JP2013053309A - Olefin polymerization catalyst and method for producing olefin polymer - Google Patents

Abstract

【選択図】なしAn olefin polymerization catalyst capable of producing an olefin polymer with high activity and an olefin polymer production method for polymerizing an olefin in the presence of the olefin polymerization catalyst.
An olefin polymerization catalyst obtained by contacting the following component (A) with an activating co-catalyst component (B) containing an element of Group 12 of the periodic table.
Component (A): Complex represented by the following general formula (1-1) or (1-2)

[Selection figure] None

Description

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

  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.

  In the polymerization of olefins, it is desirable that the catalyst for olefin polymerization exhibits high activity from the viewpoint of improving the production cost and reducing the ash content ratio derived from the catalyst component contained in the produced olefin polymer.

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

  On the other hand, diphenoxy titanium complex, zirconium complex and hafnium complex derived from trans-cyclooctane-1,2-dithiol have been reported (Non-patent Document 1), and among these complexes, zirconium complex is used as a catalyst. -Polymerization of hexene has been reported (Non-patent Document 2).

Toda et al., 58th Meeting of Coordination Chemistry, Abstracts 1Ab-07, September 20, 2008 Journal of American Chemical Society, 2009, Volume 131,13566-13567

WO2007 / 075299

However, the above method is still not satisfactory from the viewpoint of obtaining an olefin polymer with high activity.
The problem to be solved by the present invention is to provide an olefin polymerization catalyst capable of producing an olefin polymer with high activity, and a method for producing an olefin polymer in which olefin is polymerized in the presence of the olefin polymerization catalyst. is there.

（式中、ｎは１または２であり、
Ｍは、ジルコニウム原子またはハフニウム原子を表す。
Ｒ^１およびＲ^５は、それぞれ独立して、
水素原子、
ハロゲン原子、
炭素原子数１〜２０のアルキル基、
環を構成する炭素原子数が３〜１０のシクロアルキル基、
炭素原子数２〜２０のアルケニル基、
炭素原子数２〜２０のアルキニル基、
炭素原子数７〜３０のアラルキル基、
炭素原子数１〜２０のアルコキシ基、
炭素原子数７〜３０のアラルキルオキシ基、
炭素原子数６〜３０のアリールオキシ基、
または、置換シリル基を表す。
Ｒ^２〜Ｒ^４およびＲ^６〜Ｒ¹⁰は、それぞれ独立して、
水素原子、
ハロゲン原子、
炭素原子数１〜２０のアルキル基、
環を構成する炭素原子数が３〜１０のシクロアルキル基、
炭素原子数２〜２０のアルケニル基、
炭素原子数２〜２０のアルキニル基、
炭素原子数７〜３０のアラルキル基、
炭素原子数６〜３０のアリール基、
炭素原子数１〜２０のアルコキシ基、
炭素原子数７〜３０のアラルキルオキシ基、
炭素原子数６〜３０のアリールオキシ基、
置換シリル基、
または環を構成する炭素原子数が３〜２０のヘテロ環式化合物残基を表す。
Ｒ^１〜Ｒ^１0における上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記アルキニル基、上記アラルキル基、上記アリール基、上記アルコキシ基、上記アラルキルオキシ基、上記アリールオキシ基および上記ヘテロ環式化合物残基は置換基を有していてもよい。
上記Ｒ^１〜Ｒ¹⁰の定義に関わらず、Ｒ^１とＲ^２、Ｒ^２とＲ^３、Ｒ^３とＲ^４、Ｒ^５とＲ^６、Ｒ^６とＲ^７、Ｒ^７とＲ^８、Ｒ^２とＲ^９および/またはＲ^６とＲ^１０はそれぞれ相互に連結して環を形成してもよく、これらの環は置換基を有していてもよい。
Ｘは、それぞれ独立して、
水素原子、
ハロゲン原子、
炭素原子数１〜２０のアルキル基、
環を構成する炭素原子数が３〜１０のシクロアルキル基、
炭素原子数２〜２０のアルケニル基、
炭素原子数７〜３０のアラルキル基、
炭素原子数６〜３０のアリール基、
炭素原子数１〜２０のアルコキシ基、
炭素原子数７〜３０のアラルキルオキシ基、
炭素原子数６〜３０のアリールオキシ基、
置換シリル基、
置換アミノ基、
置換チオラート基、または
炭素原子数１〜２０のカルボキシラート基を表す。
Ｘにおける上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記アラルキル基、上記アリール基、上記アルコキシ基、上記アラルキルオキシ基および上記アリールオキシ基は置換基を有していてもよい。
隣接するＸ同士は、相互に連結して環を形成してもよい。
Ｌは中性のルイス塩基を表す。Ｌが複数ある場合は、複数のＬは同一でも異なっていてもよい。ｌは、０、１、または２である。） That is, the present invention comprises the following component (A) and an activation promoter component (B) containing an element of Group 12 of the periodic table (hereinafter sometimes referred to as “component (B)”). The present invention relates to an olefin polymerization catalyst obtained by contact.
Component (A): Complex represented by the following general formula (1-1) or general formula (1-2)

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

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

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

The complexes represented by formulas (1-1) and (1-2) will be described.

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

n is 1 or 2, preferably 2.

R ¹ and R ⁵ are preferably each independently a hydrogen atom,
Halogen atoms,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aralkyloxy group having 7 to 30 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms, or
A substituted silyl group,
More preferably, each independently a halogen atom,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
A substituted silyl group,
Particularly preferred forms of R ¹ and ^{R 5, R 1} and ^{R 5} are the same,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
Or it is a substituted silyl group.

R ⁹ and R ¹⁰ are preferably each independently
Halogen atoms,
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,
Particularly preferred forms of R ⁹ and ^{R 10} are, ^{R 9} and ^{R 10} are the same,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
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,
Halogen atoms,
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.
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, 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,
It is an alkyl group having 1 to 20 carbon atoms.

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

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

As the alkyl group having 1 to 20 carbon atoms in R ^{2 to} R ⁴ and R ^{6 to} R ⁸ , a perfluoromethyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an 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 -An alkyl group having 4 to 10 carbon atoms such as a decyl group,
More preferably, it is an alkyl group having 1 to 8 carbon atoms such as perfluoromethyl group, methyl group, isopropyl group, isobutyl group, tert-butyl group, isopentyl group, tert-pentyl group, neopentyl group, and texyl group.
More preferably, it is an alkyl group having 1 to 4 carbon atoms such as a perfluoromethyl group, a methyl group, an isopropyl group, an isobutyl group, or a tert-butyl group.

Examples of the substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms constituting the ring in R ^{1 to} R ¹⁰ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Group, 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-phenylcyclohexyl group, 1-indanyl group, 2-indanyl group, norbornyl group, bornyl group, menthyl group, 1-adamantyl group, 2-adamantyl group, 3 , 5-dimethyladamantyl group, 3,5,7-trimethyladamantyl group, 3,5-diethyladamantyl group, 3,5,7-triethyladamantyl group, 3,5-diisopropyladamantyl group, 3,5,7-tri Isopropyl adamantyl group, 3,5-diisobutyl adamant Group, 3,5,7-triisobutyladamantyl group, 3,5-diphenyladamantyl group, 3,5,7-triphenyladamantyl group, 3,5-di (p-toluyl) adamantyl group, 3,5,7 7-tri (p-toluyl) adamantyl group, 3,5-di (3,5-xylyl) adamantyl group, 3,5,7-tri (3,5-xylyl) adamantyl group may be mentioned, 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 ru 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, It is 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 ¹⁰ 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, etc. are mentioned, Preferably it is a C3-C6 alkenyl group, More preferably, they are an allyl group and a homoallyl group.

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

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

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

Examples of the substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms in R ^{1 to} R ¹⁰ include a perfluoromethoxy group, a perfluoroethoxy group, a perfluoro-n-propoxy group, a perfluoroisopropoxy group, and 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 ¹⁰ include 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 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 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 ¹⁰ include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4 -Methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, 2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) Nyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n- (Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group , (N-tetradecylphenyl) methoxy group, naphthylmethoxy group, and 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 ^{2 to} R ⁴ and R ^{6 to} R ¹⁰ include a thienyl group, a furyl group, and a 1-pyrrolyl group. 1-imidazolyl group, 1-pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, 2-isoindolyl group, 1-indolyl group, quinolyl group, dibenzo-1H-pyrrol-1-yl group, N-carbazolyl Group, preferably thienyl group, furyl group, 1-pyrrolyl group, pyridyl group, pyrimidinyl group, 2-isoindolyl group, 1-indolyl group, quinolyl group, dibenzo-1H-pyrrol-1-yl group, N- It is a carbazolyl group.

Regardless of the definition of R ^{1 to} R ¹⁰ above, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ² And R ⁹ and R ⁶ and R ¹⁰ may be connected to each other to form a ring, and the ring may have a substituent, and preferably two carbon atoms on the benzene ring are bonded to each other. And a 4- to 10-membered hydrocarbyl ring or a heterocyclic ring, which 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, preferably cyclopentene ring, cyclopentadiene ring, cyclohexene ring, benzene ring or naphthalene ring, more preferably R ¹ and R ² , R ⁵ and R ⁶ , A cyclopentene ring, a cyclohexene ring, a benzene ring, and a naphthalene ring in which R ² and R ⁹ and / or R ⁶ and R ¹⁰ are linked.

An alkyl group having 1 to 20 carbon atoms in X, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms constituting the ring, an alkenyl group having 2 to 20 carbon atoms, and 7 to 30 carbon atoms An aralkyl group, 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, The same as the above-mentioned groups in R ^{2 to} R ⁴ and R ^{6 to} R ⁸ .

  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, 2,3 Difluorothiophenoxy group, 2,4-fluorothiophenoxy group, 2,5-difluorothiophenoxy group, 2-chlorothiophenoxy group, 2,3-dichlorothiophenoxy group, 2,4-dichlorothiophenoxy group, 2, 5-dichlorothiophenoxy group, 2-bromothiophenoxy group, 3-bromothiophenoxy group, 4-bromothiophenoxy group, 2,3-dibromothiophenoxy group, 2,4-dibromothiophenoxy group, or 2,5 A hydrocarbylthiolate group having 6 to 12 carbon atoms such as a dibromothiophenoxy group, preferably a thiophenoxy group, 2,4,6-trimethylthiophenoxy group, 3,4,5-trimethylthiophenoxy group, 2, 3,4,5-tetramethylthiophenoxy group, 2,3,4,6-tetramethyl Lucio phenoxy group, 2,3,5,6 methylthiophenoxy group, penta methylthiophenoxy group, a pentafluoro thio phenoxy group.

  Examples of the 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, preferably It is a C2-C10 hydrocarbyl carboxylate group, more preferably an acetate group, a propionate group, a 2-ethylhexanoate group or a trifluoroacetate group.

  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, aralkyl groups having 7 to 10 carbon atoms, 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, an ethyl group, or n-butyl. Group, tert-butyl group, benzyl group, methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, phenoxy group dimethylamino group, diethylamino group And a, 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 ¹⁰ 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 Formula (1-1) include the following compounds, but are not intended to be limited to these compounds.

  In addition to these, compounds in which the benzyl group directly bonded to the zirconium atom of the above compound 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 exemplified. It is done.

  Furthermore, the compound which changed the zirconium atom in each said compound into the hafnium atom is also mentioned.

Further, mention may be made of the hydrogen atoms of the groups corresponding to R ³ and R ⁷ in each compound, a fluorine atom, a chlorine atom, a bromine atom, and the compound was changed to an iodine atom or a methyl group.

Furthermore, the compound which substituted the cyclooctane ring which bridge | crosslinks the sulfur atom of each said compound by the cycloheptane ring can also be mentioned.

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

In addition to these, compounds in which the benzyl group directly bonded to the zirconium atom of the above compound is changed to a chlorine atom or a methyl group are also included.

  Furthermore, the compound which changed the zirconium atom in each said compound into the hafnium atom is also mentioned.

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

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

In addition to these, compounds in which the benzyl group directly bonded to the zirconium atom of the above compound is changed to a chlorine atom are also included.

Furthermore, the groups corresponding to R ³ and R ⁷ in each of the above compounds can also include compounds modified methyl.

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

In addition to these, compounds in which the benzyl group directly bonded to the zirconium atom of the above compound is changed to a chlorine atom are also included.

  Furthermore, the compound which changed the zirconium atom in each said compound into the hafnium atom is also mentioned.

Furthermore, the groups corresponding to R ³ and R ⁷ in each of the above compounds can also include compounds modified methyl.

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

  In addition to these, compounds in which the benzyl group directly bonded to the titanium atom of the above compound 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 exemplified. It is done.

Further, the hydrogen atom a fluorine atom a group corresponding to R ³ and R ⁷ in each compound, a chlorine atom, a bromine atom, an iodine atom or can also include compounds modified methyl.

Furthermore, the compound which substituted the cyclooctane ring which bridge | crosslinks the sulfur atom of each said compound by the cycloheptane ring can also be mentioned.

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

In addition to these, compounds in which the benzyl group directly bonded to the titanium atom of the above compound is changed to a chlorine atom or a methyl group are also included.

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

Furthermore, the compound which substituted the cyclooctane ring which bridge | crosslinks the sulfur atom of each said compound by the cycloheptane ring can also be mentioned.

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

In addition to these, compounds in which the benzyl group directly bonded to the titanium atom of the above compound is changed to a chlorine atom are also included.

Furthermore, the compound which changed the group corresponded to R < ³ > and R < ⁷ > of each said compound into the methyl group can also be mentioned.

As the complex (1-2), the following compounds are particularly preferable.

In addition to these, compounds in which the benzyl group directly bonded to the titanium atom of the above compound is changed to a chlorine atom are also included.

Furthermore, the compound which changed the group corresponded to R < ³ > and R < ⁷ > of each said compound into the methyl group can also be mentioned.

Ｓｃｈｅｍｅ１
The complex represented by the general formula (1) (hereinafter, “represents the complex represented by the general formula (1-1) or (1-2)”) is, for example, by the method described in Non-Patent Document 2. Specifically, the compound represented by the general formula (2) (hereinafter referred to as “compound represented by the general formula (2-1) or (2-2)”) and the general formula The compound represented by (3) (hereinafter referred to as “compound represented by formula (3-1) or (3-2)”) can be produced using the following scheme 1 as a starting material. It should not be limited to the method.

Scheme1

M and X in the compound (3-1) are the same as M and X in the general formula (1-1). The MX _4, for _{example, Zr (CH 2 Ph) 4} , ZrCl 2 (CH 2 Ph) 2, Zr (CH 2 SiMe 3) 4, ZrF 4, Zr Cl 4, ZrBr 4, ZrI 4, Zr (OMe) ₄ , Zr (OEt) ₄ , Zr (Oi-Pr) ₄ , ZrCl ₂ (Oi-Pr) ₂ , Zr (On-Bu) ₄ , Zr (Oi-Bu) ₄ , Zr (Ot-Bu) ₄ , Zr (OPh) ₄ , Zr (NMe ₂ ) ₄ , ZrCl ₂ (NMe ₂ ) ₂ , Zr (NEt ₂ ) ₄ , Hf (CH ₂ Ph) ₄ , HfCl ₂ (CH _{2 Ph) 2, Hf (CH 2} SiMe 3) 4, HfF 4, Hf Cl 4, HfBr 4, HfI 4, Hf (OMe) 4, Hf (OEt) 4, Hf (O-i-Pr) 4, HfCl 2 _{(O-i-Pr) 2} , Hf (O-n-Bu) 4, Hf (O-i-Bu) 4, Hf (O-t _{Bu) 4, Hf (OPh)} 4, Hf (NMe 2) 4, HfCl 2 (NMe 2) 2, Hf (NEt 2) 4 and the like. Preferably, Zr (CH ₂ Ph) ₄ , ZrCl ₂ (CH ₂ Ph) ₂ , Zr (CH ₂ SiMe ₃ ) ₄ , ZrCl ₄ , ZrBr ₄ , Zr (OMe) ₄ , Zr (OEt) ₄ , Zr (O _{-i-Pr) 4, Zr (} O-i-Bu) 4, Zr (O-t-Bu) 4, Zr (OPh) 4, Zr (NMe 2) 4, ZrCl 2 (NMe 2) 2, Zr ( _{NEt 2) 4, Hf (CH} 2 Ph) 4, HfCl 2 (CH 2 Ph) 2, Hf (CH 2 SiMe 3) 4, HfCl 4, HfBr 4, Hf (OMe) 4, Hf (OEt) 4, Hf _{(O-i-Pr) 4} , Hf (O-i-Bu) 4, Hf (O-t-Bu) 4, Hf (OPh) 4, Hf (NMe 2) 4, HfCl 2 (NMe 2) 2, Hf (NEt ₂ ) ₄

X in the compound (3-2) is the same as X in the general formula (1-2). Examples of the TiX ₄ include Ti (CH ₂ Ph) ₄ , TiCl ₂ (CH ₂ Ph) ₂ , Ti (CH ₂ SiMe ₃ ) ₄ , TiF ₄ , Ti Cl ₄ , TiBr ₄ , TiI ₄ , Ti (OMe). _{4, Ti (OEt) 4,} Ti (O-i-Pr) 4, TiCl 2 (O-i-Pr) 2, Ti (O-n-Bu) 4, Ti (O-i-Bu) 4, Ti (Ot-Bu) ₄ , Ti (OPh) ₄ , Ti (NMe ₂ ) ₄ , TiCl ₂ (NMe ₂ ) ₂ , Ti (NEt ₂ ) ₄ may be mentioned. 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 organolithium reagents, Grignard reagents and metal hydrides. Specifically, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, lithium hexamethyldisilazane, potassium Hexamethyldisilazane, sodium hydride or potassium hydride can be mentioned, and preferably n-butyllithium, lithium diisopropylamide, potassium hexamethyldisilazane, sodium hydride or potassium hydride.

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

The usage-amount of a compound (2) should just be 1 molar equivalent or more with respect to a compound (3), Preferably, what is necessary is just to use it in the range of 1.0-1.5 molar equivalent. 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 between 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 compound (2) reacts with the base is in the temperature range of −100 ° C. to 150 ° C., and 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 performed up to the time when the yield of the product is 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) and the compound produced by reacting the base and the 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. is there. However, it is not intended to be limited to this range.

The reaction time between the compound (2) and the compound produced by reacting the base with the compound (3) may be up to the time when the yield of the product is 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.

ｓｃｈｅｍｅ ２

scheme 2

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

X ′ represents an anionic leaving group, for example, a halogen atom, an acetate group, a trifluoroacetate group, a benzoate group, a CF ₃ SO ₃ group, a CH ₃ SO ₃ group, a 4-MeC ₆ H ₄ SO ₃ group or a PhSO ₃ A group such as a 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]
1.0 to 4.0 equivalents, preferably 1.0 to 1.5 equivalents of the compound (5) (hereinafter represented by the general formula (5-1) or (5-2)) Compound] is reacted in the presence of a base to synthesize compound (6) (hereinafter referred to as [compound represented by formula (6-1) or (6-2)]). it can.

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

  This reaction can be carried out 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]
1.0 to 4.0 equivalents, preferably 1.0 to 1.5 equivalents of compound (7) (hereinafter represented by the general formula (7-1) or (7-2) Compound] is reacted in the presence of a base to synthesize compound (2).

  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.

  This reaction can be carried out 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 (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.

  By controlling the reaction conditions of [step 1], compound (6) and compound (7) produced in the reactor can be reacted to obtain compound (2).

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

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

In addition to these, compounds in which the groups corresponding to R ³ and R ⁷ of the above compound are substituted with a hydrogen atom or a methyl group can also be mentioned.

Specific examples of the compound represented by the formula (2-2) include, in addition to the specific examples of the compound (2-1), the following compounds and groups corresponding to R ³ and R ⁷ of these compounds: Although the compound substituted by the atom and the methyl group is mentioned, it is not the intention limited to these compounds.

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

In addition to these, compounds in which the group corresponding to R ³ or R ⁷ of the above compound is substituted with a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group can also be exemplified.

Specific examples of the compound (5-2) and the compound (7-2) include the following compounds and R ^{3 of} these compounds in addition to the specific examples of the compound (5-1) and the compound (7-1). And a compound in which a group corresponding to R ⁷ is substituted with a hydrogen atom or a methyl group.

As the activation promoter component (B) containing an element of Group 12 of the periodic table, an activation promoter component (hereinafter referred to as component (B-1) obtained by contacting the following (a) and (b): ))).
(A): Compound M ² L ² ₂ [B1] represented by the following general formula [B1]
(B): Compound E ¹ _t-1 T ¹ H [B2] represented by the following general formula [B2]
(In the above general formulas [B1] and [B2], M ² represents an atom of Group 12 of the periodic table, L ² represents a hydrogen atom, a halogen atom, a hydrocarbyl group, or a halogenated hydrocarbyl group, They may be the same or different, E1 represents an electron-withdrawing group or a group containing an electron-withdrawing group, T ¹ represents a group 15 or group 16 atom in the periodic table, t represents the valence of T1.)

In the above general formula [B1], M ² represents an atom of Group 12 of the Periodic Table.
M ² is a periodic table Group 12 atoms, e.g., a zinc atom, cadmium atom, such as mercury atom. M ² is preferably a zinc atom.

In the above general formula [B2], L ² represents a hydrogen atom, a halogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the two L ² may be the same or different from each other.
Examples of the halogen atom for L ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbyl group of L ² include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Is mentioned. Examples of the halogenated hydrhydrocarbyl group of L ² include a halogenated alkyl group having 1 to 20 carbon atoms.

The hydrocarbyl group of L ² may have a substituent, and examples of the substituent include a hydrocarbyloxy group. Examples of the hydrocarbyloxy group include an alkoxy group, an aryloxy group, an aralkyloxy group, and the like. Examples of the alkoxy group include a methoxy group and an ethoxy group, examples of the aryloxy group include a phenoxy group, and examples of the aralkyloxy group include a benzyloxy group.

Examples of the alkyl group having 1 to 20 carbon atoms of L ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n -Pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like. The alkyl group having 1 to 20 carbon atoms is preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or an isobutyl group.

Examples of the alkenyl group having 2 to 20 carbon atoms of L ² include a vinyl group, allyl group, propenyl group, 2-methyl-2-propenyl group, homoallyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, Nonenyl group, decenyl group, etc. are mentioned.

Examples of the aryl group having 6 to 20 carbon atoms of L ² include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2 , 5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3 , 6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethyl Phenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert- Butylphenyl group, isobutylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, A naphthyl group, an anthracenyl group, etc. are mentioned, Preferably it is a phenyl group as a C6-C20 aryl group.

Examples of the aralkyl group having 7 to 20 carbon atoms of L ² include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) 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-tetramethylphenyl) 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, etc. Can be mentioned. The aralkyl group having 7 to 20 carbon atoms is preferably a benzyl group.

The halogenated hydrocarbyl group of L ² may have a substituent, and examples of the substituent include a hydrocarbyloxy group. Examples of the hydrocarbyloxy group include an alkoxy group, an aryloxy group, an aralkyloxy group, and the like. Examples of the alkoxy group include a methoxy group and an ethoxy group, examples of the aryloxy group include a phenoxy group, and examples of the aralkyloxy group include a benzyloxy group.

Examples of the halogenated alkyl group having 1 to 20 carbon atoms of L ² include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, Pentafluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, and above Carbyl groups in which “fluoro” in chloro is replaced with chloro, bromo or iodo.

L ^{2 in the} above formula [B1] is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, More preferred are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and isobutyl group, and particularly preferred is ethyl group.

In the above general formula [B2], T ¹ represents an atom of Group 15 or Group 16 of the Periodic Table. Examples of the atom of group 15 of the periodic table of T ¹ include a nitrogen atom and a phosphorus atom, and examples of the atom of group 16 of the periodic table of T ¹ include an oxygen atom and a sulfur atom. T ¹ is preferably a nitrogen atom or an oxygen atom, and particularly preferably an oxygen atom. In the above general formula [B2], t represents the valence of T ¹ , t is 3 when T1 is a Group 15 atom, and t is 2 when T1 is a Group 16 atom.

E ¹ in the general formula [B2] represents an electron-withdrawing group or a group containing an electron-withdrawing group, and when a plurality of E ¹ are present, they may be the same as or different from each other. As an index of electron withdrawing property, the Hammett's rule substituent constant σ and the like are known, and a functional group having a positive Hammett's rule constant σ can be cited as an electron withdrawing group.

  Specific examples of the electron withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group, and a phenyl group. Examples of the group containing an electron-withdrawing group include a halogenated alkyl group, a halogenated aryl group, a (halogenated alkyl) aryl group, a cyanated aryl group, a nitrated aryl group, an ester group (an alkoxycarbonyl group, an aralkyloxycarbonyl group, Aryloxycarbonyl group) and the like.

Specific examples of the halogenated alkyl group include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, a diiodomethyl group, a trifluoromethyl group, a trichloromethyl group, and a tribromomethyl group. Group, triiodomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 2,2,2-triiodoethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,3,3,3-pentabromopropyl group, 2,2,3 , 3,3-pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 2,2,2-trichloro-1-trichloromethyl Ethyl group, 2,2,2-tribromo-1-tribromomethylethyl group, 2,2,2-triiodo-1-triiodomethylethyl group, 1,1-bis (trifluoromethyl) -2,2, 2-trifluoroethyl group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group, 1,1-bis (tribromomethyl) -2,2,2-tribromoethyl group, 1 , 1-bis (triiodomethyl) -2,2,2-triiodoethyl group and the like.

Specific examples of the halogenated aryl group include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3 -Bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 2,6-dichlorophenyl Group, 3,5-dichlorophenyl group, 2,6-dibromophenyl group, 3,5-dibromophenyl group, 2,6-diiodophenyl group, 3,5-diiodophenyl group, 2,4,6-tri Fluorophenyl group, 2,4,6-trichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-triiodophenol Group, pentafluorophenyl group, pentachlorophenyl group, pentabromophenyl group, penta-iodophenyl group, and the like.

  Specific examples of the (halogenated alkyl) aryl group include 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2,6-bis (tri Fluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group and the like.

  Specific examples of the cyanated aryl group include 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group and the like.

  Specific examples of the nitrated aryl group include 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group and the like.

  Specific examples of the ester group include methoxycarbonyl group, ethoxycarbonyl group, normal propoxycarbonyl group, isopropoxycarbonyl group, phenoxycarbonyl group, trifluoromethoxycarbonyl group, pentafluorophenoxycarbonyl group and the like.

E ¹ is preferably a halogenated hydrocarbyl group, more preferably a halogenated alkyl group or a halogenated aryl group. More preferably, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,2-trimethyl Fluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 4-fluorophenyl group, 2,6-difluorophenyl group, 3.5- Difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, 2,2,2-trichloro Ethyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,2-trichloro-1-trichloromethylethyl group, 1,1-bis ( Trichloromethyl) -2,2,2-trichloroethyl group, 4-chlorophenyl group, 2,6-dichlorophenyl group, 3.5-dichlorophenyl group, 2,4,6-trichlorophenyl group, or pentachlorophenyl group; Particularly preferred is a fluoroalkyl group or a fluoroaryl group, and most preferred is a 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2, 2-trifluoroethyl group, 3,4,5-trifluorophenyl group, or pentafluorophenyl group.

Specific examples of the compound (a) are as follows when M ² is a zinc atom: dimethyl zinc, diethyl zinc, dipropyl zinc, dinormal butyl zinc, diisobutyl zinc, dinormal hexyl zinc, diallyl zinc, bis (Cyclopentadienyl) zinc and other dialkyl zinc, diphenyl zinc, dinaphthyl zinc, bis (pentafluorophenyl) zinc and other diaryl zinc, methyl zinc chloride, ethyl zinc chloride, propyl zinc chloride, normal butyl zinc chloride, isobutyl zinc chloride , Normal hexyl chloride, methyl zinc bromide, ethyl zinc bromide, propyl zinc bromide, normal butyl zinc bromide, isobutyl zinc bromide, normal hexyl bromide zinc, methyl zinc iodide, ethyl zinc iodide, iodide Propyl zinc, normal butyl zinc iodide, isobutyl iodide Examples thereof include alkyl zinc halides such as til zinc and normal hexyl zinc iodide, zinc fluoride, zinc chloride, zinc bromide and zinc iodide.

  The compound (a) is preferably dialkylzinc, more preferably dimethylzinc, diethylzinc, dipropylzinc, dinormalbutylzinc, diisobutylzinc, dinormalhexylzinc, diallylzinc or bis (cyclopentadienyl) zinc. Particularly preferred is dimethyl zinc or diethyl zinc.

  Specific examples of the compound (b) include amines such as di (fluoromethyl) amine, di (chloromethyl) amine, di (bromomethyl) amine, di (iodomethyl) amine, bis (difluoromethyl) amine, bis (Dichloromethyl) amine, bis (dibromomethyl) amine, bis (diiodomethyl) amine, bis (trifluoromethyl) amine, bis (trichloromethyl) amine, bis (tribromomethyl) amine, bis (triiodomethyl) amine, Bis (2,2,2-trifluoroethyl) amine, bis (2,2,2-trichloroethyl) amine, bis (2,2,2-tribromoethyl) amine, bis (2,2,2-trimethyl) Iodoethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine, bis (2,2,3,3) 3-pentachloropropyl) amine, bis (2,2,3,3,3-pentabromopropyl) amine, bis (2,2,3,3,3-pentaiodopropyl) amine, bis (2,2, 2-trifluoro-1-trifluoromethylethyl) amine, bis (2,2,2-trichloro-1-trichloromethylethyl) amine, bis (2,2,2-tribromo-1-tribromomethylethyl) amine Bis (2,2,2-triiodo-1-triiodomethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine, bis (1,1 -Bis (trichloromethyl) -2,2,2-trichloroethyl) amine, bis (1,1-bis (tribromomethyl) -2,2,2-tribromoethyl) amine, bis (1,1 Bis (triiodomethyl) -2,2,2-triiodoethyl) amine, bis (2-fluorophenyl) amine, bis (3-fluorophenyl) amine, bis (4-fluorophenyl) amine, bis (2- Chlorophenyl) amine, bis (3-chlorophenyl) amine, bis (4-chlorophenyl) amine, bis (2-bromophenyl) amine, bis (3-bromophenyl) amine, bis (4-bromophenyl) amine, bis (2 -Iodophenyl) amine, bis (3-iodophenyl) amine, bis (4-iodophenyl) amine, bis (2,6-difluorophenyl) amine, bis (3,5-difluorophenyl) amine, bis (2, 6-dichlorophenyl) amine, bis (3,5-dichlorophenyl) amine, bis (2,6-dibromophenyl) Enyl) amine, bis (3,5-dibromophenyl) amine, bis (2,6-diiodophenyl) amine, bis (3,5-diiodophenyl) amine, bis (2,4,6-trifluorophenyl) ) Amine, bis (2,4,6-trichlorophenyl) amine, bis (2,4,6-tribromophenyl) amine, bis (2,4,6-triiodophenyl) amine, bis (pentafluorophenyl) Amine, bis (pentachlorophenyl) amine, bis (pentabromophenyl) amine, bis (pentaiodophenyl) amine, bis (2- (trifluoromethyl) phenyl) amine, bis (3- (trifluoromethyl) phenyl) amine Bis (4- (trifluoromethyl) phenyl) amine, bis (2,6-di (trifluoromethyl) phenyl) Bis (3,5-di (trifluoromethyl) phenyl) amine, bis (2,4,6-tri (trifluoromethyl) phenyl) amine, bis (2-cyanophenyl) amine, (3-cyanophenyl) ) Amine, bis (4-cyanophenyl) amine, bis (2-nitrophenyl) amine, bis (3-nitrophenyl) amine, bis (4-nitrophenyl) amine and the like. Moreover, the phosphine compound by which the nitrogen atom was substituted by the phosphorus atom can be illustrated similarly. These phosphine compounds are compounds represented by rewriting the amine of the above-mentioned specific examples to phosphine.

  Specific examples of the compound (b) include alcohols such as fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodethanol, trifluoromethanol, trichloromethanol, tribromomethanol, Iodomethanol, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2,2,2-tribromoethanol, 2,2,2-triiodoethanol, 2,2,3,3 3-pentafluoropropanol, 2,2,3,3,3-pentachloropropanol, 2,2,3,3,3-pentabromopropanol, 2,2,3,3,3-pentaiodopropanol, 2, 2,2-trifluoro-1-trifluoromethyl Tanol, 2,2,2-trichloro-1-trichloromethylethanol, 2,2,2-tribromo-1-tribromomethylethanol, 2,2,2-triiodo-1-triiodomethylethanol, 1,1- Bis (trifluoromethyl) -2,2,2-trifluoroethanol, 1,1-bis (trichloromethyl) -2,2,2-trichloroethanol, 1,1-bis (tribromomethyl) -2,2 , 2-tribromoethanol, 1,1-bis (triiodomethyl) -2,2,2-triiodoethanol and the like. Moreover, the thiol compound by which the oxygen atom was substituted by the sulfur atom can be illustrated similarly. These thiol compounds are compounds represented by rewriting methanol in the above specific examples to methanethiol, ethanol to ethanethiol, and propanol to propanethiol.

  Specific examples of the compound (b) include phenols such as 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3- Bromophenol, 4-bromophenol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,6-dichlorophenol, 3,5-dichlorophenol 2,6-dibromophenol, 3,5-dibromophenol, 2,6-diiodophenol, 3,5-diiodophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol 2,4,6-trichlorophenol, 2,4,6-to Bromophenol, 2,4,6-triiodophenol, pentafluorophenol, pentachlorophenol, pentabromophenol, pentaiodophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- ( Trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol, 2-cyanophenol, 3 -Cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol and the like. Moreover, the thiophenol compound by which the oxygen atom was substituted by the sulfur atom can be illustrated similarly. These thiophenol compounds are compounds represented by rewriting phenol of the above-mentioned specific examples with thiophenol.

  Specific examples of the compound (b) include carboxylic acids such as 2-fluorobenzoic acid, 3-fluorobenzoic acid, 4-fluorobenzoic acid, 2,3-difluorobenzoic acid, 2,4-difluorobenzoic acid, 2,5 -Difluorobenzoic acid, 2,6-difluorobenzoic acid, 2,3,4-trifluorobenzoic acid, 2,3,5-trifluorobenzoic acid, 2,3,6-trifluorobenzoic acid, 2,4, 5-trifluorobenzoic acid, 2,4,6-trifluorobenzoic acid, 2,3,4,5-tetrafluorobenzoic acid, 2,3,4,6-tetrafluorobenzoic acid, pentafluorobenzoic acid, fluoro Acetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropanoic acid, heptafluorobutanoic acid, 1,1-bis (trifluoromethyl) -2,2,2-trifluoro Etc. Roetanoikku acid, and the like.

  Specific examples of the compound (b) include sulfonic acids such as fluoromethanesulfonic acid, difluoromethanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, 1,1-bis (trifluoromethyl). Examples include -2,2,2-trifluoroethanesulfonic acid.

  The compound (b) is preferably a bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine. ) Amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine, or bis (Pentafluorophenyl) amine and alcohols include trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1 -Trifluoromethylethanol, or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, phenols Are 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol , Pentafluorophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis ( Trifluoromethyl) phenol or 2,4,6-tris (trifluoromethyl) phenol and carboxylic acids are pentafluorobenzoic acid, or trifluoroacetic acid and sulfonic acids are trifluoromethanesulfonic acid.

  More preferably, the compound (b) is bis (trifluoromethyl) amine, bis (pentafluorophenyl) amine, trifluoromethanol, 2,2,2-trifluoro-1-trifluoromethylethanol, 1,1-bis. (Trifluoromethyl) -2,2,2-trifluoroethanol, 4-fluorophenol, 2,6-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, pentafluoro Phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, or 2,4,6-tris (trifluoromethyl) phenol, more preferably 2,2,2- Trifluoro-1-trifluoromethylethanol, 1,1-bis (trifluoro Chill) -2,2,2-furo ethanol, 3,4,5-fluorophenol or pentafluorophenol.

  The contact between the compounds (a) and (b) is preferably carried out in an inert gas atmosphere. The temperature at the time of contacting is usually −100 to 300 ° C., preferably −80 to 200 ° C.

  The time for contacting is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours. In addition, such treatment may use a solvent, or may directly contact these compounds without using a solvent.

  As the solvent, a solvent inert to the compounds (a) and (b) and their contact products is used. Examples of the solvent include nonpolar solvents and polar solvents.

  Examples of the nonpolar solvent include an aliphatic hydrocarbyl solvent, an alicyclic hydrocarbyl solvent, and an aromatic hydrocarbyl solvent. Examples of the polar solvent include halide solvents, ether solvents, carbonyl solvents, phosphoric acid derivatives, nitrile solvents, nitro compounds, amine solvents, sulfur compounds and the like.

  Examples of the aliphatic hydrocarbyl solvent include butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, and the like. Examples of the alicyclic hydrocarbyl solvent include cyclohexane and the like. Examples of the aromatic hydrocarbyl solvent include benzene, toluene, xylene and the like. Examples of the halide solvent include dichloromethane, difluoromethane, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, Examples include bromobenzene and o-dichlorobenzene. Examples of the ether solvent include dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxy Ethyl) ether, tetrahydrofuran, tetrahydropyran and the like. Examples of the carbonyl solvent include acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2. -Pyrrolidone etc. are mentioned. Examples of phosphoric acid derivatives include hexamethylphosphoric triamide, triethyl phosphate, and the like. Examples of the nitrile solvent include acetonitrile, propionitrile, succinonitrile, benzonitrile and the like. Examples of the nitro compound include nitromethane and nitrobenzene. Examples of the amine solvent include pyridine, piperidine, morpholine and the like. Examples of the sulfur compound include dimethyl sulfoxide and sulfolane.

  The solvent is preferably the above-mentioned aliphatic hydrocarbyl solvent, alicyclic hydrocarbyl solvent, aromatic hydrocarbyl solvent or ether solvent.

  The amount of the compounds (a) and (b) to be used in contact can be such that the compound (b) can be used in an arbitrary ratio with respect to 1 mol of the compound (a), but is preferably represented by the compound (b). The compound is greater than 0 mol and less than or equal to 100 mol, more preferably the compound represented by compound (b) is greater than 0 mol and less than or equal to 20 mol, and more preferably, the compound represented by compound (b) is More than 0 mol and not more than 10 mol, particularly preferably the compound represented by compound (b) is more than 0 mol and not more than 5 mol, and most preferably, the compound represented by compound (b) is 0 mol. More than 4 moles.

  Component (B-1) may be a compound (a) and a compound (b), as a result of contact between the compound (a) and the compound (b). Good. However, it is preferable to carry out a washing treatment to remove unreacted substances in advance. The solvent at that time may be the same as or different from the solvent at the time of contact. Such cleaning treatment is preferably carried out in an inert gas atmosphere. The temperature at the time of performing the washing treatment is usually −100 to 300 ° C., preferably −80 to 200 ° C. The time for performing the washing treatment is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

  In addition, after the contact treatment between the compound (a) and the compound (b) and the washing treatment for removing unreacted substances, the solvent is distilled off from the product, and then, at a temperature of 0 ° C. or higher, under reduced pressure for 1 hour to 24 hours. It is preferable to perform drying. More preferably, it is 1 hour to 24 hours at a temperature of 0 ° C. to 200 ° C., more preferably 1 hour to 24 hours at a temperature of 10 ° C. to 200 ° C., and particularly preferably 1 at a temperature of 10 ° C. to 160 ° C. Time to 18 hours, most preferably 1 hour to 18 hours at a temperature of 15 ° C to 160 ° C.

Specific examples of the production method of component (B-1) are shown in more detail below for the case where compound (a) is diethyl zinc and compound (b) is a halogenated alcohol.
Toluene is used as a solvent, diethylzinc hexane solution is added, cooled to 0 ° C., 2 to 4 mol of halogenated alcohol is added dropwise to diethylzinc, and then 90 ° C. to 120 ° C. for 10 minutes to Stir for 24 hours. After distilling off volatile substances under reduced pressure, drying is performed at room temperature under reduced pressure for 1 to 20 hours. Thus, component (B-1) can be produced.

Component (B-1) is a compound represented by the following general formula (8), a compound represented by the following general formula (9), a compound ( The aggregate of 8), the aggregate of compound (9) and / or the aggregate of compound (8) and compound (9) are obtained.

As an activation promoter component (B) containing an element belonging to Group 12 of the periodic table, an activation promoter component (hereinafter referred to as component (B-2) obtained by contacting the following (a) to (c): )))).
(A): Compound M ² L ² ₂ [B1] represented by the following general formula [B1]
(B): Compound E ¹ _t-1 T ¹ H [B2] represented by the following general formula [B2]
(C): Compound E ² _t-1 T ¹ H ₂ [B3] represented by the following general formula [B3]
(In the above general formulas [B1] to [B3], M ² represents an atom of Group 12 of the periodic table, L represents a hydrogen atom, a halogen atom, a hydrocarbyl group, or a halogenated hydrocarbyl group, and two L ² are They may be the same or different from each other, E ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group, E ² represents a hydrocarbyl group or a halogenated hydrocarbyl group, and E ² represents When there are a plurality of them, they may be the same or different from each other, and two T ^{1 s} independently represent atoms of Group 15 or Group 16 of the periodic table, and t represents the valence of T ^1. Represent)

In the above general formula [B3], E ² represents a hydrocarbyl group or a halogenated hydrocarbyl group, and when a plurality of E ² are present, they may be the same as or different from each other. The hydrocarbyl group in E ² is preferably an alkyl group, an aryl group, or an aralkyl group, and the same hydrocarbyl group as described for L ² in the general formula [B1] is used. Examples of the halogenated hydrocarbyl group in E ² include a halogenated alkyl group, a halogenated aryl group, and a (halogenated alkyl) aryl group. Specific examples of the electron-withdrawing group in E ¹ of the above general formula [B2] The same halogenated alkyl groups, halogenated aryl groups, and (halogenated alkyl) aryl groups as those mentioned above are used.

E ² in the above general formula [B3] is preferably a halogenated hydrocarbyl group, more preferably a fluorinated hydrocarbyl group.

  The compound (c) is preferably water, hydrogen sulfide, alkylamine, arylamine, aralkylamine, halogenated alkylamine, halogenated arylamine, or (halogenated alkyl) arylamine, more preferably water, hydrogensulfide. , Methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-pentylamine, neopentylamine, amylamine, n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, n-eicosylamine, allylamine, cyclopentadienylamine, aniline, 2-tolylamine, 3-tolylamine, 4-tolylamine, 2,3-kis Rylamine, 2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine, 3,4-xylylamine, 3,5-xylylamine, 2,3,4-trimethylaniline, 2,3,5-trimethylaniline, 2,3,4-trimethylaniline, 2,4,6-trimethylaniline, 3,4,5-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,4,6-tetramethylaniline 2,3,5,6-tetramethylaniline, pentamethylaniline, ethylaniline, n-propylaniline, isopropylaniline, n-butylaniline, sec-butylaniline, tert-butylaniline, n-pentylaniline, neopentyl Aniline, n-hexylaniline, n-octylaniline, n-decylaniline n- dodecyl aniline, n- tetradecyl aniline, naphthylamine, anthracenyl amine,

Benzylamine, (2-methylphenyl) methylamine, (3-methylphenyl) methylamine, (4-methylphenyl) methylamine, (2,3-dimethylphenyl) methylamine, (2,4-dimethylphenyl) methyl Amine, (2,5-dimethylphenyl) methylamine, (2,6-dimethylphenyl) methylamine, (3,4-dimethylphenyl) methylamine, (3,5-dimethylphenyl) methylamine, (2,3 , 4-Trimethylphenyl) methylamine, (2,3,5-trimethylphenyl) methylamine, (2,3,6-trimethylphenyl) methylamine, (3,4,5-trimethylphenyl) methylamine, (2 , 4,6-trimethylphenyl) methylamine, (2,3,4,5-tetramethylphenyl) methylamine , (2,3,4,6-tetramethylphenyl) methylamine, (2,3,5,6-tetramethylphenyl) methylamine, (pentamethylphenyl) methylamine, (ethylphenyl) methylamine, (n -Propylphenyl) methylamine, (isopropylphenyl) methylamine, (n-butylphenyl) methylamine, (sec-butylphenyl) methylamine, (tert-butylphenyl) methylamine, (n-pentylphenyl) methylamine, (Neopentylphenyl) methylamine, (n-hexylphenyl) methylamine, (n-octylphenyl) methylamine, (n-decylphenyl) methylamine, (n-tetradecylphenyl) methylamine, naphthylmethylamine, anthra Cenylmethylamine, fluorome Ruamine, chloromethylamine, bromomethylamine, iodomethylamine, difluoromethylamine, dichloromethylamine, dibromomethylamine, diiodomethylamine, trifluoromethylamine, trichloromethylamine, tribromomethylamine, triiodomethylamine, 2,2,2-trifluoroethylamine, 2,2,2-trichloroethylamine, 2,2,2-tribromoethylamine, 2,2,2-triiodoethylamine, 2,2,3,3,3-penta Fluoropropylamine, 2,2,3,3,3-pentachloropropylamine, 2,2,3,3,3-pentabromopropylamine, 2,2,3,3,3-pentaiodopropylamine, 2 , 2,2-trifluoro-1-trifluoromethylethylamine, 2,2 , 2-trichloro-1-trichloromethylethylamine, 2,2,2-tribromo-1-tribromomethylethylamine, 2,2,2-triiodo-1-triiodomethylethylamine, 1,1-bis (trifluoromethyl) ) -2,2,2-trifluoroethylamine, 1,1-bis (trichloromethyl) -2,2,2-trichloroethylamine, 1,1-bis (tribromomethyl) -2,2,2-tribromo Ethylamine, 1,1-bis (triiodomethyl) -2,2,2-triiodoethylamine,

2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 2-iodoaniline, 3-iodoaniline, 4-iodoaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,6-dichloroaniline, 3,5-dichloroaniline, 2,6-dibromoaniline, 3,5-dibromo Aniline, 2,6-diiodoaniline, 3,5-diiodoaniline, 2,4,6-trifluoroaniline, 2,4,6-trichloroaniline, 2,4,6-tribromoaniline, 2,4 , 6-triiodoaniline, pentafluoroaniline, pentachloroaniline, pentabromoaniline, pentaio Aniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-di (trifluoromethyl) aniline, 3,5-di (trifluoromethyl) ) Aniline or 2,4,6-tri (trifluoromethyl) aniline.

More preferably, water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-octylamine, aniline, 2,6-xylylamine, 2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine, trifluoromethylamine, pentafluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, perfluorooctylamine Perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (tri Fluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, or 2,4,6-tris (trifluoromethyl) aniline, particularly preferably Water, trifluoromethylamine, perfluorobutylamine, perfluorooctylamine, perfluoropentadecylamine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline 2,4,6-trifluoroaniline, pen Fluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoro) Methyl) aniline or 2,4,6-tris (trifluoromethyl) aniline, most preferably water or pentafluoroaniline.

Component (B-2) is a component obtained by bringing the compounds (a), (b) and (c) into contact with each other. The order in which (a), (b) and (c) are brought into contact is not particularly limited. For example, the following order can be adopted.
(1) A method of contacting (c) after contacting (a) and (b).
(2) A method of contacting (b) after contacting (a) and (c).
(3) A method of contacting (a) after contacting (b) and (c).
The contact order is preferably (1) or (2), more preferably (1), that is, the component (B-2) is preferably obtained by bringing (a) and (b) into contact with each other. A component obtained by bringing the contact product into contact with (c), or a compound obtained by contacting (b) with the contact product obtained by bringing (a) and (c) into contact with each other, more preferably Is a component obtained by contacting (c) with a contact product obtained by contacting (a) and (b).

  The contact of the compounds represented by (a), (b) and (c) is preferably performed in an inert gas atmosphere. The temperature at the time of contacting is usually −100 to 300 ° C., preferably −80 to 200 ° C.

  The time for contacting is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours. In addition, such treatment may use a solvent, or may directly contact these compounds without using a solvent.

  As the solvent, a solvent inert to the compounds (a), (b), (c) and the components obtained by contacting them is used. Examples of the solvent include nonpolar solvents and polar solvents.

  Examples of the nonpolar solvent include an aliphatic hydrocarbyl solvent, an alicyclic hydrocarbyl solvent, and an aromatic hydrocarbyl solvent. Examples of the polar solvent include halide solvents, ether solvents, carbonyl solvents, phosphoric acid derivatives, nitrile solvents, nitro compounds, amine solvents, sulfur compounds and the like.

  Examples of the aliphatic hydrocarbyl solvent include butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, and the like. Examples of the alicyclic hydrocarbyl solvent include cyclohexane and the like. Examples of the aromatic hydrocarbyl solvent include benzene, toluene, xylene and the like. Examples of the halide solvent include dichloromethane, difluoromethane, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, Examples include bromobenzene and o-dichlorobenzene. Examples of the ether solvent include dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxy Ethyl) ether, tetrahydrofuran, tetrahydropyran and the like. Examples of the carbonyl solvent include acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2. -Pyrrolidone etc. are mentioned. Examples of phosphoric acid derivatives include hexamethylphosphoric triamide, triethyl phosphate, and the like. Examples of the nitrile solvent include acetonitrile, propionitrile, succinonitrile, benzonitrile and the like. Examples of the nitro compound include nitromethane and nitrobenzene. Examples of the amine solvent include pyridine, piperidine, morpholine and the like. Examples of the sulfur compound include dimethyl sulfoxide and sulfolane.

  The solvent is preferably the above-mentioned aliphatic hydrocarbyl solvent, alicyclic hydrocarbyl solvent, aromatic hydrocarbyl solvent or ether solvent.

The amount of each compound used is not particularly limited. When the molar ratio of the amount of each compound used is (a) :( b) :( c) = 1: y: z, the y and z are as follows: It is preferable that the expressions (9) to (11) are satisfied.
| 2-y-2z | ≦ 1 (9)
0 <y <2 (10)
0 <z (11)
In the above formulas (9) and (10), y is more preferably 0.20 to 1.80, particularly preferably 0.25 to 1.50, and most preferably 0.50 to 1. .00 number. Z in the above formula (9) is a number determined by y and the above formulas (9) and (11), and more preferably satisfies the following formula (12).
0 <z <1 (12)

  As a result of such contact treatment, the components (B-2) may remain as raw materials (a), (b), and (c) as unreacted materials. Further, after such contact treatment, it is preferable to distill off the solvent from the product and perform drying at a temperature of 25 ° C. or higher for 1 hour or longer under reduced pressure. More preferably, drying is performed at a temperature of 60 to 200 ° C. for 1 to 24 hours, most preferably at a temperature of 80 to 160 ° C. for 4 to 18 hours.

  As a result of such contact treatment, the components (B-2) may remain as raw materials (a), (b), and (c) as unreacted materials. However, it is preferable to carry out a washing treatment to remove unreacted substances in advance. The solvent at that time may be the same as or different from the solvent at the time of contact. Such cleaning treatment is preferably carried out in an inert gas atmosphere. The temperature at the time of performing the washing treatment is usually −100 to 300 ° C., preferably −80 to 200 ° C. The time for performing the washing treatment is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

  Further, after contact with the raw materials (a), (b) and (c) and a washing treatment to remove unreacted substances, the solvent is distilled off from the product, and then the pressure is reduced to 1 at a temperature of 0 ° C. or higher. It is preferable to perform drying for 24 hours. More preferably, it is 1 hour to 24 hours at a temperature of 0 ° C. to 200 ° C., more preferably 1 hour to 24 hours at a temperature of 10 ° C. to 200 ° C., and particularly preferably 1 at a temperature of 10 ° C. to 160 ° C. Time to 18 hours, most preferably 1 hour to 18 hours at a temperature of 15 ° C to 160 ° C.

  Specific examples of the production method of the component (B-2) will be described in more detail below when the compound (a) is diethyl zinc, the compound (b) is pentafluorophenol, and the compound (c) is water. Show. Tetrahydrofuran was used as a solvent, hexane solution of diethylzinc was added thereto, cooled to 0 ° C., equimolar amount of pentafluorophenol was added dropwise to diethylzinc, and the mixture was stirred at room temperature for 10 minutes to 24 hours. Thereafter, 0.5-fold molar amount of water is added dropwise to diethyl zinc, and the mixture is stirred at room temperature for 10 minutes to 24 hours. Thereafter, the solvent is distilled off, followed by drying at 120 ° C. under reduced pressure for 8 hours. Thus, component (B-2) can be produced.

  In addition, the polymerization catalyst of the present invention may contain a carrier, and any method may be used as a method for supporting the polymer on the carrier, but a method in which the component (B) is supported on the carrier is preferable. More preferably, the component (B-2) is supported on a carrier. (Hereinafter, component (B-2) supported on the carrier is referred to as component (B-3)). As the carrier, a porous material having a uniform particle diameter is preferable, and an inorganic material or an organic polymer is preferably used.

Examples of inorganic substances that can be used for the carrier include inorganic oxides and magnesium compounds, and clays and clay minerals can be used as long as they do not hinder. These may be mixed and used.
Specific examples of the inorganic oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, and mixtures thereof such as SiO ₂ — Examples thereof include MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , and SiO ₂ —TiO ₂ —MgO. Of these inorganic oxides, SiO ₂ and / or Al ₂ O ₃ are preferred. The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride Allyoxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium; phenoxymagnesium, dimethylphenoxymagnesium, etc. Allyloxymagnesium; Magne Laurate Um, and the like can be exemplified carboxylates of magnesium such as magnesium stearate.
Among these, magnesium halide or alkoxymagnesium is preferable, and magnesium chloride or butoxymagnesium is more preferable.

Examples of clay or clay mineral include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, bayophyllite, talc, unmo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite, Halloysite and the like.
Among these, preferred are smectite, montmorillonite, hectorite, laponite and saponite, and more preferred are montmorillonite and hectorite.

  These inorganic substances do not require removal of moisture before use, but those dried by heat treatment are preferably used. The heat treatment is usually performed at a temperature of 100 to 1,500 ° C., preferably 100 to 1,000 ° C., more preferably 200 to 800 ° C. After heating, for example, a method in which a dried inert gas (for example, nitrogen or argon) is allowed to flow for several hours or more at a constant flow rate, or a method in which the pressure is reduced for several hours can be mentioned. It will never be done.

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

As the organic polymer that can be used for the carrier, any organic polymer may be used, and plural kinds of organic polymers may be used as a mixture. As the organic polymer, a polymer having a non-proton donating Lewis basic functional group is preferable.

  The non-proton-donating Lewis basic functional group is not particularly limited as long as it is a functional group having a Lewis base portion that does not have an active hydrogen atom. Specific examples include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted group. Indazolyl group, nitrile group, azide group, N-substituted imino group, N, N-substituted amino group, N, N-substituted aminooxy group, N, N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group , Furyl group, carbonyl group, thiocarbonyl group, alkoxy group, alkyloxycarbonyl group, N, N-substituted carbamoyl group, thioalkoxy group, substituted sulfinyl group, substituted sulfonyl group, substituted sulfonic acid group and the like. Preferred is a heterocyclic group, and more preferred is an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring. Particularly preferred are a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, and most preferred is a pyridyl group. These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.

  The amount of such a non-proton-donating Lewis basic functional group is not particularly limited, but is preferably 0.01 to 50 mmol / g as a molar amount of the functional group per unit gram of the polymer, more preferably 0.8. 1-20 mmol / g.

  The polymer having such a functional group is obtained by, for example, homopolymerizing a monomer having a non-proton-donating Lewis basic functional group and one or more polymerizable unsaturated groups, or this and another one or more. It can be obtained by copolymerizing with a monomer having a polymerizable unsaturated group. At this time, it is preferable to copolymerize together a crosslinkable monomer having two or more polymerizable unsaturated groups.

  Such a monomer having a non-proton-donating Lewis basic functional group and one or more polymerizable unsaturated groups includes a functional group having a Lewis base moiety having no active hydrogen atom and one or more polymerizable unsaturated groups. Mention may be made of monomers having a saturated group. Examples of such polymerizable unsaturated groups include alkenyl groups such as vinyl groups and allyl groups, and alkynyl groups such as ethyne groups.

  Specific examples of the monomer having a functional group having a Lewis base moiety having no active hydrogen atom and one or more polymerizable unsaturated groups include vinylpyridine, vinyl (N-substituted) imidazole, and vinyl (N-substituted) indazole. Can be mentioned.

Examples of other monomers having one or more polymerizable unsaturated groups include ethylene, α-olefin, aromatic vinyl compounds and the like. Specific examples include ethylene, propylene, butene-1, hexene-1, 4 -Methyl-pentene-1, styrene and the like. Preferred is ethylene or styrene. Two or more of these monomers may be used.
Specific examples of the crosslinkable monomer having two or more polymerizable unsaturated groups include divinylbenzene.

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

  When supplying each catalyst component using the said hydrocarbyl solvent, the density | concentration of the zinc atom contained in a component (B) is 0.001-100 mol / liter normally, Preferably, it is 0.01-10 mol / liter. Liters. The density | concentration of a component (B) is 0.00001-1 mol / liter normally, Preferably, it is 0.0001-0.1 mol / liter.

For the olefin polymerization catalyst of the present invention, a known organoaluminum compound (hereinafter sometimes referred to as “component (C)”) may be used. Preferably, it is an organoaluminum compound represented by the following general formula (13).
(R ¹¹ ) _d Al (Y ¹ ) _3-d (13)
(Wherein R ¹¹ represents a hydrocarbyl group having 1 to 24 carbon atoms, Y ¹ represents a hydrogen atom, a halogen atom, or a hydrocarbyloxy group having 1 to 24 carbon atoms; Represents an integer, when d is 2 or 3, a plurality of R ¹¹ may be the same or different, and when d is 1, two Y ¹ are the same or different May be.)

The hydrocarbyl group having 1 to 24 carbon atoms of R ¹¹ in the general formula (13) is preferably an alkyl group having 1 to 24 carbon atoms. Examples of the alkyl group having 1 to 24 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group, 2-methylhexyl group, and n-octyl group. Preferably, they are an ethyl group, n-butyl group, isobutyl group, n-hexyl group or n-octyl group.

Examples of the halogen atom for Y ¹ in the general formula (13) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
Examples of the hydrocarbyloxy group having 1 to 24 carbon atoms in Y ¹ include an alkoxy group having 1 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and an aralkyloxy group having 7 to 24 carbon atoms. Is mentioned.

Examples of the alkoxy group having 1 to 24 carbon atoms of Y ¹ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, and an n-pentoxy group. Group, n-icosoxy group and the like, and preferred are methoxy group, ethoxy group and tert-butoxy group.

Examples of the aryloxy group having 6 to 24 carbon atoms of Y ¹ include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4 -Dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3 , 5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3 , 4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group Pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, Examples include an n-decylphenoxy group, an n-tetradecylphenoxy group, a naphthoxy group, and an anthracenoxy group.

Examples of the aralkyloxy group having 7 to 24 carbon atoms of Y ¹ include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, ( 2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) ) Methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) ) Methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5- (Trimethylphenyl) methoxy group, (2,3,4,5-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-hexyl) Phenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group, etc., preferably Benzyloxy group.

  Examples of the organoaluminum compound represented by the general formula (13) include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, dialkylaluminum hydride, alkyl (dialkoxy) aluminum, dialkyl (alkoxy) aluminum, and alkyl (diaryl). Oxy) aluminum, dialkyl (aryloxy) aluminum and the like.

  Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.

  Examples of the dialkylaluminum chloride include dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, and di-n-hexylaluminum chloride.

  Examples of the alkyl aluminum dichloride include methyl aluminum dichloride, ethyl aluminum dichloride, n-propyl aluminum dichloride, n-butyl aluminum dichloride, isobutyl aluminum dichloride, n-hexyl aluminum dichloride and the like.

  Examples of the dialkylaluminum hydride include dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, and di-n-hexylaluminum hydride.

  Examples of the alkyl (dialkoxy) aluminum include methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, and methyl (di-tert-butoxy) aluminum.

  Examples of the dialkyl (alkoxy) aluminum include dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, and methyl (tert-butoxy) aluminum.

  Examples of the alkyl (diaryloxy) aluminum include methyl (diphenoxy) aluminum, methyl bis (2,6-diisopropylphenoxy) aluminum, and methyl bis (2,6-diphenylphenoxy) aluminum.

Examples of the dialkyl (aryloxy) aluminum include dimethyl (phenoxy) aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum, and dimethyl (2,6-diphenylphenoxy) aluminum.
These organoaluminum compounds may be used alone or in combination of at least two kinds.

  The organoaluminum compound is preferably trialkylaluminum, more preferably trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum. More preferred is triisobutylaluminum or tri-n-octylaluminum.

In the olefin polymerization catalyst of the present invention, the amount of the group 12 atom contained in the component (B) is usually 1 to 1,000,000 mol with respect to 1 mol of the component (A). Preferably, it is 10-500,000 mol, More preferably, it is 100-100,000.
In the case of using an organoaluminum compound, the amount of the component (C) used is preferably as the molar ratio (C) / (B) of the aluminum atom of the component (C) to the transition metal atom of the component (A). 0.01 to 10,000,000, more preferably 0.1 to 1,000,000, still more preferably 1 to 100,000, and particularly preferably 10 to 10,000. It is.

The method for producing the olefin polymerization catalyst of the present invention formed by contacting the component (A) and the component (B) comprises the step of:
(I) a method of producing in a reactor for producing a catalyst before supplying to the polymerization reactor,
(II) a method for producing in a polymerization reactor, or (III) after contacting any two components in a catalyst production reactor in advance, and then supplying the contact to the polymerization reactor, and further other components And a method of supplying the polymer to a polymerization reactor.

In any of the above methods, the component (A) may be an isolated component, or a compound (2) and a compound (3) in contact with each other may be used as they are.

The method for producing the olefin polymerization catalyst of the present invention formed by contacting the component (A), the component (B), and the component (C),
(I) When the olefin polymerization catalyst of the present invention is produced in the catalyst production reactor before being supplied to the polymerization reactor, for example,
(1) A method in which the component (A), the component (B), and the component (C) are simultaneously supplied to a reactor for catalyst production and contacted to produce,
(2) Supplying component (A) and component (B) to the reactor for catalyst production and bringing them into contact, and then contacting component (C) with the contact product of component (A) and component (B) Manufacturing method,
(3) Supplying component (A) and component (C) to the reactor for catalyst production and bringing them into contact, and then contacting component (B) with the contact product of component (A) and component (C) Manufacturing method,
(4) Supplying the component (B) and the component (C) to the reactor for catalyst production and bringing them into contact with each other, and then bringing the component (A) into contact with the contact product of the components (B) and (C) And the like.
Among the above (I), (4) is preferable.

(II) When producing the olefin polymerization catalyst of the present invention in a polymerization reactor, for example,
(1) A method in which component (A), component (B), and component (C) are simultaneously supplied to a polymerization reactor in the presence of a monomer and brought into contact with each other.
(2) The component (A) and the component (B) are supplied to the polymerization reactor in the presence of the monomer and brought into contact with each other, and then the contact product of the component (A) and the component (B) A method of producing by contacting the component (C) in the presence;
(3) The component (A) and the component (C) are supplied to the polymerization reactor in the presence of the monomer and brought into contact with each other, and then the component (B) is added to the contact product of the component (A) and the component (C). ) In the presence of a monomer,
(4) The component (B) and the component (C) are supplied to and contacted with the polymerization reactor in the presence of the monomer, and then the component (A) is added to the contact product between the component (B) and the component (C). ) In the presence of a monomer, and the like.
Among the above (II), (4) is preferable.

(III) The catalyst for olefin polymerization of the present invention is contacted with any two components in a reactor for catalyst production in advance, and then the contacted product is supplied to the polymerization reactor to further polymerize other components. For example,
(1) Supplying component (A) and component (B) to a reactor for catalyst production and bringing them into contact with each other, and then polymerizing the contact product of component (A) and component (B) in the presence of a monomer A method of supplying the component to the reactor, and further supplying the component (C) to the polymerization reactor in the presence of the monomer and bringing it into contact therewith,
(2) Supplying the component (A) and the component (C) to the catalyst production reactor and bringing them into contact with each other, and then polymerizing the contact product of the component (A) and the component (C) in the presence of the monomer. A method of supplying to the reactor, and further supplying the component (B) to the polymerization reactor in the presence of the monomer and bringing it into contact;
(3) Supplying the component (B) and the component (C) to the catalyst production reactor and bringing them into contact with each other, and then polymerizing the contact product of the component (B) and the component (C) in the presence of the monomer. Examples thereof include a method in which a component (A) is further supplied to a polymerization reactor in the presence of a monomer and brought into contact with the reactor.
Among the above (III), (3) is preferable.

In any of the above methods, the component (A) may be an isolated component, or a compound (2) and a compound (3) in contact with each other may be used as they are.

  As a method of supplying each catalyst component to a catalyst production reactor or a polymerization reactor, a method of supplying each component in a solid state, a hydrocarbyl solvent from which components that deactivate catalyst components such as moisture and oxygen are sufficiently removed. The method of using and supplying is mentioned.

When supplying using a hydrocarbyl solvent from which components that deactivate catalyst components such as moisture and oxygen are sufficiently removed, for example,
(1) A method of supplying each catalyst component as a solution in which the hydrocarbyl solvent is dissolved,
(2) A method of supplying each catalyst component as a suspension in the hydrocarbyl solvent,
(3) A method of supplying each catalyst component as a slurry obtained by slurrying the hydrocarbyl solvent, and the like.

  When each catalyst component is supplied using the hydrocarbyl solvent, the concentration of group 12 atom in the periodic table contained in component (B) is usually 0.001 to 100 mol / liter, preferably 0. 0.01 to 10 mol / liter. The density | concentration of a component (B) is 0.00001-1 mol / liter normally, Preferably, it is 0.0001-0.1 mol / liter. The density | concentration of a component (C) is 0.0001-100 mol / liter normally in conversion of an aluminum atom, Preferably, it is 0.01-10 mol / liter.

Moreover, the manufacturing method of the olefin polymer of this invention is a manufacturing method of an olefin polymer which superposes | polymerizes an olefin using the said catalyst for olefin polymerization of this invention.
Examples of the polymerization method include a gas phase polymerization method in a gaseous monomer, a solution polymerization method using a solvent, a slurry polymerization method using a solvent, and the like. Solvents used in the solution polymerization method or slurry polymerization method include aliphatic hydrocarbyl solvents such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbyl solvents such as benzene and toluene, and halogenated hydrocarbyl solvents such as methylene chloride. It is also possible to use olefin itself as a solvent (bulk polymerization). The polymerization can be either batch polymerization or continuous polymerization, and the polymerization may be performed in two or more stages with different reaction conditions. In general, the polymerization time is appropriately determined depending on the type of the target olefin copolymer or α-olefin homopolymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours.

  The slurry polymerization method may be performed according to a known slurry polymerization method and polymerization conditions, but is not limited thereto. As a preferred polymerization method in the slurry polymerization method, a continuous reactor in which a monomer (and a comonomer), a feed, a diluent and the like are continuously added as necessary, and a polymer product is continuously or at least periodically removed. Is a polymerization method using Examples of the reactor include a loop reactor, a reactor in which a plurality of stirred reactors having different reactors or different reaction conditions are combined in series or in parallel.

  As the diluent, for example, an inert diluent (medium) such as paraffin, cycloparaffin or aromatic hydrocarbyl solvent can be used. The temperature in the polymerization reactor or reaction zone can usually range from about 0 ° C to about 150 ° C, preferably from 30 ° C to 100 ° C. The pressure can usually be changed from about 0.1 MPa to about 10 MPa, preferably 0.5 MPa to 5 MPa. A pressure can be applied to maintain the catalyst in suspension, maintain the medium and at least some of the monomer and comonomer in a liquid phase, and allow the monomer and comonomer to contact. Accordingly, the medium, temperature, and pressure may be selected such that the olefin polymer is produced as solid particles and recovered in that form.

The molecular weight of the olefin copolymer or α-olefin homopolymer produced at this time can be controlled by various known means such as adjusting the temperature of the reaction zone and introducing hydrogen.
Each catalyst component, monomer (and comonomer) can be added to the reactor or reaction zone in any order by any known method. For example, a method of simultaneously adding each catalyst component and monomer (and comonomer) to the reaction zone, a method of adding them sequentially, and the like can be used. If desired, each catalyst component can be pre-contacted in an inert atmosphere prior to contact with the monomer (and comonomer).

The gas phase polymerization method may be performed according to a known gas phase polymerization method and polymerization conditions, but is not limited thereto. Examples of the gas phase polymerization reaction apparatus used in the gas phase polymerization method include a gas phase polymerization reaction apparatus having a fluidized bed type reactor, preferably a gas phase polymerization having a fluidized bed type reactor having an enlarged portion. It is a reactor. Further, a stirring blade may be installed in the reactor.
As a method of supplying each component to the polymerization vessel, a solution or slurry is usually supplied in an inert gas such as nitrogen or argon, hydrogen, ethylene or the like in a moisture-free state or dissolved or diluted in a solvent. A method such as supplying in a state can be used. Each catalyst component may be supplied individually, or may be supplied by contacting arbitrary components in advance in an arbitrary order.

  As polymerization conditions, the polymerization temperature is preferably 0 ° C to 300 ° C, more preferably 10 ° C to 200 ° C, and particularly preferably 30 ° C to 100 ° C. Furthermore, hydrogen may be added as a molecular weight modifier for the purpose of adjusting the melt fluidity of the final product. In the polymerization, an inert gas may coexist in the mixed gas.

  In the present invention, preliminary polymerization may be performed before such polymerization (main polymerization).

As an olefin used with the manufacturing method of the olefin polymer of this invention, ethylene, a C3-C20 alpha olefin, etc. are mentioned, for example, 2 or more types of olefins can also be used simultaneously.

  Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene, 1 -Octene, 1-nonene, 1-decene, vinylcyclohexane and the like can be mentioned, preferably propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene An α-olefin having 3 to 8 carbon atoms such as 1-heptene and 1-octene, and more preferably an α-olefin having 3 to 5 carbon atoms such as propylene, 1-butene and 1-pentene. .

  Examples of the olefin polymer produced by the method for producing an olefin polymer of the present invention include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer. A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, such as an ethylene-vinylcyclohexane copolymer; a propylene-1-butene copolymer, a propylene-1-hexene copolymer, and propylene A copolymer of propylene such as vinylcyclohexane copolymer and an α-olefin having 4 to 20 carbon atoms; ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer and ethylene -Ethylene such as propylene-vinylcyclohexane copolymer, propylene and 4 to 2 carbon atoms A copolymer with 0 α-olefin; and a homopolymer of ethylene, an α-olefin with 3 to 20 carbon atoms such as a propylene polymer, a butene polymer, a hexene polymer, and a vinylcyclohexane polymer. A homopolymer can be illustrated.

The copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is preferably an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, or the like. A copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, more preferably an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-pentene copolymer, and the like. It is a copolymer of ethylene and an α-olefin having 3 to 5 carbon atoms.

As a copolymer of propylene and an α-olefin having 4 to 20 carbon atoms, propylene such as propylene-1-butene copolymer, propylene-1-hexene copolymer and propylene-vinylcyclohexane copolymer is preferable. And an α-olefin having 4 to 8 carbon atoms, such as propylene-1-butene copolymer and propylene-1-pentene copolymer, and α-olefin having 4 to 5 carbon atoms. And a copolymer.

As the copolymer of ethylene, propylene and α-olefin having 4 to 20 carbon atoms, ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer and ethylene-propylene-vinyl are preferable. A copolymer of ethylene, propylene, and an α-olefin having 4 to 8 carbon atoms, such as a cyclohexane copolymer, and more preferably an ethylene-propylene-1-butene copolymer.

The olefin homopolymer is preferably an ethylene homopolymer or an α-olefin homopolymer having 3 to 8 carbon atoms, more preferably an ethylene homopolymer or an α-olefin having 3 to 5 carbon atoms. An olefin homopolymer.

  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.

Analysis conditions (1) Melting point Measurement was performed by the following method using a thermal analyzer, a differential scanning calorimeter (manufactured by Diamond DSC Perkin Elmer).
<Polyethylene measurement conditions>
1) Hold about 10 mg of sample under 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 hold at 220 ° C. to 20 ° C. (5 ° C./min) for 2 minutes 3) Measurement 20 ° C. to 220 ° C. (5 ° C./min)

(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 condition 1>
Apparatus: TSK HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Column: TSKgel GMHHR-H (20) 2 Measurement temperature: 152 ° C
Solvent: ο-dichlorobenzene (with 0.05% BHT)
Solvent flow rate: 1 ml / min
Sample concentration: 0.05%
Sample for column / equipment calibration: TSK standard polystyrene F-2000-A-1000 (manufactured by Tosoh Corporation)
<Measurement condition 2>
Equipment: Waters 150C (Waters)
Solvent: ο-dichlorobenzene (0.05% BHT added)
Column: 3 TSKgel GMH6-HT (made by Tosoh)
Measurement temperature: 140 ° C
Solvent flow rate: 1 ml / min
Sample concentration: 0.1%
Sample for column / equipment calibration: TSK standard polystyrene F-700 to A-500 (manufactured by Tosoh)

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

Polypropylene isotactic pentad fraction ([mmmm] (%))
The [mmmm] fraction of polypropylene is 21.64 to 22.02 ppm mmmm pentad methyl relative to the peak area attributed to 19.4 to 22.2 ppm methyl carbon in the ¹³ C-NMR spectrum measured under the following conditions. It calculated | required as a ratio of the peak area attributed to carbon.
<Measurement conditions>
Apparatus: Bruker AVANCE 600 10 mm cryoprobe measurement solvent: 1,2-dichlorobenzene / 1,2-dichlorobenzene-d ₄ = 75/25 (volume ratio) mixture measurement temperature: 130 ° C.
Measuring method: Proton decoupling method Pulse width: 45 degrees Pulse repetition time: 4 seconds Chemical shift value Criteria: Tetramethylsilane

Polypropylene 2,1-insertion rate, 1,3-insertion rate (%)
In the ¹³ C NMR spectrum measured under the above conditions, 2,1-insertion rate and 1,3-insertion rate (%) were determined from the peak area in the range defined as follows.
<Calculation method>
Definition of peak area I (CH ₃ ): total peak area of 19.4 to 22.2 ppm I (2,1): total I of peak areas of 16.4 to 18.8 ppm and 14.5 to 15.8 ppm (1,3): 27.6-27.8 ppm peak area 2,1% calculation formula 2,1% = 0.5 × I (2,1) / (I (CH ₃ ) + I (2,1) + I (1,3)) × 100
1,3% calculation formula 1,3% = I (1,3) / (I (CH ₃ ) + I (2,1) + I (1,3)) × 100

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

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

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

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

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

(Reference Example 6)
(1) Preparation of activation promoter component (component (B-2)) Argon-substituted 200 ml four-necked flask was charged with 25 ml (50 mmol) of ZnEt2 (2.0 M hexane solution) and 70 ml of toluene in an ice bath. Cooled to 5 ° C. To this was added dropwise 8.6 ml (24 mmol) of pentafluorophenol (2.8 M hexane solution). After completion of dropping, the mixture was stirred at 0 to 5 ° C. for 30 minutes. Thereafter, the mixture was stirred at 40 ° C. for 1 hour, cooled to room temperature, and 0.68 mL (38 mmol) of H 2 O was added dropwise with a micro syringe over 1 hour. The contents became a yellow slurry. After completion of dropping, the mixture was stirred at room temperature for 1.5 hours, and stirred at 40 ° C. for 2 hours. Then, it stirred at 80 degreeC for 2 hours, and removed the supernatant liquid. Furthermore, 70 mL of toluene was added, washed at 95 ° C., and the supernatant was removed. After repeating this twice, 70 mL of hexane was added and the supernatant was removed. The solid was dried under reduced pressure at room temperature to obtain 7.47 g of a yellow powder (hereinafter sometimes referred to as “component (B-2)”).

(Reference Example 7)
(1) Treatment of silica Silica (manufactured by Debison Co., Ltd.) heated in a 50 liter reactor equipped with a nitrogen-substituted stirrer at 24.3 liters of toluene as a solvent and 300 ° C. under nitrogen flow as particles (d) (Sypolol 948; average particle size = 58 μm; pore volume = 1.60 ml / g; specific surface area = 316 m ² / g) 2.55 kg was added and stirred. Then, after cooling to 5 ° C., a mixed solution of 823 g of 1,1,1,3,3,3-hexamethyldisilazane and 1290 g of toluene was added dropwise over 30 minutes while maintaining the temperature of the reactor at 5 ° C. ± 3 ° C. did. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 95 ° C. for 3 hours. Thereafter, the obtained solid product was washed 5 times with 30 liters of toluene at 95 ° C. Next, 5.4 liters of toluene was added to form a slurry.

(2) Preparation of co-catalyst component for activation (component (B-3)) supported on a carrier To the toluene slurry obtained in the above Reference Example 7 (1), 32.1 wt% diethyl zinc as compound (a) A hexane solution of 2.5 kg was added and stirred. Then, after cooling to 5 ° C., 2.00 kg of a 3,4,5-trifluorophenol toluene solution prepared as a compound (b) at a concentration of 35.4 wt% was added, and the temperature of the reactor contents was changed to 5 ° C. ± While maintaining the temperature at 3 ° C., the solution was added dropwise over 60 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, 0.10 liters of water was added dropwise as compound (c) in 90 minutes while maintaining the temperature of the reactor contents at 22 ° C. ± 3 ° C. After completion of dropping, the mixture was stirred at 22 ° C. ± 3 ° C. for 1.5 hours, 40 ° C. for 2 hours, and 80 ° C. for 2 hours. Then, it left still and the upper layer part which settled the solid component was removed. Then 13 liters of toluene was added. Then, it heated up at 95 degreeC and stirred for 4 hours. Thereafter, the mixture was allowed to stand at 95 ° C. for 4 times with 30 liters of toluene and at room temperature for 9 times with 30 liters of hexane to precipitate the solid component and remove the upper layer portion. The solid component was dried at 45 ° C. under reduced pressure for 6 hours to obtain 3.12 kg of an activation promoter component (hereinafter sometimes referred to as “component (B-3)”) containing a support. As a result of elemental analysis, zinc atom = 1.6 mmol / g, fluorine atom = 3.8 mmol / g.

(Reference Example 8)
Synthesis of bis (1,1-di (trifluoromethyl) -2,2,2-trifluoroethoxy) zinc (component (B-1)) Toluene 50 mL, diethylzinc (2.06 mmol) in a nitrogen-substituted 300 mL flask / ML, toluene solution) 20 mL (41.2 mmol) was added, and 1,1-di (trifluoromethyl) -2,2,2-trifluoroethanol 16.7 mL (120 mmol) was added dropwise in an ice bath. The mixture was stirred at reflux for 5 hours. After allowing to cool to room temperature, the volatile component was distilled off under reduced pressure to give bis (1,1-di (trifluoromethyl) -2,2,2-trifluoroethoxy) zinc (hereinafter, “component ( 20.7 g (yield 95%).
¹³ C NMR (THF-d 8): δ 122.2 (q, J _CF = 292 Hz), 81.1 (q, J _CF = 28.9 Hz)
19F NMR (THF-d8): δ-73.2 (s)

Example 1
An autoclave with an internal volume of 400 mL and a stirrer was vacuum-dried and replaced with argon, 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, and 0.50 mL (0.50 mmol) of triisobutylaluminum (1 mmol / mL, toluene solution) was added, followed by [cyclooctanediyl-trans-1 , 2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 0.5 mL (0.5 μmol) was added, and then component (B -2) 6.7 mg (39.7 μmol) was added to initiate polymerization. Polymerization was carried out for 60 minutes while maintaining the temperature at 40 ° C.
As a result of the polymerization, 8.5 g of ethylene homopolymer was obtained. The polymerization activity was 1.0 × 10 ⁸ g / mol, the melting point was 111.7 ° C., M _w = 4600, M _n = 1300, and M _w / M _n = 3.5. Table 1 shows the results.

(Comparative Example 1) 1
[Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 0.5 mL (0.5 μmol) [Cyclohexanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 0.5 mL (0.5 μmol) The same procedure as in Example 1 was conducted except that 6.7 mg (39.7 μmol) of component (B-2) was changed to 35.1 mg (207.8 μmol) of component (B-2).
As a result of the polymerization, 2.8 g of ethylene homopolymer was obtained. The polymerization activity was 5.6 × 10 ⁶ g / mol, the melting point was 124.6 ° C., M _w = 5600, M _n = 2100, and M _w / M _n = 2.7. Table 1 shows the results.

(Example 2)
The autoclave with a stirrer with an internal volume of 400 mL was vacuum-dried and replaced with argon, 200 mL of hexene was charged as a solvent, and the reactor was heated to 70 ° C. After raising the temperature, the ethylene pressure was fed while adjusting the pressure to 0.6 MPa, and 0.50 mL (0.50 mmol) of triisobutylaluminum (1 mmol / mL, hexane solution) was added. , 2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 1.0 mL (1.0 μmol) -3) 11.0 mg (17.6 μmol) was added to initiate polymerization. Polymerization was performed for 60 minutes while maintaining the temperature at 70 ° C.
As a result of the polymerization, 1.0 g of ethylene homopolymer was obtained. Polymerization activity was 1.0 × 10 ⁶ g / mol, melting points = 107.5, 119.1, 121.5 ° C., M _w = 5400, M _n = 1600, M _w / M _n = 3.5. Table 1 shows the results.

(Comparative Example 2)
[Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 1.0 mL (1.0 μmol) [Cyclohexanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 1.0 mL (1.0 μmol) This was carried out in the same manner as in Example 2 except that 11.0 mg (17.6 μmol) of the component (B-3) was changed to 31.9 mg (51.0 μmol) of the component (B-3).
As a result of the polymerization, 0.62 g of ethylene homopolymer was obtained. The polymerization activity was 6.2 × 10 ⁵ g / mol, the melting point was 125.2 ° C., M _w = 4300, M _n = 1800, and M _w / M _n = 2.4. Table 1 shows the results.

(Example 3)
[Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 0.5 mL (0.5 μmol) [Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylhafnium (1.0 μmol / mL, toluene solution) 0.2 mL (0 .2 μmol) and the same procedure as in Example 1 except that 6.7 mg (39.7 μmol) of component (B-2) was changed to 52.0 mg (97.1 μmol) of component (B-1).
As a result of the polymerization, 5.5 g of ethylene homopolymer was obtained. The polymerization activity was 2.8 × 10 ⁷ g / mol, the melting point was 126.6 ° C., M _w = 43200, M _n = 11000, and M _w / M _n = 3.9. Table 1 shows the results.

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

Example 4
An autoclave with a stirrer having an internal volume of 400 mL was vacuum dried and replaced with argon, and then 40 mL of toluene and 80 g of propylene were charged as solvents, and the temperature of the reactor was raised to 40 ° C. After raising the temperature, 0.50 mL (0.50 mmol) of triisobutylaluminum (1 mmol / mL, toluene solution) was added, followed by [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3- (Cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 0.5 mL (0.5 μmol) was added, followed by addition of 12.8 mg (75.8 μmol) of component (B-2) Then, polymerization was started. Polymerization was carried out for 60 minutes while maintaining the temperature at 40 ° C.
As a result of the polymerization, 14.7 g of a propylene homopolymer was obtained. Polymerization activity was 2.9 × 10 ⁷ g / mol, melting point = 142.0 ° C., M _w = 8300, M _n = 3800, M _w / M _n = 2.2, and [mmmm] = 89.0. Table 2 shows the results.

(Comparative Example 3)
[Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 0.5 mL (0.5 μmol) [Cyclohexanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 1.0 mL (1.0 μmol) The same procedure as in Example 4 was conducted except that 12.8 mg (75.8 μmol) of component (B-2) was changed to 28.9 mg (171.0 μmol) of component (B-2).
As a result of the polymerization, 2.1 g of a propylene homopolymer was obtained. Polymerization activity was 4.2 × 10 ⁶ g / mol, melting point = 140.8 ° C., M _w = 4100, M _n = 1500, M _w / M _n = 1.8, and [mmmm] = 47.3. Table 2 shows the results.

(Example 5)
An autoclave with a stirrer with an internal volume of 400 mL was vacuum-dried and replaced with argon, and then 40 mL of hexane and 80 g of propylene were charged as solvents, and the temperature of the reactor was raised to 70 ° C. After raising the temperature, 0.50 mL (0.50 mmol) of triisobutylaluminum (1 mmol / mL, hexane solution) was added, followed by [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3- Cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 2.0 mL (2.0 μmol) was added, and then 13.0 mg (20.8 μmol) of component (B-3) was added Then, polymerization was started. Polymerization was performed for 60 minutes while maintaining the temperature at 70 ° C.
As a result of the polymerization, 0.9 g of propylene homopolymer was obtained. Polymerization activity 4.5 × 10 ⁵ g / mol, melting point = 135.6, 142.0 ° C., M _w = 8900, M _n = 4200, M _w / M _n = 2.1, [mmmm] = 86.5 Met. Table 2 shows the results.

(Comparative Example 4)
[Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 2.0 mL (2.0 μmol) [Cyclohexanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 2.0 mL (2.0 μmol) This was carried out in the same manner as in Example 5 except that 13.0 mg (20.8 μmol) of component (B-3) was changed to 25.5 mg (40.8 μmol) of component (B-3).
As a result of the polymerization, 0.2 g of propylene homopolymer was obtained. Polymerization activity was 1.0 × 10 ⁵ g / mol, melting point = 134.5 ° C., M _w = 5800, M _n = 3000, M _w / M _n = 1.9, and [mmmm] = 41.5. Table 2 shows the results.

(Example 6)
Input amount of [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 0.5 mL (0 0.5 μmol) to 2.0 mL (2.0 μmol), component (B-2) 12.8 mg (75.8 μmol) to component (B-1) 63.1 mg (117.8 μmol), polymerization The same operation as in Example 4 was performed except that the time was changed from 60 minutes to 10 minutes.
As a result of the polymerization, 13.9 g of a propylene homopolymer was obtained. Polymerization activity was 4.2 × 10 ⁷ g / mol, melting point = 140.5 ° C., M _w = 8100, M _n = 3800, M _w / M _n = 2.2, and [mmmm] = 89.0. Table 2 shows the results.

(Example 7)
[Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium (1 μmol / mL, toluene solution) 0.5 mL (0.5 μmol) [Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylhafnium (1 μmol / mL, toluene solution) 1.0 (1.0 μmol) This was carried out in the same manner as in Example 4 except that 12.8 mg (75.8 μmol) of component (B-2) was changed to 78.2 mg (146.0 μmol) of component (B-1).
As a result of the polymerization, 20.4 g of a propylene homopolymer was obtained. Polymerization activity was 2.0 × 10 ⁷ g / mol, melting point = 154.7 ° C., M _w = 43600, M _n = 19300, M _w / M _n = 2.3, and [mmmm] = 96.2. Table 2 shows the results.

  The polymerization results obtained in Examples 4 to 7 and Comparative Examples 3 and 4 are shown in Table 2.

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

Claims (13)

An olefin polymerization catalyst obtained by bringing the following component (A) into contact with an activating co-catalyst component (B) containing an element belonging to Group 12 of the periodic table.
Component (A): Complex represented by the following general formula (1-1) or (1-2)

(Wherein n is 1 or 2,
M represents a zirconium atom or a hafnium atom.
R ¹ and R ⁵ are each independently
Hydrogen atom,
Halogen atoms,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An alkenyl group having 2 to 20 carbon atoms,
An alkynyl group having 2 to 20 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms,
An aralkyloxy group having 7 to 30 carbon atoms,
An aryloxy group having 6 to 30 carbon atoms,
Or a substituted silyl group is represented.
R ^{2 to} R ⁴ and R ^{6 to} R ¹⁰ are each independently
Hydrogen atom,
Halogen atoms,
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 ¹⁰ . The residue may have a substituent.
Regardless of the definition of R ^{1 to} R ¹⁰ above, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ² And R ⁹ and R ⁶ and R ¹⁰ may be connected to each other to form a ring, and these rings may have a substituent.
Each X is independently
Hydrogen atom,
Halogen atoms,
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,
Substituted amino groups,
A substituted thiolate group or a carboxylate group having 1 to 20 carbon atoms is represented.
The alkyl group, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, and the aryloxy group in X may have a substituent.
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 polymerization catalyst according to claim 1, further comprising a support. The catalyst for polymerization according to claim 1 or 2, wherein the activating co-catalyst component (B) is obtained by bringing the following (a) and (b) into contact with each other.
(A): Compound M ² L ² ₂ [B1] represented by the following general formula [B1]
(B): Compound E ¹ _t-1 T ¹ H [B2] represented by the following general formula [B2]
(In the above general formulas [B1] and [B2], M ² represents an atom of Group 12 of the periodic table, L ² represents a hydrogen atom, a halogen atom, a hydrocarbyl group, or a halogenated hydrocarbyl group, They may be the same or different, E ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group, and T ¹ represents a group 15 or group 16 atom in the periodic table. , T represents the valence of T1) The catalyst for polymerization according to claim 1 or 2, wherein the activating co-catalyst component (B) is obtained by bringing the following (a) to (c) into contact with each other.
(A): Compound M ² L ² ₂ [B1] represented by the following general formula [B1]
(B): Compound E ¹ _t-1 T ¹ H [B2] represented by the following general formula [A2]
(C): Compound E ² _t-1 T ¹ H ₂ [B3] represented by the following general formula [B3]

(In the above general formulas [B1] to [B3], M ² represents an atom of Group 12 of the periodic table, L represents a hydrogen atom, a halogen atom, a hydrocarbyl group, or a halogenated hydrocarbyl group, and two L ² are They may be the same or different from each other, E ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group, E ² represents a hydrocarbyl group or a halogenated hydrocarbyl group, and E ² represents When there are a plurality of them, they may be the same or different from each other, and two T ^{1 s} independently represent atoms of Group 15 or Group 16 of the periodic table, and t represents the valence of T ^1. Represent) R ¹ and R ⁵ are each independently
Halogen atoms,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
Or it is a substituted silyl group, The said alkyl group, this cycloalkyl group, and this aralkyl group may have a substituent, The catalyst of any one of Claims 1-4. R ⁹ and R ¹⁰ are each independently
Halogen atoms,
An alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
An aralkyl group having 7 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms,
A substituted silyl group or a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring, and the alkyl group, the cycloalkyl group, the aralkyl group, the aryl group and the heterocyclic compound residue are The catalyst according to any one of claims 1 to 5, which may have a substituent. Alkyl groups ^{R 1,} R 5, R ⁹ and ^{R 10} is an alkyl group having a carbon number of 5-10, the alkyl group may have a substituent, any one of claims 1 to 6 2. The catalyst according to item 1. R ^{2 to} R ⁴ and R ^{6 to} R ⁸ are each independently
Hydrogen atom,
Halogen atoms,
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, The said alkyl group, this cycloalkyl group, this aralkyl group, and this aryl group may have a substituent, The catalyst of any one of Claims 1-7. R ³ and R ⁷ are each independently
Halogen atoms,
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, This alkyl group, this cycloalkyl group, this aralkyl group, and this aryl group may have a substituent, The catalyst of any one of Claims 1-8. R ^2, R ^4, catalyst according to any one of claims 1 to 9 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 10. The catalyst described. The catalyst according to any one of claims 1 to 11, wherein n is 2. The manufacturing method of an olefin polymer which polymerizes an olefin in presence of the catalyst of any one of Claims 1-12.