JP2002255918A - Transition metal compound, coordinating compound, catalyst for polymerizing olefin and method for producing polyolefin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerization catalyst capable of efficiently producing a polyolefin. SOLUTION: An olefin is polymerized by using the catalyst comprising a transition metal compound represented by the following general formula (1) (M denotes a transition metal atom selected from groups 3-12 of the periodic table; X denotes hydrogen atom, a halogen atom, a 1-20C hydrocarbon group or the like; A denotes carbon atom, nitrogen atom or phosphorus atom; R<1> denotes hydrogen atom, a 1-20C hydrocarbon group or the like; R<2> denotes hydrogen atom, a 1-20C hydrocarbon group or the like; Q denotes hydrogen atom, a 1-20C hydrocarbon group or the like; R<3> denotes hydrogen atom, a halogen atom, a 1-20C hydrocarbon atom or the like; R<4> denotes hydrogen atom, a 1-20C hydrocarbon group or the like; and L denotes a coordination- binding compound) as a constituent component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transition metal compound,
The present invention relates to a catalyst for olefin polymerization using a coordinating compound and a transition metal compound and a method for polymerizing olefin.
More specifically, the present invention relates to a transition metal compound having an azaferrocene or ferrocene structure, a coordinating compound serving as a raw material thereof, and a method for efficiently producing a polyolefin by using the transition metal compound as a component of an olefin polymerization catalyst. It is.

[0002]

2. Description of the Related Art A homogeneous olefin polymerization catalyst using a combination of a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl derivative as a ligand and an aluminoxane has high activity, and is useful for producing polyolefin. It is known to be useful (eg, Japanese Patent Application Laid-Open No. 58-19309). Furthermore, when such an organometallic complex having a cyclopentadienyl group is used for olefin polymerization as a component of the catalyst, the resulting polyolefin is known to be a polymer having a narrow molecular weight distribution and a uniform composition distribution. I have.

In recent years, in order to develop a more excellent catalyst for homogeneous olefin polymerization, a transition metal compound using a heteroatom other than a cyclopentadienyl ring as a ligand has been developed. Investigations as ingredients are being actively conducted. For example, with respect to an olefin polymerization catalyst using a transition metal compound having a nitrogen atom as a ligand, JP-A-8-176217, JP-A-8-1821-2, and US Pat.
No. 45713 discloses an olefin polymerization catalyst comprising a titanium amide compound having a dialkylamine ligand bonded to a titanium atom as a constituent. Further, JP-A-10-298216 discloses an olefin polymerization catalyst comprising a transition metal amide compound having a cross-linkable aromatic amine compound as a ligand as a catalyst component.

[0004] Many studies using a transition metal complex having a nitrogen atom as a ligand for olefin polymerization have been conducted from an academic viewpoint. H. McConville
e et al. Am. Chem. Soc. , 118, 1
0008 (1996). In [ArN (CH ₂ ) ₃
NAr] TiMe ₂ and B (C ₆ F
₅ ) Living polymerization of 1-hexene is performed using a catalyst system consisting of ₃ . In addition, R. R. Schrock et al. Am. Chem. Soc. , 119, 383
Page 0 (1997). At the tridentate diamine complex [(t-
BuN-ortho-C ₆ H ₄ ) ₂ O] ZrMe ₂ and B (C
₆ F ₅₎ using a catalyst system comprising _3, is carried out living polymerization of 1-hexene. In addition, Organometa
LLCs, 15, 562 (1996). And Or
Ganometallics, vol. 17, p. 308 (19
1998). Contains [Mes ₂ BNCH ₂ CH ₂ NBMes ₂ ]
^A Group 4 transition metal compound was synthesized using a ligand having a bis (borylamide) structure such as ^2- , and it has been shown that the transition metal compound has ethylene polymerization activity.

Recently, by using a bidentate-type diimine chelate type nickel complex as a catalyst component, a structure having many branches having a structure different from that of a polyolefin which can be produced by a conventional metallocene catalyst has been obtained. It has been reported that a polyolefin having the same can be produced. For example, there is WO96 / 23010. Furthermore, it has been disclosed and reported that when an aldimine group 4 transition metal complex having a specific structure is used as a component of a catalyst for olefin polymerization, extremely high polymerization activity is exhibited (for example, EP 874005 (1998); Am.Ch
em. Soc. 123, 6847 (2001).
Year)).

[0006]

An object of the present invention is to provide a novel transition metal compound having an azaferrocene or ferrocene structure, its use as an olefin polymerization catalyst capable of efficiently producing a polyolefin, and its use. To provide a method for producing a polyolefin.

[0007]

Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies and found a transition metal compound having an azaferrocene or ferrocene structure, and used it alone or in combination with an activating cocatalyst. As a result, they have found that polyolefins can be efficiently produced, and have completed the present invention. That is, the present invention provides a transition metal compound having an azaferrocene or ferrocene structure, a coordinating compound serving as a raw material thereof, and an olefin polymerization catalyst containing the transition metal compound as a component. An object of the present invention is to provide a method for producing a polyolefin, which comprises polymerizing an olefin using an olefin polymerization catalyst.

Hereinafter, the present invention will be described in detail.

The transition metal compound of the present invention is represented by the following general formula (1). That is,

[0010]

Embedded image (Where M is a transition metal atom selected from Groups 3 to 12 of the periodic table, X is a hydrogen atom, a halogen atom,
To 20 hydrocarbon groups, a hydrocarbon oxy group having 1 to 20 carbon atoms, an amino group having a hydrocarbon group having 1 to 20 carbon atoms, a sulfonate group having an organic group having 1 to 20 carbon atoms, or B, Al, A non-coordinating anion containing an element selected from P and Sb. When q is 2 or more, Xs may be the same or different. A represents a carbon atom, a nitrogen atom, or a phosphorus atom. R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a halogen atom, a ferrocenyl group, or a substituted ferrocenyl group;
R ² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a silicon atom, a hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, an oxygen atom or a sulfur atom, a ferrocenyl group, or a substituted ferrocenyl group. As shown, R ¹ and R ² may form a ring. Q is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, an amino group having a hydrocarbon group having 1 to 20 carbon atoms,
A phosphino group having a hydrocarbon group having 1 to 20 carbon atoms, an oxy group having a hydrocarbon group having 1 to 20 carbon atoms,
A thio group having from 20 to 20 hydrocarbon groups, a hydrocarbon group having from 1 to 20 carbon atoms including a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, oxygen or sulfur, and Q including a coordinating atom , M. R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a carbon atom containing 1 to 20 carbon atoms including a nitrogen atom, an oxygen atom, a halogen atom or a sulfur atom. Represents 20 hydrocarbon groups, and one R ³ adjacent to Q may form a ring. When m is 2 or more, R ³
May be the same or different, and adjacent R
³ may be bonded to each other to form a ring. R ⁴ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a phosphino group having a hydrocarbon group having 1 to 20 carbon atoms, An oxy group having a hydrocarbon group, a thio group having a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, a phosphorus atom, an oxygen atom, a halogen atom or a sulfur atom. , N is 2 or more, R ⁴ may be the same or different, and adjacent R ⁴ may be bonded to each other to form a ring. R ³ and R ⁴ may have a bond. L is a coordination bond compound, and represents a π electron, an ether, a nitrile, an amine, or a phosphine, and may have a bond with X. m represents an integer of 1 to 3,
n shows the integer of 1-5. p represents an integer of 0 or 1,
The bond between Q and M indicates a sigma bond when Q is oxygen or sulfur. When p is 0 and A is a nitrogen atom or a phosphorus atom,
Can coordinate to M. q shows the integer of 1-3, and r shows the integer of 0-3. ).

In the general formula (1), M represents a transition metal atom selected from Groups 3 to 12 of the periodic table. Preferably periodic table 8
A transition metal atom selected from the group consisting of Group 12 to Group 12, and more preferably Ni, Pd, Fe, and Cu.

X is a hydrogen atom, a halogen atom, and having 1 to 1 carbon atoms.
A hydrocarbon group having 20 carbon atoms, a hydrocarbon oxy group having 1 to 20 carbon atoms, an amino group having a hydrocarbon group having 1 to 20 carbon atoms, a sulfonate group having an organic group having 1 to 20 carbon atoms, or B, Al, P , Sb, a non-coordinating anion containing an element selected from the group consisting of a halogen atom and a carbon atom having 1 to 2 carbon atoms.
It is a non-coordinating anion containing a hydrocarbon group of 0, a sulfonate group having an organic group having 1 to 20 carbon atoms, or an element selected from B, Al, P, and Sb. q represents an integer of 1 to 3, and when q is 2 or more, Xs may be the same or different. Specific examples of the halogen atom for X are a chlorine atom, a bromine atom and an iodine atom, and preferably a chlorine atom and a bromine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a benzyl group, an allyl group, a phenyl group, and an o-tolyl group. Specific examples of the hydrocarbon oxy group include methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, phenoxy group and the like. Examples of the amino group having a hydrocarbon group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a diisopropylamino group, a diphenylamino group, a dialkylamino group such as a dibenzylamino group, and a diarylamino group. Examples of the sulfonate group having an organic group of numbers 1 to 20 include a trifluoromethanesulfonate group,
p-toluenesulfonate group and the like, and B, Al, P,
Specific examples of the non-coordinating anion containing an element selected from Sb include tetrakis {3,5-bis (trifluoromethyl) phenyl} borate anion, tetrakis (pentafluorophenyl) borate anion, and tetrakis (pentafluorophenyl) Aluminate anion, S
bF ₆ anion and PF ₆ anion can be exemplified.

R ¹ in the general formula (1) is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 2 carbon atoms including a halogen atom.
20 represents a hydrocarbon group, a ferrocenyl group or a substituted ferrocenyl group, and is preferably hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a benzyl group, a phenyl group, a 2-methylphenyl group, and a naphthyl group. And a methyl group and a phenyl group are preferred. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms including a halogen atom include a trifluoromethyl group, a trichloromethyl group,
Examples thereof include a 2,2-trifluoroethyl group and a difluoromethyl group, and a trifluoromethyl group is preferable.
Specific examples of the substituted ferrocenyl group include a methylferrocenyl group, a dimethylferrocenyl group, and a tert-butylferrocenyl group.

R ² in the general formula (1) represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a silicon atom, a nitrogen atom, a carbon atom having 1 to 2 carbon atoms including an oxygen atom or a sulfur atom.
0 hydrocarbon group, a ferrocenyl group, or a substituted ferrocenyl group, preferably a hydrocarbon group having 1 to 20 carbon atoms,
It is a hydrocarbon group having 1 to 20 carbon atoms including a halogen atom, a silicon atom, a nitrogen atom, an oxygen atom or a sulfur atom.
Specific examples of the hydrocarbon group having 1 to 20 carbon atoms for R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a tert group.
-Butyl group, benzyl group, phenyl group, 2-methylphenyl group, 2,6-dimethylphenyl group, 2-isopropylphenyl group, 2,6-diisopropylphenyl group,
-Tert-butylphenyl group, mesityl group, 2-biphenyl group, naphthyl group, adamantyl group and the like, preferably 2-methylphenyl group, 2-isopropylphenyl group, 2-tert-butylphenyl group, 2-biphenyl group It is. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms containing a halogen atom, a silicon atom, a nitrogen atom, an oxygen atom or a sulfur atom include a 2- (trifluoromethyl) phenyl group, a 2- (trichloromethyl) phenyl group, -Methyl-4-chlorophenyl group, 2- (trimethylsilyl) phenyl group, 2,6-di (trimethylsilyl) phenyl group, 2- (dimethylaminomethyl) phenyl group, 2-
(Diphenylaminomethyl) phenyl group, 2- (methoxymethyl) phenyl group, 2- (phenoxymethyl) phenyl group, 2- (methylthiomethyl) phenyl group, 2-
(Phenylthiomethyl) phenyl group, 2-pyridyl group,
A 2-quinolyl group, preferably a 2- (trifluoromethyl) phenyl group, a 2- (trichloromethyl) phenyl group, a 2-methyl-4-chlorophenyl group, a 2- (trimethylsilyl) phenyl group, or a 2- (diphenyl) group. An aminomethyl) phenyl group and a 2- (methoxymethyl) phenyl group. Specific examples of the substituted ferrocenyl group include a methylferrocenyl group, a dimethylferrocenyl group, and tert.
A -butylferrocenyl group, a ferrocenyl group having a tetramethylcyclopentadienyl (Cp ^* ) group, and the like.

Q in the general formula (1) is a hydrogen atom,
To 20 hydrocarbon groups, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, an amino group having a hydrocarbon group having 1 to 20 carbon atoms, a phosphino group having a hydrocarbon group having 1 to 20 carbon atoms, carbon An oxy group having a hydrocarbon group of numbers 1 to 20,
A thio group having a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, oxygen or sulfur; An amino group having 20 hydrocarbon groups and a hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom. When Q contains a coordinating atom, it can coordinate to the transition metal atom M. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms for Q include a methyl group, an ethyl group, a tert-butyl group, and a phenyl group, and specific examples of the silyl group having a hydrocarbon group having 1 to 20 carbon atoms. Is a trimethylsilyl group, te
Examples thereof include an rt-butyldimethylsilyl group and a triphenylsilyl group. Specific examples of the amino group having a hydrocarbon group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a diphenylamino group, a pyridyl group or a substituted pyridyl group bonded to an adjacent R ^3, and the like. It is preferably a pyridyl group or a substituted pyridyl group bonded to an adjacent R ³ . Carbon number 1
Examples of the phosphino group having 20 hydrocarbon groups include a dimethylphosphino group, a di (cyclohexyl) phosphino group,
Di (tert-butyl) phosphino group, diphenylphosphino group, etc. and bis (diisopropylamino) phosphino group, bis (pyrrolidinyl) phosphino group, 1- (N,
An azaphosphine such as an N-dimethyl-2,5-diaza-1-phosphinocyclopentyl) group or a 1- (N, N-diphenyl-2,5-diaza-1-phosphinocyclopentyl) group; Specific examples of the oxy group having 20 to 20 hydrocarbon groups include a methyloxy group, a phenoxy group,
Specific examples of the thio group having a hydrocarbon group having 1 to 20 carbon atoms, such as a -methylphenoxy group and a benzyloxy group, include a methylthio group, a phenylthio group, and a 2-methylphenylthio group. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom include N-phenyliminomethyl group, N- (2-tolyl) iminomethyl group, dimethylaminomethyl group, Diphenylaminomethyl group, phenylaminomethyl group, diphenylphosphinomethyl group, dicyclohexylphosphinomethyl group, di (tert-butylphosphino) methyl group, methoxymethyl group, (1-methoxymethyl) ethyl group, phenoxymethyl group, Examples thereof include a (2-methylphenoxy) methyl group, a methylthiomethyl group, and a phenylthiomethyl group, and preferably include an N-phenyliminomethyl group and an N- (2-tolyl) iminomethyl group. When Q is oxygen or sulfur, Q can form a sigma bond with the transition metal atom M. p represents an integer of 0 or 1, and is preferably 0.

R ³ in the general formula (1) is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A silyl group having a hydrocarbon group, a nitrogen atom, an oxygen atom,
A hydrocarbon group having 1 to 20 carbon atoms including a halogen atom or a sulfur atom;
A hydrocarbon group having 0 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a butyl group, an isopropyl group,
a tert-butyl group, a phenyl group, a 2-methylphenyl group, a 4-methoxyphenyl group, etc., having 1 to 20 carbon atoms.
Specific examples of the silyl group having a hydrocarbon group of: trimethylsilyl group, tert-butyldimethylsilyl group,
And a triphenylsilyl group. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, an oxygen atom, a halogen atom or a sulfur atom include a chloromethyl group, a methoxymethyl group, a dimethylaminomethyl group,
Formyl group, N- (2-methylphenyl) iminomethyl group, N- (2-isopropylphenyl) iminomethyl group, methylthiomethyl group, phenylthiomethyl group and the like. In addition, one R ³ adjacent to Q may be bonded to form a ring. A specific example of this ring is, for example, a pyridine ring. m is an integer of 1 to 3, and when m is 2 or more,
Each may be the same or different from each other, it can also be bonded is adjacent R ³ together form a ring.

In the general formula (1), _n of (R ⁴ ) _n represents an integer of 1 to 5, and when n is 2 or more, they may be the same or different from each other, and include a hydrogen atom and a carbon atom of 1 to 5. 20 hydrocarbon groups, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a phosphino group having a hydrocarbon group having 1 to 20 carbon atoms, an oxy group having a hydrocarbon group having 1 to 20 carbon atoms, A thio group having 1 to 20 hydrocarbon groups, or a hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, a phosphorus atom, an oxygen atom, a halogen atom or a sulfur atom, preferably a hydrogen atom, 20 hydrocarbon groups, 1 to 1 carbon atoms
A silyl group having 20 hydrocarbon groups, a hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, an oxygen atom, or a halogen atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms for R ⁴ include a methyl group, an ethyl group, a butyl group, an isopropyl group, a tert-butyl group, a phenyl group, a 2-methylphenyl group, and a 4-tert-butylphenyl group. And specific examples of the silyl group having a hydrocarbon group having 1 to 20 carbon atoms include a trimethylsilyl group, a tert-butyldimethylsilyl group, and a triphenylsilyl group. Examples of the phosphino group having a hydrocarbon group having 1 to 20 carbon atoms include a dimethylphosphino group, a di (cyclohexyl) phosphino group, a di (tert-butyl) phosphino group, and a diphenylphosphino group. 20
Specific examples of the oxy group having a hydrocarbon group include a methyloxy group, a phenoxy group, a 2-methylphenoxy group, a benzyloxy group, and the like. As specific examples of the thio group having a hydrocarbon group having 1 to 20 carbon atoms, Represents a methylthio group, a phenylthio group, a 2-methylphenylthio group, or the like. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, a phosphorus atom, an oxygen atom, a halogen atom or a sulfur atom include N- (tert) -butyliminomethyl group, N- (phenyl) iminomethyl group, N- (2-tolyl) iminomethyl group, 3- (dimethylaminomethyl) phenyl group, dimethylaminomethyl group, 1- (dimethylamino) ethyl group, diphenylaminomethyl group, phenylmethylaminomethyl group, diphenylphosphinomethyl group , Dicyclohexylphosphinomethyl group, di (ter
a t-butylphosphino) methyl group, a 4-methoxyphenyl group, a 3- (methoxymethyl) phenyl group, a methoxymethyl group, a 1- (methoxymethyl) ethyl group, a phenoxymethyl group, a (2-methylphenoxy) methyl group, Preferable examples include a 4-fluorophenyl group, a 3- (trifluoromethyl) phenyl group, a 2,2,2-trifluoroethyl group, a methylthiomethyl group, and a phenylthiomethyl group.

L in the general formula (1) is a coordination bond compound of π-electron, ether, nitrile, amine, and phosphine, and specifically, ethylene, propylene, styrene,
Dimethyl ether, diethyl ether, dibutyl ether, acetonitrile, benzonitrile, trimethylamine, triethylamine, N, N-dimethylaniline, N
-Methyldiphenylamine, triphenylphosphine,
And tricyclohexylphosphine. r shows the integer of 0-3.

X and L in the general formula (1) can have a bond. In this case, specific examples include a π-allyl group, a 1-methyl-π-allyl group, and a 2-methyl-π -Allyl group, 1-phenyl-π-allyl group and the like.

Preferred embodiments of the transition metal compound having an azaferrocene or ferrocene structure represented by the general formula (1) of the present invention can be represented by the general formulas (2) to (4).

[0021]

Embedded image

Embedded image

Embedded image R ^{5 in} the general formula (4) of the present invention is a hydrogen atom, having 1 to 1 carbon atoms.
An amino group having a hydrocarbon group of 20 and a hydrocarbon group having 1 to 20 carbon atoms is shown. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a butyl group, an isopropyl group, a tert-butyl group, a phenyl group, and a 2-methylphenyl group. Specific examples of the amino group having a hydrocarbon group include a dimethylamino group, a diethylamino group, an N-piperazinyl group, an N-piperidinyl group,
N-pyrrolidinyl group, diphenylamino group and the like. M in the general formula (4) of the present invention is an integer of 1 or 2.

Specific examples of the transition metal compound having an azaferrocene or ferrocene ligand of the present invention include, but are not limited to, the following transition metal complexes. Incidentally, the transition metal compound having an azaferrocene or ferrocene ligand of the present invention,
When the (aza) ferrocene ring has planar asymmetry or when the substituent R ² has an asymmetric carbon, it may be either a racemic form or an optically active form.

[0023]

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image As a method for synthesizing a transition metal compound having an azaferrocene or ferrocene structure represented by the general formula (1) of the present invention, after synthesizing a corresponding coordinating compound having an azaferrocene or ferrocene structure, And a method of synthesizing a complex. The corresponding coordinating compound having an azaferrocene structure can be represented by the following general formula (5).

[0024]

Embedded image (Where A represents a carbon atom, a nitrogen atom, or a phosphorus atom. R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a halogen atom, a ferrocenyl group) Or a substituted ferrocenyl group, and R ² is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a halogen atom, a silicon atom, a nitrogen atom, an oxygen atom or a sulfur atom, A ferrocenyl group or a substituted ferrocenyl group, wherein R ¹ and R ² may form a ring, and Q has a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. A silyl group, an amino group having a hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
A phosphino group having a hydrocarbon group of from 20 to 20;
An oxy group having 20 hydrocarbon groups, a thio group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, a hydroxyl group, or Shows a thiol group. R ³ is a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
A silyl group having a hydrocarbon group of from 20 to 20, carbon atom including a nitrogen atom, an oxygen atom, a halogen atom or a sulfur atom;
20 represents a hydrocarbon group, and one R ³ adjacent to Q may form a ring. when m is 2 or more, R ³ may be the same as or different from each other, it can also be bonded is adjacent R ³ together form a ring. R ⁴ is a hydrogen atom,
A hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a phosphino group having a hydrocarbon group having 1 to 20 carbon atoms, and an oxy group having a hydrocarbon group having 1 to 20 carbon atoms. A thio group having a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, a phosphorus atom, an oxygen atom, a halogen atom or a sulfur atom, wherein n is 2 or more At this time, R ⁴ may be the same or different, and adjacent R ⁴ may be bonded to each other to form a ring. R ³ and R ⁴ may have a bond. m shows the integer of 1-3, and n shows the integer of 1-5. p represents an integer of 0 or 1. The substituents R ^{1 to} R ⁴ of the coordinating compound represented by the general formula (5) according to the present invention may be a general formula (1) to a transition metal compound.
It is the same as the substituents R ^{1 to} R ^{4 in} (3).

Specific examples of the coordinating compound represented by formula (5) of the present invention include the following compounds, but are not limited thereto.

[0026]

Embedded image

Embedded image Among the coordinating compounds represented by the general formula (5) of the present invention, A
Is a nitrogen atom, and can be synthesized using an azaferrocene compound represented by the following general formula (6) as a raw material.

The general formula (6) is as follows:

[0028]

Embedded image(Where R^ThreeRepresents a hydrogen atom, a halogen atom, and a carbon number of 1 to
Having 20 hydrocarbon groups and 1-20 carbon atoms
Silyl group, nitrogen atom, oxygen atom, halogen atom
Represents a hydrocarbon group having 1 to 20 carbon atoms including a sulfur atom. m
Is 2 or more, R ^ThreeMay be the same or different
And adjacent R^ThreeBond with each other to form a ring
Can also. R^FourIs a hydrocarbon group having 1 to 20 carbon atoms,
Silyl group having 1 to 20 hydrocarbon groups, having 1 to 2 carbon atoms
A phosphino group having 0 hydrocarbon groups, having 1 to 20 carbon atoms
An oxy group having a hydrocarbon group of 1 to 20 carbon atoms
A thio group having a hydrogen group, or a nitrogen atom, a phosphorus atom, or oxygen
Carbon atom containing 1 atom, halogen atom or sulfur atom
20 represents a hydrocarbon group, and when n is 2 or more, R^FourAre each other
May be the same or different, and adjacent R^FourEach other
May combine to form a ring. R^ThreeAnd R^FourIs combined
Can also be provided. m represents an integer of 1 to 3, and n is
Shows an integer of 1 to 5. Where R^FourAre all methyl at the same time
It is not a group. ) Is represented by the general formula (5)
Is a precursor compound of the coordinating compound.

Specific examples of the precursor compound represented by the general formula (6) include the following compounds, but are not limited thereto.

[0030]

Embedded image The azaferrocene compound represented by the general formula (6) of the present invention is described in, for example, G.S. C. Fu et al., J. Org. Chem., 61, 7230 (1
996)) or K.K. K. The method disclosed by Joshi et al. (J. Organomet. Che.
m. , P. 471 (1964)).

The coordinating compound represented by the general formula (5) of the present invention can be synthesized using the azaferrocene compound represented by the general formula (6) as a raw material. The azaferrocene compound is lithiated with a lithiating agent such as n-butyllithium and reacted with N, N-dimethylformamide, benzonitrile, or acetonitrile to introduce a carbonyl group such as a formyl group or an acetyl group. Can be. As a method of lithiation of azaferrocene, for example, V.I. N. S
etkina et al. (J. Or.
gonomet. Chem. , 251, C41 (1
983)). When a chiral diamine such as (−)-sparteine is present during the lithiation, one enantiomer is present in excess, that is, an optically active azaferrocene can be synthesized.
Alternatively, the carbonyl group can be introduced by Friedel-Crafts acylation using an acid chloride and aluminum chloride. Further, the compound is converted into an imino by a dehydration condensation reaction with an aromatic amine or an aliphatic amine to obtain a compound represented by the general formula (5):
Can be synthesized. Examples of the conditions for the imination reaction include a method of performing the reaction in ethanol using acetic acid as a catalyst and a method of performing the reaction in toluene using p-toluenesulfonic acid as a catalyst.

The coordinating compound serving as a raw material of the transition metal compound represented by the general formula (4) of the present invention can be synthesized from a ferrocene derivative having a pyrindine ring. Ferrocene derivatives having a pyrindine ring are described, for example, in G .; C.
Fu et al. (J. Am. Che.
m. Soc. 123, p. 353 (2001)). The ferrocene having a pyrindine ring thus obtained is lithiated with a lithiating agent such as n-butyllithium and reacted with N, N-dimethylformamide, benzonitrile, acetonitrile or the like to form a formyl group or an acetyl group. A carbonyl group can be introduced. Alternatively, the carbonyl compound can be obtained by Friedel-Crafts acylation using an acid chloride and aluminum chloride. Further, the coordination compound of the general formula (5) can be synthesized by iminoization by a dehydration condensation reaction with an aromatic amine or an aliphatic amine. Examples of the conditions for the imination reaction include a method of performing the reaction in ethanol using acetic acid as a catalyst, p.
-A method in which toluene sulfonic acid is used as a catalyst in toluene.

On the other hand, among the coordinating compounds represented by the general formula (5) of the present invention, those in which A is a carbon atom can be synthesized from a ferrocene derivative. As a method for synthesizing a ferrocene compound having a substituent on the upper and lower Cp rings,
For example, J. Organomet. Chem. , 199
1 year, 412, 381 and Organometal
lics, 1999, Vol. 18, p. 1267, a method in which a formyl group is introduced into upper and lower Cp rings, and an imino group is introduced by dehydration condensation with an amine. As a method for synthesizing a ferrocene compound having a substituent on the same Cp ring, for example, B
ull. Chem. Soc. Jpn. , 1980, 5
3, page 1138 and J.M. Org. Chem. , 199
As described in Vol. 62, p. 6733, the method of introducing a substituent having various hetero atoms can be exemplified. Further, by combining these methods, it is possible to easily introduce various substituents into the upper, lower, and the same Cp rings. Also, J.I. Organo
met. Chem. Asymmetric ferrocene structures can also be constructed utilizing the specific reactions of substituted cyclopentadienyl alkali metals, as described in Chem., 2000, 598, 365.

As a method for synthesizing the transition metal compound represented by the general formula (1) having the azaferrocene or ferrocene ligand, a method used in an existing complex synthesis reaction can be used as it is. For example, WO9
6/23010 and J.M. Am. Chem. Soc. ,
The method described in 1999, vol. 121, p. 8728 can be used. The transition metal compound having an azaferrocene or ferrocene ligand can be used as a polymerization catalyst after being isolated by a conventional method. It can also be served as

The activation co-catalyst (B), which is one of the components of the olefin polymerization catalyst in the present invention, refers to the transition metal compound or the reaction product of the transition metal compound and the organometallic compound. Compounds which have a role of forming a polymerization active species capable of polymerizing an olefin by reacting are shown. An activation co-catalyst is a compound that, after forming a polymerization active species, provides a compound that weakly coordinates or interacts with the generated polymerization active species, but does not directly react with the active species. Examples of the activation promoter include trialkylaluminums such as triethylaluminum and triisobutylaluminum; alkylaluminum halides such as diethylaluminum chloride and ethylaluminum sesquichloride; 1,3-dichloro-1,3-diethylaluminoxane; Halogenated alkylaluminoxane such as 3-dichloro-1,3-diisopropylaluminoxane, alkylaluminoxane which has recently been frequently used as a promoter component of a homogeneous olefin polymerization catalyst system, and ionized ion having a non-coordinating anion And a modified clay compound. However, the present invention is not limited thereto.

For example, when the activation co-catalyst (B) is an alkylaluminoxane, its structure is represented by the following general formula (7)
And / or (8)

[0037]

Embedded image (In the formula, R ⁶ may be the same or different, and is a hydrocarbon group having 1 to 20 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a tert-butyl group. Is an integer of 2 to 60). The alkylaluminoxane may contain a small amount of an organometallic compound.

When the activating cocatalyst (B) is an ionized ionic compound having a non-coordinating anion, the structure thereof is a protonic acid represented by the following general formula (9),
0), an ionized ionic compound represented by the general formula (1)
The Lewis acid represented by 1), the Lewis acidic compound represented by the general formula (12), and a compound having any structure of AgSbF ₆ or AgPF ₆ are desirable.

[HL ¹ ] [B (Ar) ₄ ] (9) [AL ² _u ] [B (Ar) ₄ ] (10) [D] [B (Ar) ₄ ] (11) B (Ar) ₃ (12) (where H is a proton, B is a boron atom or an aluminum atom, L ¹ is a Lewis base, L ² is a Lewis base or a cyclopentadienyl group. A is lithium, iron or silver. Wherein D is a carbonium cation or a tropylium cation; Ar is a halogen-substituted aryl group having 6 to 20 carbon atoms; u is an integer of 0 to 2); Specific examples of the protonic acid represented by (9) include diethyloxonium tetrakis {3,5-bis (trifluoromethyl) phenyl} borate, diethyloxonium tetrakis (pentafluorophenyl) borate, and dioxonium tetrakis (pentafluorophenyl) borate. Methyloxonium tetrakis (pentafluorophenyl) borate, tetramethyleneoxonium tetrakis (pentafluorophenyl) borate, hydronium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl)
Borate, tri-N-butylammonium tetrakis (pentafluorophenyl) borate, diethyloxonium tetrakis (pentafluorophenyl) aluminate, dimethyloxonium tetrakis (pentafluorophenyl) aluminate, tetramethyleneoxonium tetrakis (pentafluorophenyl) aluminum Nate,
Hydronium tetrakis (pentafluorophenyl) aluminate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate, tri-n-butylammonium tetrakis (pentafluorophenyl) aluminate and the like can be mentioned. It is not limited.

Specific examples of the ionized ionic compound represented by the general formula (10) include sodium tetrakis {3,5-bis (trifluoromethyl) phenyl} borate and lithium tetrakis (pentafluorophenyl).
Lithium salts such as borate and lithium tetrakis (pentafluorophenyl) aluminate, or ether complexes thereof; ferrocenium salts such as ferrocenium tetrakis (pentafluorophenyl) borate and ferrocenium tetrakis (pentafluorophenyl) aluminate; and silver tetrakis Silver salts such as (pentafluorophenyl) borate and silver tetrakis (pentafluorophenyl) aluminate can be exemplified, but are not limited thereto.

Examples of the Lewis acid represented by the general formula (11) include trityltetrakis (pentafluorophenyl) borate, trityltetrakis (pentafluorophenyl) aluminate, tropylium tetrakis (pentafluorophenyl) borate, Examples include, but are not limited to, tropylium tetrakis (pentafluorophenyl) aluminate.

Specific examples of the Lewis acidic compound represented by the general formula (12) include tris {3,5-bis (trifluoromethyl) phenyl} borane, tris (pentafluorophenyl) borane and tris (2 , 3,5,6-tetrafluorophenyl) borane, tris (2,3,4,
5-tetraphenylphenyl) borane, tris (3
4,5-trifluorophenyl) borane, phenylbis (perfluorophenyl) borane, tris (3,4,5
-Trifluorophenyl) aluminum and the like, but are not limited thereto.

When the activation co-catalyst (B) which is a component of the catalyst for olefin polymerization of the present invention is a modified clay compound, the clay compound used preferably has a cation exchange ability. The clay compound used in the present invention is preferably subjected to chemical treatment such as treatment with an acid or alkali, salt treatment, and formation of a complex by treatment with an organic compound or an inorganic compound.

Examples of the clay compound include naturally occurring kaolinites such as kaolinite, dickite and halloysite, montmorillonite, hectorite, beidellite, and the like.
Smectites such as saponite, teniolite and sauconite; mica such as muscovite, paragonite and illite;
Vermiculite group, margarite, brittle mica group such as clintonite, dombasite, cocoaite, curdstone group such as clinochlore, sepiolite palygorskite and the like, and artificially synthesized clay compounds can be mentioned, but are not limited thereto. .

Examples of the acid used in the chemical treatment include Bronsted acids such as hydrochloric acid, sulfuric acid, nitric acid, and acetic acid. As the alkali, sodium hydroxide, potassium hydroxide and calcium hydroxide are preferably used. Compounds used in the salt treatment include ionic halides such as sodium chloride, potassium chloride, lithium chloride, magnesium chloride, aluminum chloride, iron chloride, and ammonium chloride; sulfates such as sodium sulfate, potassium sulfate, aluminum sulfate, and ammonium sulfate. Carbonates such as potassium carbonate, sodium carbonate, and calcium carbonate; inorganic salts such as sodium phosphate, potassium phosphate, aluminum phosphate, and ammonium phosphate; and sodium acetate, potassium acetate, potassium oxalate, and citrate. Organic acid salts such as sodium acid salt and sodium tartrate can be exemplified.

Examples of the organic compound used to form the organic complex of the clay compound include onium salts, compounds that form carbon cations such as trityl chloride and tropylium bromide, and complexes that form metal complex cations such as ferrocenium salts. Compounds are exemplified. Examples of the inorganic compound used for forming the inorganic composite include metal hydroxides that generate hydroxide cations such as aluminum hydroxide, zirconium hydroxide, and chromium hydroxide.

Among the modified clay compounds used in the present invention, a modified clay compound-organic ion complex in which a metal ion which is an exchangeable cation present in the clay compound is replaced with a specific organic cation component is particularly preferred. It is a clay compound. Specific examples of the organic cation to be introduced into the modified clay compound include aliphatic ammonium cations such as butyl ammonium, hexyl ammonium, decyl ammonium, dodecyl ammonium, diamyl ammonium, tributyl ammonium, N, N-dimethyldecylammonium, and anilinium. , N-methylanilinium, N, N-dimethylanilinium, N-ethylanilinium, N, N-diethylanilinium, benzylammonium, toluidinium, dibenzylammonium, tribenzylammonium, N, N, 2,4, 6
Examples thereof include ammonium ions such as aromatic ammonium cations such as pentamethylanilinium, and oxonium ions such as dimethyloxonium and diethyloxonium, but are not limited thereto.

When the activation cocatalyst (B), which is a component of the olefin polymerization catalyst of the present invention, is a topotactic reduction reaction product involving electron transfer, the reaction product is represented by the general formula (13) E ^{r +} (k / r) (L ³ ) h [G] ^k− (13) (where [G] is a host compound, k is a reduction amount, ^{Er +} is an n-valent guest cation, L ³ is a Lewis base, and h is the amount of the Lewis base.).

Here, [G] is a host compound having a three-dimensional structure, a host compound having a two-dimensional structure,
A host compound having a one-dimensional structure and a host compound which is a molecular solid can be exemplified.

The host compound having a three-dimensional structure includes hexamolybdenum octasulfide, divanadium pentoxide, tungsten trioxide, titanium dioxide, vanadium dioxide, chromium dioxide, manganese dioxide, tungsten dioxide, ruthenium dioxide, osmium dioxide, iridium dioxide. Can be exemplified.

Examples of the host compound having a two-dimensional structure include titanium disulfide, zirconium disulfide, hafnium disulfide, vanadium disulfide, niobium disulfide, tantalum disulfide, chromium disulfide, molybdenum disulfide, tungsten disulfide, and tungsten disulfide. Rhenium sulfide, platinum disulfide, tin disulfide, lead disulfide, phosphorus magnesium trisulfide, phosphorus manganese trisulfide,
Examples include tantalum sulfide carbide, molybdenum trioxide, vanadium pentoxide gel, graphite, and polyacene.

Examples of the host compound having a one-dimensional structure include titanium trisulfide and niobium triselenide.

Examples of the host compound which is a molecular solid include:
Examples thereof include tetracyanoquinodimethane and tetrathiofulvalene.

Further, as [G], a plurality of the above host compounds may be mixed and used.

Although k is not particularly limited, it is preferably 0 for the purpose of producing an olefin polymer with high catalytic activity.
A range of <k ≦ 3 can be used. More preferably, the range of 0 <k ≦ 2 can be used.

As L ³ , a Lewis base or cyclopentadienyl group capable of coordinating with ^{Er +} can be used. Examples of the Lewis base include water, an amine compound, a heterocyclic compound containing nitrogen, ethyl ether and n. Ethers such as -butyl ether; amides such as formamide, N-methylformamide or N-methylacetamide; alcohols such as methyl alcohol or ethyl alcohol; diols such as 1,2-butanediol or 1,3-butanediol. However, the present invention is not limited to these. These two or more kinds can be used as a mixture.

H can be in the range of 0 ≦ h ≦ 10.

As E ^{r +} , a cation containing at least one atom selected from the group consisting of atoms of groups 1 to 14 of the periodic table can be used, and r can be in the range of 0 <r ≦ 10. However, for the purpose of producing an olefin polymer with high catalytic activity, preferably, the compound represented by the general formula (14)
Or _{^{(15) R 7 2 R 8}} NH + (14) ( wherein, R ⁷ ₂ R ⁸ N is an amine compound, R ⁷ are each independently hydrogen atom or an aliphatic hydrocarbon having 1 to 30 carbon atoms R ⁸ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 50 carbon atoms.) (R ⁹ ) ⁺ (15) R ⁹ ) ⁺ is a carbonium cation or a tropylium cation having 1 to 50 carbon atoms.) At least one cation selected from the group consisting of cations represented by the formula:

[0059] The amine compound represented by R ⁷ ₂ R ⁸ N, methylamine, n- propylamine, isopropylamine, n- butylamine, tert- butylamine,
Allylamine, N-methylcyclohexylamine, N,
N-dimethyloctylamine, N, N-dimethyldodecylamine, N, N-dimethyloctadecylamine, N,
N-dioctadecylmethylamine, trihexylamine, triisooctylamine, tridodecylamine,
Aliphatic amines such as N, N-dimethylcyclohexylamine, aniline, N-methylaniline, N-ethylaniline, N-allylaniline, o-toluidine, p-toluidine, N, N-dimethylaniline, N-methyl-o -Toluidine, N-methyl-m-toluidine, N-ethyl-
Aromatic amines such as o-toluidine can be exemplified.

Examples of the cation represented by the general formula (15) include a triphenylmethyl cation and a tropylium cation.

The catalyst in the present invention can be prepared by a usual polymerization method,
That is, it can be used for any of slurry polymerization, gas phase polymerization, high pressure polymerization, solution polymerization and bulk polymerization. In the present invention, the polymerization means not only homopolymerization but also copolymerization, and the polyolefin obtained by these polymerizations is used in a meaning including not only a homopolymer but also a copolymer.

In the olefin polymerization catalyst of the present invention, an organometallic compound can coexist with the transition metal compound and the activating cocatalyst. The organometallic compound is
A compound capable of inactivating a catalyst poison component present in the polymerization system and capable of forming an alkyl compound of a transition metal compound is preferable. Specifically, methyl lithium and n-butyl lithium are preferable. Alkyl lithium compounds such as methyl magnesium chloride, ethyl magnesium chloride, isopropyl magnesium chloride, benzyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, isopropyl magnesium bromide, Grignard reagents such as benzyl magnesium bromide, dialkyl magnesium such as dimethyl magnesium, dimethyl Zinc, dialkyl zinc such as diethyl zinc, alkyl borane such as trimethyl borane, triethyl borane, trimethyl aluminum, Li ethylaluminum, alkyl aluminum such as tri-isobutyl aluminum, methyl aluminoxane, butyl aluminoxane, tert-
Alkyl aluminoxane such as butyl aluminoxane and the like can be mentioned.

The olefin used for the polymerization in the present invention is ethylene, propylene, 1-butene, 4-methyl-
Α-olefins such as 1-pentene, 1-hexene, 1-octene, styrene and styrene derivatives, butadiene,
Conjugated and non-conjugated dienes such as 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, cyclobutene, cyclohexene and the like Α, β-unsaturation such as cyclic olefin, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid Carboxylic acids and their metal salts such as sodium, potassium, lithium, zinc, magnesium and calcium salts, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, acrylic acid t
Α, β-unsaturated carboxylic esters such as -butyl, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and vinyl acetate , Vinyl propionate,
Vinyl esters such as vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, and monoglycidyl itaconate; methyl vinyl Ketone, ethyl vinyl ketone, vinyl ketone such as phenyl vinyl ketone, α, β-unsaturated nitrile such as acrylonitrile, methacrylonitrile, 1-phenylacrylonitrile, and ethylene and propylene; ethylene and 1-butene; 1-hexene,
Ethylene and 1-octene, ethylene and vinyl acetate, ethylene and methyl acrylate, ethylene and methyl methacrylate, ethylene and propylene and styrene, ethylene and 1-octene
Two or more components such as hexene and styrene, ethylene, propylene and ethylidene norbornene can be mixed and polymerized.

The polymerization of the olefin in the present invention can be carried out in a gas phase or a liquid phase. When the polymerization is carried out in the liquid phase, any solvent can be used as long as it is a commonly used organic solvent. , Toluene, xylene, pentane, hexane, heptane, 2,2,2-trifluoroethanol, hexafluoroisopropyl alcohol, etc., and olefin itself such as propylene, 1-butene, 1-octene, 1-hexene is used as a solvent. Can also be used.

In producing a polyolefin using the method of the present invention, polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure and monomer concentration are not particularly limited, but the polymerization temperature is -100 to 300 ° C. For 10 seconds to 20 hours, and the polymerization pressure is preferably in the range of normal pressure to 3000 kg / cm ² G. It is also possible to adjust the molecular weight using hydrogen or the like during polymerization. The polymerization can be carried out by any of a batch system, a semi-continuous system, and a continuous system, and can be carried out in two or more stages by changing the polymerization conditions. Further, the polyolefin obtained after the completion of the polymerization can be separated and recovered from the polymerization solvent by a conventionally known method, and can be obtained by drying.

[0066]

The transition metal compound having an azaferrocene or ferrocene structure of the present invention can be easily synthesized and can have various substituents. Furthermore, it is extremely effective as a polymerization catalyst for olefin polymerization. By using this catalyst as an olefin polymerization catalyst, it is possible to efficiently produce a polyolefin. Further, the transition metal compound having an azaferrocene or ferrocene structure of the present invention is also effective as a catalyst for polycarbonate synthesis or a catalyst for asymmetric synthesis other than the catalyst for olefin polymerization, for example, a catalyst for asymmetric cyclopropanation. It is believed that there is.

[0067]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The transition metal compound was synthesized using a Schlenk technique or a dry box, and all operations were performed in an argon or nitrogen atmosphere. The solvents used for the preparation of the transition metal compound were all deoxygenated by known methods,
The dehydrated one was used. The polymerization reaction was carried out at a predetermined temperature for a predetermined time while continuously supplying ethylene gas using a 2 l autoclave. The solvent used for the polymerization was deoxygenated and dehydrated by a known method. As the ethylene gas, a polymerization grade was used as it was.

Example 1 Synthesis of Complex A-1 [Synthesis of Coordinating Compound] Org. Chem. , 19
According to the method described in 1997, Vol. 62, p. 6733, 1,2-diformylferrocene was synthesized.

A 50 ml Schlenk flask was purged with nitrogen, and 1,2-diformylferrocene (625 mg, 2.
58 mmol) and dissolved in 8 ml of ethanol. Aniline (493 mg, 5.29 mmol) was added, and the mixture was stirred at room temperature overnight. After completion of the reaction, the solvent was distilled off under reduced pressure, and then cyclohexane (20 ml) was added to the obtained solid residue to perform recrystallization. The precipitated crystals were filtered and dried under reduced pressure to give a dark red solid (620 mg, 1.
58 mmol). Yield 61%.

¹ H-NMR (400 MHz, C ₆ D ₆ ) δ
= 3.99 (s, 5H), 4.25 (t, J = 2.6H)
z, 1H), 5.02 (d, J = 2.6 Hz, 2H),
7.02-7.28 (m, 10H), 8.91 (s, 2
H) MS m / z 392 (M ⁺ ) [Synthesis of Complex A-1] A 50 ml Schlenk flask was purged with nitrogen, and (1,5-cyclooctadiene) PdMe was added.
Cl (143 mg, 0.539 mmol) and the ligand obtained above (219 mg, 0.558 mmol) were added. Toluene (6 ml) was added, and the mixture was stirred at room temperature for 20 hours. The obtained reaction solution was concentrated under reduced pressure, and toluene (2 m
Washed in l). The residue was dried under reduced pressure to obtain a red solid of complex A-1 (254 mg, 0.497 mmol). 89% yield.

¹ H-NMR (400 MHz, CD ₂ C
l ₂ ) δ = 0.14 (s, 3H), 4.39 (s, 5
H), 5.12 (brs, 1H), 5.22 (brs,
2H), 7.10-7.55 (m, 6H), 7.65-
7.83 (m, 4H), 8.56 (s, 1H), 8.5
9 (s, 1H) MS m / z 549 (M ^<+> )

[0073]

Embedded image Example 2 Synthesis of complex A-2: A 50-mL Schlenk flask was purged with nitrogen, and the complex A-1 (204 m) obtained in Example 1 was replaced with nitrogen.
g, 0.371 mmol) and AgSbF ₆ (129 m
g, 0.375 mmol). After cooling to -50 ° C, a solution consisting of acetonitrile (0.15 ml) and dichloromethane (6 ml) was added dropwise. Over 4 hours
After the temperature was raised to 10 ° C., the obtained slurry solution was filtered and further extracted with dichloromethane. The combined dichloromethane solution was concentrated under reduced pressure. After dissolving the solid residue in dichloromethane (4 ml), pentane (9 ml) was added dropwise. The supernatant was removed, and the obtained residue was dried under reduced pressure.
Complex A-2 dark red solid (291 mg, 0.368 mm
ol). Yield 99%.

¹ H-NMR (400 MHz, CD ₂ C
l ₂ ) δ = 0.33 (s, 3H), 1.95 (s, 3
H), 4.47 (s, 5H), 5.28 (brs, 1
H), 5.37 (brs, 1H), 5.45 (brs,
1H), 7.42-7.75 (m, 10H), 8.60
(S, 1H), 8.73 (s, 1H) MS m / z 790 (M ^<+> )

[0075]

Embedded image Example 3 Synthesis of Complex A-3: A 50-mL Schlenk flask was purged with nitrogen, and the complex A-1 obtained in Example 1 (90 mg,
0.163 mmol) and sodium tetrakis {3
5-Bis (trifluoromethyl) phenyl diborate (165 mg, 0.187 mmol) was added. -50
After cooling to ℃, a solution consisting of acetonitrile (0.09 ml) and dichloromethane (5 ml) was added dropwise. After the temperature was raised to −10 ° C. over 4 hours, the obtained slurry solution was filtered, further extracted with dichloromethane, and the combined dichloromethane solution was concentrated under reduced pressure. After dissolving the residue in diethyl ether (3 ml), pentane (4 ml) was added. The supernatant was removed, and the obtained residue was dried under reduced pressure to give a dark red solid of complex A-3 (135 mg, 0.095 mmol).
1) was obtained. Yield 58%.

¹ H-NMR (400 MHz, CD ₂ C
l ₂ ) δ = 0.34 (s, 3H), 1.90 (s, 3
H), 4.47 (s, 5H), 5.25 (s, 1H),
5.49 (s, 1H), 5.64 (s, 1H), 7.4
0-7.67 (m, 10H), 7.58 (s, 4H),
7.73 (s, 8H), 8.58 (s, 1H), 8.6
9 (s, 1H) MS m / z 1418 (M ^<+> )

[0077]

Embedded imageExample 4 Synthesis of Complex A-4: A 50 ml Schlenk flask was
With (dimethoxyethane) NiBr _Two(115m
g, 0.373 mmol) and dichloromethane (3 m
l) was added. Coordination synthesized in Example 1 to this suspension solution
(153mg, 0.390mmol) and dichlorometa
(5 ml) was added. Shake for 3 hours at room temperature
After stirring, filter, extract with dichloromethane and combine
The dichloromethane solution was concentrated under reduced pressure. Residue is cyclohexane
(40 ml), and dried under reduced pressure.
A color solid (213 mg, 0.348 mmol) was obtained. Income
The rate is 93%.

MS m / z 610 (M ⁺ )

[0079]

Embedded image Example 5 Synthesis of Complex B-1: [Synthesis of Coordinating Compound] Organomet. Ch
em. 1,1'-Diformylferrocene was synthesized according to the method described in Vol. 412, p. 381, 1991.

A 50 ml Schlenk flask was purged with nitrogen, and 1,1′-diformylferrocene (1.04 g,
4.30 mmol), molecular sieves 4A (5
g), 8 ml of toluene and tert-butylamine (1.26 g, 17.2 mmol) were added. 1 at room temperature
After stirring for 5 hours, volatiles were distilled off under reduced pressure. Extraction with diethyl ether (20 ml), concentration under reduced pressure, and drying gave a brown solid (1.35 g, 3.83 mmol). Yield 89
%.

¹ H-NMR (400 MHz, C ₆ D ₆ ) δ
= 1.30 (s, 18H), 4.12 (t, J = 2.2)
Hz, 4H), 4.64 (t, J = 2.2 Hz, 4
H), 8.05 (s, 2H) MS m / z 352 (M ⁺ ) [Synthesis of Complex B-1] A 50-mL Schlenk flask was purged with nitrogen to obtain (1,5-cyclooctadiene) PdMe.
Cl (120 mg, 0.452 mmol) and the ligand obtained above (156 mg, 0.443 mmol) were added. Toluene (2.5 ml) was added, and the mixture was stirred at room temperature for 7 hours. The obtained slurry solution was filtered, and toluene (3
ml). The residue was dried under reduced pressure to obtain a brick-colored solid of complex B-1 (135 mg, 0.265 mmol). Yield 60%.

¹ H-NMR (400 MHz, CD ₂ C
l ₂ ) δ = 0.55 (s, 3H), 1.72 (s, 18
H), 4.55 (brs, 4H), 4.82 (brs,
2H), 6.02 (brs, 2H), 8.15 (s, 1
H), 8,70 (brs, 1H)

[0083]

Embedded image Example 6 Synthesis of Complex B-2 [Synthesis of Coordinating Compound] A 50 ml Schlenk flask was purged with nitrogen, and 1,1′-diformylferrocene (1.
00g, 4.13 mmol), ethanol 25 ml,
2,6-dimethylaniline (1.26 g, 10.4 mm
ol) and acetic acid (10 mg). 8 under reflux
After stirring for an hour, volatiles were distilled off under reduced pressure. The mixture was extracted with diethyl ether (90 ml) and concentrated under reduced pressure. The obtained solid was recrystallized from hexane / toluene (5/1), and dried by filtration to obtain an orange solid (0.90 g, 2.00 mmol). Yield 49%.

[0084]¹H-NMR (400 MHz, C₆D₆) Δ
= 2.20 (s, 12H), 4.23 (t, J = 2.2)
Hz, 4H), 4.70 (t, J = 2.2 Hz, 4
H), 6.96 (t, J = 7.8 Hz, 2H), 7.0
5 (d, J = 7.8 Hz, 4H), 7.70 (s, 2
H) MS m / z 448 (M⁺[Synthesis of Complex B-2] A 50 ml Schlenk flask was
Nitrogen substitution, (dimethoxyethane) NiBr _Two(148
mg, 0.479 mmol) and dichloromethane (3 m
l) was added. The ligand synthesized above is added to this suspension solution.
(222mg, 0.495mmol) and dichloromethane
(5 ml) was added. 48 hours stirring at room temperature
After stirring, filter, extract with dichloromethane and combine
The dichloromethane solution was concentrated under reduced pressure. The residue was dissolved in toluene (20
ml), and dried under reduced pressure to obtain a dark red solid of complex B-2.
(142 mg, 0.213 mmol) was obtained. Yield 45
%.

MS m / z 667 (M ⁺ )

[0086]

Embedded image Example 7 [Preparation of complex solution] A 100 ml Schlenk flask was purged with nitrogen, and complex A-4 (59 m) synthesized in Example 4 was synthesized.
g, 0.097 mmol) and toluene (40 ml) were added and stirred for 30 minutes.

[Ethylene polymerization] A 2-liter autoclave was charged with toluene (500 ml) and methylaluminoxane (PMAO manufactured by Tosoh Akzo, 3.5 ml, 10 mmol in terms of aluminum atom). The temperature in the autoclave is set to 40 ° C and 10 kg / cm ² G
Of ethylene. The complex solution obtained above was injected and polymerization was carried out at 40 ° C. for 1 hour while continuously supplying ethylene so that the pressure became 10 kg / cm ² G. 11. The obtained reaction solution is treated according to a standard method to obtain a liquid polymer.
8 g were obtained.

Example 8 [Ethylene polymerization] Toluene (50 ml) and the complex A-4 (33.4 mg, 0.055 mmol) synthesized in Example 4 were added to a 100 ml glass autoclave.
It was pressurized with 10 kg / cm ² G of ethylene. Tris (pentafluorophenyl) borane (Tosoh Akzo Co., Ltd.)
2.9 wt% Isopearl-E solution, 4 ml, 0.1%
16 mmol) and trimethylaluminum (20 wt% toluene solution, 0.07 ml, 0.17 mmol) were added, and polymerization was performed at room temperature under an ethylene pressure of 10 kg / cm ² G for 2 hours. The resulting reaction solution was treated according to a conventional method to obtain 1.1 g of a liquid polymer.

Example 9 [Preparation of complex solution] A 100 ml Schlenk flask was purged with nitrogen, and the complex A-4 (69 m
g, 0.11 mmol) and toluene (50 ml) were added and stirred for 30 minutes.

[Ethylene / methyl acrylate copolymerization] 2
l of toluene (450 ml) and methylaluminoxane (PMA manufactured by Tosoh Akzo Co., Ltd.)
O, 4.0 ml, 12.8 mm in terms of aluminum atoms
ol). It was pressurized with 10 kg / cm ² G of ethylene. The complex solution obtained above was press-fitted and stirred for 5 minutes, and then methyl acrylate (5 ml, 56 mmol), toluene (40 ml) and methylaluminoxane (0.5 m
The solution consisting of 1) was pressed in. While continuously supplying ethylene so that the pressure becomes 10 kg / cm ² G, room temperature
Polymerization was performed for 4 hours. The obtained reaction solution was quenched with 0.1 N hydrochloric acid (350 ml), the phases were separated, and the organic phase was washed with water. The obtained organic phase was concentrated under reduced pressure, and the obtained viscous substance was extracted with hexane and further concentrated under reduced pressure. 1.82 viscous liquid
g was obtained. ^{According to 1} H-NMR (CDCl ₃ ), it contained 19% by weight of a methyl acrylate unit. From GPC, M
w = 1.0 × 10 ³ and Mw / Mn = 1.8.

Example 10 Using Complex A-4 (67 mg) and methyl acrylate in 15 m
The same operation as in Example 9 was repeated, except that 1 was used. 1.25 g of a viscous liquid was obtained. ^{According to 1} H-NMR (CDCl ₃ ), it contained 50% by weight of a methyl acrylate unit.
According to GPC, Mw = 1.0 × 10 ³ , Mw / Mn = 1.
Nine.

Example 11 Complex B-2 (59 mg, 0.088 mmol) and methylaluminoxane 3.1 ml (Tosoh Akzo Co., Ltd.)
The same operation as in Example 7 was repeated, except that 8.8 mmol in terms of aluminum atom was used. 44mg solid
I got The melting point was 124.4 ° C.

Example 12 Synthesis of Complex C-1 [Synthesis of Coordinating Compound] Org. Chem. , 19
1 ', 2', 3 ', 4', 5'-pentamethylazaferrocene was synthesized according to the method described in Vol.

A 50 ml Schlenk flask was purged with nitrogen, and 1 ′, 2 ′, 3 ′, 4 ′, 5′-pentamethylazaferrocene (404 mg, 1.57 mmol) was added.
It was dissolved in 7 ml of diethyl ether. (-)-Sparteine (740 mg, 3.10 mmol) was added, and n-BuLi (1.59 M hexane solution, 2 ml,
3.2 mmol) was added dropwise. Stir for 1 hour under ice cooling,
N, N-dimethylformamide (240 mg, 3.3 m
mol) was added. After 20 minutes, quench by adding water,
Extracted with diethyl ether. The organic phase was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (solvent: hexane / ethyl acetate). Dark red liquid (35
0 mg, 1.22 mmol). Yield 78%.

¹ H-NMR (400 MHz, C ₆ D ₆ ) δ
= 1.59 (s, 15H), 3.99 (s, 1H),
4.63 (s, 1H), 4.99 (s, 1H), 10.
1 (s, 1H) A 50-ml Schlenk flask was purged with nitrogen, and the 2-formylazaferrocene synthesized above (341 mg, 1.
19 mmol) and ethanol (7 ml) were added. o
-Toluidine (140 mg, 1.31 mmol) and acetic acid (10 mg) were added. After stirring for 2 days at room temperature,
The reaction solution was concentrated under reduced pressure. The residue was extracted with hexane, concentrated under reduced pressure, and then a coordinating compound, a dark red liquid (455 mg)
I got

¹ H-NMR (400 MHz, C ₆ D ₆ ) δ
= 1.72 (s, 15H), 2.58 (s, 3H),
4.07 (s, 1H), 4.92 (s, 1H), 5.0
6 (s, 1H), 6.90-7.40 (m, 4H),
8.54 (s, 1H) [Synthesis of Complex C-1] A 50-mL Schlenk flask was purged with nitrogen, and (DME) NiBr ₂ (152 mg, 0.1 mL) was added.
49 mmol) and dichloromethane (2 ml) were added. Under stirring, a solution of the above coordinating compound (191 mg) in dichloromethane (6 ml) was added using a cannula. After stirring at room temperature for 2 hours, the resulting slurry reaction solution was filtered, and the obtained solid was washed with dichloromethane. The residue was dried under reduced pressure to give a red solid (210 mg, 0.35 mm
ol). Yield 71%.

¹ H-NMR (400 MHz, CD ₂ C
l ₂ ) δ = −8.15 (s, 1H), −7.70 (s,
1H), -1.80 (s, 1H), 1.48 (s, 15
H), 1.80 (s, 3H), 16.50 (s, 1
H), 22.85 (s, 1H), 23.30 (s, 1
H), 34.10 (s, 2H) FAB-MASS: m / z 593 (M ⁺ ), 513
(M ⁺ -Br), 433 (M ⁺ -2Br), 374 (M ⁺
—NiBr ₂ )

[0098]

Embedded image Example 13 Synthesis of complex C-2: A 50-mL Schlenk flask was purged with nitrogen, and iron (II) chloride (43.8 mg, 0.35 m
mol) and THF (7 ml). Under stirring, the coordinating compound synthesized in Example 12 (157 mg, 0.42
mmol) in THF (10 ml) was added using a cannula. After stirring at room temperature for 2 hours, the obtained reaction solution was filtered, and the solid was further washed with THF. After drying under reduced pressure, a red-orange solid (124 mg, 0.25 mmol)
I got Yield 71%.

FAB-MASS: m / z 465 (M ⁺
-Cl), 429 (M ⁺ -2Cl), 374 (M ⁺ -Fe
Cl ₂ )

[0100]

Embedded image Example 14 Synthesis of Complex C-3: A 50-mL Schlenk flask was purged with nitrogen, and copper (II) chloride (45.9 mg, 0.32 m) was used.
mol) and THF (10 ml) were added. Under stirring, the coordinating compound synthesized in Example 12 (133 mg, 0.3
6 mmol) in THF (12 ml) was added using a cannula. After stirring at room temperature for 2 hours, the resulting black homogeneous reaction solution was stored in a freezer overnight. The generated solid was filtered off and dried under reduced pressure to give an orange solid (47 mg, 0.09).
2 mmol). Yield 28%.

FAB-MASS: m / z 473 (M ⁺
-Cl), 437 (M ⁺ -2Cl), 374 (M ⁺ -Cu
Cl ₂ )

[0102]

Embedded image Example 15 Synthesis of Complex C-4: [Synthesis of precursor compound] A 100-mL Schlenk flask was purged with nitrogen, and iron (II) chloride (255 mg, 2.01) was used.
mmol) and THF (10 ml) were added. 5
A 0 ml Schlenk flask was purged with nitrogen, and pentaphenylcyclopentadiene (785 mg, 1.75 mmol
l) and THF (20 ml) were added. N-Bu at room temperature
Li (1.56 M hexane solution, 1.24 ml, 1.9
3 mmol) was added dropwise and stirred for 5 minutes. This solution was introduced into a THF slurry of iron chloride using a cannula. Further, potassium pyrrolide (216 mg, 2.05
mmol) and THF (10 ml) were fed using a cannula. After stirring at room temperature for 2 hours,
Water (15 ml) was added to quench. Dichloromethane (25 ml) was added for extraction, and the organic phase was concentrated under reduced pressure.
The residue was purified by silica gel column chromatography (solvent: dichloromethane, ethyl acetate), and orange solid 1 ′, 2 ′, 3 ′, 4 ′, 5′-pentaphenylazaferrocene (868 mg, 1.53 mmol).
I got Yield 87%.

¹ H-NMR (400 MHz, CD ₂ C
l ₂ ) δ = 4.71 (t, J = 0.7 Hz, 2H),
5.44 (t, J = 0.7 Hz, 2H), 7.07-
7.12 (m, 10H), 7.14-7.20 (m, 1
5H). [Synthesis of Coordinating Compound] A 50 ml Schlenk flask was purged with nitrogen, and 1 ′, 2 ′, 3 ′, 4 ′, 5′-pentaphenylazaferrocene (985 mg, 1.73 mmol)
l) and 21 ml of THF were added. Cool to -50 ° C,
n-BuLi (1.59 M hexane solution, 2.35 m
1, 3.74 mmol) were added dropwise. After stirring at −50 ° C. for 3 hours, N, N-dimethylformamide (284 m
g, 3.89 mmol). After reacting for 40 minutes while gradually increasing the temperature, water was added to quench. The mixture was extracted with ether, and the organic phase was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (solvent: hexane / dichloromethane, ethyl acetate). Orange liquid (7
43 mg, 1.25 mmol). Yield 72%.

The 50 ml Schlenk flask was purged with nitrogen, and the 2-formylazaferrocene (92) synthesized above was synthesized.
mg, 0.15 mmol) and ethanol (4 ml). o-Toluidine (25 mg, 0.23 mmol
l) and acetic acid (5 mg) were added. After stirring at room temperature for one day, the reaction solution was concentrated under reduced pressure. The residue was washed with hexane and dried under reduced pressure, and then a red solid (76 m
g, 0.11 mmol). 73% yield.

¹ H-NMR (400 MHz, C ₆ D ₆ ) δ
= 2.31 (s, 3H), 4.48 (s, 1H), 5.
45 (s, 1H), 5.55 (s, 1H), 6.14
(D, J = 7.0 Hz, 1H), 6.78-7.06
(M, 18H), 7.42 (d, J = 6.2 Hz, 10
H), 8.44 (s, 1H) [Synthesis of Complex C-4] A 50 ml Schlenk flask was purged with nitrogen, and (DME) NiBr ₂ (20 mg, 0.0
65 mmol) and dichloromethane (2 ml) were added. Under stirring, the above coordinating compound (40 mg, 0.05
(8 mmol) in dichloromethane (3 ml) was added using a cannula. After stirring at room temperature for 3 hours, the obtained reaction solution was filtered and further extracted with dichloromethane. The combined dichloromethane solution was concentrated under reduced pressure. The residue was washed with hexane and dried under reduced pressure to give a reddish brown solid (44 mg,
0.048 mmol). Yield 84%.

FAB-MASS: m / z 823 (M ⁺
-Br), 743 (M ⁺ -2Br), 684 (M ⁺ -Ni
Br ₂ )

[0107]

Embedded image Example 16 Synthesis of Complex C-5: [Synthesis of Coordinating Compound] A 50 ml Schlenk flask was purged with nitrogen, and 1 ′, 2 ′,
3 ′, 4 ′, 5′-Pentaphenyl-2-formylazaferrocene (291 mg, 0.49 mmol) and ethanol (10 ml) were added. 2-isopropylaniline (86 mg, 0.64 mmol) and acetic acid (10 m
g) was added. After stirring at room temperature for 2 days, the reaction solution was concentrated under reduced pressure. The residue was washed with a small amount of ethanol, dried under reduced pressure, and then a red solid as a coordinating compound (289 mg, 0.1 g).
41 mmol). Yield 83%.

¹ H-NMR (400 MHz, C ₆ D ₆ ) δ
= 1.16 (d, J = 6.4 Hz, 3H), 1.31
(D, J = 6.4 Hz, 3H), 3.65-3.78
(M, 1H), 4.46 (s, 1H), 5.47 (s,
1H), 5.55 (s, 1H), 6.01 (d, J =
7.0 Hz, 1H), 6.78-7.04 (m, 18
H), 7.40 (d, J = 6.2 Hz, 10H), 8.
49 (s, 1H) [Synthesis of Complex C-5] A 50-mL Schlenk flask was purged with nitrogen, and (DME) NiBr ₂ (56 mg, 0.1
8 mmol) and dichloromethane (2 ml) were added.
Under stirring, the above coordinating compound (129 mg, 0.18 m
mol) in dichloromethane (6 ml) was added using a cannula. After stirring at room temperature for 3 hours, the obtained reaction solution was concentrated under reduced pressure, and the residue was washed with a small amount of dichloromethane. After drying under reduced pressure, a red solid (160 mg, 0.17 m
mol). 95% yield.

FAB-MASS: m / z 712 (M ⁺
—NiBr ₂ )

[0110]

Embedded image Example 17 Synthesis of Complex C-6: [Synthesis of Coordinating Compound] A 50 ml Schlenk flask was replaced with nitrogen, and 1 ′, 2 ′,
3 ′, 4 ′, 5′-Pentaphenyl-2-formylazaferrocene (132 mg, 0.22 mmol) and ethanol (6 ml) were added. 2-aminobiphenyl (4
9 mg, 0.29 mmol) and acetic acid (5 mg) were added. After stirring at room temperature for 2 days, the reaction solution was concentrated under reduced pressure. The residue was washed with a small amount of ethanol, dried under reduced pressure, and then a red solid (122 mg, 0.16 mm
ol). Yield 74%.

¹ H-NMR (400 MHz, C ₆ D ₆ ) δ
= 4.39 (s, 1H), 5.29 (s, 1H), 5.
51 (s, 1H), 6.99 (d, J = 7.6 Hz, 1
H), 6.80-7.10 (m, 18H), 7.12-
7.20 (m, 3H), 7.36 (d, J = 7.0H)
z, 10H), 7.51 (d, J = 7.0 Hz, 2
H), 8.53 (s, 1H) [Synthesis of Complex C-6] A 50-mL Schlenk flask was purged with nitrogen, and (DME) NiBr ₂ (40 mg, 0.1
3 mmol) and dichloromethane (2 ml) were added.
Under stirring, the above coordinating compound (105 mg, 0.14 m
mol) in dichloromethane (5 ml) was added using a cannula. After stirring at room temperature for 3 hours, the resulting reaction solution was concentrated under reduced pressure, and the residue was washed with hexane. Drying under reduced pressure gave a red solid (110 mg, 0.11 mmol). Yield 85%.

FAB-MASS: m / z 885 (M ⁺
-Br), 805 (M ⁺ -2Br), 747 (M ⁺ -Ni
Br ₂ )

[0113]

Embedded image Example 18 [Synthesis of precursor compound] Chem. Commun. , 19
1998, p. 1889,
1 ′, 2 ′, 3 ′, 4 ′, 5′-penta (p-fluorophenyl) cyclopentadiene was synthesized.

Instead of 1 ', 2', 3 ', 4', 5'-pentaphenylcyclopentadiene, 1 ', 2',
The method for synthesizing the precursor compound of Example 15 was repeated, except that 3 ′, 4 ′, 5′-penta (p-fluorophenyl) cyclopentadiene was used. 1 ′, 2 ′, 3 ′, 4 ′, 5′-penta (p-fluorophenyl) azaferrocene as an orange solid was obtained in a yield of 47%.

¹ H-NMR (400 MHz, C ₆ D ₆ ) δ
= 4.08 (d, J = 0.8 Hz, 2H), 5.10
(T, J = 0.8 Hz, 2H), 6.58-6.68
(M, 10H), 7.00-7.10 (m, 10H). Example 19 [Synthesis of precursor compound] Chem. Commun. , 19
1998, p. 1889,
1 ′, 2 ′, 3 ′, 4 ′, 5′-penta (p-methoxyphenyl) cyclopentadiene was synthesized.

Instead of 1 ′, 2 ′, 3 ′, 4 ′, 5′-pentaphenylcyclopentadiene, 1 ′, 2 ′,
The method for synthesizing the precursor compound of Example 15 was repeated, except that 3 ′, 4 ′, 5′-penta (p-methoxyphenyl) cyclopentadiene was used. 1 ′, 2 ′, 3 ′, 4 ′, 5′-penta (p-methoxyphenyl) azaferrocene as an orange solid was obtained with a yield of 72%.

¹ H-NMR (400 MHz, C ₆ D ₆ ) δ
= 3.23 (s, 15H), 4.47 (s, 2H),
5.48 (s, 2H), 6.60 (d, J = 8.8H)
z, 10H), 7.40 (d, J = 8.8 Hz, 10
H). Example 20 [Preparation of complex solution] A 100-mL Schlenk flask was purged with nitrogen, and the complex C-1 (28 m
g, 47 μmol) and toluene (50 ml).
Stirred for 20 minutes.

[Ethylene polymerization] To a 2-liter autoclave were added toluene (500 ml) and methylaluminoxane (1.6 ml, PMAO manufactured by Tosoh Akzo Co., Ltd., 4.6 mmol in terms of aluminum atoms). 10
After charging ethylene / kg ² cm ² G, the complex solution obtained above was injected at room temperature, and polymerization was carried out for 1 hour while continuously supplying ethylene so that the pressure became 10 kg / cm ² G. . The reaction was quenched by injection of methanol and depressurized. Methanol was further charged to precipitate a polymer. After filtration, the polymer was washed with methanol. Drying under reduced pressure gave 82.7 g of a solid polymer (activity: 1.7).
Kg / Ni · mmol · h). The melting point by DSC is 7
7.5 ° C., and as a result of GPC (1,2,4-trichlorobenzene, 140 ° C.) measurement, Mw = 1.0 × 10 ⁴ ,
The molecular weight distribution (Mw / Mn) was 2.2.

Examples 21 to 24 Example 2 was repeated except that the compounds shown in Table 1 were used as the complexes.
The same operation as 0 was repeated. The results are shown in Table 1.

[0120]

[Table 1] Example 25 [Preparation of complex solution] A 100 ml Schlenk flask was purged with nitrogen, and the complex C-5 (52 m
g, 0.056 mmol) and toluene (60 ml) were added and stirred for 20 minutes.

[Ethylene / methyl acrylate copolymerization] 2
l of toluene (450 ml) and methylaluminoxane (PMA manufactured by Tosoh Akzo Co., Ltd.)
O, 2.0ml, 5.7mmo in terms of aluminum atom
l) was charged. It was pressurized with 1 kg / cm ² G of ethylene. The above-obtained complex solution is press-fitted and stirred for 5 minutes.
Methyl acrylate (5 ml, 56 mmol), toluene (40 ml) and methylaluminoxane (0.5 ml)
The solution consisting of Polymerization was carried out at room temperature for 27 hours while continuously supplying ethylene so as to obtain a pressure of 5 kg / cm ² G. The obtained reaction solution was washed with 0.1N hydrochloric acid (350
ml), the phases were separated, and the organic phase was washed with water. The obtained organic phase was filtered, and the filtrate was concentrated under reduced pressure to obtain 4.0 g of a rubbery viscous solid. ^{According to 1} H-NMR (CDCl ₃ ), methyl acrylate units were contained at 7% by weight.

Example 26 Synthesis of complex C-7: A 100 ml Schlenk flask was purged with nitrogen, and the coordinating compound (15) synthesized in Example 16 was synthesized.
2 mg, 0.21 mmol) and (1,5-cyclooctadiene) Pd (Me) Cl (55.4 mg, 0.21 mmol).
mmol). Diethyl ether (12 ml) was added, and the mixture was stirred at room temperature for 3 hours. The supernatant was removed, and the residue was further washed with diethyl ether (6 ml). The resulting solid was dried and a pink solid (166 mg,
0.19 mmol). Yield 92%.

¹ H-NMR (400 MHz, CD ₂ C
l ₂ ) δ = 0.40 (s, 3H), 0.86 (d, J =
6.6 Hz, 3H), 1.26 (d, J = 6.6 Hz,
3H), 3.34-3.50 (m, 1H), 5.29
(S, 1H), 5.35 (s, 1H), 5.84 (s,
1H), 5.90 (d, J = 8.4 Hz, 1H), 6.
93-7.44 (m, 28H), 8.23 (s, 1H)

[0124]

Embedded image Example 27 Synthesis of complex C-8: A transition metal compound (71) synthesized in Example 25 by replacing a 50-mL Schlenk flask with nitrogen.
mg, 0.082 mmol) and AgSbF ₆ (29 m
g, 0.085 mmol). After cooling to -50 ° C, diethyl ether (8 ml) was added. The cold bath was removed and the mixture was stirred at room temperature for 1 hour. The obtained reaction solution is filtered,
Furthermore, the residue was diluted with dichloromethane and diethyl ether 1:
One solution (16 ml) was extracted and combined with the previous filtrate. The mixture was concentrated under reduced pressure until the total volume became 10 ml, and hexane (20 m
l) was added and a solid precipitated. The supernatant was removed and the resulting solid was dried to give a maroon solid (76 mg). Yield 81%.

¹ H-NMR (400 MHz, CD ₃ CN)
δ = 1.13 (t, J = 7.0 Hz, 6H), 1.20
(S, 1.5H), 1.22 (s, 1.5H), 2.0
4-2.30 (brs), 3.43 (q, J = 7.0H)
z, 4H), 5.72 (d, J = 1.5 Hz, 1H),
5.81 (d, J = 2.5 Hz, 1H), 6.08
(S, 1H), 6.26 (d, J = 7.7 Hz, 1
H), 7.00-7.37 (m, 28H), 8.80
(S, 1H)

[0126]

Embedded image

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 10/00 C08F 10/00 // C07F 15/00 C07F 15/00 C 15/04 15/04 C07M 1 : 00 C07M 1:00 F term (reference) 4C069 AC07 BB03 BB42 CC04 4H006 AA01 AA03 AB40 AB80 4H050 AA01 AA03 AB40 AB80 4J028 AA01A AB01A AC01A AC08A AC09A AC10A AC26A AC27A AC28A AC31A AC37A AC38A AC38AACBA AC39B BC06B BC09B BC12B BC13B BC15B BC16B BC19B BC25B CA30B EA01 EB02 EB04 EB05 EB07 EB09 EB10 EB13 EB14 EB16 EB17 EB18 EB21 EB24 EB25 EB26 EC01 EC02 EC03 EC05 FA01 FA02 FA03 FA04 FA06 FA07 GA01 GA01

Claims (11)

[Claims] (1) The following general formula (1): (Where M is a transition metal atom selected from Groups 3 to 12 of the periodic table, X is a hydrogen atom, a halogen atom,
To 20 hydrocarbon groups, a hydrocarbon oxy group having 1 to 20 carbon atoms, an amino group having a hydrocarbon group having 1 to 20 carbon atoms, a sulfonate group having an organic group having 1 to 20 carbon atoms, or B, Al, A non-coordinating anion containing an element selected from P and Sb. When q is 2 or more, Xs may be the same or different. A represents a carbon atom, a nitrogen atom, or a phosphorus atom. R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a halogen atom, a ferrocenyl group, or a substituted ferrocenyl group;
R ² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a silicon atom, a hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, an oxygen atom or a sulfur atom, a ferrocenyl group, or a substituted ferrocenyl group. As shown, R ¹ and R ² may form a ring. Q is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, an amino group having a hydrocarbon group having 1 to 20 carbon atoms,
A phosphino group having a hydrocarbon group having 1 to 20 carbon atoms, an oxy group having a hydrocarbon group having 1 to 20 carbon atoms,
A thio group having from 20 to 20 hydrocarbon groups, a hydrocarbon group having from 1 to 20 carbon atoms including a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, oxygen or sulfur, and Q including a coordinating atom , M. R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a carbon atom containing 1 to 20 carbon atoms including a nitrogen atom, an oxygen atom, a halogen atom or a sulfur atom. Represents 20 hydrocarbon groups, and one R ³ adjacent to Q may form a ring. When m is 2 or more, R ³
May be the same or different, and adjacent R
³ may be bonded to each other to form a ring. R ⁴ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a phosphino group having a hydrocarbon group having 1 to 20 carbon atoms, An oxy group having a hydrocarbon group, a thio group having a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, a phosphorus atom, an oxygen atom, a halogen atom or a sulfur atom. , N is 2 or more, R ⁴ may be the same or different, and adjacent R ⁴ may be bonded to each other to form a ring. R ³ and R ⁴ may have a bond. L is a coordination bond compound, and represents a π electron, an ether, a nitrile, an amine, or a phosphine, and may have a bond with X. m represents an integer of 1 to 3,
n shows the integer of 1-5. p represents an integer of 0 or 1,
The bond between Q and M indicates a sigma bond when Q is oxygen or sulfur. When p is 0 and A is a nitrogen atom or a phosphorus atom,
Can coordinate to M. q shows the integer of 1-3, and r shows the integer of 0-3. The transition metal compound represented by). 2. A compound represented by the following general formula (2): (Where M is a transition metal atom selected from Groups 3 to 12 of the periodic table, X is a hydrogen atom, a halogen atom,
A non-coordinating anion containing an element selected from B, Al, P, and Sb, and a sulfonate group having an organic group having 1 to 20 carbon atoms, or when q is 2 or more,
Xs may be the same or different. R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a halogen atom, a ferrocenyl group, or a substituted ferrocenyl group, and R ² represents a hydrogen atom, a 1 to 20 carbon atom.
20 hydrocarbon group, a halogen atom, a silicon atom, a nitrogen atom, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a sulfur atom, a ferrocenyl group, or a substituted ferrocenyl group, R ¹ and R ² are the ring Can be formed. R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a carbon atom containing 1 to 20 carbon atoms including a nitrogen atom, an oxygen atom, a halogen atom or a sulfur atom. And 20 hydrocarbon groups. When m is 2 or more,
R ³ may be the same as or different from each other, can also be bonded is adjacent R ³ together form a ring. R ⁴ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A silyl group having a hydrocarbon group of 0, a phosphino group having a hydrocarbon group of 1 to 20 carbon atoms, an oxy group having a hydrocarbon group of 1 to 20 carbon atoms, and a thio group having a hydrocarbon group of 1 to 20 carbon atoms. Group or nitrogen atom, phosphorus atom, oxygen atom,
A hydrocarbon group having 1 to 20 carbon atoms including a halogen atom or a sulfur atom, and when n is 2 or more, R ⁴ may be the same or different, and adjacent R ⁴ may be bonded to form a ring It can also be formed. R ³ and R ⁴ may have a bond. L is a coordination bond compound, represents a π electron, an ether, a nitrile, an amine, a phosphine,
It can also have a bond with X. m shows the integer of 1-3, and n shows the integer of 1-5. q shows the integer of 1-3, and r shows the integer of 0-3. The transition metal compound represented by). 3. The following general formula (3):(Where M is a transition gold selected from Groups 3 to 12 of the periodic table)
X is a hydrogen atom, a halogen atom, a carbon atom of 1
To 20 hydrocarbon groups, hydrocarbon oxy having 1 to 20 carbon atoms
Group, an amino group having a hydrocarbon group having 1 to 20 carbon atoms,
A sulfonate group having an organic group having a prime number of 1 to 20, or
Non-coordinating alloy containing an element selected from B, Al, P and Sb
When q is 2 or more, X is the same or different
It may be. R¹Is a hydrogen atom, having 1 to 20 carbon atoms
C1-20 carbons including hydrocarbon groups and halogen atoms
Represents a hydrogen group, a ferrocenyl group, or a substituted ferrocenyl group
Then R ^TwoRepresents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
Logene atom, silicon atom, nitrogen atom, oxygen atom or
A hydrocarbon group having 1 to 20 carbon atoms containing a sulfur atom,
A phenyl group or a substituted ferrocenyl group;¹And R^TwoIs a ring
Can also be formed. Q is a hydrogen atom, having 1-2 carbon atoms
Having a hydrocarbon group of 0, a hydrocarbon group having 1 to 20 carbon atoms
Amino having a silyl group or a hydrocarbon group having 1 to 20 carbon atoms
Having a hydrocarbon group having 1 to 20 carbon atoms
Group, an oxy group having a hydrocarbon group having 1 to 20 carbon atoms,
A thio group having a hydrocarbon group having a prime number of 1 to 20, a nitrogen atom,
1 to 1 carbon atoms including a phosphorus atom, an oxygen atom or a sulfur atom
Represents 20 hydrocarbon groups, oxygen or sulfur, and has a coordinating property for Q
If it contains an atom, it can coordinate to M. R^Three
Is a hydrogen atom, a halogen atom, a hydrocarbon having 1 to 20 carbon atoms
A silyl group having a hydrocarbon group having 1 to 20 carbon atoms,
Containing an atom, oxygen atom, halogen atom or sulfur atom
A hydrocarbon group having 1 to 20 carbon atoms.
Two R^ThreeMay form a ring. m is 2 or more
Hour, R^ThreeMay be the same or different from each other, and
Touching R^ThreeThe two may combine to form a ring.
R^FourIs a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
Silyl group having 1 to 20 hydrocarbon groups, having 1 to 2 carbon atoms
A phosphino group having 0 hydrocarbon groups, having 1 to 20 carbon atoms
An oxy group having a hydrocarbon group of 1 to 20 carbon atoms
A thio group having a hydrogen group, or a nitrogen atom, a phosphorus atom, or oxygen
Carbon atom containing 1 atom, halogen atom or sulfur atom
20 represents a hydrocarbon group, and when n is 2 or more, R^FourAre each other
May be the same or different, and adjacent R^FourEach other
May combine to form a ring. R^ThreeAnd R^FourIs combined
Can also be provided. L is a coordination compound,
Indicates π electron, ether, nitrile, amine, phosphine
However, it may have a bond with X. m is 1-3
And n represents an integer of 1 to 5. The bond between Q and M is
When Q is oxygen or sulfur, it indicates a sigma bond. q is 1-3
And r represents an integer of 0 to 3. )
Transition metal compounds. 4. A compound represented by the following general formula (4): (Where M is a transition metal atom selected from Groups 3 to 12 of the periodic table, X is a hydrogen atom, a halogen atom,
A non-coordinating anion containing an element selected from B, Al, P, and Sb, and a sulfonate group having an organic group having 1 to 20 carbon atoms, or when q is 2 or more,
Xs may be the same or different. R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a trifluoromethyl group, a ferrocenyl group, or a substituted ferrocenyl group;
R ² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing a silicon atom, a nitrogen atom, an oxygen atom or a sulfur atom, a ferrocenyl group, or a substituted ferrocenyl group; ¹ and R ² can also form a ring. R ³ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
It represents a silyl group having a hydrocarbon group having 1 to 20 carbon atoms.
When m is 2, R ³ may be the same or different. R ⁴ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms,
A phosphino group having a hydrocarbon group of from 20 to 20;
An oxy group having 20 hydrocarbon groups, a thio group having 1 to 20 carbon atoms, or a nitrogen atom, a phosphorus atom,
Oxygen atom, a hydrocarbon group having 1 to 20 carbon atoms containing a halogen atom or a sulfur atom, and when n is 2 or more, R ⁴ may be the same as or different from each other, also adjacent R ⁴
The two may combine to form a ring. R ⁵ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an amino group having a hydrocarbon group having 1 to 20 carbon atoms. L is a coordination bond compound, and represents a π electron, an ether, a nitrile, an amine, or a phosphine, and may have a bond with X. m represents an integer of 1 or 2, and n represents an integer of 1 to 5. q shows the integer of 1-3, and r shows the integer of 0-3. The transition metal compound represented by). 5. The method according to claim 1, wherein M is a transition metal atom selected from Groups 8 to 12 of the periodic table.
The transition metal compound according to the above. 6. The transition metal compound according to claim 1, wherein M is a transition metal atom selected from Ni, Pd, Fe and Cu. 7. A compound represented by the following general formula (5): (Where A represents a carbon atom, a nitrogen atom, or a phosphorus atom. R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a halogen atom, a ferrocenyl group) Or a substituted ferrocenyl group, and R ² is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a halogen atom, a silicon atom, a nitrogen atom, an oxygen atom or a sulfur atom, A ferrocenyl group or a substituted ferrocenyl group, wherein R ¹ and R ² may form a ring, and Q has a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. A silyl group, an amino group having a hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
A phosphino group having a hydrocarbon group of from 20 to 20;
An oxy group having 20 hydrocarbon groups, a thio group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, a hydroxyl group, or Shows a thiol group. R ³ is a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
A silyl group having a hydrocarbon group of from 20 to 20, carbon atom including a nitrogen atom, an oxygen atom, a halogen atom or a sulfur atom;
20 represents a hydrocarbon group, and one R ³ adjacent to Q may form a ring. when m is 2 or more, R ³ may be the same as or different from each other, it can also be bonded is adjacent R ³ together form a ring. R ⁴ is a hydrogen atom,
A hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a phosphino group having a hydrocarbon group having 1 to 20 carbon atoms, and an oxy group having a hydrocarbon group having 1 to 20 carbon atoms. A thio group having a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, a phosphorus atom, an oxygen atom, a halogen atom or a sulfur atom, wherein n is 2 or more At this time, R ⁴ may be the same or different, and adjacent R ⁴ may be bonded to each other to form a ring. R ³ and R ⁴ may have a bond. m shows the integer of 1-3, and n shows the integer of 1-5. p represents an integer of 0 or 1. ). 8. The following general formula (6):(Where R^ThreeRepresents a hydrogen atom, a halogen atom, and a carbon number of 1 to
Having 20 hydrocarbon groups and 1-20 carbon atoms
Silyl group, nitrogen atom, oxygen atom, halogen atom
Represents a hydrocarbon group having 1 to 20 carbon atoms including a sulfur atom. m
Is 2 or more, R ^ThreeMay be the same or different
And adjacent R^ThreeBond with each other to form a ring
Can also. R^FourIs a hydrocarbon group having 1 to 20 carbon atoms,
Silyl group having 1 to 20 hydrocarbon groups, having 1 to 2 carbon atoms
A phosphino group having 0 hydrocarbon groups, having 1 to 20 carbon atoms
An oxy group having a hydrocarbon group of 1 to 20 carbon atoms
A thio group having a hydrogen group, or a nitrogen atom, a phosphorus atom, or oxygen
Carbon atom containing 1 atom, halogen atom or sulfur atom
20 represents a hydrocarbon group, and when n is 2 or more, R^FourAre each other
May be the same or different, and adjacent R^FourEach other
May combine to form a ring. R^ThreeAnd R^FourIs combined
Can also be provided. m represents an integer of 1 to 3, and n is
Shows an integer of 1 to 5. Where R^FourAre all methyl at the same time
It is not a group. ) Is represented by the general formula (5)
Precursor compound of the coordinating compound to be formed. 9. An olefin polymerization catalyst comprising (A) the transition metal compound according to claim 1 as a constituent. 10. An olefin polymerization catalyst comprising (A) the transition metal compound according to any one of claims 1 to 6 and (B) an activation promoter. 11. A method for producing a polyolefin, comprising polymerizing an olefin using the catalyst for olefin polymerization according to claim 9.