JP2006328034A - Transition metal complex, catalyst for cyclic olefin polymerization, and method for producing cyclic olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel transition metal complex that is relatively stable and easy to handle and can be a highly active polymerization catalyst for cyclic olefins, a cyclic olefin polymerization catalyst containing the transition metal complex, and the polymerization catalyst A method for producing a cyclic olefin polymer to be used is provided.
A group 8-10 transition metal complex of a periodic table in which a bidentate ligand is coordinated via two nitrogen atoms, wherein the nitrogen atom and one carbon in the bidentate ligand A transition metal complex (A) characterized in that an atom and a transition metal atom form a four-membered ring, the transition metal complex (A), an organoaluminum compound (B-1), and a transition metal complex (A ) And a cyclic olefin polymerization catalyst containing at least one compound (B) selected from the compound (B-2) selected from the compound (B-2) that forms an ion pair, and the cyclic olefin in the presence of the polymerization catalyst. For producing a cyclic olefin polymer.
[Selection figure] None

Description

  The present invention relates to a novel group 8-10 transition metal complex of the periodic table, a cyclic olefin polymerization catalyst containing the transition metal complex, and a method for producing a cyclic olefin polymer using the polymerization catalyst.

  Cyclic olefin polymers, particularly vinyl addition polymers of norbornene monomers, have recently attracted attention as polymer materials for use in electrical and electronic parts because of their excellent heat resistance, low water absorption, and electrical properties. Accordingly, for example, in Patent Documents 1 to 3 and the like, many catalysts for polymerization of cyclic olefins such as norbornene monomers have been proposed in order to more efficiently obtain a polymer having excellent physical properties. However, the catalysts described in any of the documents have problems such as low polymerization activity, unstable catalysts, and difficult handling, and satisfactory polymerization catalysts have not yet been obtained. Absent.

  On the other hand, as a transition metal complex that is generally relatively stable and easy to handle, a group 8-10 transition metal complex in which a bidentate or more multidentate ligand coordinates via a hetero atom is known. Studies using this as a polymerization catalyst are also actively conducted.

  For example, Patent Document 4 reports that a nickel complex or palladium complex of a substituted diimine formed by coordination of neutral diimine to form a five-membered ring is a highly active polymerization catalyst for ethylene. Yes. Further, this document describes that such a diimine complex is not only a highly active polymerization catalyst for ethylene, but also a polymerization catalyst for cyclic olefins such as norbornene and cyclopentene. However, the metal complex described in this document has a significantly lower polymerization activity for cyclic olefins than that for ethylene.

  In addition, in Patent Document 5, diiminopyridine iron, cobalt complex, and the like have been reported as group 8-10 transition metal complexes having a polydentate ligand, but there is no description regarding the polymerization of cyclic olefins. .

  Furthermore, as a transition metal complex in which a bidentate ligand and a Group 8-10 transition metal atom form a four-membered ring via a hetero atom, Patent Document 6 discloses a phosphorus atom and a nitrogen atom or an oxygen atom. Ni complexes that form four-membered rings are described. Patent Document 7 describes a Ni complex coordinated with (bisphosphino) methane. Patent Document 8 describes a Ni complex coordinated with neutral diiminosilane. However, there is no description regarding the polymerization of cyclic olefin in any literature.

JP-A-4-63807 Japanese National Patent Publication No. 9-508649 JP 2004-107442 A W096 / 23010 Publication Special table 2002-506090 gazette Japanese translation of PCT publication No. 2004-502652 Japanese translation of PCT publication No. 2004-502697 JP 2003-128678 A

  The present invention has been made in view of the above-described prior art, and is a novel transition metal complex that is relatively stable and easy to handle, and can be a highly active polymerization catalyst for cyclic olefins. It is an object of the present invention to provide a cyclic olefin polymerization catalyst containing a complex and a method for producing a cyclic olefin polymer using the polymerization catalyst.

  As a result of intensive studies to solve the above problems, the present inventors synthesized a transition metal complex in which a benzamidinate is coordinated to a nickel atom or a palladium atom to form a four-membered ring. The inventors have found that these transition metal complexes are easy to synthesize, are relatively stable and easy to handle, and exhibit high polymerization activity with respect to cyclic olefins, thereby completing the present invention.

Thus, according to the first aspect of the present invention, the following transition metal complexes (A) of (1) and (2) are provided.
(1) A periodic table group 8-10 transition metal complex in which a bidentate ligand is coordinated via two nitrogen atoms, wherein two nitrogen atoms and one carbon atom in the bidentate ligand A transition metal complex (A), wherein the transition metal atom forms a four-membered ring.
(2) General formula (1)

(In the formula, M ¹ is a transition metal atom of Groups 8 to 10 of the periodic table, and R ^{1 to} R ³ are each independently a hydrogen atom; a halogen atom; a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, or silicon. A functional group containing an atom; or a C1-C20 hydrocarbon group which may have a substituent.
L ¹ represents a neutral electron donating ligand, and X ¹ represents an anionic ligand. L ¹ and X ¹ may be bonded to each other to form a multidentate ligand.
a and b are each independently an integer of 0 to 3, and when a and b are each 2 or more, L ¹ and X ¹ may be the same or different. (1) The transition metal complex (A) shown by this.

According to a second aspect of the present invention, there are provided the following cyclic olefin polymerization catalysts (3) and (4).
(3) A cyclic olefin polymerization catalyst comprising the transition metal complex (A) of (1) or (2).
(4) Compound (B-2) which reacts with the transition metal complex (A) of (1) or (2), the organoaluminum compound (B-1), and the transition metal complex (A) to form an ion pair. And a cyclic olefin polymerization catalyst comprising at least one compound (B) selected from.
According to 3rd aspect of this invention, the manufacturing method of the cyclic olefin polymer of following (5) is provided.
(5) A method for producing a cyclic olefin polymer, comprising polymerizing a cyclic olefin in the presence of the polymerization catalyst according to (3) or (4).

  According to the present invention, there are provided a transition metal complex that is easy to synthesize, relatively stable and easy to handle, a highly active polymerization catalyst for cyclic olefin, and a method for producing a cyclic olefin polymer using this polymerization catalyst. The

Hereinafter, the present invention will be described in detail.
1) Transition metal complex (A)
The transition metal complex (A) of the present invention is a group 8-10 transition metal complex of a periodic table in which a bidentate ligand is coordinated via two nitrogen atoms, One nitrogen atom, one carbon atom and a transition metal atom form a four-membered ring. The transition metal complex (A) of the present invention is a novel compound.

  Examples of the transition metal of Group 8 to 10 of the periodic table that is the central metal of the transition metal complex (A) of the present invention include Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt. Fe, Ru, Co, Rh, Ni, and Pd are preferable, Fe, Co, Ni, and Pd are more preferable, and Ni and Pd are particularly preferable.

The transition metal complex in which two nitrogen atoms and one carbon atom in the bidentate ligand of the present invention form a four-membered ring is a transition metal complex in which two nitrogen atoms are a central metal with one carbon atom in between. A transition metal complex having a bidentate ligand bonded to an atom.
The transition metal complex of the present invention preferably has the general formula (2)

(In the formula, M ² is a group 8-10 transition metal atom, and R ^{4 to} R ⁶ are each independently a hydrogen atom; a halogen atom; a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom. A functional group containing; or a C1-C20 hydrocarbon group which may have a substituent.
N—C—N (thick line) represents a single bond or a double bond, and... (Dotted line) represents coordination.
L ² represents a neutral electron donating ligand, X ² represents an anionic ligand, and L ² and X ² may be bonded to each other to form a multidentate ligand.
Here, p, q and r each independently represent 1 or 2, preferably 1, and c and d each represent an integer of 0 to 3. When p, q, r, c and d are each 2 or more, R ⁴ , R ⁵ , R ⁶ , X ² and L ² may be the same or different. )
It is a transition metal complex represented by these.

Preferred specific examples of R ^{4 to} R ⁶ include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group, a nitro group, a nitroso group, an alkoxy group, an aryloxy group, an amide group, A functional group such as a carboxyl group, a carbonyl group, a cyano group, a sulfonyl group, an alkylsulfonyl group, and an arylsulfonyl group; an alkyl group having 1 to 20 carbon atoms that may have a substituent; A hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, such as an alkenyl group having 2 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms which may have a substituent. ;

  Examples of the substituent for the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms include a halogen atom and the same functional group as described above. Examples of the substituent of the aryl group having 6 to 20 carbon atoms include a halogen atom, the same functional group as described above, an alkyl group, an alkoxy group, a nitro group, and a cyano group.

Among these, R ^{4 to} R ⁶ have an alkyl group having 1 to 20 carbon atoms and a substituent, which may have a substituent, from the viewpoint of catalyst stability and ease of synthesis. An alkenyl group having 2 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms which may have a substituent are preferable, and an alkyl group having 1 to 20 carbon atoms which may have a substituent And an aryl group having 6 to 20 carbon atoms which may have a substituent is more preferred, an aryl group having 6 to 20 carbon atoms which may have a substituent is further preferred, and has a substituent. An optionally substituted phenyl group is particularly preferred.

The anionic ligand (X ² ) may be any ligand as long as it has a negative charge when separated from the central metal.
Specific examples of X ² include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydrogen atom; diketonate group such as acetylacetonate; cyclopentadienyl group which may have a substituent Allyl group, alkenyl group, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, carboxyl group, alkyl sulfonate group, aryl sulfonate group, alkylthio group which may have a substituent Alkenylthio group, arylthio group, alkylsulfonyl group and alkylsulfinyl group.

  Among these, a halogen atom, a cyclopentadienyl group which may have a substituent, an allyl group which may have a substituent, an alkenyl group, an alkyl group and an aryl group are preferable, and a halogen atom and a substituent An allyl group, an alkenyl group, an alkyl group, and an aryl group, which may have a hydrogen atom, are more preferable.

The neutral ligand (L ² ) may be any ligand as long as it has a neutral charge when separated from the central metal.
Specific examples of L ² include oxygen atom, water, carbonyl, amines, pyridines, ethers, nitriles, esters, phosphines, phosphinites, phosphites, sulfoxides, thioethers, amides, aromatics Group compounds, cyclic diolefins, olefins, isocyanides, thiocyanates, and heterocyclic carbene compounds. Among these, pyridines, phosphines, ethers and heterocyclic carbene compounds are preferable.

In the compound represented by the general formula (2), L ² and X ² may be bonded to each other to form a multidentate ligand. For example, L ² and X ² may be bonded to each other to form a bidentate ligand having the N—C—N structure of the general formula (2). That is, the transition metal complex represented by the following general formula (3) is also included in the present invention.

[Wherein, R ^{4 to} R ⁶ , M ² , p, q, and r represent the same meaning as described above. Moreover,-(thick line) and ... (dotted line) of N-C-N represent the same meaning as described above. ]
Furthermore, the transition metal complex of the present invention may be a compound obtained by dimerizing the compound represented by the general formula (2). That is, the transition metal complex represented by the general formula (4) is also included in the present invention.

[Wherein, R ^{4 to} R ⁶ , M ² , X ² , p, q, and r represent the same meaning as described above. Moreover,-(thick line) and ... (dotted line) of N-C-N represent the same meaning as described above. ]
Among these, in the present invention, the general formula (1)

[Wherein, M ¹ is a transition metal atom of Groups 8 to 10 of the periodic table, and R ^{1 to} R ³ are each independently a hydrogen atom; a halogen atom; a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, or silicon. A functional group containing an atom; or a C1-C20 hydrocarbon group which may have a substituent. L ¹ represents a neutral electron donating ligand, and X ¹ represents an anionic ligand. L ¹ and X ¹ may be bonded to each other to form a multidentate ligand. a and b are each independently an integer of 0 to 3, and when a and b are each 2 or more, L ¹ and X ¹ may be the same or different. Moreover, ... (dotted line) represents the same meaning as described above. A transition metal complex represented by the formula is particularly preferred.
Such a transition metal complex has a structure in which two nitrogen atoms of an amidinate compound are coordinated to a transition metal atom to form a four-membered ring. At this time, the amidinate compound is coordinated to the transition metal atom by a π bond. Therefore, the compound represented by the general formula (1) can also be represented by the chemical formula represented by the general formula (5).

(In the formula, R ^{1 to} R ³ , M ¹ , X ¹ , L ¹ , a and b represent the same meaning as described above.)
Specific examples of R ^{1 to} R ^{3 in} the general formulas (1) and (5) include the same as those listed as specific examples of R ^{4 to} R ⁶ . Among these, as R ¹ to R ^3, alkyl group of carbon atoms which may 20 have a substituent, an alkenyl group which may 2-20 carbon atoms which may have a substituent, and substituents An aryl group having 6 to 20 carbon atoms which may have a substituent is preferable, an aryl group having 6 to 20 carbon atoms which may have a substituent is more preferable, and a phenyl group which may have a substituent Is particularly preferred.

In the general formulas (1) and (5), X ¹ represents an anionic ligand, and specific examples thereof include those listed as specific examples of X ² . Among them, X ¹ is preferably a halogen atom; a cyclopentadienyl group which may have a substituent, an allyl group which may have a substituent, an alkenyl group, an alkyl group, and an aryl group, A halogen atom, an allyl group optionally having a substituent, an alkenyl group, an alkyl group, and an aryl group are more preferable.

In general formulas (1) and (5), L ¹ represents a neutral ligand. Specific examples thereof include the same as listed as specific examples of the L ^2. Among these, as L ¹ , pyridines, phosphines, ethers, and heterocyclic carbene compounds are preferable.

L ¹ and X ¹ may be bonded to each other to form a multidentate ligand. That is, the transition metal complex represented by the general formula (6) is also included in the present invention.

(Wherein R ^{1 to} R ³ and M ¹ represent the same meaning as described above.)
Moreover, the transition metal complex which the compound shown by General formula (1) dimerized is also contained in this invention. Specifically, the transition metal complex represented by the general formula (7) is also included in the present invention.

(Wherein R ^{1 to} R ³ , M ¹ and X ¹ represent the same meaning as described above.)
Preferable specific examples of the amidinate coordination transition metal complex represented by the general formulas (1) and (5) include N, N′-bis (2,6-diisopropylphenyl) benzamidinate iron (triphenylphosphine) chloride. N, N′-bis (phenyl) benzamidinate iron (triphenylphosphine) chloride, N, N′-bis (2,4,6-trimethylphenyl) benzamidinate iron (triphenylphosphine) chloride, N, N′-bis (2-methylphenyl) benzamidinate iron (triphenylphosphine) chloride, N, N′-bis (4-methylphenyl) benzamidinate iron (triphenylphosphine) chloride, N, N′-bis (4-t-butylphenyl) benzamidinate iron (triphenylphosphine) chloride, N, N′-bis (2,3 , 4,5,6-pentafluorophenyl) benzamidinate iron (triphenylphosphine) chloride, N, N′-bis (2,4,6-tri-tert-butylphenyl) benzamidinate iron (tri Phenylphosphine) chloride, N, N′-bis- (2,6-diisopropylphenyl) benzamidinate iron (triphenylphosphine) bromide, N, N′-bis (phenyl) benzamidinate iron (triphenylphosphine) ) Bromide, N, N′-bis (2,4,6-trimethylphenyl) benzamidinate iron (triphenylphosphine) bromide, N, N′-bis (2-methylphenyl) benzamidinate iron (tri Phenylphosphine) bromide, N, N′-bis (4-methylphenyl) benzamidinate iron (triphenylphosphine) bromide N, N′-bis (4-t-butylphenyl) benzamidinate iron (triphenylphosphine) bromide, N, N′-bis (2,3,4,5,6-pentafluorophenyl) benz Amidinate iron (triphenylphosphine) bromide, N, N′-bis (2,4,6-tri-tert-butylphenyl) benzamidinate iron (triphenylphosphine) bromide, N, N′-bis ( 2,3,4,5,6-pentafluorophenyl) benzamidinate (allyl) iron, N, N′-bis (2,6-diisopropylphenyl) benzamidinate iron (triphenylphosphine) iodide, N , N′-bis (phenyl) benzamidinate iron (triphenylphosphine) iodide, N, N′-bis (2,4,6-trimethylphenyl) benzamidinate iron ( Riphenylphosphine) iodide, N, N′-bis (2-methylphenyl) benzamidinate iron (triphenylphosphine) iodide, N, N′-bis (4-methylphenyl) benzamidinate iron (triphenyl) Phosphine) iodide, N, N′-bis (4-t-butylphenyl) benzamidinate iron (triphenylphosphine) iodide, N, N′-bis (2,3,4,5,6-pentafluorophenyl) ) Benzamidinate iron (triphenylphosphine) iodide, N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate iron (triphenylphosphine) iodide, N, N′— Bis (2,6-diisopropylphenyl) benzamidinate iron (tricyclohexylphosphine) chloride, N, N′-bis (phenyl) Nazimidinate iron (tricyclohexylphosphine) chloride, N, N'-bis (2,4,6-trimethylphenyl) benzamidinate iron (tricyclohexylphosphine) chloride, N, N'-bis (2-methylphenyl) benzamid Nate iron (tricyclohexylphosphine) chloride, N, N′-bis (4-methylphenyl) benzamidinate Iron (tricyclohexylphosphine) chloride, N, N′-bis (4-t-butylphenyl) benzamidite Nate iron (tricyclohexylphosphine) chloride, N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate iron (tricyclohexylphosphine) chloride, N, N′-bis (2 , 4,6-Tri-t-butylphenyl) benzamidinate iron Rohexylphosphine) chloride, N, N′-bis (2,6-diisopropylphenyl) benzamidinate iron (tricyclohexylphosphine) bromide, N, N′-bis (phenyl) benzamidinate iron (tricyclohexylphosphine) ) Bromide, N, N′-bis (2,4,6-trimethylphenyl) benzamidinate iron (tricyclohexylphosphine) bromide, N, N′-bis (2-methylphenyl) benzamidinate iron (tri Cyclohexylphosphine) bromide, N, N′-bis (4-methylphenyl) benzamidinate iron (tricyclohexylphosphine) bromide, N, N′-bis (4-t-butylphenyl) benzamidinate iron (tri (Cyclohexylphosphine) bromide, N, N′-bis (2,3,4,5,6- Ntafluorophenyl) benzamidinate iron (tricyclohexylphosphine) bromide, N, N′-bis (2,4,6-tri-tert-butylphenyl) benzamidinate iron (tricyclohexylphosphine) bromide, N, N'-bis (2,6-diisopropylphenyl) benzamidinate iron (tricyclohexylphosphine) iodide, N, N'-bis (phenyl) benzamidinate iron (tricyclohexylphosphine) iodide, N, N'- Bis (2,4,6-trimethylphenyl) benzamidinate iron (tricyclohexylphosphine) iodide, N, N′-bis (2-methylphenyl) benzamidinate iron (tricyclohexylphosphine) iodide, N, N '-Bis (4-methylphenyl) benzamidinate iron (tricyclo Hexylphosphine) iodide, N, N′-bis (4-tert-butylphenyl) benzamidinate iron (tricyclohexylphosphine) iodide, N, N′-bis (2,3,4,5,6-pentafluoro Phenyl) benzamidinate iron (tricyclohexylphosphine) iodide, N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate iron (tricyclohexylphosphine) iodide, N, N ′ -Bis (2,6-diisopropylphenyl) benzamidinate (allyl) carbonyl iron, N, N'-bis (phenyl) benzamidinate iron (allyl) carbonyl iron, N, N'-bis (2,4 , 6-Trimethylphenyl) benzamidinate (allyl) carbonyl iron, N, N′-bis (2-methylphenyl) benzamidinate ( Allyl) carbonyl iron, N, N′-bis (4-methylphenyl) benzamidinate (allyl) carbonyl iron, N, N′-bis (4-t-butylphenyl) benzamidinate (allyl) carbonyl iron N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate (allyl) carbonyl iron, and N, N′-bis (2,4,6-tri-t- Fe complexes such as butylphenyl) benzamidinate (allyl) carbonyliron;

Bis (triphenylphosphine) N, N′-bis (2,6-diisopropylphenyl) benzamidinate cobalt, bis (triphenylphosphine) N, N′-bis (phenyl) benzamidinate cobalt, bis (tri Phenylphosphine) N, N′-bis (2,4,6-trimethylphenyl) benzamidinate cobalt, bis (triphenylphosphine) N, N′-bis (2-methylphenyl) benzamidinate cobalt, bis (Triphenylphosphine) N, N′-bis (4-methylphenyl) benzamidinate cobalt, bis (triphenylphosphine) N, N′-bis (4-t-butylphenyl) benzamidinate cobalt, bis (Triphenylphosphine) N, N′-bis (2,3,4,5,6-pentafluorophene B) benzamidinate cobalt, bis (triphenylphosphine) N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate cobalt, bis (tricyclohexylphosphine) N, N ′ -Bis (2,6-diisopropylphenyl) benzamidinate cobalt, bis (tricyclohexylphosphine) N, N'-bis (phenyl) benzamidinatecobalt, bis (tricyclohexylphosphine) N, N'-bis ( 2,4,6-trimethylphenyl) benzamidinate cobalt, bis (tricyclohexylphosphine) N, N'-bis (2-methylphenyl) benzamidinate cobalt, bis (tricyclohexylphosphine) N, N'- Bis (4-methylphenyl) benzamidinate cobalt, bis ( Licyclohexylphosphine) N, N′-bis (4-t-butylphenyl) benzamidinate cobalt, bis (tricyclohexylphosphine) N, N′-bis (2,3,4,5,6-pentafluorophenyl ) Benzamidinate cobalt, bis (tricyclohexylphosphine) N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate cobalt, N, N′-bis (2,6- Diisopropylphenyl) benzamidinate (allyl) cobalt, N, N′-bis (phenyl) benzamidinate (allyl) cobalt, N, N′-bis (2,4,6-trimethylphenyl) benzamidinate (Allyl) cobalt, N, N′-bis (2-methylphenyl) benzamidinate (allyl) cobalt, N, N′-bis (4 -Methylphenyl) benzamidinate (allyl) cobalt, N, N'-bis (4-t-butylphenyl) benzamidinate (allyl) cobalt, N, N'-bis (2,3,4,5) Co complexes such as, 6-pentafluorophenyl) benzamidinate (allyl) cobalt and N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate (allyl) cobalt;

  N, N′-bis (2,6-diisopropylphenyl) benzamidinate nickel (triphenylphosphine) chloride, N, N′-bis (phenyl) benzamidinate nickel (triphenylphosphine) chloride, N, N '-Bis (2,4,6-trimethylphenyl) benzamidinate nickel (triphenylphosphine) chloride, N, N'-bis (2-methylphenyl) benzamidinate nickel (triphenylphosphine) chloride, N , N′-bis (4-methylphenyl) benzamidinate nickel (triphenylphosphine) chloride, N, N′-bis (4-t-butylphenyl) benzamidinate nickel (triphenylphosphine) chloride, N , N′-bis- (2,3,4,5,6-pentafluorophenyl Benzamidinate nickel (triphenylphosphine) chloride, N, N'-bis (2,4,6-tri-t-butylphenyl) benzamidinate nickel (triphenylphosphine) chloride, N, N'-bis (2,6-diisopropylphenyl) benzamidinate nickel (triphenylphosphine) bromide, N, N′-bis (phenyl) benzamidinate nickel (triphenylphosphine) bromide, N, N′-bis (2, 4,6-trimethylphenyl) benzamidinate nickel (triphenylphosphine) bromide, N, N′-bis (2-methylphenyl) benzamidinate nickel (triphenylphosphine) bromide, N, N′-bis ( 4-methylphenyl) benzamidinate nickel (triphenylphos) ) Bromide, N, N′-bis (4-t-butylphenyl) benzamidinate nickel (triphenylphosphine) bromide, N, N′-bis (2,3,4,5,6-pentafluoro Phenyl) benzamidinate nickel (triphenylphosphine) bromide, N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate nickel (triphenylphosphine) bromide, N, N ′ -Bis- (2,6-diisopropylphenyl) benzamidinate nickel (triphenylphosphine) iodide, N, N'-bis (phenyl) benzamidinate nickel (triphenylphosphine) iodide, N, N'-bis (2,4,6-trimethylphenyl) benzamidinate nickel (triphenylphosphine) iodide, N, N′-bis- (2-methylphenyl) benzamidinate nickel (triphenylphosphine) iodide, N, N′-bis (4-methylphenyl) benzamidinate nickel (triphenylphosphine) iodide, N , N′-bis (4-t-butylphenyl) benzamidinate nickel (triphenylphosphine) iodide, N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate Nickel (triphenylphosphine) iodide, N, N′-bis (2,4,6-tri-tert-butylphenyl) benzamidinate nickel (triphenylphosphine) iodide, N, N′-bis (2,6 -Diisopropylphenyl) benzamidinate nickel (tricyclohexylphosphine) chloride, N, N'-bi (Phenyl) benzamidinate nickel (tricyclohexylphosphine) chloride, N, N′-bis (2,4,6-trimethylphenyl) benzamidinate nickel (tricyclohexylphosphine) chloride, N, N′-bis ( 2-methylphenyl) benzamidinate nickel (tricyclohexylphosphine) chloride, N, N′-bis (4-methylphenyl) benzamidinate nickel (tricyclohexylphosphine) chloride, N, N′-bis (4- t-butylphenyl) benzamidinate nickel (tricyclohexylphosphine) chloride, N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate nickel (tricyclohexylphosphine) chloride, N, N′-bis (2,4, -Tri-t-butylphenyl) benzamidinate nickel (tricyclohexylphosphine) chloride, N, N'-bis (2,6-diisopropylphenyl) benzamidinate nickel (tricyclohexylphosphine) bromide, N, N ' -Bis (phenyl) benzamidinate nickel (tricyclohexylphosphine) bromide, N, N'-bis (2,4,6-trimethylphenyl) benzamidinate nickel (tricyclohexylphosphine) bromide, N, N'- Bis (2-methylphenyl) benzamidinate nickel (tricyclohexylphosphine) bromide, N, N′-bis (4-methylphenyl) benzamidinate nickel (tricyclohexylphosphine) bromide, N, N′-bis ( 4-t-butylpheny L) benzamidinate nickel (tricyclohexylphosphine) bromide, N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate nickel (tricyclohexylphosphine) bromide, N, N '-Bis (2,4,6-tri-t-butylphenyl) benzamidinate nickel (tricyclohexylphosphine) bromide, N, N'-bis (2,6-diisopropylphenyl) benzamidinate nickel (tri Cyclohexylphosphine) iodide, N, N′-bis (phenyl) benzamidinate nickel (tricyclohexylphosphine) iodide, N, N′-bis (2,4,6-trimethylphenyl) benzamidinate nickel (tricyclohexyl) Phosphine) iodide, N, N′-bis (2 Methylphenyl) benzamidinate nickel (tricyclohexylphosphine) iodide, N, N′-bis (4-methylphenyl) benzamidinate nickel (tricyclohexylphosphine) iodide, N, N′-bis (4-t- Butylphenyl) benzamidinate nickel (tricyclohexylphosphine) iodide, N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate nickel (tricyclohexylphosphine) iodide, N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate nickel (tricyclohexylphosphine) iodide, methyl (triphenylphosphine) N, N′-bis (2,6-diisopropylphenyl) Benzamidinate nickel, methyl Phenylphosphine) N, N′-bis (phenyl) benzamidinate nickel, methyl (triphenylphosphine) N, N′-bis (2,4,6-trimethylphenyl) benzamidinate nickel, methyl (triphenyl) Phosphine) N, N′-bis (2-methylphenyl) benzamidinate nickel, methyl (triphenylphosphine) N, N′-bis (4-methylphenyl) benzamidinate nickel, methyl (triphenylphosphine) N, N′-bis (4-t-butylphenyl) benzamidinate nickel, methyl (triphenylphosphine) N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidite Nickelate, methyl (triphenylphosphine) N, N′-bis (2,4,6-tri-tert-butyl) Tylphenyl) benzamidinate nickel, methyl (tricyclohexylphosphine) N, N′-bis (2,6-diisopropylphenyl) benzamidinate nickel, methyl (tricyclohexylphosphine) N, N′-bis (phenyl) benz Amidinate nickel, methyl (tricyclohexylphosphine) N, N′-bis (2,4,6-trimethylphenyl) benzamidinate nickel, methyl (tricyclohexylphosphine) N, N′-bis (21-methylphenyl) ) Benzamidinate nickel, methyl (tricyclohexylphosphine) N, N'-bis (4-methylphenyl) benzamidinate nickel, methyl (tricyclohexylphosphine) N, N'-bis (4-t-butylphenyl) Benz amidinate nits , Methyl (tricyclohexylphosphine) N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate nickel, methyl (tricyclohexylphosphine) N, N′-bis (2, 4,6-tri-t-butylphenyl) benzamidinate nickel, phenyl (triphenylphosphine) N, N′-bis (2,6-diisopropylphenyl) benzamidinate nickel, phenyl (triphenylphosphine) N , N′-bis (phenyl) benzamidinate nickel, phenyl (triphenylphosphine) N, N′-bis (2,4,6-trimethylphenyl) benzamidinate nickel, phenyl (triphenylphosphine) N, N′-bis (2-methylphenyl) benzamidinate nickel, phenyl Triphenylphosphine) N, N′-bis (4-methylphenyl) benzamidinate nickel, phenyl (triphenylphosphine) N, N′-bis (4-t-butylphenyl) benzamidinate nickel, phenyl ( Triphenylphosphine) N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate nickel, phenyl (triphenylphosphine) N, N′-bis (2,4,6- Tri-t-butylphenyl) benzamidinate nickel, phenyl (tricyclohexylphosphine) N, N'-bis (2,6-diisopropylphenyl) benzamidinate nickel, phenyl (tricyclohexylphosphine) N, N'- Bis (phenyl) benzamidinate nickel, phenyl (tricyclohexyl) Phosphine) N, N′-bis (2,4,6-trimethylphenyl) benzamidinate nickel, phenyl (tricyclohexylphosphine) N, N′-bis (2-methylphenyl) benzamidinate nickel, phenyl ( Tricyclohexylphosphine) N, N′-bis (4-methylphenyl) benzamidinate nickel, phenyl (tricyclohexylphosphine) N, N′-bis (4-t-butylphenyl) benzamidinate nickel, phenyl ( Tricyclohexylphosphine) N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate nickel, phenyl (tricyclohexylphosphine) N, N′-bis (2,4,6- Tri-t-butylphenyl) benzamidinate nickel, N, N′-bi (2,6-diisopropylphenyl) benzamidinate (allyl) nickel, N, N'-bis (phenyl) benzamidinate (allyl) nickel, N, N'-bis (2,4,6-trimethylphenyl) ) Benzamidinate (allyl) nickel, N, N′-bis (2-methylphenyl) benzamidinate (allyl) nickel, N, N′-bis (4-methylphenyl) benzamidinate (allyl) ) Nickel, N, N′-bis (4-t-butylphenyl) benzamidinate (allyl) nickel, N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamid Ni complexes such as nate (allyl) nickel and N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate (allyl) nickel;

  N, N′-bis (2,6-diisopropylphenyl) benzamidinate palladium (triphenylphosphine) chloride, N, N′-bis (phenyl) benzamidinate palladium (triphenylphosphine) chloride, N, N '-Bis (2,4,6-trimethylphenyl) benzamidinate palladium (triphenylphosphine) chloride, N, N'-bis (2-methylphenyl) benzamidinate palladium (triphenylphosphine) chloride, N , N′-bis (4-methylphenyl) benzamidinate palladium (triphenylphosphine) chloride, N, N′-bis (4-t-butylphenyl) benzamidinate palladium (triphenylphosphine) chloride, N , N′-bis (2,3,4,5,6-pentafluoro Phenyl) benzamidinate palladium (triphenylphosphine) chloride, N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate palladium (triphenylphosphine) chloride, N, N ′ -Bis (2,6-diisopropylphenyl) benzamidinate palladium (triphenylphosphine) bromide, N, N'-bis (phenyl) benzamidinate palladium (triphenylphosphine) bromide, N, N'-bis ( 2,4,6-trimethylphenyl) benzamidinate palladium (triphenylphosphine) bromide, N, N′-bis (2-methylphenyl) benzamidinate palladium (triphenylphosphine) bromide, N, N′— Bis (4-methylphenyl) benzamidinate para Um (triphenylphosphine) bromide, N, N′-bis (4-t-butylphenyl) benzamidinate palladium (triphenylphosphine) bromide, N, N′-bis (2,3,4,5,6) -Pentafluorophenyl) benzamidinate palladium (triphenylphosphine) bromide, N, N'-bis (2,4,6-tri-t-butylphenyl) benzamidinate palladium (triphenylphosphine) bromide, N , N′-bis (2,6-diisopropylphenyl) benzamidinate palladium (triphenylphosphine) iodide, N, N′-bis (phenyl) benzamidinate palladium (triphenylphosphine) iodide, N, N ′ -Bis (2,4,6-trimethylphenyl) benzamidinate palladium ( Triphenylphosphine) iodide, N, N′-bis (2-methylphenyl) benzamidinate palladium (triphenylphosphine) iodide, N, N′-bis (4-methylphenyl) benzamidinate palladium (triphenyl) Phosphine) iodide, N, N′-bis (4-t-butylphenyl) benzamidinate palladium (triphenylphosphine) iodide, N, N′-bis (2,3,4,5,6-pentafluorophenyl) ) Benzamidinate palladium (triphenylphosphine) iodide, N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate palladium (triphenylphosphine) iodide, N, N′— Bis (2,6-diisopropylphenyl) benzamidinate palladium (Tricycl Hexylphosphine) chloride, N, N′-bis (phenyl) benzamidinate palladium (tricyclohexylphosphine) chloride, N, N′-bis (2,4,6-trimethylphenyl) benzamidinate palladium (tricyclohexyl) Phosphine) chloride, N, N′-bis (2-methylphenyl) benzamidinate palladium (tricyclohexylphosphine) chloride, N, N′-bis (4-methylphenyl) benzamidinate palladium (tricyclohexylphosphine) Chloride, N, N′-bis (4-t-butylphenyl) benzamidinate palladium (tricyclohexylphosphine) chloride, N, N′-bis (2,3,4,5,6-pentafluorophenyl) benz Amidinate palladium Hexylphosphine) chloride, N, N′-bis (2,4,6-tri-tert-butylphenyl) benzamidinate palladium (tricyclohexylphosphine) chloride, N, N′-bis (2,6-diisopropylphenyl) ) Benzamidinate palladium (tricyclohexylphosphine) bromide, N, N′-bis (phenyl) benzamidinate palladium (tricyclohexylphosphine) bromide, N, N′-bis (2,4,6-trimethylphenyl) Benzamidinate palladium (tricyclohexylphosphine) bromide, N, N′-bis (2-methylphenyl) benzamidinate palladium (tricyclohexylphosphine) bromide, N, N′-bis (41-methylphenyl) benzamide Dinate palladium Rohexylphosphine) bromide, N, N′-bis (4-t-butylphenyl) benzamidinate palladium (tricyclohexylphosphine) bromide, N, N′-bis (2,3,4,5,6-penta Fluorophenyl) benzamidinate palladium (tricyclohexylphosphine) bromide, N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate palladium (tricyclohexylphosphine) bromide, N, N '-Bis (2,6-diisopropylphenyl) benzamidinate palladium (tricyclohexylphosphine) iodide, N, N'-bis (phenyl) benzamidinate palladium (tricyclohexylphosphine) iodide, N, N'-bis (2,4,6-trimethylphenyl) benza Dinate palladium (tricyclohexylphosphine) iodide, N, N′-bis (2-methylphenyl) benzamidinate Palladium (tricyclohexylphosphine) iodide, N, N′-bis (4-methylphenyl) benzamidinate Palladium (tricyclohexylphosphine) iodide, N, N′-bis (4-tert-butylphenyl) benzamidinate palladium (tricyclohexylphosphine) iodide, N, N′-bis (2,3,4,5,6) -Pentafluorophenyl) benzamidinate palladium (tricyclohexylphosphine) iodide, N, N'-bis (2,4,6-tri-t-butylphenyl) benzamidinate palladium (tricyclohexylphosphine) iodide,

  Methyl (triphenylphosphine) N, N′-bis (2,6-diisopropylphenyl) benzamidinate palladium, methyl (triphenylphosphine) N, N′-bis (phenyl) benzamidinate palladium, methyl (tri Phenylphosphine) N, N′-bis (2,4,6-trimethylphenyl) benzamidinate palladium, methyl (triphenylphosphine) N, N′-bis (2-methylphenyl) benzamidinate palladium, methyl (Triphenylphosphine) N, N′-bis- (4-methylphenyl) benzamidinate palladium, methyl (triphenylphosphine) N, N′-bis (4-t-butylphenyl) benzamidinate palladium, Methyl (triphenylphosphine) N, N′-bis (2,3,4 5,6-pentafluorophenyl) benzamidinate palladium, methyl (triphenylphosphine) N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate palladium, methyl (tricyclohexyl) Phosphine) N, N′-bis (2,6-diisopropylphenyl) benzamidinate palladium, methyl (tricyclohexylphosphine) N, N′-bis (phenyl) benzamidinate palladium, methyl (tricyclohexylphosphine) N , N′-bis (2,4,6-trimethylphenyl) benzamidinate palladium, methyl (tricyclohexylphosphine) N, N′-bis (2-methylphenyl) benzamidinate palladium, methyl (tricyclohexylphosphine) ) N, N'-bis (4 Methylphenyl) benzamidinate palladium, methyl (tricyclohexylphosphine) N, N′-bis (4-tert-butylphenyl) benzamidinate palladium, methyl (tricyclohexylphosphine) N, N′-bis (2, 3,4,5,6-pentafluorophenyl) benzamidinate palladium, methyl (tricyclohexylphosphine) N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate palladium, Phenyl (triphenylphosphine) N, N′-bis- (2,6-diisopropylphenyl) benzamidinate palladium, phenyl (triphenylphosphine) N, N′-bis (phenyl) benzamidinate palladium, phenyl ( Triphenylphosphine) N, N′-bis (2,4,4) 6-trimethylphenyl) benzamidinate palladium, phenyl (triphenylphosphine) N, N′-bis (2-methylphenyl) benzamidinate palladium, phenyl (triphenylphosphine) N, N′-bis (4- Methylphenyl) benzamidinate palladium, phenyl (triphenylphosphine) N, N′-bis (4-tert-butylphenyl) benzamidinate palladium, phenyl (triphenylphosphine) N, N′-bis (2, 3,4,5,6-pentafluorophenyl) benzamidinate palladium, phenyl (triphenylphosphine) N, N′-bis (2,4,6-tri-tert-butylphenyl) benzamidinate palladium, Phenyl (tricyclohexylphosphine) N, N′-bis (2,6-di Sopropylphenyl) benzamidinate palladium, phenyl (tricyclohexylphosphine) N, N′-bis (phenyl) benzamidinate palladium, phenyl (tricyclohexylphosphine) N, N′-bis (2,4,6- Trimethylphenyl) benzamidinate palladium, phenyl (tricyclohexylphosphine) N, N′-bis (2-methylphenyl) benzamidinate palladium, phenyl (tricyclohexylphosphine) N, N′-bis (4-methylphenyl) ) Benzamidinate palladium, phenyl (tricyclohexylphosphine) N, N′-bis (4-tert-butylphenyl) benzamidinate palladium, phenyl (tricyclohexylphosphine) N, N′-bis (2,3,3) 4,5,6-pe Motor-fluorophenyl) benz amidinate palladium, phenyl (tricyclohexylphosphine) N, N'-bis (2,4,6-tri -t- butylphenyl) benz amidinate palladium,

  N, N′-bis (2,6-diisopropylphenyl) benzamidinate (allyl) palladium, N, N′-bis (phenyl) benzamidinate (allyl) palladium, N, N′-bis (2, 4,6-trimethylphenyl) benzamidinate (allyl) palladium, N, N′-bis (2-methylphenyl) benzamidinate (allyl) palladium, N, N′-bis (4-methylphenyl) benz Amidinate (allyl) palladium, N, N′-bis (4-t-butylphenyl) benzamidinate (allyl) palladium, N, N′-bis (2,3,4,5,6-pentafluoro) Phenyl) benzamidinate (allyl) palladium, N, N′-bis (2,4,6-tri-tert-butylphenyl) benzamidinate (allyl) palladium N, N′-bis (2,6-diisopropylphenyl) benzamidinate palladium (benzonitrile) chloride, N, N′-bis (phenyl) benzamidinate palladium (benzonitrile) chloride, N, N′— Bis (2,4,6-trimethylphenyl) benzamidinate palladium (benzonitrile) chloride, N, N'-bis (2-methylphenyl) benzamidinate palladium (benzonitrile) chloride, N, N'- Bis (4-methylphenyl) benzamidinate palladium (benzonitrile) chloride, N, N′-bis (4-t-butylphenyl) benzamidinate palladium (benzonitrile) chloride, N, N′-bis ( 2,3,4,5,6-pentafluorophenyl) benzamidinate palladium Nitrile) chloride, N, N'-bis (2,4,6-tri-t-butylphenyl) benzamidinate palladium (benzonitrile) chloride, N, N'-bis (2,6-diisopropylphenyl) benz Amidinate palladium (benzonitrile) bromide, N, N'-bis (phenyl) benzamidinate palladium (benzonitrile) bromide, N, N'-bis (2,4,6-trimethylphenyl) benzamidinate Palladium (benzonitrile) bromide, N, N′-bis (2-methylphenyl) benzamidinate palladium (benzonitrile) bromide, N, N′-bis (4-methylphenyl) benzamidinate palladium (benzonitrile ) Bromide, N, N′-bis (4-t-butylphenyl) benzamidinate para Palladium (benzonitrile) bromide, N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate palladium (benzonitrile) bromide, N, N′-bis (2,4,4) 6-tri-t-butylphenyl) benzamidinate palladium (benzonitrile) bromide, N, N′-bis (2,6-diisopropylpropyl) benzamidinate palladium (benzonitrile) iodide, N, N '-Bis (phenyl) benzamidinate palladium (benzonitrile) iodide, N, N'-bis (2,4,6-trimethylphenyl) benzamidinate palladium (benzonitrile) iodide, N, N'-bis (2-Methylphenyl) benzamidinate palladium (benzonitrile) iodide, N, N′-bis (4-methyl) Phenyl) benzamidinate palladium (benzonitrile) iodide, N, N′-bis (4-tert-butylphenyl) benzamidinate palladium (benzonitrile) iodide, N, N′-bis (2,3,4) , 5,6-pentafluorophenyl) benzamidinate palladium (benzonitrile) iodide, and N, N′-bis (2,4,6-tri-tert-butylphenyl) benzamidinate palladium (benzonitrile) Pd complexes such as iodide;

  Among these, in the present invention, N, N′-bis (2-methylphenyl) benzamidinate nickel (triphenylphosphine) chloride, N, N′-bis (2,4,6-tri-t-) Butylphenyl) benzamidinate nickel (triphenylphosphine) chloride, phenyl (triphenylphosphine) N, N′-bis- (2-methylphenyl) benzamidinate nickel, phenyl (triphenylphosphine) N, N ′ -Bis- (2,3,4,5,6-pentafluorophenyl) benzamidinate nickel, phenyl (triphenylphosphine) N, N'-bis- (2,4,6-tri-t-butyl Phenyl) benzamidinate nickel, N, N′-bis (2-methylphenyl) benzamidinate palladium (triphenyl) Sphine) chloride, N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate palladium (triphenylphosphine) chloride, N, N′-bis (2,4,6- Tri-t-butylphenyl) benzamidinate palladium (triphenylphosphine) chloride, N, N′-bis (2-methylphenyl) benzamidinate (allyl) palladium, N, N′-bis (2,3 , 4,5,6-pentafluorophenyl) benzamidinate (allyl) palladium and N, N′-bis (2,4,6-tri-tert-butylphenyl) benzamidinate (allyl) palladium. preferable.

  The transition metal complex (A) of the present invention is preferably a bidentate ligand (hereinafter simply referred to as “bidentate ligand”) in which two nitrogen atoms are bonded to a central metal atom across one carbon atom. Can be produced by a so-called ligand substitution reaction, in which a transition metal compound not having (b) is reacted with a bidentate ligand.

  The transition metal compound having no bidentate ligand is not particularly limited as long as it is a compound that gives the transition metal complex (A) of the present invention by a ligand exchange reaction. Examples thereof include dichlorobis (triphenylphosphine) nickel and allyl palladium chloride dimer [bis (η-allyl) dichlorodipalladium].

The bidentate ligand used has a structure in which two nitrogen atoms are arranged through a carbon atom in the molecule, the two nitrogen atoms are bonded to a transition metal atom, and the two nitrogen atoms and One in which one carbon atom and a transition metal atom form a four-membered ring is preferable. Among them, the formula: R ¹ —C (═NR ² ) NHR ³ (wherein R ^{1 to} R ³ have the same meaning as above), which gives the transition metal complex (A) having the structure of the general formula (1). Are particularly preferred.

Specific examples of such amidine compounds include N, N′-di (methyl) benzamidine, N, N′-di (ethyl) benzamidine, N, N′-di (isopropyl) benzamidine, N, N′-di (t-butyl) benzamidine, N, N′-di (cyclohexyl) benzamidine, N-methyl-N ′-(phenyl) benzamidine, Nt-butyl-N ′ -(Phenyl) benzamidine, N-methyl-N '-(2,4,6-tri-t-butylphenyl) benzamidine, N-methyl-N'-(2,6-diisopropylphenyl) benzamida In, N-methyl-N ′-(phenyl) benzamidine,
N-methyl-N ′-(2,4,6-trimethylphenyl) benzamidine, N-methyl-N ′-(2-methylphenyl) benzamidine, N-methyl-N ′-(4-methylphenyl) ) Benzamidine, N-methyl-N ′-(4-t-butylphenyl) benzamidine, N-methyl-N ′-(2,3,4,5,6-pentafluorophenyl) benzamidine, N, N′-bis (2,6-diisopropylphenyl) benzamidine N, N′-bis (phenyl) benzamidine, N, N′-bis (2,4,6-trimethylphenyl) benzamidine, N, N′-bis (2-methylphenyl) benzamidine, N, N′-bis (4-methylphenyl) benzamidine, N, N′-bis (4-t-butylphenyl) benzamidine, N, N'-Bi (2,3,4,5,6-pentafluorophenyl) benzamidine-in, and N, N'-bis (2,4,6-tri -t- butylphenyl) benzamidine in like.
In addition, the above compound is an illustration to the last, and the amidine compound which can be used for this invention is not limited to said thing.
The amount of the bidentate ligand used is usually 0.5 to 5 times mol for 1 mol of the transition metal compound.

The bidentate ligand can be produced by a known production method. For example, an amidine compound represented by the formula: R ¹ —C (═NR ² ) NHR ² includes a carboxylic acid represented by the formula: R ¹ —COOH and an amine compound represented by the formula: R ² NH ^2. And can be obtained by reacting in the presence of polyphosphoric acid silyl ether (see Chem. Commun., 2003, 522-523, Bull. Chem. Soc. Jp., 1986, 2171-2177, etc.). .
Moreover, what is marketed can also be used as a bidentate ligand as it is.

  More specifically, the ligand substitution reaction is carried out by adding the bidentate ligand to a solvent solution of a transition metal compound having no bidentate ligand, and optionally in the presence of a base at a predetermined temperature. Can be carried out by stirring for a predetermined time.

  The solvent to be used is not particularly limited as long as it is an inert solvent for the reaction. For example, aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-octane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclooctane And halogenated hydrocarbon solvents such as dichloroethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and the like. These solvents can be used alone or in combination of two or more. The solvent used is preferably sufficiently dried and degassed.

  The amount of the solvent used is not particularly limited and can be appropriately determined according to the type of transition metal compound, reaction scale, and the like. Usually, it is the range of 0.01-100g with respect to 1g of transition metal compounds.

This reaction is preferably performed in an inert gas atmosphere such as nitrogen gas, helium gas, and argon gas.
The reaction can be carried out in the temperature range from −100 ° C. to the boiling point of the solvent used.
The reaction time is usually several minutes to several days.
After completion of the reaction, the intended transition metal complex (A) can be isolated by carrying out ordinary separation / purification operations.

The structure of the target product can be identified and confirmed by elemental analysis, IR spectrum, NMR spectrum, mass spectrum, X-ray crystal analysis, and the like.
The transition metal compound (A) of the present invention obtained as described above is useful as an active component of a cyclic olefin polymerization catalyst, as will be described later.

2) Cyclic Olefin Polymerization Catalyst The cyclic olefin polymerization catalyst of the present invention is characterized by containing the above-described transition metal complex (A) of the present invention.
The cyclic olefin polymerization catalyst of the present invention may contain at least one kind of the transition metal complex (A) of the present invention, but the organoaluminum compound (B-1) and the transition metal complex (A) What further contains at least 1 type of compound (B) chosen from the compound (B-2) which reacts and forms an ion pair is preferable from having higher catalyst activity.

Organoaluminum compound (B-1)
The organoaluminum compound (B-1) includes any aluminum compound having an organic group. Specific examples include trialkylaluminums such as trimethylaluminum, triethylaluminum, trioctylaluminum, triisopropylaluminum, triisobutylaluminum, and trisec-butylaluminum; triarylaluminums such as triphenylaluminum and tritolylaluminum; Dialkylaluminum hydrides such as diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; R ^d _{2 .5} Al (OR ^e ) _0.5 ( R ^d , R ^e represents an alkyl group) Partially alkoxylated alkylaluminum having an average composition represented by: diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methyl Phenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), and isobutylaluminum bis (2,6 Dialkylaluminum aryloxides such as -di-t-butyl-4-methylphenoxide); dialkylaluminiums such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride Halides; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; partially halogenated such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromide Alkyl aluminum; dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride; other partially hydrogenated alkyl aluminums such as alkyl aluminum dihydride such as ethyl aluminum dihydride and propyl aluminum dihydride; Ethoxy chloride, butyl aluminum butoxy chloride, and ethyl acetate Such as mini um ethoxy bromide, partially alkylaluminum is alkoxylated and halogenated; and the like can be given.

  Further, the organoaluminum compound (B-1) may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. .

Compound that reacts with transition metal compound to form ion pair (B-2)
As the compound (B-2) which reacts with the transition metal complex (A) used as necessary in the present invention to form an ion pair, JP-A-1-501950, JP-A-1-502020, Lewis acids, ionic compounds, borane compounds and the like described in Kaihei 3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, etc. Examples thereof include carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, the Lewis acid is BR ^f ₃ (R ^f represents a phenyl group or a fluorine atom which may have a substituent such as a fluorine atom, a methyl group, or a trifluoromethyl group). For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluoro) Phenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.

Examples of the ionic compound include lithium tetrakis (2-fluorophenyl) borate, sodium tetrakis (3-fluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, thallium tetrakis (4-fluorophenyl) borate, ferrocenium (3 , 5-difluorophenyl) borate, trityltetrakis (3,4,5-trifluorophenyl) borate, sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N, N′-dimethylaniliniumtetrakis ( 2,3,4,5-tetrafluorophenyl) borate, triethylsilylium tetrakis (pentafluorophenyl) borate, triphenylsilylliumtetrakis (pentafluorophenyl) borate, lithium tetra Trakis [tris (trifluoromethyl) methoxy] borate, thallium tetrakis [1,1-bis (trifluoromethyl) ethoxy] borate, trityltetrakis [bis (trifluoromethyl) methoxy] borate, silver [1,1-bis ( Borate salts such as (trifluoromethyl) ethoxy] borate, lithium bis (tetrafluorocatechol) borate, [silver (toluene) ₂ ] bis (tetrafluorocatechol) borate, and thallium bis (tetrachlorocatechol) borate;

  Lithium tetrakis (pentafluorophenyl) aluminate, trityltetrakis (pentafluorophenyl) aluminate, trityl (perfluorobiphenyl) fluoroaluminate, sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] aluminate, potassium ( Octyloxy) tris (pentafluorophenyl) aluminate, magnesium tetrakis (pentafluorophenyl) aluminate, calcium tetrakis (pentafluorophenyl) aluminate, lithium tetrakis [bis (trifluoromethyl) phenylmethoxy] aluminate, thallium tetrakis [ 1,1-bis (trifluoromethyl) ethoxy] aluminate, trityltetrakis [bis (trifluoromethyl) methoxy] alumine Silver tetrakis [1,1-bis (trifluoromethyl) ethoxy] aluminate, lithium bis (tetrafluorocatechol) aluminate, lithium tetrakis [bis (trifluoromethyl) -4-isopropylphenylmethoxy] aluminate, etc. Of aluminate salts.

The transition metal complex (A) of the present invention, at least one compound selected from the compound (B-2) that reacts with the organoaluminum compound (B-1) and the transition metal complex (A) to form an ion pair ( The mixing ratio with B) can be appropriately selected according to various conditions. Usually, for the transition metal complex (A) and the organoaluminum compound (B-1), the transition metal atom of (A): ( The molar ratio of aluminum atoms in B-1) is from 1: 0.1 to 1: 10000, preferably from 1: 0.5 to 1: 5000, more preferably from 1: 1 to 1: 2000. For the transition metal complex (A) and the compound (B-2), the molar ratio of (A) :( B-2) is 1: 0.1 to 1: 100, preferably 1: 0.5 to 1:50. More preferably, it is 1: 1 to 1:20.
In addition, as said compound (B), you may contain both the said compounds (B-1) and (B-2).

  Although the temperature at the time of mixing a transition metal complex (A) and a compound (B) is not specifically limited, Usually -200 degreeC-+200 degreeC, Preferably it is -150 degreeC-+150 degreeC, More preferably, it is -100 degreeC-+100 degreeC. Range.

The transition metal complex (A) and the compound (B) may be mixed in a solvent.
Although it does not specifically limit as a solvent to be used, It is inert and an industrially general purpose thing is preferable. Specific examples of such a solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane. , Alicyclic hydrocarbons such as decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindene, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, and xylene; nitrogen-containing compounds such as nitromethane, nitrobenzene, and acetonitrile Solvents; ethers such as diethyl ether and tetrahydrofuran; halogen solvents such as dichloromethane, chloroform, chlorobenzene, and dichlorobenzene; and the like can be used. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers and halogen solvents are preferable.

3) Method for Producing Cyclic Olefin Polymer The method for producing a cyclic olefin polymer of the present invention is characterized by polymerizing a cyclic olefin in the presence of the polymerization catalyst of the present invention.
The production method of the present invention includes a case where a cyclic olefin is subjected to ring-opening polymerization to obtain a cyclic olefin ring-opening polymer, and a case where a cyclic olefin is subjected to addition polymerization to obtain a cyclic olefin addition polymer. It is preferable to carry out addition polymerization to obtain an addition polymer of cyclic olefin.

  More specifically, in the production method of the present invention, (i) a method for obtaining a homoaddition polymer of a cyclic olefin by addition polymerization of one kind of cyclic olefin, and (ii) an addition copolymerization of two or more kinds of cyclic olefins. To obtain a cyclic olefin addition copolymer, or (iii) cyclic olefin by addition copolymerization with at least one cyclic olefin and at least one other monomer copolymerizable with the cyclic olefin. Any of the methods for obtaining an addition copolymer is preferred.

Cyclic Olefin The cyclic olefin used in the present invention is a hydrocarbon which has a ring structure and has a double bond in the ring structure and may have a substituent. Specific examples include monocyclic olefins such as cyclobutene, cyclopentene, and cyclooctene; compounds having a norbornene ring structure such as norbornene and dicyclopentadiene (hereinafter simply referred to as “norbornenes”). However, particularly when the polymerization catalyst of the present invention is used, norbornenes can be polymerized with high activity.
As norbornene, what is shown by General formula (8) is preferable.

(Wherein R ^{7 to} R ¹⁰ each independently represent a hydrogen atom; a halogen atom; a functional group containing a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom; a halogen atom or the above functional group) And may be a hydrocarbon group having 1 to 20 carbon atoms, and R ^{7 to} R ¹⁰ may be bonded to each other to form a ring, and m is 0 or 1.)

Norbornenes is, m is hept-2-enes bicyclo [2.2.1] is 0 in the general formula (8); and, m is 1 tetracyclo [6.2.1.1 ^{3, 6} . 0 ^2,7 ] dodec-4-enes, any of which can be used.

R ^{7 to} R ¹⁰ are specifically hydrogen atoms; halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms; hydroxyl groups, alkoxy groups, aryloxy groups, carbonyl groups, hydroxycarbonyl groups, alkoxycarbonyl groups, aryls. Functional groups containing oxygen atoms such as oxycarbonyl groups and acid anhydride groups; nitrogen atoms such as amino groups, alkylamino groups, arylamino groups, cyano groups, aminocarbonyl groups, alkylaminocarbonyl groups, and arylaminocarbonyl groups Functional groups containing sulfur; functional groups containing sulfur atoms such as mercapto groups, alkoxythio groups, and aryloxythio groups; silicon atoms such as silyl groups, alkylsilyl groups, arylsilyl groups, alkoxysilyl groups, and aryloxysilyl groups And a functional group containing: Furthermore, hydrocarbon groups, such as a C1-C20 alkyl group, an alkenyl group, and an aryl group which may have these functional groups, are also mentioned. R ^{7 to} R ¹⁰ may be bonded to each other to form a ring.

Specific examples of norbornenes suitably used in the present invention include 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, and 5-hexyl-2-norbornene. 5-decyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-cyclopentyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5 - cyclohexenyl-2-norbornene, 5-cyclopentenyl-2-norbornene, 5-phenyl-2-norbornene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0. ^2,11 . 0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene), dicyclopentadiene, methyldicyclo Bicyclo [2,2,1] hept-2- with unsubstituted or hydrocarbon substituents such as pentadiene and dihydrodicyclopentadiene (tricyclo [5.2.1.0 ^2,6 ] dec-8-ene) Ens;

Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyltetracyclo [6,2.1,1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclohexyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclopentyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylenetetracyclo [6.2.1,1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidenetetracyclo [6.2.1,1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyltetracyclo [6.2.1,1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-propenyltetracyclo [6.2.1,1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclohexenyltetracyclo [6.2.1,1 ^3,6 . 0 ^2,7 ] dodec-4-ene, and 9-phenyltetracyclo [6.2.1,1 ^3,6 . 0 ^2,7 ] dodeca-4-ene or an unsubstituted or hydrocarbon-containing tetracyclo [6.2.1,1 ^3,6 . 0 ^2,7 ] dodec-4-enes;

Such as methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, and ethyl 2-methyl-5-norbornene-2-carboxylate Picyclo [2.2.1] hept-2-enes having an alkoxycarbonyl group;
Tetracyclo [6,2,1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate and 4-methyltetracyclo [6,2,1.1 ^3,6 . 0 ^2,7] tetracyclo with dodeca-9-ene-4-alkoxycarbonyl group methyl carboxylic acid [6,2,1.1 ^3,6. 0 ^2,7 ] dodec-9-enes;

Bicyclo [2,2 having a hydroxycarbonyl group or an acid anhydride group such as 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, and 5-norbornene-2,3-dicarboxylic acid anhydride .1] hept-2-enes;
Tetracyclo [6,2,1.1 ^3,6 . ^02,7 ] dodec-9-ene-4-carboxylic acid; tetracyclo [6.2.1.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic acid and tetracyclo [6.2.1.1.1 ^3,6 . Tetracyclo [6.2.1.1.1 ^3,6 . Having a hydroxycarbonyl group or acid anhydride group such as 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic acid anhydride. 0 ^2,7 ] dodec-9-enes;

5-hydroxy-2-norbornene, 5-hydroxymethyl-2-norbornene, 5,6-di (hydroxymethyl) -2-norbornene, 5,5-di (hydroxymethyl) -2-norbornene, 5- (2- Tetracyclo [2.2.1] hept-2-enes having a hydroxyl group such as hydroxyethoxycarbonyl) -2-norbornene and 5-methyl-5- (2-hydroxyethoxycarbonyl) -2-norbornene; 6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-methanol and tetracyclo [6,2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a hydroxyl group such as 0 ^2,7 ] dodec-9-en-4-ol. 0 ^2,7 ] dodec-4-enes;

Bicyclo [2.2.1] hept-2-enes having a hydrocarbonyl group such as 5-norbornene-2-carbaldehyde;
Tetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a hydrocarbonyl group such as 0 ^2,7 ] dodec-9-ene-4-carbaldehyde. 0 ^2,7 ] dodec-4-enes;

  Bicyclo [2.2.1] hept-2-enes having an alkoxylcarbonyl group and a hydroxycarbonyl group such as 3-methoxycarbonyl-5-norbornene-2-carboxylic acid;

Bicyclo having a carbonyloxy group such as 5-norbornen-2-yl acetate, 2-methyl-5-norbornen-2-yl acetate, 5-norbornen-2-yl acrylate, and 5-norbornen-2-yl methacrylate [2.2.1] hept-2-enes;

Acetic acid 9-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-enyl, acetic acid 9-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-enyl, 9-tetracycloacrylic acid [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-enyl, and 9-tetracyclomethacrylic acid [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a carbonyloxy group such as 0 ^2,7 ] dodec-4-enyl. 0 ^2,7 ] dodec-4-enes;

Bicyclo [2.2.1] hept- having functional groups containing nitrogen atoms such as 5-norbornene-2-carbonitrile, 5-norbornene-2-carboxamide, and 5-norbornene-2,3-dicarboxylic imide 2-enes; tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carbonitrile, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxamide, tetracyclo [6,2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a functional group containing a nitrogen atom such as 0 ^2,7 ] dodec-9-ene-4 and 5-dicarboxylic imide. 0 ^2,7 ] dodec-4-enes;

Bicyclo [2.2.1] hept-2-enes having a halogen atom such as 5-chloro-2-norbornene; 9-chlorotetracyclo [6,2.1.1 ^3,6 . Tetracyclo [6,2.1.1 ^3,6 . Having a halogen atom such as 0 ^2,7 ] dodec-4-ene. 0 ^2,7 ] dodec-4-enes;

Bicyclo [2.2.1] hept-2-enes having a functional group containing a silicon atom such as 5-trimethoxy-2-norbornene and 5-triethoxy-2-norbornene; 4-trimethoxysilyltetracyclo [6 , 2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene and 4-triethoxysilyltetracyclo [6,2.1.1 ^3,6 . Tetracyclo [6,2.1.1 ^3,6 . Having a functional group containing a silicon atom such as 0 ^2,7 ] dodec-9-ene. 0 ^2,7 ] dodec-4-enes; and the like.
These cyclic olefins can be used alone or in combination of two or more.

  Examples of the monomer copolymerizable with the cyclic olefin include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, and 1-hexene; styrene, α-methylstyrene, p-methylstyrene, Styrenes such as p-chlorostyrene and indene; chain conjugated dienes such as 1,3-butadiene and isoprene; vinyl ethers such as ethyl vinyl ether and isobutyl vinyl ether; methyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate, etc. Acrylates; metal acrylates such as methyl methacrylate and ethyl methacrylate; and the like.

  In the production method of the present invention, as a polymerization catalyst, the transition metal complex (A), the organoaluminum compound (B-1), and the compound (B-2) that reacts with the transition metal complex (A) to form an ion pair. In the case of using a product obtained by mixing at least one compound (B) selected from the above, the order of mixing (A), (B) and the cyclic olefin is not particularly limited. That is, the mixture of (A) and (B) may be added to and mixed with the cyclic olefin, or (B) may be added and mixed with the mixture of the cyclic olefin and (A). You may add and mix (A) to the mixture of an olefin and (B).

  The polymerization catalyst is used in a molar ratio of (transition metal atom in transition metal complex (A): cyclic olefin) in a molar ratio of usually 1: 100 to 1: 2,000,000, preferably 1: 200. To 1: 1,000,000, more preferably 1: 500 to 1: 500,000. If the amount of catalyst is too large, the operation becomes difficult when catalyst removal is necessary, and if the amount is too small, sufficient polymerization activity may not be obtained.

  A solvent can be used in the production method of the present invention. The solvent used is not particularly limited as long as it does not affect the polymerization, but industrially general-purpose solvents are preferable. As such a solvent, any solvent that can be used for mixing (A) and (B) can be used. Of these, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, halogen solvents, or a mixed solvent of two or more of these are preferable.

  When the polymerization is carried out in a solvent, the concentration of the cyclic olefin is preferably 1 to 50% by weight in the solution, more preferably 2 to 45% by weight, and particularly preferably 5 to 40% by weight. When the monomer concentration is 1% by weight or less, the productivity is poor, and when it is 50% by weight or more, the solution viscosity after polymerization is too high, and subsequent handling may be difficult.

  The polymerization temperature is not particularly limited, but is generally −30 ° C. to + 200 ° C., preferably 0 ° C. to 180 ° C. The polymerization time is not particularly limited, and is usually 1 minute to 100 hours.

  The molecular weight of the resulting cyclic olefin addition polymer can be adjusted by changing the ratio of the cyclic olefin to the catalyst, the polymerization temperature, and the like. The molecular weight of the polymer can also be controlled by adding α-olefin, hydrogen, alcohol or the like.

  The cyclic olefin polymer obtained as described above is excellent in heat resistance, low water absorption, and electrical characteristics, and can be preferably used as a polymer material for electrical / electronic parts.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples. Parts and% in the examples are based on weight unless otherwise specified.
The test and evaluation in an Example and a comparative example were performed with the following method.

(1) The synthesized transition metal complex was identified by elemental analysis and IR spectrum (ATR method).
(2) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured as polystyrene conversion values by gel permeation chromatography (GPC) using tetrahydrofuran or chloroform as a solvent.
(3) The copolymerization ratio of the polymer was determined by ¹ H-NMR measurement.

Synthesis Example 1: Synthesis of N, N′-bis (2,6-diisopropylphenyl) benzamidine (N, N′-bis (2,6-diisopropylphenyl) benzamidine was synthesized by Chem. Commun., According to the method described in 2003, 522-523 pages, the following procedure was used.
To the eggplant flask substituted with nitrogen, 15 parts of diphosphorus pentoxide, 34 parts of hexamethyldisiloxane and 30 parts of distilled dichloromethane were added and heated to reflux for 30 minutes. After refluxing, the product was heated to 160 ° C., and dichloromethane and unreacted hexamethyldisiloxane were distilled off to obtain an oily polyphosphate trimethylsilyl ether.
To this trimethylsilyl ether of polyphosphate, 1.5 parts of benzoic acid and 0.45 part of diisopropylaniline were added and heated at 170 ° C. for 6 hours. After heating, the mixture was cooled to room temperature, and the reaction solution was poured into 500 parts of 1M aqueous potassium hydroxide solution. The resulting oily substance was solid after standing for 2 days. This solid was washed with water and recrystallized from a mixed solvent of ethanol-water to obtain 3 parts of a white title compound.

By ¹ H-NMR spectrum measurement of the obtained compound, it was confirmed that this compound was N, N′-bis (2,6-diisopropylphenyl) benzamidine. The spectrum data is shown below.

¹ H-NMR (CDC1 ₃ ) (δ ppm): 6.8 to 7.4 (m, 11H), 5.70 (s, 1H), 3.12 to 3.38 (m, 4H), 1.35 (D, 6H), 1.23 (d, 6H), 0.98 (d, 6H), 0.84 (d, 6H)

Synthesis Example 2: Synthesis of N, N′-bis (phenyl) benzamidyne The synthesis of N, N′-bis (phenyl) benzamidine is described in Bull. Chem. Soc. Jp. , 1986, pages 2171 to 2177, and the following procedure was used.
30 parts of diphosphorus pentoxide, 64 parts of hexamethyldisiloxane and 60 parts of distilled dichloromethane were added to a nitrogen-substituted eggplant flask and heated to reflux for 30 minutes. After refluxing, the product was heated to 160 ° C., and dichloromethane and unreacted hexamethyldisiloxane were distilled off to obtain an oily polyphosphate trimethylsilyl ether.
3 parts of benzoic acid and 4.7 parts of aniline were added to this trimethylsilyl ether of polyphosphate and heated at 170 ° C. for 6 hours. After heating, the mixture was cooled to room temperature, and the reaction solution was poured into 500 parts of 1M potassium hydroxide. The resulting oily substance was solid after standing for 2 days. This solid was washed with water and recrystallized from a mixed solvent of ethanol-water to obtain 6.2 parts of the white title compound.

It was confirmed by ¹ H-NMR spectrum measurement of the obtained compound that this compound was N, N′-bis (phenyl) benzamidine. The spectrum data is shown below.

¹ H-NMR (CDC1 ₃ ) (δ ppm): 6.7 to 7.6 (m, 15H), 5.58 (s, lH)

Synthesis Example 3: Synthesis of N, N'-bis (2,4,6-trimethylphenyl) benzamidine In a nitrogen-substituted eggplant flask, 13 parts of diphosphorus pentoxide, 26 parts of hexamethyldisiloxane and distilled dichloromethane 25 parts was added and heated to reflux for 30 minutes. After refluxing, the product was heated to 160 ° C., and dichloromethane and unreacted hexamethyldisiloxane were distilled off to obtain an oily polyphosphate trimethylsilyl ether.
To this trimethylsilyl ether of polyphosphate, 1.5 parts of benzoic acid and 3.4 parts of 2,4,6-trimethylaniline were added and heated at 170 ° C. for 6 hours. After heating, the mixture was cooled to room temperature, and the reaction solution was poured into 500 parts of 1M aqueous potassium hydroxide solution. The resulting oily substance was solid after standing for 2 days. This solid was washed with water and recrystallized from a mixed solvent of ethanol-water to obtain 3.4 parts of the white title compound.

It was confirmed by ¹ H-NMR spectrum measurement of the obtained compound that this compound was N, N′-bis (2,4,6-trimethylphenyl) benzamidine. The spectrum data is shown below.

¹ H-NMR (CDC1 ₃ ) (δ ppm): 6.5 to 7.5 (m, 9H), 5.69 (s, 1H), 2.00 to 2.43 (m, 18H)

Synthesis Example 4: Synthesis of N, N′-bis (2-methylphenyl) benzamidine To a nitrogen-substituted eggplant flask, 30 parts of diphosphorus pentoxide, 65 parts of hexamethyldisiloxane and 60 parts of distilled dichloromethane were added. The mixture was heated to reflux for 30 minutes. After refluxing, the product was heated to 160 ° C., and dichloromethane and unreacted hexamethyldisiloxane were distilled off to obtain an oily polyphosphate trimethylsilyl ether.
To this trimethylsilyl ether of polyphosphate, 3 parts of benzoic acid and 5.4 parts of toluidine were added and heated at 170 ° C. for 6 hours. After heating, the mixture was cooled to room temperature, and the reaction solution was poured into 500 parts of 1M aqueous potassium hydroxide solution. The resulting oily substance was solid after standing for 2 days. This solid was washed with water and recrystallized from a mixed solvent of ethanol-water to obtain 4.9 parts of a white title compound.

It was confirmed by ¹ H-NMR spectrum measurement of the obtained compound that this compound was N, N′-bis (2-methylphenyl) benzamidine. The spectrum data is shown below.

¹ H-NMR (CDC1 ₃ ) (δ ppm): 6.7 to 7.5 (m, 13H), 5.99 (s, 1H), 2.22 (s, 3H), 2.09 (s, 3H) )

Synthesis Example 5 Synthesis of N, N′-bis (4-methylphenyl) benzamidine To a nitrogen-substituted eggplant flask, 30 parts of diphosphorus pentoxide, 65 parts of hexamethyldisiloxane and 60 parts of distilled dichloromethane were added. The mixture was heated to reflux for 30 minutes. After refluxing, the product was heated to 160 ° C., and dichloromethane and unreacted hexamethyldisiloxane were distilled off to obtain an oily polyphosphate trimethylsilyl ether.
To this trimethylsilyl ether of polyphosphate, 3 parts of benzoic acid and 5.4 parts of p-methylaniline were added and heated at 170 ° C. for 6 hours. After heating, the mixture was cooled to room temperature, and the reaction solution was poured into 500 parts of 1M potassium hydroxide. The resulting oily substance was solid after standing for 2 days. This solid was washed with water and recrystallized from a mixed solvent of ethanol-water to obtain 2.8 parts of a pale yellow title compound.

By ¹ H-NMR spectrum measurement of the obtained compound, it was confirmed that this compound was N, N′-bis (4-methylphenyl) benzamidine. The spectrum data is shown below.

¹ H-NMR (CDCl ₃ ) (δ ppm): 6, 9 to 7.7 (m, 13H), 5.33 (s, 1H), 2.31 (s, 3H), 2.19 (s, 3H) )

Synthesis Example 6 Synthesis of N, N′-bis (4-t-butylphenyl) benzamidine In a nitrogen-substituted eggplant flask, 30 parts of diphosphorus pentoxide, 65 parts of hexamethyldisiloxane and 60 parts of distilled dichloromethane were added. In addition, the mixture was heated to reflux for 30 minutes. After refluxing, the product was heated to 160 ° C., and dichloromethane and unreacted hexamethyldisiloxane were distilled off to obtain an oily polyphosphate trimethylsilyl ether.
2 parts of benzoic acid and 4.7 parts of pt-butylaniline were added to this trimethylsilyl ether of polyphosphate, and heated at 170 ° C. for 6 hours. After heating, the mixture was cooled to room temperature, and the reaction solution was poured into 500 parts of 1M aqueous potassium hydroxide solution. The resulting oily substance was solid after standing for 2 days. This solid was washed with water and recrystallized from a mixed solvent of ethanol-water to obtain 1.4 parts of the white title compound.

It was confirmed by ¹ H-NMR spectrum measurement of the obtained compound that this compound was N, N′-bis (4-t-butylphenyl) benzamidine.
The spectrum data is shown below.

¹ H-NMR (CDC1 ₃ ) (δ ppm): 6.7 to 7.8 (m, 13H), 5.57 (s, 1H), 1.14 (s, 18H)

Synthesis Example 7 Synthesis of N, N′-bis (2,4,6-tri-tert-butylphenyl) benzamidine In a nitrogen-substituted eggplant flask, 15 parts of niline pentoxide, 30 parts of hexamethyldisiloxane, and 30 parts of distilled dichloromethane was added and heated to reflux for 30 minutes. After refluxing, the product was heated to 160 ° C., and dichloromethane and unreacted hexamethyldisiloxane were distilled off to obtain an oily polyphosphate trimethylsilyl ether.
1.2 parts of benzoic acid and 5 parts of 2,4,6-tri-t-butylaniline were added to this trimethylsilyl ether of polyphosphate, and heated at 170 ° C. for 6 hours. After heating, the mixture was cooled to room temperature, and the reaction solution was poured into 500 parts of 1M aqueous potassium hydroxide solution. The resulting oily substance was solid after standing for 2 days. This solid was washed with water and recrystallized from a mixed solvent of ethanol-water to obtain 4.5 parts of a white title compound.

By ¹ H-NMR spectrum measurement of the obtained compound, it was confirmed that this compound was N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidine. The spectrum data is shown below.

¹ H-NMR (CDC1 ₃ ) (δ ppm): 6, 7 to 7.4 (m, 5H), 5.62 (s, 1H), 1.14 to 1.42 (m, 54H)

Synthesis Example 8 Synthesis of N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidine In a nitrogen-substituted eggplant flask, 30 parts of diphosphorus pentoxide, 67 parts of hexamethyldisiloxane, And 30 parts of distilled dichloromethane was added and heated to reflux for 30 minutes. After refluxing, the product was heated to 160 ° C., and dichloromethane and unreacted hexamethyldisiloxane were distilled off to obtain an oily polyphosphate trimethylsilyl ether.
To this trimethylsilyl ether of polyphosphate, 3 parts of benzoic acid and 9.1 parts of 2,3,4,5,6-pentafluoroaniline were added and heated at 170 ° C. for 6 hours. After heating, the mixture was cooled to room temperature, and the reaction solution was poured into 500 parts of 1M aqueous potassium hydroxide solution. The resulting oily substance was solid after standing for 2 days. This solid was washed with water and recrystallized from a mixed solvent of ethanol-water to obtain 6.2 parts of the white title compound.

¹ H-NMR spectrum measurement of the obtained compound confirmed that this compound was N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidine. The spectrum data is shown below.

¹ H-NMR (CDC1 ₃ ) (δ ppm): 7.2 to 7.5 (m, 5H)

Example 1: Synthesis of N, N'-bis (2,6-diisopropylphenyl) benzamidinate nickel (triphenylphosphine) chloride (complex a)

  Argon-substituted Schlenk tube was charged with 3.1 parts of dichlorobis (triphenylphosphine) nickel and 2 parts of N, N′-bis (2,6-diisopropylphenyl) benzamidine. Part was added. The reaction solution was filtered after stirring at room temperature for 16 hours, and the solvent was depressurizingly distilled from the filtrate. The residue was washed twice with 300 parts of n-hexane and dried under reduced pressure to obtain 2.1 parts of complex a.

The results of elemental analysis of the complex a were 74.6% carbon, 6.3% hydrogen, and 2.9% nitrogen. The elemental analysis results are calculated for N, N'-bis (2,6-diisopropylphenyl) benzamidinate nickel (triphenylphosphine) chloride (carbon 73.9%, hydrogen 6.8%, nitrogen 3.5). %).
From the above, the complex a was identified as N, N′-bis (2,6-diisopropylphenyl) benzamidinate nickel (triphenylphosphine) chloride.

Example 2: Synthesis of N, N'-bis (phenyl) benzamidinate nickel (triphenylphosphine) chloride (complex b)

  Add 6.5 parts of dichlorobis (triphenylphosphine) nickel and 2.7 parts of N, N'-bis (phenyl) benzamidine to a Schlenk tube substituted with argon, and add 200 parts of dichloromethane that has been dehydrated and degassed in advance. It was. The reaction solution was filtered after stirring at room temperature for 16 hours, and the solvent was depressurizingly distilled from the filtrate. The residue was washed twice with 300 parts of n-hexane and dried under reduced pressure to obtain 4 parts of complex b.

As a result of elemental analysis of the complex b, carbon was 71.9%, hydrogen was 5.4%, and nitrogen was 3.7%. The elemental analysis results are almost the same as the calculated values of N, N'-bis (phenyl) benzamidinate nickel (triphenylphosphine) chloride (carbon 70.8%, hydrogen 4.8%, nitrogen 4.5%). did.
From the above, the complex b was identified as N, N′-bis (phenyl) benzamidinate nickel (triphenylphosphine) chloride.

Example 3: Synthesis of N, N'-bis (2,4,6-trimethylphenyl) benzamidinate nickel (triphenylphosphine) chloride (complex c)

  Put 9.2 parts of dichlorobis (triphenylphosphine) nickel and 4.8 parts of N, N'-bis (2,4,6-trimethylphenyl) benzamidine in a Schlenk tube purged with argon, and dehydrate and dehydrate in advance. 500 parts of vaporized dichloromethane were added. The reaction solution was filtered after stirring at room temperature for 16 hours, and the solvent was depressurizingly distilled from the filtrate. The residue was washed twice with 500 parts of n-hexane and dried under reduced pressure to obtain 4.8 parts of complex c.

As a result of elemental analysis of the complex c, carbon was 72.1%, hydrogen was 5.4%, and nitrogen was 3.1%. The results of elemental analysis are calculated values of N, N′-bis (2,4,6-trimethylphenyl) benzamidinate nickel (triphenylphosphine) chloride (carbon 72.5%, hydrogen 6.0%, nitrogen 3 9%).
From the above, the complex c was identified as N, N′-bis (2,4,6-trimethylphenyl) benzamidinate nickel (triphenylphosphine) chloride.

Example 4: Synthesis of N, N'-bis (2-methylphenyl) benzamidinate nickel (triphenylphosphine) chloride (complex d)

  Into a Schlenk tube purged with argon, 18.1 parts of dichlorobis (triphenylphosphine) nickel and 8 parts of N, N′-bis (2-methylphenyl) benzamidine were added, and 700 parts of dichloromethane dehydrated and degassed in advance. added. The reaction solution was filtered after stirring at room temperature for 16 hours, and the solvent was depressurizingly distilled from the filtrate. The residue was washed twice with 800 parts of n-hexane and dried under reduced pressure to obtain 14.4 parts of complex d.

As a result of elemental analysis of the complex d, carbon was 72.1%, hydrogen was 5.8%, and nitrogen was 3.6%. The elemental analysis results are calculated values of N, N′-bis (2-methylphenyl) benzamidinate nickel (triphenylphosphine) chloride (carbon 71.4%, hydrogen 5.2%, nitrogen 4.3%). Almost matched.
Further, the IR spectrum (ATR method) of this product was measured. The measured IR chart is shown in FIG. In FIG. 1, the vertical axis represents transmittance (%), and the horizontal axis represents wave number (cm ⁻¹ ).
From the above, the complex d was identified as N, N′-bis (2-methylphenyl) benzamidinate nickel (triphenylphosphine) chloride.

Example 5: Synthesis of N, N'-bis (4-methylphenyl) benzamidinate nickel (triphenylphosphine) chloride (complex e)

  Into a Schlenk tube purged with argon, 6.5 parts of dichlorobis (triphenylphosphine) nickel and 3 parts of N, N′-bis (4-methylphenyl) benzamidine were added, and 200 parts of dichloromethane dehydrated and degassed in advance. added. The reaction solution was filtered after stirring at room temperature for 16 hours, and the solvent was depressurizingly distilled from the filtrate. The residue was washed twice with 200 parts of n-hexane and dried under reduced pressure to obtain 4.3 parts of complex e.

The elemental analysis results of the complex e were 73.4% carbon, 6.1% hydrogen, and 3.8% nitrogen. The elemental analysis results are calculated values of N, N′-bis (4-methylphenyl) benzamidinate nickel (triphenylphosphine) chloride (carbon 71.4%, hydrogen 5.2%, nitrogen 4.3%). Almost matched.
From the above, the complex e was identified as N, N′-bis (4-methylphenyl) benzamidinate nickel (triphenylphosphine) chloride.

Example 6: Synthesis of N, N'-bis (4-t-butylphenyl) benzamidinate nickel (triphenylphosphine) chloride (complex f)

  Into an argon-substituted Schlenk tube, 6.5 parts of dichlorobis (triphenylphosphine) nickel and 3.8 parts of N, N′-bis (4-t-butylphenyl) benzamidine were put, and dehydrated and degassed in advance. 700 parts of dichloromethane were added. The reaction solution was filtered after stirring at room temperature for 16 hours, and the solvent was depressurizingly distilled from the filtrate. The residue was washed twice with 300 parts of n-hexane and dried under reduced pressure to obtain 5.6 parts of complex f.

The results of elemental analysis of the complex f were as follows: carbon 74.3%, hydrogen 6.9%, and nitrogen 3.1%. The result of elemental analysis is calculated value of N, N′-bis (4-t-butylphenyl) benzamidinate nickel (triphenylphosphine) chloride (carbon 73.0%, hydrogen 6.3%, nitrogen 3.8 %).
From the above, the complex f was identified as N, N′-bis (4-t-butylphenyl) benzamidinate nickel (triphenylphosphine) chloride.

Example 7: Synthesis of N, N'-bis (2,4,6-tri-t-butylphenyl) benzamidinate nickel (triphenylphosphine) chloride (complex g)

  Into an argon-substituted Schlenk tube, 6.5 parts of dichlorobis (triphenylphosphine) nickel and 6.1 parts of N, N′-bis (2,4,6-tri-tert-butylphenyl) benzamidine are placed. 200 parts of dichloromethane previously dehydrated and degassed were added. The reaction solution was filtered after stirring at room temperature for 16 hours, and the solvent was depressurizingly distilled from the filtrate. The residue was washed twice with 200 parts of n-hexane and dried under reduced pressure to obtain 1.4 parts of complex g.

The elemental analysis results of Complex g were 77.2% carbon, 7.6% hydrogen, and 2.2% nitrogen. The results of elemental analysis are calculated values of N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate nickel (triphenylphosphine) chloride (carbon 76.0%, hydrogen 8.2). %, Nitrogen 2.9%).
From the above, the complex g was identified as N, N′-bis (2,4,6-tri-t-butylphenyl) benzamidinate nickel (triphenylphosphine) chloride.

Example 8: Synthesis of N, N'-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate nickel (triphenylphosphine) chloride (complex h)

  Into an argon-substituted Schlenk tube, 6.5 parts of dichlorobis (triphenylphosphine) nickel and 4.5 parts of N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidine are placed. 200 parts of dichloromethane previously dehydrated and degassed were added. The reaction solution was filtered after stirring at room temperature for 16 hours, and the solvent was depressurizingly distilled from the filtrate. The residue was washed twice with 200 parts of n-hexane and dried under reduced pressure to obtain 1.1 parts of complex h.

The elemental analysis results of Complex h were 56.0% carbon, 2.2% hydrogen, and 3.2% nitrogen. The result of elemental analysis is the calculated value of N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate nickel (triphenylphosphine) chloride (carbon 55.0%, hydrogen 2. 5% and nitrogen 3.5%).
From the above, the complex h was identified as N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate nickel (triphenylphosphine) chloride.

Example 9: Synthesis of (allyl) palladium (N, N'-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate (complex i)

  Place 1.8 parts of allyl palladium chloride dimer and 5.4 parts of N, N'-bis (2,3,4,5,6-pentafluorophenyl) benzamidine into an argon-substituted Schlenk tube and dehydrate it beforehand. And 200 parts of degassed dichloromethane were added. The reaction solution was filtered after stirring at room temperature for 16 hours, and the solvent was depressurizingly distilled from the filtrate. The residue was washed twice at −70 ° C. with 100 parts of n-pentane and dried under reduced pressure to obtain 3.2 parts of complex i.

The elemental analysis results of Complex i were 43.5% carbon, 2.1% hydrogen, and 3.9% nitrogen. The results of elemental analysis are calculated values for (allyl) palladium (N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate) complex (carbon 44.1%, hydrogen 1. 7% and nitrogen 4.7%).
From the above, the complex i was identified as an (allyl) palladium (N, N′-bis (2,3,4,5,6-pentafluorophenyl) benzamidinate) complex.

Example 10: Production of cyclic olefin polymer Into a nitrogen-substituted glass reactor, 6.5 parts of the complex a obtained in Example 1 and 551 parts of a toluene solution of methylaluminoxane having an aluminum content of 9.0% were placed. Further, 500 parts of toluene was added to prepare a catalyst solution.
Subsequently, 1175 parts of bicyclo [2.2.1] hept-2-ene (hereinafter referred to as “cyclic olefin A”) and 5-ethylidenebicyclo [2.2.1] were added to a pressure-resistant glass reactor equipped with a nitrogen-substituted stirrer. ] 1500 parts of hept-2-ene (hereinafter referred to as “cyclic olefin B”) and 5000 parts of toluene as a polymerization solvent were added, and the above catalyst solution was added to initiate polymerization. After reacting at 60 ° C. for 3 hours, the polymerization reaction solution was poured into a large amount of methanol to completely precipitate the polymer, washed by filtration and dried under reduced pressure at 50 ° C. for 18 hours to obtain 143 parts of a polymer. The obtained polymer was soluble in toluene, chloroform and the like.

  Type and amount of cyclic olefin used, type and amount of complex used, polymerization reaction conditions, yield of the obtained polymer, number average molecular weight, weight average molecular weight, and repeating unit B content (in all repeating units) Table 1 shows the abundance of the repeating units derived from cyclic olefin B (mol%).

Examples 11 to 18: Production of cyclic olefin polymer A polymer was obtained in the same manner as in Example 10 except that the type and amount of the complex used were as shown in Table 1. Table 1 shows the yield, number average molecular weight, weight average molecular weight, and repeating unit B content of the obtained polymer (existing ratio (mol%) of repeating units derived from cyclic olefin B in all repeating units).

実施例１９：環状オレフィン重合体の製造
窒素置換したガラス反応器に、実施例８で得た錯体ｈ１０．１部及びアルミニウム分が９．０％であるメチルアルミノキサンのトルエン溶液８２５部を入れ、さらにトルエン５００部を加えて触媒液を調製した。
次いで、窒素置換した攪拌機付きの耐圧ガラス反応器に、環状オレフィンＡ ｌ１７５部、環状オレフィンＢ ２２３０部、及び重合溶媒としてトルエン５０００部を仕込み、上記の触媒液を添加して重合を開始した。２５℃で１時間反応させた後、重合反応液を多量のメタノールに注いでポリマーを完全に析出させ、ろ別洗浄後、５０℃で１８時間減圧乾燥して重合体３１８９部を得た。得られた重合体はトルエン、クロロホルム等に可溶であった。

Example 19 Production of Cyclic Olefin Polymer A nitrogen-replaced glass reactor was charged with 10.1 parts of the complex h obtained in Example 8 and 825 parts of a toluene solution of methylaluminoxane having an aluminum content of 9.0%. 500 parts of toluene was added to prepare a catalyst solution.
Subsequently, 175 parts of cyclic olefin A, 2230 parts of cyclic olefin B, and 5000 parts of toluene as a polymerization solvent were charged into a pressure-resistant glass reactor equipped with a stirrer purged with nitrogen, and the above catalyst solution was added to initiate polymerization. After reacting at 25 ° C. for 1 hour, the polymerization reaction solution was poured into a large amount of methanol to completely precipitate the polymer, washed by filtration and dried under reduced pressure at 50 ° C. for 18 hours to obtain 3189 parts of a polymer. The obtained polymer was soluble in toluene, chloroform and the like.

  Type and amount of cyclic olefin used, type and amount of complex used, polymerization reaction conditions, yield of the obtained polymer, number average molecular weight, weight average molecular weight, and repeating unit B content (in all repeating units) Table 2 shows the ratio of the repeating unit derived from cyclic olefin B (mol%).

Examples 20 and 21: Polymers were obtained in the same manner as in Example 19 except that the types and amounts used of the cyclic olefin polymer production complexes were changed as shown in Table 2. Table 2 shows the yield, number average molecular weight, weight average molecular weight, and repeating unit B content (existing ratio (mol%) of repeating units derived from cyclic olefin B in all repeating units) of the obtained polymer.

実施例２２：環状オレフィン重合体の製造
窒素置換したガラス反応器に、実施例４で得た錯体ｄ８．２部、及びアルミニウム分が９．０％であるメチルアルミノキサンのトルエン溶液８２５部を入れ、さらにトルエン５００部を加えて触媒液を調製した。
次いで、窒素置換した攪拌機付きの耐圧ガラス反応器に、環状オレフィンＡ ｌ１７５部、１，４−メタノ−１，４，４ａ，９ａ−テトラヒドロ−９Ｈ−フルオレン（以下、「環状オレフィンＣ」という）２３００部、及び重合溶媒としてトルエン５０００部を仕込み、上記の触媒液を添加して重合を開始した。２５℃で１０時間反応させた後、重合反応液を多量のメタノールに注いでポリマーを完全に析出させ、ろ別洗浄後、５０℃で１８時間減圧乾燥して重合体２１５８部を得た。
得られた重合体はトルエン、クロロホルム等に可溶であった。

Example 22: Preparation of cyclic olefin polymer A nitrogen-substituted glass reactor was charged with 8.2 parts of the complex d obtained in Example 4 and 825 parts of a toluene solution of methylaluminoxane having an aluminum content of 9.0%. Further, 500 parts of toluene was added to prepare a catalyst solution.
Next, in a pressure-resistant glass reactor equipped with a nitrogen-substituted stirrer, 1175 parts of cyclic olefin A, 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene (hereinafter referred to as “cyclic olefin C”) 2300 And 5000 parts of toluene as a polymerization solvent were added, and the above catalyst solution was added to initiate polymerization. After reacting at 25 ° C. for 10 hours, the polymerization reaction solution was poured into a large amount of methanol to completely precipitate the polymer, washed by filtration and dried under reduced pressure at 50 ° C. for 18 hours to obtain 2158 parts of a polymer.
The obtained polymer was soluble in toluene, chloroform and the like.

  Type and amount of cyclic olefin used, type and amount of complex used, polymerization reaction conditions, yield of the obtained polymer, number average molecular weight, weight average molecular weight, and repeating unit C content (in all repeating units) Table 3 shows the abundance of the repeating units derived from cyclic olefin C (mol%).

Examples 23 to 26: Polymers were obtained in the same manner as in Example 22 except that the types and amounts used of the cyclic olefin polymer production complex were changed as shown in Table 3. Table 3 shows the yield, number average molecular weight, weight average molecular weight, and repeating unit C content (existing ratio (mol%) of repeating units derived from cyclic olefin C in all repeating units) of the obtained polymer.

本発明の遷移金属錯体は保存安定性が極めて高く、空気中で取扱いが可能である。また、イオン対を形成する化合物との組み合わせは、他のＮｉ触媒に比べ、置換基を有する環状オレフィンの付加重合活性に優れている。

The transition metal complex of the present invention has extremely high storage stability and can be handled in air. Moreover, the combination with the compound which forms an ion pair is excellent in the addition polymerization activity of the cyclic olefin which has a substituent compared with another Ni catalyst.

6 is an IR spectrum chart of the complex d obtained in Example 4. FIG.

Claims (5)

  A bidentate group 8-10 transition metal complex in which a bidentate ligand is coordinated through two nitrogen atoms, the two bidentate ligands, one carbon atom and one transition metal in the bidentate ligand A transition metal complex (A), wherein the atoms form a four-membered ring. General formula (1)

(In the formula, M ¹ is a transition metal atom of Groups 8 to 10 of the periodic table, and R ^{1 to} R ³ are each independently a hydrogen atom; a halogen atom; a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom or silicon. A functional group containing an atom; or a C1-C20 hydrocarbon group which may have a substituent.
L ¹ represents a neutral electron donating ligand, and X ¹ represents an anionic ligand. L ¹ and X ¹ may be bonded to each other to form a multidentate ligand.
a and b are each independently an integer of 0 to 3, and when a and b are each 2 or more, L ¹ and X ¹ may be the same or different. The transition metal complex (A) according to claim 1, which is a compound represented by   A catalyst for polymerization of a cyclic olefin, comprising the transition metal complex (A) according to claim 1 or 2.   The transition metal complex (A) according to claim 1 or 2, the organoaluminum compound (B-1), and the compound (B-2) that reacts with the transition metal complex (A) to form an ion pair. A cyclic olefin polymerization catalyst comprising at least one compound (B). A method for producing a cyclic olefin polymer, comprising polymerizing a cyclic olefin in the presence of the polymerization catalyst according to claim 3.

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