JP2005290057A - Olefin polymerization catalyst component and process for producing olefin polymer - Google Patents

Abstract

（式中、ｎは０又は１を表し、Ｒ^１は水素原子、置換されていてもよい炭素数１〜１０のアルキル基、置換されていてもよい炭素数６〜２０のアリール基、置換されていてもよい炭素数７〜２０のアラルキル基、置換されていてもよい炭素数１〜１０のアルコキシ基、置換されていてもよい炭素数６〜２０のアリールオキシ基等、Ｒ^２及びＲ^３は同一又は相異なり、水素原子、置換されていてもよい炭素数１〜１０のアルキル基、置換されていてもよい炭素数６〜２０のアリール基等、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は同一又は相異なり、水素原子、ハロゲン原子、置換されていてもよい炭素数１〜１０のアルキル基等を示す。）で示される２−アミノフェニルホスフィン化合物と、周期表第８−１０族の遷移金属を含む遷移金属化合物とを組合わせてなることを特徴とするオレフィン重合触媒成分。
【選択図】 なしPROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst.
SOLUTION: Formula (1)

(In the formula, n represents 0 or 1, R ¹ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or substituted. R ² and R ³ such as an optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, and an optionally substituted aryloxy group having 6 to 20 carbon atoms. Are the same or different and are a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, R ⁴ , R ⁵ , R ⁶ and R ⁷ is the same or different and represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, etc.) and a group 8-10 of the periodic table Transition metal compounds including Olefin polymerization catalyst component characterized by comprising in combination.
[Selection figure] None

Description

  The present invention relates to a novel polymerization catalyst component and a method for producing an olefin polymer using the same.

A catalyst using a Group 10 transition metal compound in the periodic table is known to be useful as an olefin polymerization catalyst (see, for example, Non-Patent Document 1 and Non-Patent Document 2). For example, diimine is coordinated. Catalyst system using nickel and palladium compounds (for example, see Patent Document 1), catalyst system using monoimine and amine compounds as catalyst components (for example, see Patent Document 2), catalyst system using phosphine compounds as catalyst components (for example, Patent Documents 3 and 4) are known. However, the catalyst is easily deactivated, and is not necessarily practical in terms of polymerization activity in an olefin polymerization reaction with a large exotherm.
WO96 / 23010 WO97 / 02298 US6555926 US4472525 Chem. Rev. 2000, 100, 1169-1203 Chem. Rev. 2003, 103, 283-315

  Under such circumstances, it has been desired to develop a catalyst that can produce an olefin polymer having excellent activity using a late transition metal compound typified by Group 10.

  As a result of intensive studies to solve the above problems, the present inventors have found a late metal catalyst exhibiting high activity, and have reached the present invention.

（式中、ｎは０又は１を表し、Ｒ^１は水素原子、置換されていてもよい炭素数１〜１０のアルキル基、置換されていてもよい炭素数６〜２０のアリール基、置換されていてもよい炭素数７〜２０のアラルキル基、置換されていてもよい炭素数１〜１０のアルコキシ基、置換されていてもよい炭素数６〜２０のアリールオキシ基、置換されていてもよい炭素数７〜２０のアラルキルオキシ基又は炭素数１〜２０の炭化水素基で置換されたアミノ基を示し、Ｒ^２及びＲ^３は同一又は相異なり、水素原子、置換されていてもよい炭素数１〜１０のアルキル基、置換されていてもよい炭素数６〜２０のアリール基、置換されていてもよい炭素数７〜２０のアラルキル基、置換されていてもよい炭素数２から２０のアシル基、又は置換されていてもよい炭素数１から２０のスルホニル基を示し、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は同一又は相異なり、水素原子、ハロゲン原子、置換されていてもよい炭素数１〜１０のアルキル基、置換されていてもよい炭素数１〜１０のアルコキシ基、置換されていてもよい炭素数６〜２０のアリール基、置換されていてもよい炭素数６〜２０のアリールオキシ基、置換されていてもよい炭素数７〜２０のアラルキル基、置換されていてもよい炭素数７〜２０のアラルキルオキシ基、炭素数１〜２０の炭化水素で置換されたシリル基又は炭素数１〜２０の炭化水素で置換されたシリルオキシ基を示し、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７間で隣接する基は互いに結合して環を形成していてもよい。）
で示される２−アミノフェニルホスフィン化合物と、
周期表第８−１０族の遷移金属を含む遷移金属化合物とを組合わせてなることを特徴とするオレフィン重合触媒成分、及びこれを用いてオレフィンを重合させるオレフィン重合体の製造方法を提供するものである。 That is, the present invention provides the formula (1)

(In the formula, n represents 0 or 1, R ¹ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or substituted. An optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 6 to 20 carbon atoms, and optionally substituted. An amino group substituted with an aralkyloxy group having 7 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, R ² and R ³ are the same or different and are a hydrogen atom or an optionally substituted carbon number. An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted, an aralkyl group having 7 to 20 carbon atoms which may be substituted, and an acyl having 2 to 20 carbon atoms which may be substituted Group or may be substituted Indicates a sulfonyl group having a carbon number of 1 to ^{20, R 4, R 5,} R 6 and ^{R 7} are the same or different, a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a substituted An optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, an optionally substituted aryloxy group having 6 to 20 carbon atoms, and optionally substituted. A good aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms which may be substituted, a silyl group substituted with a hydrocarbon having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms A substituted silyloxy group, and adjacent groups among R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be bonded to each other to form a ring.
A 2-aminophenylphosphine compound represented by:
An olefin polymerization catalyst component comprising a combination of a transition metal compound containing a transition metal of Group 8-10 of the periodic table, and a method for producing an olefin polymer for polymerizing an olefin using the same It is.

The present invention can provide an olefin polymerization catalyst component having excellent activity.

Hereinafter, the present invention will be described in detail.
In the 2-aminophenylphosphine compound represented by the formula (1) (hereinafter referred to as 2-aminophenylphosphine compound (1)), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R Specific examples of the optionally substituted alkyl group having 1 to 10 carbon atoms in ⁷ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, and these substituents are halogen atoms, alkoxy groups, aryloxy groups or hydrocarbons Examples of the substituents substituted with a silyl group substituted with are, for example, a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group. , Fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorooctyl group Examples include a fluorodecyl group, a trichloromethyl group, a methoxymethyl group, a phenoxymethyl group, and a trimethylsilylmethyl group.

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. .

Specific examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ include benzyl group, naphthylmethyl group, anthra Exemplified are senylmethyl groups, diphenylmethyl groups, and those in which these substituents are substituted with halogen atoms, alkyl groups, alkoxy groups, aryloxy groups, or silyl groups substituted with hydrocarbons. Specific examples of the aralkyl group having 7 to 20 carbon atoms which may be present include, for example, (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. 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-pentyl) Enyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, Examples include fluorophenyl) methyl group, (difluorophenyl) methyl group, (pentafluorophenyl) methyl group, (chlorophenyl) methyl group, (methoxyphenyl) methyl group, (phenoxyphenyl) methyl group, and (trimethylsilylphenyl) methyl group Preferred examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted include a benzyl group.

Specific 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 and R ⁷ include a phenyl group, a naphthyl group, and an anthracenyl group. And those in which these substituents are substituted with a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or a silyl group substituted with a hydrocarbon, and specific examples thereof include 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-tetramethylphenyl 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, 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, pentafluorophenyl group, 4 -Chlorophenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methyl Examples thereof include a xyphenyl group, a 4-phenoxyphenyl group, a 4-dimethylaminophenyl group, and a 4-trimethylsilylphenyl group. Preferred examples of the optionally substituted aryl group having 6 to 20 carbon atoms include a phenyl group. It is done.

Specific examples of the optionally substituted alkoxy group having 1 to 10 carbon atoms in R ¹ , R ⁴ , R ⁵ , R ⁶ and R ⁷ include a methoxy group, an ethoxy group, an n-propoxy group, and an 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, and And those substituted by a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or a silyl group substituted with a hydrocarbon, and specific examples thereof include a fluoromethoxy group, a difluoromethoxy group, and the like. Group, trifluoromethoxy group, fluoroethoxy group, difluoroethoxy group, trifluoroethoxy group, tetrafluoro group Ethoxy group, pentafluoroethoxy group, perfluoropropoxy group, perfluorobutyloxy group, perfluoropentyloxy group, perfluorohexyloxy group, perfluorooctyloxy group, perfluorodecyloxy group, trichloromethyloxy group, methoxymethoxy Group, phenoxymethoxy group, trimethylsilylmethoxy group and the like are exemplified. Preferable examples of the optionally substituted alkoxy group having 1 to 10 carbon atoms include a methoxy group and an ethoxy group.

Specific examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted in R ¹ , R ⁴ , R ⁵ , R ⁶ and R ⁷ include a benzyloxy group, a naphthylmethoxy group, and an anthracenylmethoxy group. , Diphenylmethoxy groups, and those substituents substituted with halogen atoms, alkyl groups, alkoxy groups, aryloxy groups, amino groups substituted with hydrocarbons, silyl groups substituted with hydrocarbons, or the like 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, , 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-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetra) (Methylphenyl) 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 Si 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. Preferred examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group.

Specific examples of the optionally substituted aryloxy group having 6 to 20 carbon atoms in R ¹ , R ⁴ , R ⁵ , R ⁶ and R ⁷ include a phenoxy group, a naphthoxy group, an anthracenoxy group, and these Examples in which the substituent is substituted with a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or a silyl group substituted with a hydrocarbon are exemplified, and specific examples thereof include 2-methylphenoxy group, 3-methyl Phenoxy 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, n-decylphenoxy group, n-tetradecylphenoxy group, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-fluoro Phenoxy group, 3,5-difluorophenoxy group, pentafluor Examples include a lophenoxy group, 4-chlorophenoxy group, 2-methoxyphenoxy group, 3-methoxyphenoxy group, 4-methoxyphenoxy group, 4-phenoxyphenoxy group, 4-trimethylsilylphenoxy group. Preferable examples of the optionally substituted aryloxy group having 7 to 20 carbon atoms include a phenoxy group.

Examples of the hydrocarbon group in the silyl group substituted with an optionally substituted hydrocarbon having 1 to 20 carbon atoms in R ⁴ , R ⁵ , R ⁶ and R ⁷ include, for example, a methyl group, 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, cyclohexyl group, n-octyl group, n-decyl group, etc. And an aryl group having 6 to 20 carbon atoms such as an alkyl group having 1 to 10 carbon atoms, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and an anthracenyl group. Examples of the silyl group substituted with are monosubstituted silyl groups such as methylsilyl group, ethylsilyl group, and phenylsilyl group, dimethylsilyl group, and diethylsilyl group. Group, diphenylsilyl group and other 2-substituted silyl groups, 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, etc. Preferred examples of the silyl group substituted with an optionally substituted hydrocarbon having 1 to 20 carbon atoms include a trimethylsilyl group, a tert-butyldimethylsilyl group, and a triphenylsilyl group.

The amino group substituted with an optionally substituted hydrocarbon having 1 to 20 carbon atoms in R ¹ is an amino group substituted with two hydrocarbon groups, and the hydrocarbon group here is For example, 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, n-hexyl group, cyclohexyl group And alkyl groups having 1 to 10 carbon atoms such as n-octyl group and n-decyl group, aryl groups having 6 to 20 carbon atoms such as phenyl group, tolyl group, xylyl group, naphthyl group and anthracenyl group. It is done. 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 acyl group having 2 to 20 carbon atoms which may be substituted in R ² and R ³ is an acetyl group, propioyl group, pivaloyl group, hexanoyl group, octanoyl group, decanoyl group, benzoyl group, trifluoroacetyl group, trichloro group. An acetyl group, a pentafluorobenzoyl group, a p-chlorobenzoyl group, etc. are mentioned, Preferably an acetyl group, a benzoyl group, etc. are mentioned.

Examples of the optionally substituted sulfonyl group having 1 to 20 carbon atoms in R ² and R ³ include a methanesulfonyl group, a trifluoromethanesulfonyl group, a benzenesulfonyl group, a p-toluenesulfonyl group, and a p-chlorobenzenesulfonyl group. Preferably, a p-toluenesulfonyl group, a methanesulfonyl group, etc. are mentioned.

Specific examples of the halogen atom in R ⁴ , R ⁵ , R ⁶ and R ⁷ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom and a chlorine atom.

The groups adjacent to R ² , R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring.

Specific examples of the 2-aminophenylphosphine compound (1) include bis (2-aminophenyl) phenylphosphine, bis (2-amino-3-methylphenyl) phenylphosphine, and bis (2-amino-3-phenylphenyl). Phenylphosphine, bis (2-amino-3-benzylphenyl) phenylphosphine, bis (2-amino-3-trimethylsilylphenyl) phenylphosphine, bis (2-amino-5-methoxyphenyl) phenylphosphine, bis (2-amino) -5-phenoxyphenyl) phenylphosphine, bis (2-amino-5-benzyloxyphenyl) phenylphosphine bis (2-amino-5-trimethylsilyloxyphenyl) phenylphosphine, bis (2-amino-3-fluorophenyl) phenyl Hosphy Bis (2-amino-3,5-dimethylphenyl) phenylphosphine, bis (2-amino-3,5-difluorophenyl) phenylphosphine, bis (2-amino-5-fluoro-3-methylphenyl) phenylphosphine Bis (2-aminophenyl) methylphosphine, bis (2-amino-3-methylphenyl) methylphosphine, bis (2-amino-3-phenylphenyl) methylphosphine, bis (2-amino-3-benzylphenyl) Methylphosphine, bis (2-amino-3-trimethylsilylphenyl) methylphosphine, bis (2-amino-5-methoxyphenyl) methylphosphine, bis (2-amino-5-phenoxyphenyl) methylphosphine, bis (2-amino) -5-Benzyloxyphenyl) methylphosphie Bis (2-amino-5-trimethylsilyloxyphenyl) methylphosphine, bis (2-amino-3-fluorophenyl) methylphosphine, bis (2-amino-3,5-dimethylphenyl) methylphosphine, bis (2-amino) -3,5-difluorophenyl) methylphosphine, bis (2-amino-5-fluoro-3-methylphenyl) methylphosphine, bis (2-aminophenyl) -tert-butylphosphine, bis (2-amino-3- Methylphenyl) -tert-butylphosphine, bis (2-amino-3-phenylphenyl) -tert-butylphosphine, bis (2-amino-3-benzylphenyl) -tert-butylphosphine, bis (2-amino-3) -Trimethylsilylphenyl) -tert-butylphosphine Bis (2-amino-5-methoxyphenyl) -tert-butylphosphine, bis (2-amino-5-phenoxyphenyl) -tert-butylphosphine, bis (2-amino-5-benzyloxyphenyl) -tert- Butylphosphine bis (2-amino-5-trimethylsilyloxyphenyl) -tert-butylphosphine, bis (2-amino-3-fluorophenyl) -tert-butylphosphine, bis (2-amino-3,5-dimethylphenyl) -Tert-butylphosphine, bis (2-amino-3,5-difluorophenyl) -tert-butylphosphine, bis (2-amino-5-fluoro-3-methylphenyl) -tert-butylphosphine, bis (2- Aminophenyl) methoxyphosphine, bis (2-amino) 3-methylphenyl) methoxyphosphine, bis (2-amino-3-phenylphenyl) methoxyphosphine, bis (2-amino-3-benzylphenyl) methoxyphosphine, bis (2-amino-3-trimethylsilylphenyl) methoxyphosphine, Bis (2-amino-5-methoxyphenyl) methoxyphosphine, bis (2-amino-5-phenoxyphenyl) methoxyphosphine, bis (2-amino-5-benzyloxyphenyl) methoxyphosphine bis (2-amino-5- Trimethylsilyloxyphenyl) methoxyphosphine, bis (2-amino-3-fluorophenyl) methoxyphosphine, bis (2-amino-3,5-dimethylphenyl) methoxyphosphine, bis (2-amino-3,5-difluorophenyl) Metoki Phosphine, bis (2-amino-5-fluoro-3-methylphenyl) methoxyphosphine, bis (2-aminophenyl) diethylaminophosphine, bis (2-amino-3-methylphenyl) diethylaminophosphine, bis (2-amino- 3-phenylphenyl) diethylaminophosphine, bis (2-amino-3-benzylphenyl) diethylaminophosphine, bis (2-amino-3-trimethylsilylphenyl) diethylaminophosphine, bis (2-amino-5-methoxyphenyl) diethylaminophosphine, Bis (2-amino-5-phenoxyphenyl) diethylaminophosphine, bis (2-amino-5-benzyloxyphenyl) diethylaminophosphine bis (2-amino-5-trimethylsilyloxyphenyl) di Ethylaminophosphine, bis (2-amino-3-fluorophenyl) diethylaminophosphine, bis (2-amino-3,5-dimethylphenyl) diethylaminophosphine, bis (2-amino-3,5-difluorophenyl) diethylaminophosphine, Bis (2-amino-5-fluoro-3-methylphenyl) diethylaminophosphine,

Bis (2-N, N-dimethylamino-phenyl) phenylphosphine, bis (2-N, N-dimethylamino-3-methylphenyl) phenylphosphine, bis (2-N, N-dimethylamino-3-phenylphenyl) ) Phenylphosphine, bis (2-N, N-dimethylamino-3-benzylphenyl) phenylphosphine, bis (2-N, N-dimethylamino-3-trimethylsilylphenyl) phenylphosphine, bis (2-N, N- Dimethylamino-5-methoxyphenyl) phenylphosphine, bis (2-N, N-dimethylamino-5-phenoxyphenyl) phenylphosphine, bis (2-N, N-dimethylamino-5-benzyloxyphenyl) phenylphosphine bis (2-N, N-dimethylamino-5-trimethylsilyloxyphenyl) Phenylphosphine, bis (2-N, N-dimethylamino-3-fluorophenyl) phenylphosphine, bis (2-N, N-dimethylamino-3,5-dimethylphenyl) phenylphosphine, bis (2-N, N -Dimethylamino-3,5-difluorophenyl) phenylphosphine, bis (2-N, N-dimethylamino-5-fluoro-3-methylphenyl) phenylphosphine, bis (2-N, N-dimethylamino-phenyl) Methylphosphine, bis (2-N, N-dimethylamino-3-methylphenyl) methylphosphine, bis (2-N, N-dimethylamino-3-phenylphenyl) methylphosphine, bis (2-N, N-dimethyl) Amino-3-benzylphenyl) methylphosphine, bis (2-N, N-dimethylamino-3-trimethyl) Ruphenyl) methylphosphine, bis (2-N, N-dimethylamino-5-methoxyphenyl) methylphosphine, bis (2-N, N-dimethylamino-5-phenoxyphenyl) methylphosphine, bis (2-N, N -Dimethylamino-5-benzyloxyphenyl) methylphosphine bis (2-N, N-dimethylamino-5-trimethylsilyloxyphenyl) methylphosphine, bis (2-N, N-dimethylamino-3-fluorophenyl) methylphosphine Bis (2-N, N-dimethylamino-3,5-dimethylphenyl) methylphosphine, bis (2-N, N-dimethylamino-3,5-difluorophenyl) methylphosphine, bis (2-N, N -Dimethylamino-5-fluoro-3-methylphenyl) methylphosphine, bis (2-N, N-dimethylamino-phenyl) -tert-butylphosphine, bis (2-N, N-dimethylamino-3-methylphenyl) -tert-butylphosphine, bis (2-N, N-dimethylamino-3-phenylphenyl) ) -Tert-butylphosphine, bis (2-N, N-dimethylamino-3-benzylphenyl) -tert-butylphosphine, bis (2-N, N-dimethylamino-3-trimethylsilylphenyl) -tert-butylphosphine Bis (2-N, N-dimethylamino-5-methoxyphenyl) -tert-butylphosphine, bis (2-N, N-dimethylamino-5-phenoxyphenyl) -tert-butylphosphine, bis (2-N , N-dimethylamino-5-benzyloxyphenyl) -tert-butylphosphine bi (2-N, N-dimethylamino-5-trimethylsilyloxyphenyl) -tert-butylphosphine, bis (2-N, N-dimethylamino-3-fluorophenyl) -tert-butylphosphine, bis (2-N , N-dimethylamino-3,5-dimethylphenyl) -tert-butylphosphine, bis (2-N, N-dimethylamino-3,5-difluorophenyl) -tert-butylphosphine, bis (2-N, N -Dimethylamino-5-fluoro-3-methylphenyl) -tert-butylphosphine, bis (2-N, N-dimethylamino-phenyl) methoxyphosphine, bis (2-N, N-dimethylamino-3-methylphenyl) ) Methoxyphosphine, bis (2-N, N-dimethylamino-3-phenylphenyl) methoxyphosphine Bis (2-N, N-dimethylamino-3-benzylphenyl) methoxyphosphine, bis (2-N, N-dimethylamino-3-trimethylsilylphenyl) methoxyphosphine, bis (2-N, N-dimethylamino-5) -Methoxyphenyl) methoxyphosphine, bis (2-N, N-dimethylamino-5-phenoxyphenyl) methoxyphosphine, bis (2-N, N-dimethylamino-5-benzyloxyphenyl) methoxyphosphine bis (2-N , N-dimethylamino-5-trimethylsilyloxyphenyl) methoxyphosphine, bis (2-N, N-dimethylamino-3-fluorophenyl) methoxyphosphine, bis (2-N, N-dimethylamino-3,5-dimethyl) Phenyl) methoxyphosphine, bis (2-N, N-dimethylamino-3, 5-difluorophenyl) methoxyphosphine, bis (2-N, N-dimethylamino-5-fluoro-3-methylphenyl) methoxyphosphine, bis (2-N, N-dimethylamino-phenyl) diethylaminophosphine, bis (2 -N, N-dimethylamino-3-methylphenyl) diethylaminophosphine, bis (2-N, N-dimethylamino-3-phenylphenyl) diethylaminophosphine, bis (2-N, N-dimethylamino-3-benzylphenyl) ) Diethylaminophosphine, bis (2-N, N-dimethylamino-3-trimethylsilylphenyl) diethylaminophosphine, bis (2-N, N-dimethylamino-5-methoxyphenyl) diethylaminophosphine, bis (2-N, N- Dimethylamino-5-phenoxyphenyl) Ethylaminophosphine, bis (2-N, N-dimethylamino-5-benzyloxyphenyl) diethylaminophosphine bis (2-N, N-dimethylamino-5-trimethylsilyloxyphenyl) diethylaminophosphine, bis (2-N, N -Dimethylamino-3-fluorophenyl) diethylaminophosphine, bis (2-N, N-dimethylamino-3,5-dimethylphenyl) diethylaminophosphine, bis (2-N, N-dimethylamino-3,5-difluorophenyl) ) Diethylaminophosphine, bis (2-N, N-dimethylamino-5-fluoro-3-methylphenyl) diethylaminophosphine,

Bis (2-N-tert-butylamino-phenyl) phenylphosphine, bis (2-N-tert-butylamino-3-methylphenyl) phenylphosphine, bis (2-N-tert-butylamino-3-phenylphenyl) ) Phenylphosphine, bis (2-N-tert-butylamino-3-benzylphenyl) phenylphosphine, bis (2-N-tert-butylamino-3-trimethylsilylphenyl) phenylphosphine, bis (2-N-tert- Butylamino-5-methoxyphenyl) phenylphosphine, bis (2-N-tert-butylamino-5-phenoxyphenyl) phenylphosphine, bis (2-N-tert-butylamino-5-benzyloxyphenyl) phenylphosphine bis (2-N-tert-butylamino- -Trimethylsilyloxyphenyl) phenylphosphine, bis (2-N-tert-butylamino-3-fluorophenyl) phenylphosphine, bis (2-N-tert-butylamino-3,5-dimethylphenyl) phenylphosphine, bis ( 2-N-tert-butylamino-3,5-difluorophenyl) phenylphosphine, bis (2-N-tert-butylamino-5-fluoro-3-methylphenyl) phenylphosphine, bis (2-N-tert- Butylamino-phenyl) methylphosphine, bis (2-N-tert-butylamino-3-methylphenyl) methylphosphine, bis (2-N-tert-butylamino-3-phenylphenyl) methylphosphine, bis (2- N-tert-butylamino-3-benzylphenyl) Methylphosphine, bis (2-N-tert-butylamino-3-trimethylsilylphenyl) methylphosphine, bis (2-N-tert-butylamino-5-methoxyphenyl) methylphosphine, bis (2-N-tert-butyl) Amino-5-phenoxyphenyl) methylphosphine, bis (2-N-tert-butylamino-5-benzyloxyphenyl) methylphosphine bis (2-N-tert-butylamino-5-trimethylsilyloxyphenyl) methylphosphine, bis (2-N-tert-butylamino-3-fluorophenyl) methylphosphine, bis (2-N-tert-butylamino-3,5-dimethylphenyl) methylphosphine, bis (2-N-tert-butylamino- 3,5-difluorophenyl) methylphosphie Bis (2-N-tert-butylamino-5-fluoro-3-methylphenyl) methylphosphine, bis (2-N-tert-butylamino-phenyl) -tert-butylphosphine, bis (2-N-tert -Butylamino-3-methylphenyl) -tert-butylphosphine, bis (2-N-tert-butylamino-3-phenylphenyl) -tert-butylphosphine, bis (2-N-tert-butylamino-3- Benzylphenyl) -tert-butylphosphine, bis (2-N-tert-butylamino-3-trimethylsilylphenyl) -tert-butylphosphine, bis (2-N-tert-butylamino-5-methoxyphenyl) -tert- Butylphosphine, bis (2-N-tert-butylamino-5-phenoxy Phenyl) -tert-butylphosphine, bis (2-N-tert-butylamino-5-benzyloxyphenyl) -tert-butylphosphinebis (2-N-tert-butylamino-5-trimethylsilyloxyphenyl) -tert- Butylphosphine, bis (2-N-tert-butylamino-3-fluorophenyl) -tert-butylphosphine, bis (2-N-tert-butylamino-3,5-dimethylphenyl) -tert-butylphosphine, bis (2-N-tert-butylamino-3,5-difluorophenyl) -tert-butylphosphine, bis (2-N-tert-butylamino-5-fluoro-3-methylphenyl) -tert-butylphosphine, bis (2-N-tert-butylamino-phenyl) methoxy Phosphine, bis (2-N-tert-butylamino-3-methylphenyl) methoxyphosphine, bis (2-N-tert-butylamino-3-phenylphenyl) methoxyphosphine, bis (2-N-tert-butylamino) -3-benzylphenyl) methoxyphosphine, bis (2-N-tert-butylamino-3-trimethylsilylphenyl) methoxyphosphine, bis (2-N-tert-butylamino-5-methoxyphenyl) methoxyphosphine, bis (2 -N-tert-butylamino-5-phenoxyphenyl) methoxyphosphine, bis (2-N-tert-butylamino-5-benzyloxyphenyl) methoxyphosphine bis (2-N-tert-butylamino-5-trimethylsilyloxy) Phenyl) methoxyphosphine Bis (2-N-tert-butylamino-3-fluorophenyl) methoxyphosphine, bis (2-N-tert-butylamino-3,5-dimethylphenyl) methoxyphosphine, bis (2-N-tert-butyl) Amino-3,5-difluorophenyl) methoxyphosphine, bis (2-N-tert-butylamino-5-fluoro-3-methylphenyl) methoxyphosphine, bis (2-N-tert-butylamino-phenyl) diethylaminophosphine Bis (2-N-tert-butylamino-3-methylphenyl) diethylaminophosphine, bis (2-N-tert-butylamino-3-phenylphenyl) diethylaminophosphine, bis (2-N-tert-butylamino- 3-Benzylphenyl) diethylaminophosphine, bi (2-N-tert-butylamino-3-trimethylsilylphenyl) diethylaminophosphine, bis (2-N-tert-butylamino-5-methoxyphenyl) diethylaminophosphine, bis (2-N-tert-butylamino-5- Phenoxyphenyl) diethylaminophosphine, bis (2-N-tert-butylamino-5-benzyloxyphenyl) diethylaminophosphine bis (2-N-tert-butylamino-5-trimethylsilyloxyphenyl) diethylaminophosphine, bis (2-N -Tert-butylamino-3-fluorophenyl) diethylaminophosphine, bis (2-N-tert-butylamino-3,5-dimethylphenyl) diethylaminophosphine, bis (2-N-tert-butylamino-3,5- Fluorophenyl) diethylamino phosphine, bis (2-N-tert- butylamino-5-fluoro-3-methylphenyl) diethylamino phosphine,

Bis (2-N-acetylamino-phenyl) phenylphosphine, bis (2-N-acetylamino-3-methylphenyl) phenylphosphine, bis (2-N-acetylamino-3-phenylphenyl) phenylphosphine, bis ( 2-N-acetylamino-3-benzylphenyl) phenylphosphine, bis (2-N-acetylamino-3-trimethylsilylphenyl) phenylphosphine, bis (2-N-acetylamino-5-methoxyphenyl) phenylphosphine, bis (2-N-acetylamino-5-phenoxyphenyl) phenylphosphine, bis (2-N-acetylamino-5-benzyloxyphenyl) phenylphosphine bis (2-N-acetylamino-5-trimethylsilyloxyphenyl) phenylphosphine Bis (2-N-acetate) Tilamino-3-fluorophenyl) phenylphosphine, bis (2-N-acetylamino-3,5-dimethylphenyl) phenylphosphine, bis (2-N-acetylamino-3,5-difluorophenyl) phenylphosphine, bis ( 2-N-acetylamino-5-fluoro-3-methylphenyl) phenylphosphine, bis (2-N-acetylamino-phenyl) methylphosphine, bis (2-N-acetylamino-3-methylphenyl) methylphosphine, Bis (2-N-acetylamino-3-phenylphenyl) methylphosphine, bis (2-N-acetylamino-3-benzylphenyl) methylphosphine, bis (2-N-acetylamino-3-trimethylsilylphenyl) methylphosphine Bis (2-N-acetylamino-5-methoxy Phenyl) methylphosphine, bis (2-N-acetylamino-5-phenoxyphenyl) methylphosphine, bis (2-N-acetylamino-5-benzyloxyphenyl) methylphosphine bis (2-N-acetylamino-5- Trimethylsilyloxyphenyl) methylphosphine, bis (2-N-acetylamino-3-fluorophenyl) methylphosphine, bis (2-N-acetylamino-3,5-dimethylphenyl) methylphosphine, bis (2-N-acetyl) Amino-3,5-difluorophenyl) methylphosphine, bis (2-N-acetylamino-5-fluoro-3-methylphenyl) methylphosphine, bis (2-N-acetylamino-phenyl) -tert-butylphosphine, Bis (2-N-acetylamino-3-methylphenyl) -Tert-butylphosphine, bis (2-N-acetylamino-3-phenylphenyl) -tert-butylphosphine, bis (2-N-acetylamino-3-benzylphenyl) -tert-butylphosphine, bis (2- N-acetylamino-3-trimethylsilylphenyl) -tert-butylphosphine, bis (2-N-acetylamino-5-methoxyphenyl) -tert-butylphosphine, bis (2-N-acetylamino-5-phenoxyphenyl) -Tert-butylphosphine, bis (2-N-acetylamino-5-benzyloxyphenyl) -tert-butylphosphine bis (2-N-acetylamino-5-trimethylsilyloxyphenyl) -tert-butylphosphine, bis (2 -N-acetylamino-3-fluoroph Nyl) -tert-butylphosphine, bis (2-N-acetylamino-3,5-dimethylphenyl) -tert-butylphosphine, bis (2-N-acetylamino-3,5-difluorophenyl) -tert-butyl Phosphine, bis (2-N-acetylamino-5-fluoro-3-methylphenyl) -tert-butylphosphine, bis (2-N-acetylamino-phenyl) methoxyphosphine, bis (2-N-acetylamino-3) -Methylphenyl) methoxyphosphine, bis (2-N-acetylamino-3-phenylphenyl) methoxyphosphine, bis (2-N-acetylamino-3-benzylphenyl) methoxyphosphine, bis (2-N-acetylamino-) 3-trimethylsilylphenyl) methoxyphosphine, bis (2-N-acetate) Ruamino-5-methoxyphenyl) methoxyphosphine, bis (2-N-acetylamino-5-phenoxyphenyl) methoxyphosphine, bis (2-N-acetylamino-5-benzyloxyphenyl) methoxyphosphine bis (2-N- Acetylamino-5-trimethylsilyloxyphenyl) methoxyphosphine, bis (2-N-acetylamino-3-fluorophenyl) methoxyphosphine, bis (2-N-acetylamino-3,5-dimethylphenyl) methoxyphosphine, bis ( 2-N-acetylamino-3,5-difluorophenyl) methoxyphosphine, bis (2-N-acetylamino-5-fluoro-3-methylphenyl) methoxyphosphine, bis (2-N-acetylamino-phenyl) diethylamino Phosphine, bis (2-N- Acetylamino-3-methylphenyl) diethylaminophosphine, bis (2-N-acetylamino-3-phenylphenyl) diethylaminophosphine, bis (2-N-acetylamino-3-benzylphenyl) diethylaminophosphine, bis (2-N -Acetylamino-3-trimethylsilylphenyl) diethylaminophosphine, bis (2-N-acetylamino-5-methoxyphenyl) diethylaminophosphine, bis (2-N-acetylamino-5-phenoxyphenyl) diethylaminophosphine, bis (2- N-acetylamino-5-benzyloxyphenyl) diethylaminophosphine bis (2-N-acetylamino-5-trimethylsilyloxyphenyl) diethylaminophosphine, bis (2-N-acetylamino-3-fluoro) Phenyl) diethylaminophosphine, bis (2-N-acetylamino-3,5-dimethylphenyl) diethylaminophosphine, bis (2-N-acetylamino-3,5-difluorophenyl) diethylaminophosphine, bis (2-N-acetyl) Amino-5-fluoro-3-methylphenyl) diethylaminophosphine,

Bis (2-N-tosylamino-phenyl) phenylphosphine, bis (2-N-tosylamino-3-methylphenyl) phenylphosphine, bis (2-N-tosylamino-3-phenylphenyl) phenylphosphine, bis (2-N -Tosylamino-3-benzylphenyl) phenylphosphine, bis (2-N-tosylamino-3-trimethylsilylphenyl) phenylphosphine, bis (2-N-tosylamino-5-methoxyphenyl) phenylphosphine, bis (2-N-tosylamino) -5-phenoxyphenyl) phenylphosphine, bis (2-N-tosylamino-5-benzyloxyphenyl) phenylphosphine bis (2-N-tosylamino-5-trimethylsilyloxyphenyl) phenylphosphine, bis (2-N-tosylamino- 3-full Orophenyl) phenylphosphine, bis (2-N-tosylamino-3,5-dimethylphenyl) phenylphosphine, bis (2-N-tosylamino-3,5-difluorophenyl) phenylphosphine, bis (2-N-tosylamino-5) -Fluoro-3-methylphenyl) phenylphosphine, bis (2-N-tosylamino-phenyl) methylphosphine, bis (2-N-tosylamino-3-methylphenyl) methylphosphine, bis (2-N-tosylamino-3- Phenylphenyl) methylphosphine, bis (2-N-tosylamino-3-benzylphenyl) methylphosphine, bis (2-N-tosylamino-3-trimethylsilylphenyl) methylphosphine, bis (2-N-tosylamino-5-methoxyphenyl) ) Methylphosphine, bis (2-N -Tosylamino-5-phenoxyphenyl) methylphosphine, bis (2-N-tosylamino-5-benzyloxyphenyl) methylphosphine bis (2-N-tosylamino-5-trimethylsilyloxyphenyl) methylphosphine, bis (2-N- Tosylamino-3-fluorophenyl) methylphosphine, bis (2-N-tosylamino-3,5-dimethylphenyl) methylphosphine, bis (2-N-tosylamino-3,5-difluorophenyl) methylphosphine, bis (2- N-tosylamino-5-fluoro-3-methylphenyl) methylphosphine, bis (2-N-tosylamino-phenyl) -tert-butylphosphine, bis (2-N-tosylamino-3-methylphenyl) -tert-butylphosphine Bis (2-N-tosylamino) 3-phenylphenyl) -tert-butylphosphine, bis (2-N-tosylamino-3-benzylphenyl) -tert-butylphosphine, bis (2-N-tosylamino-3-trimethylsilylphenyl) -tert-butylphosphine, bis (2-N-tosylamino-5-methoxyphenyl) -tert-butylphosphine, bis (2-N-tosylamino-5-phenoxyphenyl) -tert-butylphosphine, bis (2-N-tosylamino-5-benzyloxyphenyl) ) -Tert-butylphosphine bis (2-N-tosylamino-5-trimethylsilyloxyphenyl) -tert-butylphosphine, bis (2-N-tosylamino-3-fluorophenyl) -tert-butylphosphine, bis (2-N -Tosylamino-3,5- Dimethylphenyl) -tert-butylphosphine, bis (2-N-tosylamino-3,5-difluorophenyl) -tert-butylphosphine, bis (2-N-tosylamino-5-fluoro-3-methylphenyl) -tert- Butylphosphine, bis (2-N-tosylamino-phenyl) methoxyphosphine, bis (2-N-tosylamino-3-methylphenyl) methoxyphosphine, bis (2-N-tosylamino-3-phenylphenyl) methoxyphosphine, bis ( 2-N-tosylamino-3-benzylphenyl) methoxyphosphine, bis (2-N-tosylamino-3-trimethylsilylphenyl) methoxyphosphine, bis (2-N-tosylamino-5-methoxyphenyl) methoxyphosphine, bis (2- N-tosylamino-5-pheno Ciphenyl) methoxyphosphine, bis (2-N-tosylamino-5-benzyloxyphenyl) methoxyphosphine bis (2-N-tosylamino-5-trimethylsilyloxyphenyl) methoxyphosphine, bis (2-N-tosylamino-3-fluorophenyl) ) Methoxyphosphine, bis (2-N-tosylamino-3,5-dimethylphenyl) methoxyphosphine, bis (2-N-tosylamino-3,5-difluorophenyl) methoxyphosphine, bis (2-N-tosylamino-5- Fluoro-3-methylphenyl) methoxyphosphine, bis (2-N-tosylamino-phenyl) diethylaminophosphine, bis (2-N-tosylamino-3-methylphenyl) diethylaminophosphine, bis (2-N-tosylamino-3-phenyl) Feni ) Diethylaminophosphine, bis (2-N-tosylamino-3-benzylphenyl) diethylaminophosphine, bis (2-N-tosylamino-3-trimethylsilylphenyl) diethylaminophosphine, bis (2-N-tosylamino-5-methoxyphenyl) diethylamino Phosphine, bis (2-N-tosylamino-5-phenoxyphenyl) diethylaminophosphine, bis (2-N-tosylamino-5-benzyloxyphenyl) diethylaminophosphine bis (2-N-tosylamino-5-trimethylsilyloxyphenyl) diethylaminophosphine Bis (2-N-tosylamino-3-fluorophenyl) diethylaminophosphine, bis (2-N-tosylamino-3,5-dimethylphenyl) diethylaminophosphine, bis (2 N- tosylamino-3,5-difluorophenyl) diethylamino phosphine, bis (2-N- tosylamino-5-fluoro-3-methylphenyl) diethylamino phosphine,

(2-N-tert-butylaminophenyl) (2-aminophenyl) phenylphosphine, (2-N-tert-butylaminophenyl) (2-aminophenyl) methylphosphine, (2-N-tert-butylaminophenyl) ) (2-aminophenyl) -tert-butylphosphine, (2-N-tert-butylaminophenyl) (2-aminophenyl) methoxyphosphine, (2-N-tert-butylaminophenyl) (2-aminophenyl) Diethylaminophosphine, (2-N, N-dimethylaminophenyl) (2-aminophenyl) phenylphosphine, (2-N, N-dimethylaminophenyl) (2-aminophenyl) methylphosphine, (2-N, N- Dimethylaminophenyl) (2-aminophenyl) -tert-butyl Ruphosphine, (2-N, N-dimethylaminophenyl) (2-aminophenyl) methoxyphosphine, (2-N, N-dimethylaminophenyl) (2-aminophenyl) diethylaminophosphine, (2-N-acetylamino) Phenyl) (2-aminophenyl) phenylphosphine, (2-N-acetylaminophenyl) (2-aminophenyl) methylphosphine, (2-N-acetylaminophenyl) (2-aminophenyl) -tert-butylphosphine, (2-N-acetylaminophenyl) (2-aminophenyl) methoxyphosphine, (2-N-acetylaminophenyl) (2-aminophenyl) diethylaminophosphine, (2-N-tosylaminophenyl) (2-aminophenyl) ) Phenylphosphine, (2-N-tosyl) Minophenyl) (2-aminophenyl) methylphosphine, (2-N-tosylaminophenyl) (2-aminophenyl) -tert-butylphosphine, (2-N-tosylaminophenyl) (2-aminophenyl) methoxyphosphine, (2-N-tosylaminophenyl) (2-aminophenyl) diethylaminophosphine,

Tris (2-aminophenyl) phosphine, tris (2-amino-3-methylphenyl) phosphine, tris (2-amino-3-phenylphenyl) phosphine, tris (2-amino-3-benzylphenyl) phosphine, tris ( 2-amino-3-trimethylsilylphenyl) phosphine, tris (2-amino-5-methoxyphenyl) phosphine, tris (2-amino-5-phenoxyphenyl) phosphine, tris (2-amino-5-benzyloxyphenyl) phosphine Tris (2-amino-5-trimethylsilyloxyphenyl) phosphine, tris (2-amino-3-fluorophenyl) phosphine, tris (2-amino-3-chlorophenyl) phosphine, tris (2-amino-5-fluorophenyl) Phosphine, Tris ( - amino-5-chlorophenyl) phosphine, tris (2-amino-3,5-dimethylphenyl) phosphine, tris (2-amino-3,5-difluorophenyl) phosphine,

Tris (2-N, N-dimethylaminophenyl) phosphine, Tris (2-N, N-dimethylamino-3-methylphenyl) phosphine, Tris (2-N, N-dimethylamino-3-phenylphenyl) phosphine, Tris (2-N, N-dimethylamino-3-benzylphenyl) phosphine, tris (2-N, N-dimethylamino-3-trimethylsilylphenyl) phosphine, tris (2-N, N-dimethylamino-5-methoxyphenyl) ) Phosphine, tris (2-N, N-dimethylamino-5-phenoxyphenyl) phosphine, tris (2-N, N-dimethylamino-5-benzyloxyphenyl) phosphinetris (2-N, N-dimethylamino-) 5-trimethylsilyloxyphenyl) phosphine, tris (2-N, N-dimethyl) Amino-3-fluorophenyl) phosphine, tris (2-N, N-dimethylamino-3-chlorophenyl) phosphine, tris (2-N, N-dimethylamino-5-fluorophenyl) phosphine, tris (2-N, N-dimethylamino-5-chlorophenyl) phosphine, tris (2-N, N-dimethylamino-3,5-dimethylphenyl) phosphine, tris (2-N, N-dimethylamino-3,5-difluorophenyl) phosphine ,

Tris (2-N-tert-butylaminophenyl) phosphine, tris (2-N-tert-butylamino-3-methylphenyl) phosphine, tris (2-N-tert-butylamino-3-phenylphenyl) phosphine, Tris (2-N-tert-butylamino-3-benzylphenyl) phosphine, Tris (2-N-tert-butylamino-3-trimethylsilylphenyl) phosphine, Tris (2-N-tert-butylamino-5-methoxyphenyl) ) Phosphine, tris (2-N-tert-butylamino-5-phenoxyphenyl) phosphine, tris (2-N-tert-butylamino-5-benzyloxyphenyl) phosphinetris (2-N-tert-butylamino-) 5-trimethylsilyloxyphenyl) pho Fins, Tris (2-N-tert-butylamino-3-fluorophenyl) phosphine, Tris (2-N-tert-butylamino-3-chlorophenyl) phosphine, Tris (2-N-tert-butylamino-5- Fluorophenyl) phosphine, tris (2-N-tert-butylamino-5-chlorophenyl) phosphine, tris (2-N-tert-butylamino-3,5-dimethylphenyl) phosphine, tris (2-N-tert- Butylamino-3,5-difluorophenyl) phosphine,

Tris (2-N-acetylaminophenyl) phosphine, Tris (2-N-acetylamino-3-methylphenyl) phosphine, Tris (2-N-acetylamino-3-phenylphenyl) phosphine, Tris (2-N- Acetylamino-3-benzylphenyl) phosphine, tris (2-N-acetylamino-3-trimethylsilylphenyl) phosphine, tris (2-N-acetylamino-5-methoxyphenyl) phosphine, tris (2-N-acetylamino) -5-phenoxyphenyl) phosphine, tris (2-N-acetylamino-5-benzyloxyphenyl) phosphinetris (2-N-acetylamino-5-trimethylsilyloxyphenyl) phosphine, tris (2-N-acetylamino-) 3-Fluorophenyl) phosph , Tris (2-N-acetylamino-3-chlorophenyl) phosphine, tris (2-N-acetylamino-5-fluorophenyl) phosphine, tris (2-N-acetylamino-5-chlorophenyl) phosphine, tris ( 2-N-acetylamino 3,5-dimethylphenyl) phosphine, tris (2-N-acetylamino-3,5-difluorophenyl) phosphine,

Tris (2-N-tosylaminophenyl) phosphine, Tris (3-methyl-2-N-tosylaminophenyl) phosphine, Tris (3-phenyl-2-N-tosylaminophenyl) phosphine, Tris (3-benzyl- 2-N-tosylaminophenyl) phosphine, tris (2-N-tosylamino-3-trimethylsilylphenyl) phosphine, tris (5-methoxy-2-N-tosylaminophenyl) phosphine, tris (5-phenoxy-2-N -Tosylaminophenyl) phosphine, tris (5-benzyloxy-2-N-tosylaminophenyl) phosphinetris (2-N-tosylamino-5-trimethylsilyloxyphenyl) phosphine, tris (3-fluoro-2-N-tosyl) Aminophenyl) phosphine, tris (3-c Ro-2-N-tosylaminophenyl) phosphine, tris (5-fluoro-2-N-tosylaminophenyl) phosphine, tris (5-chloro-2-N-tosylaminophenyl) phosphine, tris (3,5- Examples thereof include dimethyl-2-N-tosylaminophenyl) phosphine and tris (3,5-difluoro-2-N-tosylaminophenyl) phosphine.

Examples of the transition metal in the transition metal compound containing a transition metal of Group 8-10 of the periodic table include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum, preferably iron, cobalt. , Nickel and palladium, and more preferably nickel and palladium.

The transition metal compound may have an anionic ligand. Examples of the anionic ligand include halogen, alkyl group, allyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group. Group, amino group, acyloxy group, sulfonoxy group, 1,3-diketonate group, borate group, phosphate group, antimonate group, etc., specifically, chlorine, bromine, iodine, methyl group, trimethylsilylmethyl group, Ethyl group, allyl group, phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, benzyl group, methoxy group, ethoxy group, ethylenedioxy group, phenoxy group, 2-methylphenoxy group, 3-methyl Phenoxy group, 4-methylphenoxy group, 1,2-phenylenedioxy group, 1,1′-binaphthyl-2,2 ′ Dioxy group, benzyloxy group, dimethylamino group, diethylamino group, acetoxy group, trifluoroacetoxy group, benzoyloxy group, methanesulfonyloxy group, benzenesulfonyloxy group, 2-toluenesulfonyloxy group, 3-toluenesulfonyloxy group, 4-toluenesulfonyloxy group, acetylacetonate group, 1,3-diphenyl-1,3-propanedionate group, 3-methyl-2,4-pentanedionate group, tetrafluoroborate group, tetraphenylborate group, Examples include tetra (pentafluorophenyl) borate group, hexafluorophosphate group, hexafluoroantimonate group, preferably chlorine, bromine, acetylacetonate group, 3-methyl-2,4-pentanedionate group, ,further Mashiku is acetyl acetonate group.

The transition metal compound may also have a neutral ligand.

Examples of such a neutral ligand include molecules having a neutral functional group such as ether, sulfide, amine, phosphine, olefin, and nitrile, and also having a plurality of coordination functional groups in the molecule. Specifically, dimethyl ether, diethyl ether, methyl tert-butyl ether, furan, tetrahydrofuran, dimethoxyethane, dimethoxyethane, dimethyl sulfide, diethyl sulfide, methyl tert-butyl sulfide, thiophene, tetrahydrothiophene, ethylenedithiol dimethyl Sulfide, ethylenedithiol diethylsulfide, trimethylamine, triethylamine, triphenylamine, tricyclohexylamine, pyridine, 2,2'-bipyridine, ethylenediamine, tetramethyl Ruethylenediamine, tetraethylethylenediamine, triphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, bis (diphenylphosphino) methane, bis (diphenylphosphino) ethane, bis (diphenylphosphino) propane, bis (diphenylphosphino) ) Binaphthyl, ethylene, propylene, butene, butadiene, octene, octadiene, cyclohexene, cyclohexadiene, norbornene, norbornadiene, benzonitrile, acetonitrile and the like.

Specific examples of such transition metal compounds include iron dichloride, iron trichloride, iron (II) acetate, triisopropoxy iron, dimesityl iron, iron (II) acetylacetonate, iron (III) acetylacetonate, bis ( Trifluoroacetoxy) iron, tris (trifluoroacetoxy) iron, iron (II) fexafluoroacetylacetonate

Ruthenium dichloride, ruthenium trichloride, tetrakis (triphenylphosphine) ruthenium dihydride, ruthenium (III) acetylacetonate, ruthenium dichloride (cyclooctadiene)

Cobalt dichloride, cobalt (II) acetate, dimesityl cobalt, trimesityl cobalt, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, bis (trifluoroacetoxy) cobalt, tris (trifluoroacetoxy) cobalt Bis (tris [trimethylsilyl] methyl) cobalt, tris (triphenylphosphine) cobalt methyl

Nickel dichloride, nickel acetate (II), nickel (II) acetylacetonate, allyl nickel chloride, nickel (0) dicyclooctadiene, tetrakis (triphenylphosphine) nickel, bis (triphenylphosphine) phenylnickel chloride, bis (Trimethylsilylmethyl) nickel dipyridine, dimethylnickel tetramethylethylenediamine, dibromonickel dimethoxyethane, bis (trifluoroacetoxy) nickel, bis (hexafluoroacetylacetonate) nickel

Palladium (II) acetate, tris (dibenzylideneacetone) bispalladium, palladium (II) acetylacetonate, (cyclooctadiene) methylpalladium chloride, (cyclooctene) methylpalladium chloride, (cyclooctadiene) methylpalladium triflate, allyl Palladium chloride, dimethylpalladium tetramethylethylenediamine, tetrakis (acetonitrile) palladium bis (tetrafluoroborate)

Bis (ethylenediamine) platinum (II) chloride, cyclooctadiene platinum (II) bromide, cyclooctadiene platinum (II) chloride, bis (benzonitrile) platinum (II) chloride, bis (pyridine) platinum (II) chloride, bis (Triphenylphosphine) platinum (II) chloride, dimethylplatinum (cyclooctadiene), dicyclopentadiene platinum (II) chloride and the like are exemplified, preferably nickel compound, more preferably nickel (II) acetylacetonate.

The polymerization catalyst component used in the present invention is a combination of a 2-aminophenylphosphine compound (1) and a transition metal compound containing a transition metal of Group 8-10 of the periodic table, and is usually prepared by mixing the two. Is done.

The molar ratio of the 2-aminophenylphosphine compound (1) and the transition metal compound containing a transition metal of Group 8-10 of the periodic table is not particularly limited, but is preferably in the range of 1: 0.1 to 1:10, more preferably Is in the range of 1: 0.3 to 1: 3.

The polymerization catalyst component is usually prepared in a solvent. 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. These solvents are used alone or in combination of two or more, and the amount of the solvent used is not particularly limited.

The obtained reaction mixture is concentrated to precipitate a solid, and in some cases, the polymerization catalyst component can be taken out by a technique such as recrystallization purification, but it can also be used for polymerization without taking it out.

The polymerization catalyst component thus prepared can be used for polymerization by reacting with an activated cocatalyst, and examples of the activated cocatalyst include compounds commonly used such as zinc compounds, aluminum compounds, and boron compounds.

Preferred activating cocatalysts include aluminum compounds and non-aluminum compounds that form ion pairs in pairs with transition metals. By reacting a single or combined compound with a polymerization catalyst component, polymerization can be achieved. Can be used.

A non-aluminum compound that forms an ion pair by pairing with a polymerization catalyst component, an aluminum compound, and a transition metal can be charged and used in any order at the time of polymerization. The reaction product obtained can also be used.

Examples of the aluminum compound used in the present invention include known organoaluminum compounds, for example, compounds represented by the following formulas (A1), (A2), and (A3), and aluminate compounds. Can be used in combination.
(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 a 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 and triisobutylaluminum 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.

The above aluminoxane can be prepared commercially or by various methods. 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.

Examples of the aluminate compound that can be used in the present invention include triphenylcarbenium tetrakis (pentafluorophenyl) aluminate, triphenylcarbenium tris (2,2 ′, 2 ″ -nonafluorobiphenyl) fluoroaluminate. And triphenylcarbenium tetrakis (pentafluorophenoxy) aluminate.

Non-aluminum compounds that form an ion pair by pairing with a transition metal include compounds that are bulky and / or have an electroattractive substituent and have an anionic atom paired with a transition metal. Examples of such atoms include boron atoms. For example, compounds represented by the following formulas (B1), (B2), and (B3) can be used, and they can be used alone or in combination of two or more. be able to.
(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)-

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, alkoxy groups having 1 to 20 carbon atoms or disubstituted with hydrocarbons having 1 to 20 carbon atoms An amino group, 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 can be mentioned. Preferably, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, etc. Is mentioned.

The boron compound used in the present invention similarly includes a boron compound containing two or more boron atoms in the molecule via a crosslinking group. Examples of the crosslinking group include an optionally substituted phenylene group and a heterocyclic ring such as imidazole. Specific examples thereof include bis (triphenylcarbenium) [2,3,5,6-tetrafluorophenylene-1 , 4-bis [tris (pentafluorophenyl) borate]], lithium imidazole-bis (tris (pentafluorophenyl) borane) adduct, triethylammonium imidazole-bis (tris (pentafluorophenyl) borane) adduct, etc. It is done.

The amount of each catalyst component used is such that the molar ratio of the compound (A) [the (A1)-(A3) is collectively referred to as (A)] / the transition metal in the polymerization catalyst component is 0.1 to 10,000. Preferably, each component is used so that the molar ratio of the transition metal in the compound (B) / polymerization catalyst component is 0.01-100, preferably 0.5-10. Is desirable.
Regarding the concentration when each catalyst component is used in a solution state, the transition metal in the polymerization catalyst component 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. 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 the present invention is 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 monomers 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 hydrocarbons such as methylene dichloride. Can be used for solvent polymerization, slurry polymerization, gas phase polymerization in a gaseous monomer, etc., and continuous polymerization or batch polymerization can be used.

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 may 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

配位子１
配位子１：ビス（２−アミノフェニル）フェニルホスフィンの０．０２Mトルエン溶液、ビス（アセチルアセトナート）ニッケル（ＩＩ）０．０２Mトルエン溶液を０．３ｍｌずつバイアル瓶にサンプリングし、室温で２分間混合させた。
オートクレーブに窒素下で、トルエン５．０ｍＬを仕込み、４０℃で安定させた後、エチレンを０．６０ＭＰａまで加圧し安定させた。ここに、MMAO（０．２５Ｍ、１００μｍｏｌ）、上記に記載の重合触媒成分溶液（ニッケル濃度０．０１Ｍ、３μｍｏｌ）を加え、２分間重合した。重合の結果、分子量（Ｍｗ）＝１６６，７００、分子量分布（Ｍｗ／Ｍｎ）=７２．４のポリマーをニッケル１ｍｏｌ当たり、1時間当たり、２．９×１０^６ｇ製造した。 [Example 1]
[Polymerization using ligand 1]

Ligand 1
Ligand 1: 0.02M toluene solution of bis (2-aminophenyl) phenylphosphine and 0.02M toluene solution of bis (acetylacetonato) nickel (II) were sampled in 0.3 ml aliquots at room temperature. Mix for minutes.
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. MMAO (0.25 M, 100 μmol) and the polymerization catalyst component solution described above (nickel concentration 0.01 M, 3 μmol) were added thereto, and polymerization was performed for 2 minutes. As a result of the polymerization, a polymer having a molecular weight (Mw) = 166,700 and a molecular weight distribution (Mw / Mn) = 72.4 was produced at a rate of 2.9 × 10 ⁶ g per hour per 1 mol of nickel.

[Example 2]
Ligand 1: 0.02M toluene solution of bis (2-aminophenyl) phenylphosphine and 0.02M toluene solution of bis (acetylacetonato) nickel (II) were sampled in 0.3 ml aliquots at room temperature. Mix for minutes.
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. Triisobutylaluminum (40 μmol), trispentafluorophenylborane (9 μmol) and the above-described polymerization catalyst component solution (nickel concentration 0.01 M, 3 μmol) were added thereto, and polymerization was performed for 4 minutes. As a result of the polymerization, a polymer having a molecular weight (Mw) = 71,100 and a molecular weight distribution (Mw / Mn) = 7.2 was produced at 1.3 × 10 ⁶ g per hour per 1 mol of nickel.

配位子２
配位子２：（２−N−ｔｅｒｔ−ブチルアミノフェニル）（２−アミノフェニル）フェニルホスフィンの０．０２Mトルエン溶液、ビス（アセチルアセトナート）ニッケル（ＩＩ）０．０２Mトルエン溶液を０．３ｍｌずつバイアル瓶にサンプリングし、室温で２分間混合させた。
オートクレーブに窒素下で、トルエン５．０ｍＬを仕込み、４０℃で安定させた後、エチレンを０．６０ＭＰａまで加圧し安定させた。ここに、トリイソブチルアルミニウム（４０μｍｏｌ）、トリスペンタフルオロフェニルボラン（９μｍｏｌ）及び上記に記載の重合触媒成分溶液（ニッケル濃度０．０１Ｍ、３μｍｏｌ）を加え、５分間重合した。重合の結果、ポリマーをニッケル１ｍｏｌ当たり、1時間当たり、１．２×１０^６ｇ製造した。 [Example 3]
[Polymerization using ligand 2]

Ligand 2
Ligand 2: 0.02M toluene solution of (2-N-tert-butylaminophenyl) (2-aminophenyl) phenylphosphine, 0.3 ml of bis (acetylacetonato) nickel (II) 0.02M toluene solution Each sample was taken into a vial and mixed at room temperature for 2 minutes.
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, triisobutylaluminum (40 μmol), trispentafluorophenylborane (9 μmol) and the above-described polymerization catalyst component solution (nickel concentration 0.01 M, 3 μmol) were added and polymerized for 5 minutes. As a result of the polymerization, 1.2 × 10 ⁶ g of polymer was produced per hour per 1 mol of nickel.

配位子３
配位子３：ビス（２−Ｎ，Ｎ−ジメチルアミノフェニル）フェニルホスフィンの０．０２Mトルエン溶液、ビス（アセチルアセトナート）パラジウム（ＩＩ）０．０２Mトルエン溶液を０．３ｍｌずつバイアル瓶にサンプリングし、室温で２分間混合させた。
オートクレーブに窒素下で、トルエン５．０ｍＬを仕込み、４０℃で安定させた後、エチレンを０．６０ＭＰａまで加圧し安定させた。ここに、トリイソブチルアルミニウム（４０μｍｏｌ）、トリスペンタフルオロフェニルボラン（９μｍｏｌ）及び上記に記載の重合触媒成分溶液（パラジウム濃度０．０１Ｍ、３μｍｏｌ）を加え、３８分間重合した。重合の結果、ポリマーをパラジウム１ｍｏｌ当たり、1時間当たり、６．３×１０^４ｇ製造した。 [Example 4]
[Polymerization using ligand 3]

Ligand 3
Ligand 3: Sampling 0.3 ml of 0.02M toluene solution of bis (2-N, N-dimethylaminophenyl) phenylphosphine and 0.02M toluene solution of bis (acetylacetonato) palladium (II) into vials. And mixed for 2 minutes at room temperature.
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, triisobutylaluminum (40 μmol), trispentafluorophenylborane (9 μmol) and the polymerization catalyst component solution described above (palladium concentration 0.01 M, 3 μmol) were added and polymerized for 38 minutes. As a result of the polymerization, 6.3 × 10 ⁴ g of polymer was produced per hour per 1 mol of palladium.

[Example 5]
Ligand 3: Sampling bis (2-N, N-dimethylaminophenyl) phenylphosphine in 0.02M toluene solution and bis (acetylacetonato) nickel (II) 0.02M in toluene into 0.3 ml vials And mixed for 2 minutes at room temperature.
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. MMAO (0.25 M, 100 μmol) and the polymerization catalyst component solution described above (nickel concentration 0.01 M, 3 μmol) were added thereto, and polymerization was performed for 107 minutes. As a result of the polymerization, 1.4 × 10 ⁴ g of polymer was produced per hour per 1 mol of nickel.

配位子４
配位子４：トリス（２−Ｎ，Ｎ−ジメチルアミノフェニル）ホスフィンの０．０２Mトルエン溶液、ビス（アセチルアセトナート）ニッケル（ＩＩ）０．０２Mトルエン溶液を０．３ｍｌずつバイアル瓶にサンプリングし、室温で２分間混合させた。
オートクレーブに窒素下で、トルエン５．０ｍＬを仕込み、４０℃で安定させた後、エチレンを０．６０ＭＰａまで加圧し安定させた。ここに、MMAO（０．２５Ｍ、１００μｍｏｌ）、上記に記載の重合触媒成分溶液（ニッケル濃度０．０１Ｍ、３μｍｏｌ）を加え、１８０分間重合した。重合の結果、分子量（Ｍｗ）＝１９００、分子量分布（Ｍｗ／Ｍｎ）=１．４のポリマーをニッケル１ｍｏｌ当たり、1時間当たり、３．６×１０^３ｇ製造した。
[Example 6]
[Polymerization using ligand 4]

Ligand 4
Ligand 4: Sampling tris (2-N, N-dimethylaminophenyl) phosphine in 0.02M toluene solution and bis (acetylacetonato) nickel (II) 0.02M toluene solution in 0.3 ml aliquots. And mixed for 2 minutes at room temperature.
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. MMAO (0.25 M, 100 μmol) and the polymerization catalyst component solution described above (nickel concentration 0.01 M, 3 μmol) were added thereto, and polymerization was performed for 180 minutes. As a result of the polymerization, a polymer having a molecular weight (Mw) = 1900 and a molecular weight distribution (Mw / Mn) = 1.4 was produced at 3.6 × 10 ³ g per hour per 1 mol of nickel.

Claims (12)

Formula (1)

(In the formula, n represents 0 or 1, R ¹ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or substituted. An optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 6 to 20 carbon atoms, and optionally substituted. An amino group substituted with an aralkyloxy group having 7 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, R ² and R ³ are the same or different and are a hydrogen atom or an optionally substituted carbon number. An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted, an aralkyl group having 7 to 20 carbon atoms which may be substituted, and an acyl having 2 to 20 carbon atoms which may be substituted Group or may be substituted Indicates a sulfonyl group having a carbon number of 1 to ^{20, R 4, R 5,} R 6 and ^{R 7} are the same or different, a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a substituted An optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, an optionally substituted aryloxy group having 6 to 20 carbon atoms, and optionally substituted. A good aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms which may be substituted, a silyl group substituted with a hydrocarbon having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms A substituted silyloxy group, and adjacent groups among R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be bonded to each other to form a ring.
A 2-aminophenylphosphine compound represented by:
An olefin polymerization catalyst component comprising a combination of a transition metal compound containing a transition metal of Group 8-10 of the periodic table. The R ¹ in the 2-aminophenylphosphine compound represented by the formula (1) is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. The olefin polymerization catalyst component. The olefin polymerization catalyst component according to claim 1 or 2, wherein n in the 2-aminophenylphosphine compound represented by the formula (1) is 1. In the 2-aminophenylphosphine compound represented by the formula (1), R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. The olefin polymerization catalyst component according to any one of claims 1 to 3, which is a silyl group substituted with a 20 aryl group, an aralkyl group having 7 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms. The olefin polymerization catalyst according to any one of claims 1 to 4, wherein the molar ratio of the 2-aminophenylphosphine compound represented by the formula (1) and the transition metal compound is in the range of 1: 0.3 to 1: 3. component. The olefin polymerization catalyst component according to any one of claims 1 to 5, wherein the transition metal compound is a nickel or palladium compound. The olefin polymerization catalyst component according to any one of claims 1 to 5, wherein the transition metal compound is a nickel or palladium compound having an acetylacetonate type anion. An olefin polymerization catalyst comprising an activated cocatalyst in combination with the olefin polymerization catalyst component according to claim 1. The olefin polymerization catalyst according to claim 8, wherein the activated cocatalyst is an aluminum compound. The olefin polymerization catalyst according to claim 8, wherein the activating cocatalyst is an aluminum compound and / or a non-aluminum compound that forms an ion pair with a transition metal. The olefin polymerization catalyst according to claim 10, wherein the non-aluminum compound that forms an ion pair with a transition metal is a boron compound. The manufacturing method of the olefin polymer characterized by polymerizing an olefin using the olefin polymerization catalyst in any one of Claims 8-11.