]} Performed in the same manner as in Example 1 except that dibenzylzirconium was used. did. The results are shown in Table 1.

(Comparative Example 5)
The amount of d-MAO input was 122 mg, and synthesized in Reference Example 12 instead of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium. [Cycloheptanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorozirconium (0.5 mmol / L, toluene solution) 0.1 mL (0.05 μmol) This was carried out in the same manner as in Example 1 except that was used. The results are shown in Table 1.

(Comparative Example 6)
Instead of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium with a polymerization time of 15 minutes and a d-MAO charge of 117 mg {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzylsulfanyl]} dichlorozirconium (0. The same procedure as in Example 1 was carried out except that 0.2 mL (0.01 μmol) of 05 mmol / L, toluene solution) was used. The results are shown in Table 1.

(Comparative Example 7)
The amount of d-MAO used was 123 mg, and synthesized in Reference Example 18 instead of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium. {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl]} dichlorozirconium (0.05 mmol / L, toluene solution ) The same procedure as in Example 1 was performed except that 0.1 mL (0.05 μmol) was used. The results are shown in Table 1.

(Comparative Example 8)
The amount of d-MAO input was 142 mg, and synthesized in Reference Example 21 instead of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium. {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl]} dichlorozirconium (0.05 mmol / L, toluene solution) It implemented like Example 1 except having used 2 mL (0.01 micromol). The results are shown in Table 1.

(Comparative Example 9)
The amount of d-MAO input was 122 mg, and synthesized in Reference Example 26 instead of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium. [Cyclooctanediyl-trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl)] dichlorozirconium (0.05 mmol / L, toluene solution) 0.2 mL (0 .01 μmol) was carried out in the same manner as in Example 1. The results are shown in Table 1.
Table 1 shows the polymerization results obtained in Examples 1 to 10 and Comparative Examples 1 to 9.

<Propylene homopolymerization>
(Example 11)
The autoclave with a stirrer having an internal volume of 400 mL was vacuum-dried and replaced with argon, and then 40 mL of toluene as a solvent and 80 g of propylene as a monomer were charged, and the reactor was heated to 40 ° C. After raising the temperature, 125 mg of d-MAO was added, and then [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichloro synthesized in Reference Example 2 Polymerization was initiated by adding 1.0 mL (0.50 μmol) of titanium (0.5 mmol / L, toluene solution). Polymerization was carried out for 60 minutes while maintaining the temperature at 40 ° C. About the obtained polymer, melting | fusing point, molecular weight, and molecular weight distribution were measured. The results are shown in Table 2.

(Example 12)
The autoclave with a stirrer having an internal volume of 400 mL was vacuum-dried and replaced with argon, and then 40 mL of toluene as a solvent and 80 g of propylene as a monomer were charged, and the reactor was heated to 40 ° C. After raising the temperature, 125 mg of d-MAO was added, and subsequently trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane synthesized in Reference Example 1 and TiBn ₄ Polymerization was started by charging 3.0 mL of a 1: 1 reaction mixture (titanium concentration 1.0 mmol / L, toluene solution) (titanium complex 3.0 μmol). Polymerization was carried out for 60 minutes while maintaining the temperature at 40 ° C. About the obtained polymer, melting | fusing point, molecular weight, and molecular weight distribution were measured. The results are shown in Table 2.

(Example 13)
The amount of d-MAO input was 144 mg, and trans-1,2 synthesized in Reference Example 5 was used instead of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane. -Bis (5-tert-butyl-3-cumyl-2-hydroxybenzylsulfanyl) cyclooctane was used, and the input amount of the reaction mixture (titanium concentration 1.0 mmol / L, toluene solution) was 1.0 mL (titanium amount 1. This was carried out in the same manner as in Example 12 except that the amount was 0 μmol). The results are shown in Table 2.

(Example 14)
The trans-1 synthesized in Reference Example 7 was used instead of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane, with an input amount of d-MAO of 131.6 mg. , 2-bis [3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl] cyclooctane was used in the same manner as Example 12, except that 2-bis [3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl] cyclooctane was used. The results are shown in Table 2.

(Example 15)
The amount of d-MAO input was 144 mg, and trans-1,2 synthesized in Reference Example 9 was used instead of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane. -Bis [3- (N-carbazolyl) -2-hydroxy-5-methylbenzylsulfanyl] cyclooctane was used, and the reaction mixture (titanium concentration 2.0 mmol / L, toluene solution) was added in 2.5 mL (titanium amount) The same procedure as in Example 12 was carried out except that the amount was 5.0 μmol). The results are shown in Table 2.

(Example 16)
The amount of d-MAO used was 134 mg and synthesized in Reference Example 14 instead of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium. {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzylsulfanyl]} dichlorotitanium (1.0 mmol / L, toluene solution) ) The same procedure as in Example 11 was performed except that 5.0 mL (5.0 μmol) was used. The results are shown in Table 2.

(Example 17)
The amount of d-MAO input was 119 mg, and synthesized in Reference Example 20 instead of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium. {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl]} dichlorotitanium (1.0 mmol / L, toluene solution) 5. It implemented like Example 11 except having used 0 mL (5.0 micromol). The results are shown in Table 2.

(Example 18)
The trans-1,2 synthesized in Reference Example 22 was used instead of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane, with a d-MAO input of 124 mg. Except that -bis (2-hydroxy-3-trimethylsilyl-5-methylbenzylsulfanyl) cyclooctane was used and the input amount of the reaction mixture (titanium concentration 10 mmol / L, toluene solution) was 1.0 mL (titanium amount 10 μmol) Was carried out in the same manner as in Example 12. The results are shown in Table 2.

(Example 19)
The amount of d-MAO input was 119 mg, and synthesized in Reference Example 25 instead of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium. [Cyclooctanediyl-trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl)] dichlorotitanium (1.0 mmol / L, toluene solution) 5.0 mL ( The same procedure as in Example 11 was carried out except that 5.0 μmol) was used. The results are shown in Table 2.

(Comparative Example 10)
The amount of d-MAO used was 123 mg, and synthesized in Reference Example 3 instead of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium. [Cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (5.0 mmol / L, toluene solution) 0.5 mL (5.0 μmol) ) Was carried out in the same manner as in Example 11 except that. The results are shown in Table 2.

(Comparative Example 11)
The trans-1,2 synthesized in Reference Example 4 was used instead of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane, with a d-MAO input of 123 mg. -Bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclohexane was used, and the reaction mixture (titanium concentration 2.0 mmol / L, toluene solution) was added in 2.5 mL (titanium amount 5.0 μmol). This was carried out in the same manner as in Example 12 except that. The results are shown in Table 2.

(Comparative Example 12)
The amount of d-MAO input was 131 mg, and synthesized in Reference Example 6 instead of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium. [Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium (0.5 mmol / L, toluene solution) 1.0 mL (0. The same procedure as in Example 11 was carried out except that 5 μmol) was used. The results are shown in Table 2.

(Comparative Example 13)
The amount of d-MAO input was 140 mg, and synthesized in Reference Example 8 instead of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium. {Cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl]} dibenzylzirconium (0.5 mmol / L, toluene solution) 1.0 mL (0 0.5 μmol) was carried out in the same manner as in Example 11. The results are shown in Table 2.

(Comparative Example 14)
The polymerization temperature was 40 ° C., the d-MAO charge was 118 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium Instead, {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzylsulfanyl]} dichlorozirconium synthesized in Reference Example 15 ( The same procedure as in Example 11 was performed except that 0.10 mL (0.050 μmol) of 0.5 mmol / L, toluene solution) was used. The results are shown in Table 2.

(Comparative Example 15)
The polymerization temperature was 40 ° C., the amount of d-MAO charged was 144 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium Instead, {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl]} dichlorozirconium synthesized in Reference Example 21 (0.5 The same procedure as in Example 11 was carried out except that 0.10 mL (0.050 μmol) of mmol / L, toluene solution) was used. The results are shown in Table 2.

(Comparative Example 16)
The polymerization temperature was 40 ° C., the amount of d-MAO charged was 129 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium Instead, [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3-trimethylsilyl-5-methylbenzylsulfanyl)] dichlorozirconium synthesized in Reference Example 24 (0.5 mmol / L, toluene solution) 1 The same procedure as in Example 11 was performed except that 0.0 mL (0.50 μmol) was used. The results are shown in Table 2.

(Comparative Example 17)
The amount of d-MAO charged was 111 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorotitanium (0.5 mmol / L, toluene Solution) [cyclooctanediyl-trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl) synthesized in Reference Example 26 instead of 0.1 mL (0.050 μmol) It carried out like Example 11 except having used 1.0 mL (0.10 micromol) of dichloro zirconium (0.1 mmol / L, toluene solution). The results are shown in Table 2.

The polymerization results obtained in Examples 11 to 19 and Comparative Examples 10 to 17 are shown in Table 2.

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

Claims

An olefin polymerization catalyst obtained by bringing a complex represented by the general formula (1) into contact with an activation promoter component.

(Wherein n is 1 or 2,
R 1 to R 12 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,
Substituted silyl groups,
Alternatively, it represents 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 12 The residue may have a substituent.
Regardless of the definition of R 1 to R 12 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 9 And R 10 , and R 11 and R 12 may be independently connected to each other to form a ring, and these rings may have a substituent.
X is independently a 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 may have a substituent. 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. )
R 9 to R 12 are
The catalyst according to claim 1, which is a hydrogen atom.
The catalyst according to claim 1 or 2, wherein the activating co-catalyst 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,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms,
Substituted silyl groups,
Or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring, and the alkyl group, the cycloalkyl group, the aralkyl group, and the aryl group may have a substituent, Item 4. The catalyst according to any one of Items 1 to 3.
The catalyst according to any one of claims 1 to 4, wherein the alkyl group of R 1 and R 5 is a substituted or unsubstituted alkyl group having 5 to 20 carbon atoms.
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,
An aryl group having 6 to 30 carbon atoms,
The catalyst according to any one of claims 1 to 5, which is a substituted silyl group, and the alkyl group, the cycloalkyl group, the aralkyl group and the aryl group may have a substituent.
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,
The catalyst according to any one of claims 1 to 6, which is a substituted silyl group, and the alkyl group, the cycloalkyl group, the aralkyl group and the aryl group may have a substituent.
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 may have a substituent, according to any one of claims 1 to 8. The catalyst described.
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 olefins having 2 to 6 carbon atoms or for copolymerization of two or more olefins having 2 to 6 carbon atoms.
An olefin polymer production method using the catalyst according to any one of claims 1 to 11.
A complex represented by the general formula (1 ′).

(Wherein n ′ is 1 or 2,
R 1 ′ to R 12 ′ 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,
Substituted silyl groups,
Alternatively, it represents a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring. However, R 1 ′ and R 5 ′ are not simultaneously a tert-butyl group.
R 1 ′ to R 12 ′ 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 ring The formula compound residue may have a substituent.
Despite the definition of the R 1 '~ R 12', R 1 ' and R 2', R 2 'and R 3', R 3 'and R 4', 'a R 6' R 5, and R 6 ' R 7 ′, R 7 ′ and R 8 ′, R 9 ′ and R 10 ′, and R 11 ′ and R 12 ′ may be independently connected to each other to form a ring. May have a substituent.
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 ′ have a substituent. Also good.
Adjacent X ′ 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. )
R 9 'to R 12 ' are
The complex according to claim 13, which is a hydrogen atom.
R 1 ′ and R 5 ′ are each independently
A halogen atom,
An alkyl group having 5 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,
Substituted silyl groups,
Or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring, and the alkyl group, the cycloalkyl group, the aralkyl group, the aryl group, and the heterocyclic compound residue are substituted. The complex according to claim 13 or 14, which may have.
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,
The aryl group or substituted silyl group having 6 to 30 carbon atoms, wherein the alkyl group, the cycloalkyl group, the aralkyl group, and the aryl group may have a substituent. The complex according to claim 1.
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,
The complex according to any one of claims 13 to 16, which is a substituted silyl group, and the alkyl group, the cycloalkyl group, the aralkyl group and the aryl group may have a substituent.
The complex according to any one of claims 13 to 17, 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 may have a substituent, according to any one of claims 13 to 18; The complex described.
The complex according to any one of claims 13 to 19, wherein n 'is 2.
A compound represented by the general formula (2 ′).

(Wherein n ′ is 1 or 2,
R 1 ′ to R 12 ′ 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,
Substituted silyl groups,
Alternatively, it represents a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring. However, R 1 ′ and R 5 ′ are not simultaneously a tert-butyl group.
R 1 ′ to R 12 ′ 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 ring The formula compound residue may have a substituent.
Despite the definition of the R 1 '~ R 12', R 1 ' and R 2', R 2 'and R 3', R 3 'and R 4', 'a R 6' R 5, and R 6 ' R 7 ′, R 7 ′ and R 8 ′, R 9 ′ and R 10 ′, and R 11 ′ and R 12 ′ may be independently connected to each other to form a ring. May have a substituent. )
R 9 'to R 12 ' are
The compound according to claim 21, which is a hydrogen atom.
R 1 ′ and R 5 ′ are each independently
A halogen atom,
An alkyl group having 5 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,
Substituted silyl groups,
Or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring, and the alkyl group, the cycloalkyl group, the aralkyl group, the aryl group, and the heterocyclic compound residue are substituted. 23. The compound according to claim 21 or 22, which may be present.
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,
The aryl group or substituted silyl group having 6 to 30 carbon atoms, wherein the alkyl group, the cycloalkyl group, the aralkyl group, and the aryl group may have a substituent. 2. The compound according to item 1.
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,
The compound according to any one of claims 21 to 24, wherein the compound is a substituted silyl group, and the alkyl group, the cycloalkyl group, the aralkyl group, and the aryl group may have a substituent.
The compound according to any one of claims 21 to 25, wherein R 2 ', R 4 ', R 6 'and R 8 ' are hydrogen atoms.
The compound according to any one of claims 21 to 26, wherein n 'is 2.