JP2005179322A - Transition metal complex, olefin polymerization catalyst and method for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a transition metal complex as an excellent polymerization catalyst. <P>SOLUTION: The transition metal complex is represented by formula (1) (wherein M is an element in the group 4 of the periodic table; R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, R<SP>6</SP>, R<SP>7</SP>, and R<SP>8</SP>are the same or different and each hydrogen, a halogen, a 1-10C alkyl group which may be substituted, a 7-20C aralkyl group which may be substituted, or the like; and R<SP>9</SP>and R<SP>10</SP>are the same or different and each hydrogen, a halogen or a 1-10C alkyl group which may be substituted; and (n) is 0 or 1). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a transition metal complex, a catalyst for olefin polymerization, and a method for producing an olefin polymer.

Conventionally, a reaction product of an organic compound having at least two hydroxyl groups and phosphine and a transition metal (for example, 2,2 ′-(phenylphosphido) bis (6-tert-butyl-4-methylphenoxy) (tetrahydrofuran) titanium An example (for example, refer to Patent Document 1) using dichloride) in a method for producing an olefin polymer has been reported.
Japanese Patent Laid-Open No. 10-218922

  The object of the present invention is to develop an excellent polymerization catalyst.

In order to achieve the above-mentioned object, the present inventors have continued intensive studies on transition metal complexes and olefin polymerization catalysts. As a result, a novel transition metal complex was discovered and the present invention was completed.

（式中、Ｍは元素の周期律表の第４族の元素を示し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、同一または相異なり、水素原子、ハロゲン原子、置換されていてもよい炭素原子数１〜１０のアルキル基、置換されていてもよい炭素原子数７〜２０のアラルキル基、置換されていてもよい炭素原子数６〜２０のアリール基、置換されていてもよい炭素原子数１〜２０の炭化水素で置換されたシリル基、置換されていてもよい炭素原子数１〜１０のアルコキシ基、置換されていてもよい炭素原子数７〜２０のアラルキルオキシ基、置換されていてもよい炭素原子数６〜２０のアリールオキシ基または置換されていてもよい炭素原子数１〜２０の炭化水素で置換されていてもよいアミノ基を示し、Ｒ^９およびＲ^１０は、同一または相異なり、水素原子、ハロゲン原子または置換されていてもよい炭素原子数１〜１０のアルキル基を示し、ｎは０または１を示す。）
で示される遷移金属錯体、製造方法；該遷移金属錯体と、下記化合物（Ａ）を組合わせてなるオレフィン重合用触媒；およびさらに下記化合物（Ｂ）を組合わせてなるオレフィン重合用触媒ならびにオレフィン重合体の製造方法を提供するものである。

化合物（Ａ）： 下記化合物（Ａ１）〜（Ａ３）のいずれか、あるいはそれらの２種以上の混合物
（Ａ１）： 式 （Ｅ1）a Ａｌ（Ｚ）3-a で示される有機アルミニウム化合物、
（Ａ２）: 式 ｛−Ａｌ（Ｅ2 ）−Ｏ−｝b で示される構造を有する環状のアルミノキサン、
（Ａ３）： 式 （Ｅ3） ｛−Ａｌ（Ｅ3 ）−Ｏ−｝c Ａｌ（Ｅ3）2 で示される構造を有する線状のアルミノキサン
（式中、Ｅ1 〜Ｅ3 は同一または相異なり、炭素原子数１〜８の炭化水素基であり、Ｚは同一または相異なり、水素原子またはハロゲン原子を表し、ａは１、２または３を、ｂは２以上の整数を、ｃは１以上の整数を表す。）

化合物（Ｂ）: 下記化合物（Ｂ１）〜（Ｂ３）のいずれか、あるいはそれらの２種以上の混合物
（Ｂ１）： 式 ＢＱ1 Ｑ2 Ｑ3 で表されるホウ素化合物、
（Ｂ２）： 式 Ｚ+ （ＢＱ1 Ｑ2 Ｑ3 Ｑ4 ）- で表されるホウ素化合物、
（Ｂ３）： 式（Ｌ−Ｈ）+ （ＢＱ1 Ｑ2 Ｑ3 Ｑ4 ）- で表されるホウ素化合物
（式中、Ｂは３価の原子価状態のホウ素原子であり、Ｑ1 〜Ｑ4 は同一または相異なり、ハロゲン原子、炭素原子数１〜２０の炭化水素基、炭素原子数１〜２０のハロゲン化炭化水素基、炭素原子数１〜２０の炭化水素で置換されたシリル基、炭素原子数１〜２０のアルコキシ基または炭素原子数１〜２０の炭化水素で置換されたアミノ基を示す。） That is, the present invention provides the formula (1)

(In the formula, M represents an element belonging to Group 4 of the periodic table of elements, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different, A hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, and an optionally substituted carbon atom having 6 to 20 carbon atoms Aryl groups, silyl groups substituted with optionally substituted hydrocarbons having 1 to 20 carbon atoms, optionally substituted alkoxy groups with 1 to 10 carbon atoms, optionally substituted carbon atoms An aralkyloxy group having 7 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms which may be substituted, or an amino group which may be substituted with an optionally substituted hydrocarbon having 1 to 20 carbon atoms R ⁹ and R ¹⁰ are The same or different, and represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms, and n represents 0 or 1.)
A transition metal complex represented by the formula: a production method; an olefin polymerization catalyst comprising a combination of the transition metal complex and the following compound (A); and an olefin polymerization catalyst comprising a combination of the following compound (B); A method for producing a coalescence is provided.

Compound (A): Any of the following compounds (A1) to (A3), or a mixture of two or more thereof (A1): an organoaluminum compound represented by the formula (E1) a Al (Z) 3-a,
(A2): a cyclic aluminoxane having a structure represented by the formula {-Al (E2) -O-} b;
(A3): Formula (E3) {-Al (E3) -O-} c Linear aluminoxane having a structure represented by Al (E3) 2 (wherein E1 to E3 are the same or different, and the number of carbon atoms 1 to 8 hydrocarbon groups, Z is the same or different and represents a hydrogen atom or a halogen atom, a represents 1, 2 or 3, b represents an integer of 2 or more, and c represents an integer of 1 or more .)

Compound (B): Any of the following compounds (B1) to (B3), or a mixture of two or more thereof (B1): A boron compound represented by the formula BQ1 Q2 Q3,
(B2): a boron compound represented by the formula Z + (BQ1 Q2 Q3 Q4)-
(B3): Boron compound represented by the formula (LH) + (BQ1 Q2 Q3 Q4)-(wherein B is a boron atom in a trivalent valence state, and Q1 to Q4 are the same or different) A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silyl group substituted with a hydrocarbon having 1 to 20 carbon atoms, or 1 to 20 carbon atoms An amino group substituted with an alkoxy group or a hydrocarbon having 1 to 20 carbon atoms.)

By using the transition metal complex obtained by the present invention as a catalyst component, polyolefin can be produced with excellent catalytic activity.

Hereinafter, the present invention will be described in detail.
In the transition metal complex represented by the formula (1), specific examples of the halogen atom in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ include , Fluorine atom, chlorine atom, bromine atom, iodine atom, etc., preferably fluorine atom.

Specific examples of the alkyl group having 1 to ¹⁰ carbon atoms in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ include a methyl group and an ethyl group. , N-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, etc. Examples of these substituents include halogen atoms, alkoxy groups, aryloxy groups, amino groups substituted with hydrocarbons, and substituents substituted with silyl groups substituted with hydrocarbons. Specific examples thereof include Is a fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafur Oroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group, trichloromethyl group, methoxymethyl group, phenoxymethyl group, dimethylaminomethyl group, Examples include a trimethylsilylmethyl group. Among the optionally substituted alkyl groups having 1 to 10 carbon atoms, preferred examples include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an amyl group, and the like, more preferably a methyl group, a tert- A butyl group is mentioned.

Examples of the aralkyl group having 7 to 20 carbon atoms in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ include benzyl group, naphthylmethyl group, anthracenylmethyl group, diphenyl Examples include methyl groups, and these groups include, for example, halogen atoms, alkyl groups, alkoxy groups, aryloxy groups, amino groups substituted with hydrocarbons, and silyl groups substituted with hydrocarbons. Illustrated, and specific examples thereof include
(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,
(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, (n-pentylphenyl) methyl Group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, (fluorophenyl) Methyl group, (difluorophenyl) methyl group, (pentafluorophenyl) methyl group, (chlorophenyl) methyl group, (methoxyphenyl) methyl group, (phenoxyphenyl) methyl group, (dimethylaminophenyl) methyl group, (trimethylsilylphenyl) A methyl group etc. are illustrated. A benzyl group is illustrated as a preferable aralkyl group having 7 to 20 carbon atoms which may be substituted.

Examples of the optionally substituted aryl group having 6 to 20 carbon atoms in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ include a phenyl group, a naphthyl group, and an anthracenyl group. Etc.
Examples of these groups include those substituted with a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amino group substituted with a hydrocarbon, or a silyl group substituted with a hydrocarbon, and specific examples thereof. Are 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl Group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3 , 4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethyl Phenyl group, Tilphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n- Octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 3,5-difluorophenyl group, penta Examples include fluorophenyl group, 4-chlorophenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 4-phenoxyphenyl group, 4-dimethylaminophenyl group, 4-trimethylsilylphenyl group and the like. . Particularly preferred examples of the optionally substituted aryl group having 6 to 20 carbon atoms include a phenyl group.

Specific examples of the alkoxyl group having 1 to 10 carbon atoms in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ include a methoxy group, an ethoxy group, an n-propoxy group, Isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy Examples are groups. These may be further substituted, and examples thereof include those substituted with a halogen atom, an alkoxy group, an aryloxy group, an amino group substituted with a hydrocarbon, or a silyl group substituted with a hydrocarbon.
Specific examples of the substituted alkoxyl group include fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, fluoroethoxy group, difluoroethoxy group, trifluoroethoxy group, tetrafluoroethoxy group, pentafluoroethoxy group, perfluoropropoxy group. Group, perfluorobutyloxy group, perfluoropentyloxy group, perfluorohexyloxy group, perfluorooctyloxy group, perfluorodecyloxy group, trichloromethyloxy group, methoxymethoxy group, phenoxymethoxy group, dimethylaminomethoxy group, Examples include a trimethylsilylmethoxy group. Preferred examples of the optionally substituted alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, and a tert-butoxy group.

As a hydrocarbon group of a silyl group substituted with an optionally substituted hydrocarbon having 1 to 20 carbon atoms in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ Is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, cyclohexyl Group, an alkyl group having 1 to 10 carbon atoms such as n-octyl group and n-decyl group, an aryl group having 6 to 20 carbon atoms such as phenyl group, tolyl group, xylyl group, naphthyl group and anthracenyl group. Can be mentioned. Examples of the silyl group substituted with a hydrocarbon having 1 to 20 carbon atoms include 2 substituted silyl groups such as a methylsilyl group, an ethylsilyl group, and a phenylsilyl group, a dimethylsilyl group, a diethylsilyl group, and a diphenylsilyl group. Substituted silyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, tri-isopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri-isobutylsilyl Group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, and the like, preferably trimethylsilyl group, tert-butyldimethylsilyl group, trif An enylsilyl group is mentioned. Examples of these substituted silyl groups include those in which the hydrocarbon group is substituted with a halogen atom, for example, a fluorine atom.

Examples of the aralkyloxy group having 7 to 20 carbon atoms in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ include a benzyloxy group, a naphthylmethoxy group, and an anthracenylmethoxy group. , A diphenylmethoxy group is exemplified,
These may be further substituted, for example, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amino group substituted with a hydrocarbon, or a silyl group substituted with a hydrocarbon. Specific examples thereof include (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, (2,3,4-trimethylphenyl) methoxy Group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (3,4,5- Limethylphenyl) methoxy group, (2,4,6-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-pentylphenyl) methoxy group, (neopentylphenyl) methoxy group, (n-hexylphenyl) methoxy Group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n Dodecylphenyl) methoxy, (fluorophenyl) methyl, (difluorophenyl) methyl, (pentafluorophenyl) methyl, (chlorophenyl) methyl, (methoxyphenyl) methyl, (phenoxyphenyl) methyl, (dimethyl) Examples include aminophenyl) methyl group and (trimethylsilylphenyl) methyl group. A particularly preferred aralkyloxy group having 7 to 20 carbon atoms which may be substituted is exemplified by a benzyloxy group.

Examples of the aryloxy group having 6 to 20 carbon atoms in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ include a phenoxy group, a naphthoxy group, and an anthracenoxy group.
These may be further substituted, for example, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amino group substituted with a hydrocarbon, or a silyl group substituted with a hydrocarbon. As a specific example,
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, 2,4,4 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 Group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, Sopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, 2-fluoro Phenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, 3,5-difluorophenoxy group, pentafluorophenoxy group, 4-chlorophenoxy group, 2-methoxyphenoxy group, 3-methoxyphenoxy group, 4-methoxyphenoxy group Group, 4-phenoxyphenoxy group, 4-dimethylaminophenoxy group, 4-trimethylsilylphenoxy group and the like. As a particularly preferred aryloxy group having 7 to 20 carbon atoms which may be substituted, a phenoxy group is exemplified.

Carbonization of an amino group which may be substituted with an optionally substituted hydrocarbon having 1 to 20 carbon atoms in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ Examples of the hydrogen group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, and n-hexyl. Group, cyclohexyl group, n-octyl group, n-decyl group and other alkyl groups having 1 to 10 carbon atoms, phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group and other aryl groups having 6 to 20 carbon atoms Group or a pyrrole group. Examples of the amino group substituted with a hydrocarbon having 1 to 20 carbon atoms include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec. -Butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenyl An amino group, a cyclohexylamino group, a pyrrole group, etc. are mentioned. Preferred examples of the amino group which may be substituted with an optionally substituted hydrocarbon having 1 to 20 carbon atoms include an unsubstituted amino group, a dimethylamino group, a cyclohexylamino group, and a pyrrole group.

M in the transition metal complex represented by the formula (1) represents a group 4 element in the periodic table of the elements, and specifically includes a titanium atom, a zirconium atom, a hafnium atom, and the like, preferably a titanium atom. It is done.

As a transition metal complex shown by Formula (1), the compound shown below is mentioned, for example.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０およびｎは、前記と同じ意味を表す。）
で示される置換フェノールと式（３）

（式中、Ｍは前記と同じ意味を表し、Ｘ^１、Ｘ^２およびＸ^３は同一または相異なり、水素原子、ハロゲン原子、置換されていてもよい炭素原子数１〜１０のアルキル基、置換されていてもよい炭素原子数７〜２０のアラルキル基、置換されていてもよい炭素原子数６〜２０のアリール基、置換されていてもよい炭素原子数１〜１０のアルコキシ基、置換されていてもよい炭素原子数７〜２０のアラルキルオキシ基、置換されていてもよい炭素原子数６〜２０のアリールオキシ基または炭素原子数１〜２０の炭化水素で置換されたアミノ基を示し、Ｌはエーテル、スルフィド、アミン、ホスフィン、オレフィンなどの中性配位子を示し、ｌとｍは独立に０〜２の整数を示す。）
で示される遷移金属化合物とを反応させることにより製造することができる。
式（２）で示される置換フェノールと式（３）で示される遷移金属化合物の反応モル比は特に限定されないが、１：０．１から１：１０の範囲が好ましく、さらに好ましくは１：０．５から１：５の範囲である。 The transition metal complex represented by the formula (1) has the formula (2)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and n represent the same meaning as described above.)
A substituted phenol represented by formula (3)

(In the formula, M represents the same meaning as described above, and X ¹ , X ² and X ³ are the same or different and are a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or a substituted group. An optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, and a substituted group. An aralkyloxy group having 7 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms which may be substituted, or an amino group substituted with a hydrocarbon having 1 to 20 carbon atoms, Represents a neutral ligand such as ether, sulfide, amine, phosphine or olefin, and l and m independently represent an integer of 0 to 2.)
It can manufacture by making the transition metal compound shown by react.
The reaction molar ratio of the substituted phenol represented by the formula (2) and the transition metal compound represented by the formula (3) is not particularly limited, but is preferably in the range of 1: 0.1 to 1:10, more preferably 1: 0. .5 to 1: 5 range.

In the reaction, a base is used if necessary. Examples of such bases include metal hydrides such as sodium hydride and potassium hydride, such as methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilyl acetylide, lithium acetylide, and trimethylsilylmethyl. Examples include organic alkali metal compounds such as organic lithium compounds such as lithium, vinyl lithium, phenyl lithium, and allyl lithium, and the amount used is usually 0.5 to 5 mol times the substituted phenol represented by the formula (2). It is a range.

The above reaction is usually performed in a solvent inert to the reaction. Examples of such solvents include aromatic hydrocarbon solvents such as benzene and toluene, aliphatic hydrocarbon solvents such as hexane and heptane, ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane, hexamethylphosphoric. Amide solvents such as amide and dimethylformamide, polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone, aprotic solvents such as halogen solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene Is mentioned. Each of these solvents is used alone or in admixture of two or more, and the amount used is usually 1 to 200 times by weight, preferably 3 to 50 times by weight with respect to the substituted phenol represented by formula (2). .

The above reaction can be performed, for example, by adding a transition metal compound represented by the formula (3) after adding a base to the substituted phenol represented by the formula (2) as necessary. The reaction temperature is usually from −100 ° C. to the boiling point of the solvent, preferably from −80 to 100 ° C.

The transition metal complex represented by the formula (1) can be obtained from the obtained reaction mixture by a conventional method, for example, by filtering the generated precipitate and then concentrating the filtrate to precipitate a solid. .

Specific examples of the substituted phenol represented by the formula (2) include the following compounds.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０およびｎは、前記と同じ意味を表し、Ｒ^１１は、置換されていてもよい炭素原子数１〜１０のアルキル基、置換されていてもよい炭素原子数７〜２０のアラルキル基または置換されていてもよい炭素原子数６〜２０のアリール基を表す。） The substituted phenol represented by the formula (2) is synthesized, for example, by the method shown below.

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and n represent the same meaning as described above, and R ¹¹ is substituted. Represents an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms.)

Specific examples of the halogen atom in X ¹ , X ² or X ³ of the transition metal complex represented by the formula (3) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom Can be mentioned.

Specific examples of the optionally substituted alkyl group having 1 to 10 carbon atoms for X ¹ , X ² or X ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec -Butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group are exemplified, and further these groups are halogen atom, alkoxy group, aryl Examples include substituents substituted with an oxy group, an amino group substituted with a hydrocarbon, or a silyl group substituted with a hydrocarbon. Specific examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoro group Ethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, perfluoropropyl , Perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group, trichloromethyl group, methoxymethyl group, phenoxymethyl group, dimethylaminomethyl group, trimethylsilylmethyl group, etc. The
Of the optionally substituted alkyl groups having 1 to 10 carbon atoms, preferred are methyl, ethyl, isopropyl, tert-butyl, amyl, etc., and more preferred is methyl. .

Examples of the aralkyl group having 7 to 20 carbon atoms in X ¹ , X ² or X ³ include a benzyl group, a naphthylmethyl group, an anthracenylmethyl group, a diphenylmethyl group and the like. Atoms, alkyl groups, alkoxy groups, aryloxy groups, those substituted with an amino group substituted with a hydrocarbon or a silyl group substituted with a hydrocarbon are exemplified, and specific examples thereof include:
(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,
(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, (n-pentylphenyl) methyl Group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, (fluorophenyl) Methyl group, (difluorophenyl) methyl group, (pentafluorophenyl) methyl group, (chlorophenyl) methyl group, (methoxyphenyl) methyl group, (phenoxyphenyl) methyl group, (dimethylaminophenyl) methyl group, (trimethylsilylphenyl) A methyl group etc. are illustrated. A particularly preferred aralkyl group having 7 to 20 carbon atoms which may be substituted is exemplified by a benzyl group.

Examples of the aryl group having 6 to 20 carbon atoms in X ¹ , X ² or X ³ include a phenyl group, a naphthyl group, and an anthracenyl group.
Examples of these groups include those substituted with a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amino group substituted with a hydrocarbon, or a silyl group substituted with a hydrocarbon, and specific examples thereof. Are 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl Group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3 , 4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethyl Phenyl group, Tilphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n- Octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 3,5-difluorophenyl group, penta Examples include fluorophenyl group, 4-chlorophenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 4-phenoxyphenyl group, 4-dimethylaminophenyl group, 4-trimethylsilylphenyl group and the like. . Particularly preferred examples of the optionally substituted aryl group having 6 to 20 carbon atoms include a phenyl group.

Specific examples of the alkoxyl group having 1 to 10 carbon atoms in X ¹ , X ² or X ³ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert -Butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group are exemplified. These may be further substituted, and examples thereof include those substituted with a halogen atom, an alkoxy group, an aryloxy group, an amino group substituted with a hydrocarbon, or a silyl group substituted with a hydrocarbon.
Specific examples of the substituted alkoxyl group include fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, fluoroethoxy group, difluoroethoxy group, trifluoroethoxy group, tetrafluoroethoxy group, pentafluoroethoxy group, perfluoropropoxy group. Group, perfluorobutyloxy group, perfluoropentyloxy group, perfluorohexyloxy group, perfluorooctyloxy group, perfluorodecyloxy group, trichloromethyloxy group, methoxymethoxy group, phenoxymethoxy group, dimethylaminomethoxy group, Examples include a trimethylsilylmethoxy group. A particularly preferred optionally substituted alkoxy group having 1 to 10 carbon atoms is a methoxy group.

Examples of the aralkyloxy group having 7 to 20 carbon atoms in X ¹ , X ² or X ³ include a benzyloxy group, a naphthylmethoxy group, an anthracenylmethoxy group and a diphenylmethoxy group,
These may be further substituted, for example, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amino group substituted with a hydrocarbon, or a silyl group substituted with a hydrocarbon. Specific examples thereof include (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, (2,3,4-trimethylphenyl) methoxy Group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (3,4,5- Limethylphenyl) methoxy group, (2,4,6-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-pentylphenyl) methoxy group, (neopentylphenyl) methoxy group, (n-hexylphenyl) methoxy Group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n Dodecylphenyl) methoxy, (fluorophenyl) methyl, (difluorophenyl) methyl, (pentafluorophenyl) methyl, (chlorophenyl) methyl, (methoxyphenyl) methyl, (phenoxyphenyl) methyl, (dimethyl) Examples include aminophenyl) methyl group and (trimethylsilylphenyl) methyl group. A particularly preferred aralkyloxy group having 7 to 20 carbon atoms which may be substituted is exemplified by a benzyloxy group.

Examples of the aryloxy group having 6 to 20 carbon atoms in X ¹ , X ² or X ³ include a phenoxy group, a naphthoxy group, and an anthracenoxy group.
These may be further substituted, for example, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amino group substituted with a hydrocarbon, or a silyl group substituted with a hydrocarbon. As a specific example,
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, 2,4,4 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 Group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, Sopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, 2-fluoro Phenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, 3,5-difluorophenoxy group, pentafluorophenoxy group, 4-chlorophenoxy group, 2-methoxyphenoxy group, 3-methoxyphenoxy group, 4-methoxyphenoxy group Group, 4-phenoxyphenoxy group, 4-dimethylaminophenoxy group, 4-trimethylsilylphenoxy group and the like. As a particularly preferred aryloxy group having 7 to 20 carbon atoms which may be substituted, a phenoxy group is exemplified.

Examples of the hydrocarbon group of the amino group substituted with an optionally substituted hydrocarbon having 1 to 20 carbon atoms in X ¹ , X ² or X ³ include a methyl group, an ethyl group, an n-propyl group, Carbon atoms such as isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, cyclohexyl, n-octyl and n-decyl Examples thereof include aryl groups having 6 to 20 carbon atoms such as alkyl groups having 1 to 10 carbon atoms, phenyl groups, tolyl groups, xylyl groups, naphthyl groups, and anthracenyl groups. Examples of the amino group substituted with a hydrocarbon having 1 to 20 carbon atoms include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec. -Butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenyl An amino group etc. are mentioned, Preferably a dimethylamino group, a diethylamino group, etc. are mentioned.

The neutral ligand represented by L represents a molecule having a neutral functional group such as ether, sulfide, amine, phosphine, or olefin, and may have a coordination functional group at a plurality of positions in the molecule. .

Examples of the neutral ligand include dimethyl ether, diethyl ether, methyl tert-butyl ether, furan, tetrahydrofuran, dimethoxymethane, dimethoxyethane, dimethyl sulfide, diethyl sulfide, methyl tert-butyl sulfide, thiophene, tetrahydrothiophene, and ethylenedithiol. Dimethyl sulfide, ethylenedithiol diethyl sulfide, trimethylamine, triethylamine, triphenylamine, tricyclohexylamine, pyridine, 2,2'-bipyridine, tetramethylethylenediamine, tetraethylethylenediamine, triphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine , Bis (diphenylphosphino) methane, bis (diph Niruhosufino) ethane, bis (diphenylphosphino) propane, bis (diphenylphosphino) binaphthyl, ethylene, propylene, butene, butadiene, octene, octadiene, cyclohexene, cyclohexadiene, norbornene, norbornadiene, and the like.

Examples of the transition metal compound represented by the formula (3) include tetrabenzyl titanium, tetraneopentyl titanium, titanium tetrachloride, tetraisopropoxy titanium, diisopropoxy titanium dichloride, tetrakis (dimethylamino) titanium, tetrakis (diethylamino) titanium. Bis (dimethylamino) titanium dichloride, bis (diethylamino) titanium dichloride, tetrakis (trifluoroacetoxy) titanium, bis (trifluoroacetoxy) titanium dichloride, titanium trichloride-3tetrahydrofuran complex, titanium tetrachloride-2tetrahydrofuran complex,

Tetrabenzylzirconium, tetraneopentylzirconium, zirconium tetrachloride, tetraisopropoxyzirconium, diisopropoxyzirconium dichloride, tetrakis (dimethylamino) zirconium, tetrakis (diethylamino) zirconium, bis (dimethylamino) zirconium dichloride, bis (diethylamino) zirconium Dichloride, tetrakis (trifluoroacetoxy) zirconium, bis (trifluoroacetoxy) zirconium dichloride, zirconium trichloride-3tetrahydrofuran complex, zirconium tetrachloride-2tetrahydrofuran complex,

Tetrabenzylhafnium, tetraneopentylhafnium, hafnium tetrachloride, tetraisopropoxyhafnium, diisopropoxyhafnium dichloride, tetrakis (dimethylamino) hafnium, tetrakis (diethylamino) hafnium, bis (dimethylamino) hafnium dichloride, bis (diethylamino) hafnium Examples include dichloride, tetrakis (trifluoroacetoxy) hafnium, bis (trifluoroacetoxy) hafnium dichloride, hafnium trichloride-3 tetrahydrofuran complex, and hafnium tetrachloride-2 tetrahydrofuran complex. Preferred examples include titanium tetrachloride, titanium tetrachloride-2 tetrahydrofuran complex, and zirconium tetrachloride-2 tetrahydrofuran complex.

In the transition metal complex represented by the formula (1) thus produced, the compound (A) or the compound (B) can be charged and used in any order during the polymerization. A reaction product obtained by previously contacting a combination of the above compounds can also be used.

[Compound (A)]
As the compound (A) used in the present invention, a known organoaluminum compound can be used. Preferably, any one of the above-mentioned compounds (A1) to (A3) or a mixture of two or more thereof can be mentioned.
(A1): an organoaluminum compound represented by the formula E1 a Al (Z) 3-a,
(A2): a cyclic aluminoxane having a structure represented by the formula {-Al (E2) -O-} b;
(A3): A linear aluminoxane having the structure represented by the formula E3 {-Al (E3) -O-} c Al (E3) 2 (wherein E1 to E3 are the same or different and have 1 to 8 is a hydrocarbon group, Z is the same or different and represents a hydrogen atom or a halogen atom, a is 1, 2 or 3, b is an integer of 2 or more, and c is an integer of 1 or more.)

Specific examples of the organoaluminum compound (A1) represented by the formula E1 a AlZ3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum; dimethylaluminum chloride, diethylaluminum Dialkylaluminum chlorides such as chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; Examples thereof include dialkylaluminum hydrides such as id, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride. Trialkylaluminum is preferable, and triethylaluminum, triisobutylaluminum, and the like are more preferable.

A linear aluminoxane (A2) having a structure represented by the formula {-Al (E2) -O-} b or a linear structure having a structure represented by the formula E3 {-Al (E3) -O-} c AlE3 2 Specific examples of E2 and E3 in the aluminoxane (A3) include alkyl groups such as methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal pentyl group and neopentyl group. it can. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E2 or E3 is a methyl group or an isobutyl group, b is 2 to 40, and c is 1 to 40. Specific examples thereof include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), butylaluminoxane (BAO) and the like.

Commercially available aluminoxanes may be used, and those produced by various methods may be used. There is no restriction | limiting in particular about the method, What is necessary is just to produce according to a well-known method. For example, a solution in which trialkylaluminum (for example, trimethylaluminum) is dissolved in a suitable organic solvent (benzene, aliphatic hydrocarbon, etc.) is made by contacting with water. Moreover, the method of making a trialkylaluminum (for example, trimethylaluminum etc.) contact with the metal salt (for example, copper sulfate hydrate etc.) containing crystal water can be illustrated.

[Compound B]
In the present invention, the compound (B) includes (B1) a boron compound represented by the formula BQ1 Q2 Q3, (B2) a boron compound represented by the formula Z + (BQ1 Q2 Q3 Q4)-, (B3) the formula (L Any one of boron compounds represented by -H) + (BQ1 Q2 Q3 Q4)-or a mixture of two or more thereof is used.

In the boron compound (B1) represented by the formula BQ1 Q2 Q3, B is a boron atom in a trivalent valence state, Q1 to Q3 are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a carbon number of 1 ~ 20 halogenated hydrocarbon groups, silyl groups substituted with 1 to 20 carbon atoms, amino groups substituted with 1 to 20 carbon atoms or alkoxy groups having 1 to 20 carbon atoms Groups, which may be the same or different. Preferred examples of Q1 to Q3 include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of (B1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane, and tris. (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, and the like are preferable, but tris (pentafluorophenyl) is preferable. For example, borane.

In the boron compound (B2) represented by the formula Z + (BQ1 Q2 Q3 Q4)-, Z + is an inorganic or organic cation, B is a boron atom in a trivalent valence state, and Q1 to Q4 are The same thing as Q1-Q3 in said (B1) is mentioned.

As a specific example of a compound represented by the formula Z + (BQ1 Q2 Q3 Q4)-, an inorganic cation Z + includes a ferrocenium cation, an alkyl-substituted ferrocenium cation, a silver cation, and the like. Examples of the cation Z + include triphenylmethyl cation. (BQ1 Q2 Q3 Q4)-includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, Tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) Examples include borate.

Specific combinations of these include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylmethyl tetrakis (Pentafluorophenyl) borate, triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned, and triphenylmethyltetrakis (pentafluorophenyl) borate is preferable.

In the boron compound (B3) represented by the formula (LH) + (BQ1 Q2 Q3 Q4)-, L is a neutral Lewis base, (LH) + is a Bronsted acid, B is a boron atom in a trivalent valence state, and Q1 to Q4 are the same as Q1 to Q3 in (B1) above.

Specific examples of the compound represented by the formula (LH) + (BQ1 Q2 Q3 Q4)-include Bronsted acid (LH) + include trialkyl-substituted ammonium, N, N-dialkylaniline. Ni, dialkylammonium, triarylphosphonium and the like, and (BQ1 Q2 Q3 Q4)-include the same as described above.

Specific combinations of these include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium Tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2,4 , 6-Pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl Borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethyl) Phenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like, and preferably tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. Can be mentioned.

The amount of each catalyst component used is such that the molar ratio of compound (A) / transition metal complex (1) is 0.1 to 10,000, preferably 5 to 2000, and molar ratio of compound (B) / transition metal complex (1). It is desirable to use each component so that is in the range of 0.01 to 100, preferably 0.5 to 10.
Regarding the concentration when each catalyst component is used in a solution state, the transition metal complex (1) is 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter, and the compound (A) is In terms of Al atom, 0.01 to 500 mmol / liter, preferably 0.1 to 100 mmol / liter, and compound (B) is 0.0001 to 5 mmol / liter, preferably 0.001 to It is desirable to use each component so that it is in the range of 1 mmol / liter.

In the present invention, the monomer used for the polymerization may be any olefin or diolefin having 2 to 20 carbon atoms, and two or more types of monomers may be used at the same time. Such monomers are exemplified below, but are not limited to the following compounds. Specific examples of such olefins include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, 5-methyl-2-pentene-1, Vinylcyclohexene and the like are exemplified. Examples of the diolefin compound include conjugated dienes and nonconjugated dienes of hydrocarbon compounds. Specific examples of such compounds include 1,5-hexadiene, 1,4-hexadiene, 1 , 4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6 -Octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5 , 8-endomethylenehexahydronaphthalene and the like, and specific examples of the conjugated diene compound include 1,3 Butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, can be exemplified 1,3-cyclohexadiene and the like.
Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, propylene and butene-1, and 5-ethylidene-2-norbornene. Combinations and the like are exemplified, but the present invention is not limited to the above compounds.

In the present invention, an aromatic vinyl compound can also be used as a monomer. Specific examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o -Chlorostyrene, p-chlorostyrene, α-methylstyrene, divinylbenzene and the like.

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

The polymerization temperature can range from −50 ° C. to 200 ° C., but the range of about −20 ° C. to 100 ° C. is particularly preferable, and the polymerization pressure is preferably normal pressure to 6 MPa (60 kg / cm 2 G). In general, the polymerization time is appropriately selected depending on the kind of the target polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours. In the present invention, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the copolymer.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these Examples. Moreover, the property of the polymer in an Example was measured with the following method.

[Molecular weight and molecular weight distribution]
It measured on condition of the following using RapidGPC (made by Symyx).
Liquid feeding device: (LC pump) manufactured by Gilson
Model305 (pump head 25.SC)
Column: manufactured by Polymer Laboratories (PL)
PLgel Mixed-B 10 μm
7.5mmφ × 300mm
Mobile phase: o-dichlorobenzene Dissolving solvent: 1,2,4-trichlorobenzene
Flow rate: 2 ml / min Column temperature: 160 ° C
Calibration curve: 8 standard samples of polystyrene (PS)
(Standard PS molecular weight) 5,000, 10,050, 28,500, 65,500
185,400, 483,000, 1,013,000, 3,390,000

[Melting point]
The measurement was performed under the following conditions using SAMMS (Sensor Array Modular System) (manufactured by Symyx).
Measurement mode: Melting temperature measurement by heat capacity spectroscopy Atmospheric gas: Vacuum condition (3.0 × 10 ^-4 Torr or less)
Temperature program: (start) room temperature
(Temperature increase rate) Approximately 50 ° C / min
(Hold) 200 ° C (0 min)

[Me branch]
Measurement was performed under the following conditions using IR (EQUINOX55 manufactured by Bruker).
Measurement mode: reflection transmission method (film creation on mirror surface)
Blank: Mirror surface (Air)
Measurement conditions: (Resolution) 2cm ^-1 , (Integration count) 128 times,
(Wavelength) 400-4000cm ^-1

１-メトキシメトキシ−２−ｔｅｒｔ−ブチル−４−メチルベンゼン（２０．８ｇ、１００．０ｍｍｏｌ）のテトラヒドロフラン溶液（１４０．７ｍＬ）に−７８℃でｎ―ブチルリチウム１．５６Ｍヘキサン溶液（６７．３ｍL）を滴下し、室温まで昇温し１時間攪拌した。反応混合液を三塩化リン（７．９５g、５０．０ｍｍｏｌ）のテトラヒドロフラン溶液（９３．８mL）に−７８℃にて滴下し、室温に昇温し５時間攪拌した。不溶物を濾別した濾液を減圧留去することにより化合物［１］を定量的に得た。
ペンタフルオロブロモベンゼン（７．４１ｇ、３０．０ｍｍｏｌ）のジエチルエーテル溶液（１１６．８ｍＬ）に、−７８℃でｎ―ブチルリチウム１．５６Ｍヘキサン溶液（２１．２ｍL）を滴下し１時間攪拌した。反応混合溶液に化合物［１］（１４．４３ｇ、３０．０ｍｍｏｌ）のジエチルエーテル溶液（５０．０ｍＬ）を滴下し室温まで昇温し５時間攪拌した。脱イオン水（１００ｍＬ）とトルエン（１００ｍＬ）を加え反応を停止し、有機層を飽和食塩水（１００ｍＬ）で洗浄した後、溶媒を留去し白色固体として化合物［２］を１７．９ｇ（収率９８．０％）得た。
化合物［２］（４．１４ｇ、６．７６ｍｍｏｌ）の酢酸エチル/メタノール=１/１溶液（１６５．０ｍＬ）に室温でアセチルクロライド（２．６５ｇ、３３．８ｍｍｏｌ）を加え室温で１５時間攪拌した。溶媒を減圧留去することにより、白色固体として化合物［３］を２，５５ｇ（７２．０％）で得た。 Synthesis [Synthesis Reference Example 1]
[Synthesis of Compound 3]

To a solution (140.7 mL) of 1-methoxymethoxy-2-tert-butyl-4-methylbenzene (20.8 g, 100.0 mmol) in tetrahydrofuran (140.7 mL) at −78 ° C. is a 1.56 M hexane solution (67.3 mL). ) Was added dropwise, and the mixture was warmed to room temperature and stirred for 1 hour. The reaction mixture was added dropwise to a tetrahydrofuran solution (93.8 mL) of phosphorus trichloride (7.95 g, 50.0 mmol) at −78 ° C., warmed to room temperature, and stirred for 5 hours. Compound [1] was quantitatively obtained by distilling off the filtrate obtained by filtering insolubles under reduced pressure.
To a diethyl ether solution (116.8 mL) of pentafluorobromobenzene (7.41 g, 30.0 mmol), an n-butyllithium 1.56M hexane solution (21.2 mL) was added dropwise at −78 ° C. and stirred for 1 hour. A solution of compound [1] (14.43 g, 30.0 mmol) in diethyl ether (50.0 mL) was added dropwise to the reaction mixture, and the mixture was warmed to room temperature and stirred for 5 hours. The reaction was stopped by adding deionized water (100 mL) and toluene (100 mL), and the organic layer was washed with saturated brine (100 mL), and then the solvent was distilled off to obtain 17.9 g (yield) of Compound [2] as a white solid. (Rate 98.0%).
Acetyl chloride (2.65 g, 33.8 mmol) was added to a solution of compound [2] (4.14 g, 6.76 mmol) in ethyl acetate / methanol = 1/1 (165.0 mL) at room temperature, and the mixture was stirred at room temperature for 15 hours. . The solvent was distilled off under reduced pressure to obtain 2,55 g (72.0%) of Compound [3] as a white solid.

６０％のＮａＨ（０．１８ｇ、４．５ｍｍｏｌ）のテトラヒドロフランスラリー（２．６６ｍＬ）に、０℃で化合物３（０．３９ｇ、０．７５ｍｍｏｌ）のテトラヒドロフラン溶液（３．５４ｍＬ）を滴下し、室温まで昇温し１時間攪拌した。過剰のＮａＨを濾過することで除去し、濾液にトリクロロチタニウム−３テトラヒドロフラン錯体（０．２８ｇ、０．７５ｍｍｏｌ）のテトラヒドロフラン溶液（２．６６ｍＬ）を０℃で滴下した。室温まで昇温し１０時間攪拌し溶媒を減圧留去後、トルエン（５．０ｍＬ）を加え、不溶物を濾別した濾液を減圧留去することにより、錯体［４］を赤色固体として、２４８．２ｍｇ（６０．６％）得た。
ＭＳスペクトル（ＥＩ） １０９２（Ｍ＋） [Example 1]
[Synthesis of Complex 4]

To a tetrahydrofuran slurry (2.66 mL) of 60% NaH (0.18 g, 4.5 mmol), a tetrahydrofuran solution (3.54 mL) of compound 3 (0.39 g, 0.75 mmol) was added dropwise at 0 ° C. The mixture was heated up to 1 hour and stirred for 1 hour. Excess NaH was removed by filtration, and a tetrahydrofuran solution (2.66 mL) of trichlorotitanium-3 tetrahydrofuran complex (0.28 g, 0.75 mmol) was added dropwise to the filtrate at 0 ° C. The mixture was warmed to room temperature and stirred for 10 hours, and the solvent was distilled off under reduced pressure. Toluene (5.0 mL) was added, and the filtrate obtained by filtering off the insoluble matter was distilled off under reduced pressure. Obtained 2 mg (60.6%).
MS spectrum (EI) 1092 (M +)

Polymerization [Example 2]
In an autoclave, 5.0 mL of toluene was charged under nitrogen and stabilized at 40 ° C. Then, ethylene was pressurized to 0.60 MPa and stabilized. To this, MMAO (100 μmol) and complex [4] (0.10 μmol) were added and polymerized for 20 minutes. As a result of the polymerization, 1.5 × 10 ⁶ g of polymer was produced per hour per 1 mole of titanium.

[Example 3]
Polymerization was conducted in the same manner as in Example 2 except that hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical) and pentafluorophenylborane (0.30 μmol) were used instead of MMAO. As a result of the polymerization, 1.0 × 10 ⁵ g of polymer was produced per hour per 1 mole of titanium.

[Example 4]
Polymerization was conducted in the same manner as in Example 2 except that hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical) and dimethylanilinium tetrakis (pentafluorophenyl) borate (0.30 μmol) were used instead of MMAO. went. As a result of the polymerization, 4.3 × 10 ⁶ g of polymer was produced per hour per 1 mole of titanium.

[Example 5]
Polymerization was conducted in the same manner as in Example 2 except that hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical) and triphenylmethyltetrakis (pentafluorophenyl) borate (0.30 μmol) were used instead of MMAO. went. As a result of the polymerization, 3.9 × 10 ⁶ g of polymer was produced per hour per 1 mole of titanium.

[Example 6]
Under nitrogen, 5.0 mL of toluene and 1-hexene (60 μL) were charged in an autoclave and stabilized at 40 ° C. Then, ethylene was pressurized to 0.60 MPa and stabilized. MMAO (100 μmol) and complex 4 (0.10 μmol) were added thereto and polymerized for 3.6 minutes. As a result of polymerization, a polymer having a molecular weight (Mw) = 3.4 × 10 ⁵ , a molecular weight distribution (Mw / Mn) = 6.3, and a melting point (Tm) = 12.5 ° C. 3 × 10 ⁶ g were produced.

[Example 7]
Polymerization was performed in the same manner as in Example 6 except that hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical) and pentafluorophenylborane (0.30 μmol) were used instead of MMAO. As a result of the polymerization, 1.0 × 10 ⁵ g of polymer was produced per hour per 1 mole of titanium.

[Example 8]
Polymerization was conducted in the same manner as in Example 6 except that hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical) and dimethylanilinium tetrakis (pentafluorophenyl) borate (0.30 μmol) were used instead of MMAO. went. As a result of the polymerization, a polymer having a molecular weight (Mw) = 6.2 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 6.5, a melting point (Tm) = 124.8 ° C., and a Me branch of 11 per 1000 carbons is titanium. 4.0 × 10 ⁶ g was produced per hour per mole.

[Example 9]
Polymerization was conducted in the same manner as in Example 6 except that hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical) and triphenylmethyltetrakis (pentafluorophenyl) borate (0.30 μmol) were used instead of MMAO. went. As a result of the polymerization, a polymer having a molecular weight (Mw) = 4.60 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 5.5, a melting point (Tm) = 124.8 ° C., and a Me branch of 10 per 1000 carbons is titanium. 3.6 × 10 ⁶ g was produced per hour per mol.

[Example 10]
Under nitrogen, toluene was charged with 5.0 mL of toluene and 1-hexene (50 μL) and stabilized at 70 ° C. Then, ethylene was pressurized to 0.60 MPa and stabilized. MMAO (100 μmol) and complex [4] (0.10 μmol) were added thereto and polymerized for 20 minutes. As a result of the polymerization, 7.0 × 10 ⁵ g of polymer was produced per hour per 1 mole of titanium.

[Example 11]
Polymerization was performed in the same manner as in Example 10 except that hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical) and dimethylanilinium tetrakis (pentafluorophenyl) borate (0.30 μmol) were used instead of MMAO. went. As a result of the polymerization, a polymer having a molecular weight (Mw) = 6.7 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 3.8, and a melting point (Tm) = 120.9 ° C. is 2 per hour per 1 mole of titanium. 0.0 × 10 ⁶ g was produced.

[Example 12]
Polymerization was conducted in the same manner as in Example 10 except that hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical) and triphenylmethyltetrakis (pentafluorophenyl) borate (0.30 μmol) were used instead of MMAO. went. As a result of the polymerization, a polymer having a molecular weight (Mw) = 6.7 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 3.7, and a melting point (Tm) = 121.0 ° C. is 2 per hour per 1 mole of titanium. 3 × 10 ⁷ g were produced.

[Example 13]
Under nitrogen, 5.0 mL of toluene and 1-hexene (40 μL) were charged in an autoclave and stabilized at 130 ° C., and then ethylene was pressurized to 0.60 MPa and stabilized. MMAO (10 μmol) and complex [4] (0.10 μmol) were added thereto and polymerized for 5 minutes. As a result of the polymerization, 2.0 × 10 ⁵ g of polymer was produced per hour per 1 mole of titanium.

[Example 14]
Polymerization was conducted in the same manner as in Example 13 except that hexane solution of triisobutylaluminum (4 μL, 1.0 M, Kanto Chemical) and dimethylanilinium tetrakis (pentafluorophenyl) borate (0.030 μmol) were used instead of MMAO. went. As a result of the polymerization, 3.00 × 10 ⁵ g of polymer was produced per hour per 1 mole of titanium.

[Example 15]
Polymerization was conducted in the same manner as in Example 13 except that hexane solution of triisobutylaluminum (4 μL, 1.0 M, Kanto Chemical) and triphenylmethyltetrakis (pentafluorophenyl) borate (0.30 μmol) were used instead of MMAO. went. As a result of the polymerization, 3.0 × 10 ⁵ g of polymer was produced per hour per 1 mole of titanium.

Claims (7)

Formula (1)

(In the formula, M represents an element belonging to Group 4 of the periodic table of elements, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different, A hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, and an optionally substituted carbon atom having 6 to 20 carbon atoms Aryl groups, silyl groups substituted with optionally substituted hydrocarbons having 1 to 20 carbon atoms, optionally substituted alkoxy groups with 1 to 10 carbon atoms, optionally substituted carbon atoms An aralkyloxy group having 7 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms which may be substituted, or an amino group which may be substituted with an optionally substituted hydrocarbon having 1 to 20 carbon atoms R ⁹ and R ¹⁰ are The same or different, and represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms, and n represents 0 or 1.)
A transition metal complex represented by The transition metal complex according to claim 1, wherein M is a titanium atom. Formula (2)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and n represent the same meaning as described above.)
A substituted phenol represented by formula (3)

(In the formula, M represents an element belonging to Group 4 of the periodic table of elements, and X ¹ , X ² and X ³ are the same or different, and each represents a hydrogen atom, a halogen atom, or an optionally substituted carbon atom. -10 alkyl group, optionally substituted aralkyl group having 7 to 20 carbon atoms, optionally substituted aryl group having 6 to 20 carbon atoms, optionally substituted carbon atom 1 to 10 Substituted with an optionally substituted aralkyloxy group having 7 to 20 carbon atoms, an optionally substituted aryloxy group having 6 to 20 carbon atoms or a hydrocarbon having 1 to 20 carbon atoms. L represents a neutral ligand, and l and m independently represent an integer of 0 to 2.)
A process for producing a transition metal complex represented by the formula (1), wherein the transition metal compound represented by formula (1) is reacted. The production method according to claim 3, wherein the reaction is carried out in the presence of a base. An olefin polymerization catalyst comprising the transition metal complex according to claim 1 and the following compound (A) in combination.
Compound (A): Any of the following compounds (A1) to (A3), or a mixture of two or more thereof (A1): an organoaluminum compound represented by the formula (E1) a Al (Z) 3-a,
(A2): a cyclic aluminoxane having a structure represented by the formula {-Al (E2) -O-} b;
(A3): Formula (E3) {-Al (E3) -O-} c Linear aluminoxane having a structure represented by Al (E3) 2 (wherein E1 to E3 are the same or different, and the number of carbon atoms 1 to 8 hydrocarbon groups, Z is the same or different and represents a hydrogen atom or a halogen atom, a represents 1, 2 or 3, b represents an integer of 2 or more, and c represents an integer of 1 or more .) An olefin polymerization catalyst comprising a combination of the transition metal complex according to claim 1, the compound (A) and the following compound (B).
Compound (B): Any of the following compounds (B1) to (B3), or a mixture of two or more thereof (B1): A boron compound represented by the formula BQ1 Q2 Q3,
(B2): a boron compound represented by the formula Z + (BQ1 Q2 Q3 Q4)-
(B3): Boron compound represented by the formula (LH) + (BQ1 Q2 Q3 Q4)-(wherein B is a boron atom in a trivalent valence state, and Q1 to Q4 are the same or different) A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silyl group substituted with a hydrocarbon having 1 to 20 carbon atoms, or 1 to 20 carbon atoms An amino group substituted with an alkoxy group or a hydrocarbon having 1 to 20 carbon atoms.) A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 5.