JP2005200380A - Transition metal compound, catalyst component for addition polymerization, catalyst for addition polymerization, and method for producing addition polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transition metal compound and an addition polymerization catalyst component used for preparing a highly active addition polymerization catalyst, a highly active addition polymerization catalyst, and an efficient method for producing an addition polymer.
A transition metal compound represented by the formula [1]. Other.
(L _p X _o M) [(N ₂ ) _n M′X ′ _m L ′ _l ] _q X ″ _k [1]
(M and M ′ are group 3-10 transition metal atoms. X and X ′ are hydrogen atoms, halogen atoms, alkyl groups, aralkyl groups, aryl groups, substituted silyl groups, alkoxy groups, aralkyloxy groups, aryloxy groups. A group having a disubstituted amino group, an azide group, a cyano group, an isothiocyanate group, an oxo group or a cyclopentadiene type anion skeleton, L and L ′ are groups bonded to M or M ′ by a lone electron pair or π electron; "Is a counter anion. K, o and p are integers of 0 to 5, l is an integer of 2 to 5, m is an integer of 0 to 2, n is an integer of 1 to 3, and q is 2 or 3.)
[Selection figure] None

Description

  The present invention relates to a transition metal compound having three or four transition metal atoms in one molecule used for the preparation of an addition polymerization catalyst, an addition polymerization catalyst component, an addition polymerization catalyst and an addition weight obtained using the same. The present invention relates to a method for manufacturing coalescence.

Many reports have already been made on a method for producing an addition polymer such as an olefin polymer using a transition metal compound that forms a single site catalyst such as a metallocene complex (for example, see Patent Document 1).
In addition, as a catalyst for addition polymerization using a transition metal compound having a plurality of transition metal atoms in one molecule, for example, a complex having rhodium as a substituent on a bridging group of a bridged zirconocene has been reported (for example, , See Non-Patent Document 1.) There have been very few reported examples so far.

JP 60-245604 A Organometallics, 18, 996-1001

  The addition polymerization catalyst used in the production of the addition polymer is more efficient as its activity increases, and a highly active addition polymerization catalyst is required. The problem to be solved by the present invention, that is, the object of the present invention, is to provide transition metal compounds and addition polymerization catalyst components used in the preparation of highly active addition polymerization catalysts, highly active addition polymerization catalysts and efficient attachments. It is providing the manufacturing method of a polymer.

That is, the present invention relates to a transition metal compound represented by the following general formula [1] and an addition polymerization catalyst component comprising the transition metal compound. The present invention also relates to an addition polymerization catalyst obtained by bringing the transition metal compound (A) into contact with the following (B) and / or the following (C). The present invention relates to a method for producing an addition polymer in which addition polymerization of an addition polymerizable unsaturated monomer is carried out.
(L _p X _o M) [(N ₂ ) _n M′X ′ _m L ′ _l ] _q X ″ _k [1]
(In the formula, M and M ′ each independently represent a transition metal atom of Groups 3 to 10 of the periodic table of elements, and X and X ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an aralkyl group. An aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, a disubstituted amino group, an azide group, a cyano group, an isothiocyanate group, an oxo group or a group having a cyclopentadiene type anion skeleton, and L and L ′ each independently represents a group bonded to M or M ′ by a lone pair or π electron. X ″ is a counter anion, k, o and p are each independently an integer of 0 to 5; Is an integer of 2 to 5, m is an integer of 0 to 2, n is an integer of 1 to 3, and q is 2 or 3.)
(B): One or more aluminum compounds selected from the following (B1) to (B3) (B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) General formula {-Al (E ² ) -O-} cyclic aluminoxane having a structure represented by _b (B3) a linear aluminoxane having a structure represented by the general formula E ³ {-Al (E ³ ) -O—} _c AlE ³ ₂ (the above ( In B1) to (B3), a represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, c represents an integer of 1 or more, and E ¹ , E ^2, and E ³ are carbonized. It represents a hydrogen group, if E ¹ is more, each E ¹ may be different be the same as each other. in addition, E ² each may be different, even the same as each other, respectively E ³ is optionally different from one another identical .Z represents a hydrogen atom or Ha It represents a Gen atom, if Z is a plurality, Z each may be different, even the same as each other.)
(C): one or more boron compounds selected from the following (C1) to (C3) (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ ,
(C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^-
(C3) A boron compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (in the above (C1) to (C3), B represents a trivalent boron atom, ¹ to Q ¹¹ represents a halogen atom, a hydrocarbon group, halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, Q ¹ to Q ¹¹ good be different even in the same .G ⁺ Represents an inorganic or organic cation, L represents a neutral Lewis base, and (LH) ⁺ represents a Bronsted acid.)

  ADVANTAGE OF THE INVENTION According to this invention, the transition metal compound used for adjustment of the highly active addition polymerization catalyst, the catalyst component for addition polymerization, the highly active addition polymerization catalyst, and the efficient manufacturing method of an addition polymer are provided.

(A) Transition Metal Compound M and M ′ in the transition metal compound represented by the above general formula [1] are each independently Group 3 to Group 10 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989) Represents a transition metal atom.
M is preferably a Group 3-5 transition metal atom, more preferably a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a niobium atom or a tantalum atom, and still more preferably a titanium atom or a zirconium atom.
Further, M ′ is preferably a Group 6-10 transition metal atom, more preferably a chromium atom, a molybdenum atom, a tungsten atom, a ruthenium atom, a rhodium atom, or a palladium atom, and further preferably a chromium atom, a molybdenum atom. Or it is a tungsten atom.

  X and X ′ in the general formula [1] are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, or a disubstituted amino group. , An azide group, a cyano group, an isothiocyanate group, an oxo group or a group having a cyclopentadiene type anion skeleton, and all Xs may be the same or different.

  Examples of the halogen atom in the substituents X and X ′ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The alkyl group in the substituents X and X ′ is preferably an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert group. -Butyl group, n-pentyl group, neopentyl group, isoamyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group, etc. A methyl group, an ethyl group, an isopropyl group, a tert-butyl group or an isoamyl group is preferred.

Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl group. , Tribromomethyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group , Tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, -Fluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl Group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromododecyl group Examples include a bromopentadecyl group and a perbromoeicosyl group.
Any of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The aralkyl group in the substituents X and X ′ is preferably an aralkyl group having 7 to 20 carbon atoms, such as benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methyl). Phenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, ( 3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2, 3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4, 5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, ( (Ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-tetradecylphenyl) A methyl group, a naphthylmethyl group, an anthracenylmethyl group, etc. are mentioned, More preferably, it is a benzyl group.
These aralkyl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

As the aryl group in the substituents X and X ′, an aryl group having 6 to 20 carbon atoms is preferable, for example, a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5 -Trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2, 3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group , Sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n- A tetradecylphenyl group, a naphthyl group, an anthracenyl group, etc. are mentioned, More preferably, it is a phenyl group.
These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group or aralkyloxy groups such as benzyloxy group Etc. may be partially substituted.

The substituted silyl group in the substituents X and X ′ is a silyl group substituted with a hydrocarbon group, and examples of the hydrocarbon group include a methyl group, ethyl group, n-propyl group, isopropyl group, n- Examples thereof include alkyl groups having 1 to 10 carbon atoms such as butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group and cyclohexyl group, and aryl groups such as phenyl group. . Examples of the substituted silyl group having 1 to 20 carbon atoms include monosubstituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group, and phenylsilyl group, dimethylsilyl group, diethylsilyl group, and diphenylsilyl group. A disubstituted silyl group having 2 to 20 carbon atoms, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert 3 -carbon atoms such as -butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl group 20 trisubstituted silyl groups, etc. Group, a tert- butyldimethylsilyl group or triphenylsilyl group.
All of these substituted silyl groups have a hydrocarbon group such as a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group or a benzyloxy group. A part thereof may be substituted with an aralkyloxy group such as a group.

As the alkoxy group in the substituents X and X ′, an alkoxy group having 1 to 20 carbon atoms is preferable. For example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, t-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group and the like, preferably methoxy group, ethoxy group, Or a t-butoxy group.
All of these alkoxy groups are partially substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and aralkyloxy groups. May be.

The aralkyloxy group in the substituents X and X ′ is preferably an aralkyloxy group having 7 to 20 carbon atoms, such as a benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, ( 4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy Group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6- Trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n -Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy Group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy group, anthracenyl group Such as carboxymethyl group and the like, preferably benzyl group.
Some of these aralkyloxy groups are fluorine atoms, chlorine atoms, bromine atoms, halogen atoms such as iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups. May be substituted.

As the aryloxy group in the substituents X and X ′, an aryloxy group having 1 to 20 carbon atoms is preferable. For example, a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, 2, 3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3, 4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4, 5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group Group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group Groups, n-hexylphenoxy groups, n-octylphenoxy groups, n-decylphenoxy groups, n-tetradecylphenoxy groups, naphthoxy groups, anthracenoxy groups, and the like, and the like.
Some of these aryloxy groups are fluorine atoms, chlorine atoms, bromine atoms, halogen atoms such as iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups. May be substituted.

  The disubstituted amino group in the substituents X and X ′ is an amino group substituted with two hydrocarbon groups, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. , N-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group and other alkyl groups having 1 to 10 carbon atoms, and aryl groups such as phenyl group, etc. Is mentioned. Examples of the disubstituted amino group include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group, di-tert-butylamino group. Group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenylamino group, bistrimethylsilylamino group, bis-tert -A butyl dimethyl silylamino group etc. are mentioned, Preferably it is a dimethylamino group or a diethylamino group.

The azido group, cyano group, isothiocyanate group and oxo group in the substituents X and X ′ are groups represented by —N ₃ , —CN, —N═C═S and ═O, respectively.

Examples of the group having a cyclopentadiene-type anion skeleton in the substituents X and X ′ include η ^5- (substituted) cyclopentadienyl group, η ^5- (substituted) indenyl group, η ^5- (substituted) fluorenyl group and the like. . Specifically, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵ -dimethylcyclopentadienyl group, η ⁵ -trimethylcyclopentadienyl group, η ⁵ -tetra methylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ⁵ - Echirushikuro Bae Ntajieniru group, eta ^5-n-propyl cyclopentadienyl group, eta ⁵ - isopropyl cyclopentadienyl group, eta ⁵ -n-butylcyclopentadienyl group, eta ^{5-sec-butylcyclopentadienyl} group, eta ^{5-tert-Buchirushikuro} Bae Ntajieniru group, eta ^{5-n-Penchirushikuro} Bae Ntajieniru group, eta ⁵ - Neopenchirushikurope Ntajieniru group, eta ^{5-n-hexylcyclopentadienyl} Bae Ntajieniru group, eta ^5-n-octyl cyclopentane Bae Ntajieniru group, eta ⁵ - phenylene Rucyclopentadienyl group, η ⁵ -naphthylcyclopentadienyl group, η ⁵ -trimethylsilylcyclopentadienyl group, η ⁵ -triethylsilylcyclopentadienyl group, η ⁵ -tert-butyldimethylsilylcyclopentadienyl group, η ⁵ -indenyl Group, η ⁵ -methyl indenyl group, η ⁵ -dimethyl indenyl group, η ⁵ -ethyl indenyl group, η ⁵ -n-propyl indenyl group, η ⁵ -isopropyl indenyl group, η ⁵ -n-butyl indenyl group, eta ^5-sec-butyl indenyl group, eta ^5-tert-butyl indenyl group, eta ^5-n-pentyl indenyl group, eta ⁵ - neopentyl indenyl group, eta ^5-n-hexyl indenyl alkenyl group, eta ^5-n-octyl indenyl group, eta ^{5-n-Deshiruindeniru} group, eta ⁵ - phenyl indenyl group, eta ⁵ - Mechirufu Eniruindeniru group, eta ⁵ - naphthyl indenyl group, eta ⁵ - trimethylsilyl indenyl group, eta ⁵ - triethylsilyl indenyl group, eta ^{5-tert-butyldimethylsilyl} indenyl group, eta ⁵ - tetrahydroindenyl group, eta ⁵ - fluorenyl group, eta ⁵ - methyl fluorenyl group, eta ⁵ - dimethyl fluorenyl group, eta ⁵ - ethyl fluorenyl group, eta ⁵ - diethyl fluorenyl group, eta ^5-n-propyl fluorenyl group , eta ⁵ - di-n-propyl-fluorenyl group, eta ⁵ - isopropyl fluorenyl group, eta ⁵ - diisopropyl fluorenyl group, eta ^{5-n-butyl-fluorenyl} group, eta ^{5-sec-Buchirufuru} Oreniru group, eta ^{5-tert-butyl-fluorenyl} group, eta ⁵ - di -n- butyl fluorenyl group, eta ⁵ - di -sec- butyl-fluorenyl group, eta ⁵ - di -ter t- butylfluorenyl group, eta ^{5-n-pentyl-fluorenyl} group, eta ⁵ - Neopentyl fluorenyl group, eta ^{5-n-hexyl-fluorenyl} group, eta ^5-n-octyl fluorenyl group , eta ^{5-n-decyl-fluorenyl} group, eta ^{5-n-dodecyl-fluorenyl} group, eta ⁵ - phenyl fluorenyl group, eta ⁵ - di - phenyl fluorenyl group, eta ⁵ - methylphenyl fluorenyl alkenyl group, eta ⁵ - naphthyl fluorenyl group, eta ⁵ - trimethylsilyl fluorenyl group, eta ⁵ - bis - trimethylsilyl fluorenyl group, eta ⁵ - triethylsilyl fluorenyl group, eta ^{5-tert-butyldimethylsilyl} fluorenyl group and the like, preferably eta ⁵ - cyclopentadienyl group, eta ⁵ - methylcyclopentadienyl group, eta ^{5-tert-butylcyclopentadienyl} group, eta ⁵ - tetra Chill cyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ⁵ - fluorenyl group - indenyl group or eta ^5,.
Note that “η ⁵ −” may be omitted.

X ″ in the general formula [1] represents a counter anion, and is an anionic group that is ionically released instead of being covalently bonded to M, and includes, for example, a conjugate base of Bronsted acid. X ″ is preferably F ^−. , Cl ⁻ , Br ⁻ , I ⁻ , BF ₄ ⁻ , BPh ₄ ⁻ or PF ₆ ⁻ .

L and L ′ in the general formula [1] each independently represent a group bonded to M or M ′ by a lone electron pair or a π electron.
The group that binds to M or M ′ through a lone pair of electrons is a neutral ligand that binds to M or M ′ through a coordinate bond. For example, ethers such as diethyl ether, tetrahydrofuran, dimethoxyethane, triethylamine, N, Amines such as N, N ′, N′-tetramethylethylenediamine, pyridines such as pyridine, 2,6-dimethylpyridine and quinoline, trimethylphosphine, triethylphosphine, triphenylphosphine, dimethylphenylphosphine, methyldiphenylphosphine, 1,2 Phosphines such as bis (dimethylphosphino) ethane, 1,2-bis (diethylphosphino) ethane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, acetonitrile, Benzonit Examples include nitriles such as ril, end-on type nitrogen molecules and carbon monoxide, preferably tetrahydrofuran, N, N, N ′, N′-tetramethylethylenediamine, pyridine, dimethylphenylphosphine, and 1,2-bis. (Dimethylphosphino) ethane, 1,2-bis (diethylphosphino) ethane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, acetonitrile, or carbon monoxide is there.

  The group bonded to M or M ′ by π-electrons is a neutral ligand bonded to M or M ′ through multiple bond orbitals, such as olefins such as ethylene and propylene, butadiene, and 2,4-hexadiene. , Dienes such as 1,4-diphenylbutadiene, ketones such as acetone and benzophenone, side-on type nitrogen molecules, and the like, preferably olefins or dienes, more preferably ethylene, butadiene, 2, 4-hexadiene or 1,4-diphenylbutadiene.

  K, o and p in the general formula [1] are each independently an integer of 0 to 5, l is an integer of 2 to 5, m is an integer of 0 to 2, and n is 1 to 3. It is an integer and q is 2 or 3. l, m, n, o, p, and q are r ≧ o + n × q; s ≧ m + n; nxq + o + p ≦ 6, where r and s are group numbers in the periodic table of M and M ′, respectively. It is preferable to select so as to satisfy o + p ≧ 1; m + l ≧ 1; and n + l + m ≦ 6. k is preferably selected so as to satisfy k = t−o + q × (u−m−2n) where the formal oxidation numbers of M and M ′ are t and u, respectively.

M and M ′ in the transition metal compound represented by the general formula [1] are connected by (N ₂ ) _n . The partial structure M (N ₂ ) _n M ′ is, for example, the following structure.

Specific examples of the compound represented by the general formula [1] include dichlorobis {[chlorotetrakis (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chlorotris (trimethylphosphine) (pyridine) tungsten]. ] (mu ₂ - dinitrogen)} titanium, dichlorobis {[chloro tetrakis (triethylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, dichlorobis {[chlorotris (triethylphosphine) (pyridine) tungsten] (mu ₂ - two Nitrogen)} titanium, dichlorobis {[chlorotetrakis (triphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chlorotris (triphenylphosphine) (pyridine) tungsten] (μ ₂ -dinitrogen)} titanium , Dichlorobis {[ Rorotetorakisu (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, dichlorobis {[chlorotris (dimethylphenylphosphine) (pyridine) tungsten] (mu ₂ - dinitrogen)} titanium, dichlorobis {[chloro tetrakis (methyl Diphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chlorotris (methyldiphenylphosphine) (pyridine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chlorobis {1,2-bis ( Dimethylphosphino) ethane} tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chlorobis {1,2-bis (diethylphosphino) ethane} tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[ Chlorobis {1,2-bis ( Phenyl phosphino) ethane} tungsten] (mu ₂ - dinitrogen)} titanium, dichlorobis {[chlorobis {1,3-bis (diphenylphosphino) propane} tungsten] (mu ₂ - dinitrogen)} titanium,

Dichlorobis {[chlorotris (trimethylphosphine) (2,6-dimethylpyridine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chlorotris (triethylphosphine) (2,6-dimethylpyridine) tungsten] (μ ₂ − Dinitrogen)} titanium, dichlorobis {[chlorotris (triphenylphosphine) (2,6-dimethylpyridine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chlorotris (dimethylphenylphosphine) (2,6-dimethyl Pyridine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chlorotris (trimethylphosphine) (quinoline) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chlorotris (triethylphosphine) (quinoline) tungsten] (Μ ₂ -dinitrogen)} titanium, dichlorobis {[chlorotris (triphenylphosphine) (quinoline) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chlorotris (dimethylphenylphosphine) (quinoline) tungsten] (μ _2- dinitrogen)} titanium, dichlorobis {[chloro (tetrahydrofuran) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chloro (tetrahydrofuran) tris (triethylphosphine) tungsten] (μ ₂ − dinitrogen)} titanium, dichlorobis {[chloro (tetrahydrofuran) tris (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, dichlorobis {[chloro (tetrahydrofuran) tris (dimethylphenylphosphine) Tan Sten] (μ ₂ - dinitrogen)} titanium,

Dichlorobis {[chloro (diethylether) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chloro (diethylether) tris (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, Dichlorobis {[chloro (diethyl ether) tris (triphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chloro (diethyl ether) tris (dimethylphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chloro (acetonitrile) tris (trimethylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, dichlorobis {[chloro (acetonitrile) tris (triethylphosphine) tungsten] (mu ₂ - dinitrogen)} inch Emissions, dichlorobis {[chloro (acetonitrile) tris (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, dichlorobis {[chloro (acetonitrile) tris (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen)} Titanium, dichlorobis {[chloro (benzonitrile) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chloro (benzonitrile) tris (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chloro (benzonitrile) tris (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, dichlorobis {[chloro (benzonitrile) tris (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen } Titanium,

Dichlorobis {[chloro (carbonyl) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chloro (carbonyl) tris (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis { [Chloro (carbonyl) tris (triphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[Chloro (carbonyl) tris (dimethylphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis { [Chloro (dimethoxyethane) bis (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chloro (dimethoxyethane) bis (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis { [K B (dimethoxyethane) bis (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, dichlorobis {[chloro (dimethoxyethane) bis (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, dichlorobis {[Chloro (dimethoxyethane) bis (methyldiphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[Chloro (diphenylphosphinoethane) (dimethoxyethane) tungsten] (μ ₂ -dinitrogen)} titanium , Dichlorobis {[chloro (diphenylphosphinopropane) (dimethoxyethane) tungsten] (μ ₂ -dinitrogen)} titanium,

Dichlorobis {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chloro (N, N, N ′, N ′ - tetramethylethylenediamine) bis (triethylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, dichlorobis {[chloro (N, N, N ', N'-tetramethylethylenediamine) bis (triphenyl phosphine) tungsten] ( μ ₂ -dinitrogen)} titanium, dichlorobis {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (dimethylphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, dichlorobis {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (methyldiphenylphosphine) Tungsten] (mu ₂ - dinitrogen)} titanium, dichlorobis {[chloro (N, N, N ', N'-tetramethylethylenediamine) (diphenylphosphino ethane) tungsten] (mu ₂ - dinitrogen)} titanium, dichlorobis {[Chloro (N, N, N ′, N′-tetramethylethylenediamine) (diphenylphosphinopropane) tungsten] (μ ₂ -dinitrogen)} titanium,
These compounds are compounds in which tungsten is changed to molybdenum, chromium, ruthenium, rhodium or palladium, compounds in which titanium is changed to zirconium or hafnium, chloro is fluoro, bromo, iodo, methyl, benzyl, methoxy, phenoxy, azide Transition metal compounds such as compounds changed to groups, cyano groups or isothiocyanate groups.

Also trichlorobis {[chlorotetrakis (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chlorotris (trimethylphosphine) (pyridine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis { [chloro tetrakis (triethylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[chlorotris (triethylphosphine) (pyridine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[chloro tetrakis ( triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[chlorotris (triphenylphosphine) (pyridine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[Kurorote Rakisu (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[chlorotris (dimethylphenylphosphine) (pyridine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[chloro tetrakis ( methyl diphenyl phosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[chlorotris (methyl diphenylphosphine) (pyridine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[chlorobis {1,2 -Bis (dimethylphosphino) ethane} tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chlorobis {1,2-bis (diethylphosphino) ethane} tungsten] (μ ₂ -dinitrogen)} vanadium , Trichlorobis { Chlorobis {1,2-bis (diphenylphosphino) ethane} tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[chlorobis {1,3-bis (diphenylphosphino) propane} tungsten] (mu ₂ - Dinitrogen)} vanadium,

Trichlorobis {[chlorotris (trimethylphosphine) (2,6-dimethylpyridine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chlorotris (triethylphosphine) (2,6-dimethylpyridine) tungsten] (μ _2- dinitrogen)} vanadium, trichlorobis {[chlorotris (triphenylphosphine) (2,6-dimethylpyridine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chlorotris (dimethylphenylphosphine) (2 , 6-dimethylpyridine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chlorotris (trimethylphosphine) (quinoline) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chlorotris (triethylphosphine) ) (Quinoline) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chlorotris (triphenylphosphine) (quinoline) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chlorotris (dimethyl) Phenylphosphine) (quinoline) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (tetrahydrofuran) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (tetrahydrofuran) ) tris (triethylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[chloro (tetrahydrofuran) tris (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[ Lolo (tetrahydrofuran) tris (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium,

Trichlorobis {[chloro (diethylether) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (diethylether) tris (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} Vanadium, trichlorobis {[chloro (diethyl ether) tris (triphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (diethyl ether) tris (dimethylphenylphosphine) tungsten] (μ ₂ − Dinitrogen)} vanadium, trichlorobis {[chloro (acetonitrile) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (acetonitrile) tris (triethylphosphine) ta Ngsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (acetonitrile) tris (triphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (acetonitrile) tris (dimethylphenyl) Phosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (benzonitrile) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (benzonitrile) tris (triethylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[chloro (benzonitrile) tris (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[chloro (Benzonitori ) Tris (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium,

Trichlorobis {[chloro (carbonyl) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (carbonyl) tris (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, Trichlorobis {[chloro (carbonyl) tris (triphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (carbonyl) tris (dimethylphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichloro-bis {[chloro (dimethoxyethane) bis (trimethylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[chloro (dimethoxyethane) bis (triethylphosphine) tungsten] (mu ₂ - two nitrogen )} Vanadium, trichloro-bis {[chloro (dimethoxyethane) bis (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[chloro (dimethoxyethane) bis (dimethylphenylphosphine) tungsten] (mu _2- nitrogen)} vanadium, trichlorobis {[chloro (dimethoxyethane) bis (methyldiphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (diphenylphosphinoethane) (dimethoxyethane) Tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (diphenylphosphinopropane) (dimethoxyethane) tungsten] (μ ₂ -dinitrogen)} vanadium,

Trichlorobis {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (triphenylphosphine) Tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (dimethylphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, Trichlorobis {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis ( Chill diphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, trichloro-bis {[chloro (N, N, N ', N'-tetramethylethylenediamine) (diphenylphosphino ethane) tungsten] (mu ₂ - dinitrogen )} Vanadium, trichlorobis {[chloro (N, N, N ′, N′-tetramethylethylenediamine) (diphenylphosphinopropane) tungsten] (μ ₂ -dinitrogen)} vanadium,
These compounds are compounds in which tungsten is changed to molybdenum, chromium, ruthenium, rhodium or palladium, compounds in which vanadium is changed to niobium or tantalum, chloro is fluoro, bromo, iodo, methyl, benzyl, methoxy, phenoxy, azide Transition metal compounds such as compounds changed to groups, cyano groups or isothiocyanate groups.

In addition, chlorobis {[chlorotetrakis (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chlorotris (trimethylphosphine) (pyridine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chlorotetrakis (Triethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chlorotris (triethylphosphine) (pyridine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chlorotetrakis (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, chlorobis {[chlorotris (triphenylphosphine) (pyridine) tungsten] (mu ₂ - dinitrogen)} vanadium, chlorobis {[chloro tetrakis (dimethyl phenylene Phosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, chlorobis {[chlorotris (dimethylphenylphosphine) (pyridine) tungsten] (mu ₂ - dinitrogen)} vanadium, chlorobis {[chloro tetrakis (methyl diphenyl phosphine) tungsten] (Μ ₂ -dinitrogen)} vanadium, chlorobis {[chlorotris (methyldiphenylphosphine) (pyridine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chlorobis {1,2-bis (dimethylphosphino) ethane } Tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chlorobis {1,2-bis (diethylphosphino) ethane} tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chlorobis {1,2 -Bis (diphenylphosphino Ethane} tungsten] (mu ₂ - dinitrogen)} vanadium, chlorobis {[chlorobis {1,3-bis (diphenylphosphino) propane} tungsten] (mu ₂ - dinitrogen)} vanadium,

Chlorobis {[chlorotris (trimethylphosphine) (2,6-dimethylpyridine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chlorotris (triethylphosphine) (2,6-dimethylpyridine) tungsten] (μ ₂ − Dinitrogen)} vanadium, chlorobis {[chlorotris (triphenylphosphine) (2,6-dimethylpyridine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chlorotris (dimethylphenylphosphine) (2,6-dimethyl Pyridine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chlorotris (trimethylphosphine) (quinoline) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chlorotris (triethylphosphine) (quinoline) tongue Sten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chlorotris (triphenylphosphine) (quinoline) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chlorotris (dimethylphenylphosphine) (quinoline) tungsten] (Μ ₂ -dinitrogen)} vanadium, chlorobis {[chloro (tetrahydrofuran) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chloro (tetrahydrofuran) tris (triethylphosphine) tungsten] (μ ₂ - dinitrogen)} vanadium, chlorobis {[chloro (tetrahydrofuran) tris (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, chlorobis {[chloro (tetrahydrofuran) tris (dimethyl Fe Le phosphine) tungsten] (μ ₂ - dinitrogen)} vanadium,

Chlorobis {[chloro (diethylether) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chloro (diethylether) tris (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, Chlorobis {[chloro (diethylether) tris (triphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chloro (diethylether) tris (dimethylphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chloro (acetonitrile) tris (trimethylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, chlorobis {[chloro (acetonitrile) tris (triethylphosphine) tungsten] (mu ₂ - two nitrogen )} Vanadium, chlorobis {[chloro (acetonitrile) tris (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, chlorobis {[chloro (acetonitrile) tris (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen )} Vanadium, chlorobis {[chloro (benzonitrile) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chloro (benzonitrile) tris (triethylphosphine) tungsten] (μ ₂ -dinitrogen) )} vanadium, chlorobis {[chloro (benzonitrile) tris (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, chlorobis {[chloro (benzonitrile) tris (dimethylphenylphosphine) tungsten Down] (μ ₂ - dinitrogen)} vanadium,

Chlorobis {[chloro (carbonyl) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chloro (carbonyl) tris (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis { [Chloro (carbonyl) tris (triphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[Chloro (carbonyl) tris (dimethylphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis { [chloro (dimethoxyethane) bis (trimethylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, chlorobis {[chloro (dimethoxyethane) bis (triethylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, chloro Scan {[chloro (dimethoxyethane) bis (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, chlorobis {[chloro (dimethoxyethane) bis (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen)} Vanadium, chlorobis {[chloro (dimethoxyethane) bis (methyldiphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, trichlorobis {[chloro (diphenylphosphinoethane) (dimethoxyethane) tungsten] (μ ₂ -2 Nitrogen)} vanadium, chlorobis {[chloro (diphenylphosphinopropane) (dimethoxyethane) tungsten] (μ ₂ -dinitrogen)} vanadium,

Chlorobis {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chloro (N, N, N ′, N ′ - tetramethylethylenediamine) bis (triethylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, chlorobis {[chloro (N, N, N ', N'-tetramethylethylenediamine) bis (triphenyl phosphine) tungsten] ( μ ₂ -dinitrogen)} vanadium, chlorobis {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (dimethylphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, chlorobis {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (methyldiphenylphos Fin) tungsten] (mu ₂ - dinitrogen)} vanadium, chlorobis {[chloro (N, N, N ', N'-tetramethylethylenediamine) (diphenylphosphino ethane) tungsten] (mu ₂ - dinitrogen)} Vanadium, chlorobis {[chloro (N, N, N ′, N′-tetramethylethylenediamine) (diphenylphosphinopropane) tungsten] (μ ₂ -dinitrogen)} vanadium,
These compounds are compounds in which tungsten is changed to molybdenum, chromium, ruthenium, rhodium or palladium, compounds in which vanadium is changed to vanadyl or scandium, chloro is fluoro, bromo, iodo, methyl, benzyl, methoxy, phenoxy, azide Transition metal compounds such as compounds changed to groups, cyano groups or isothiocyanate groups.

Furthermore, specific examples of the compound containing four transition metal atoms represented by the general formula [1] include chlorotris {[chlorotetrakis (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chlorotris (Trimethylphosphine) (pyridine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chlorotetrakis (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chlorotris (triethylphosphine) (pyridine ) Tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chlorotetrakis (triphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chlorotris (triphenylphosphine) (pyridine) tungsten] ( μ ₂ - two nitrogen )} Titanium, chlorotris {[chloro tetrakis (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, chlorotris {[chlorotris (dimethylphenylphosphine) (pyridine) tungsten] (mu ₂ - dinitrogen)} titanium, Chlorotris {[chlorotetrakis (methyldiphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chlorotris (methyldiphenylphosphine) (pyridine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chlorobis {1,2-bis (dimethylphosphino) ethane} tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chlorobis {1,2-bis (diethylphosphino) ethane} tungsten] (μ ₂ -dinitrogen) )} Titanium, Chlorotris [Chlorobis {1,2-bis (diphenylphosphino) ethane} tungsten] (mu ₂ - dinitrogen)} titanium, chlorotris {[chlorobis {1,3-bis (diphenylphosphino) propane} tungsten] (mu ₂ - Dinitrogen)} titanium,

Chlorotris {[chlorotris (trimethylphosphine) (2,6-dimethylpyridine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chlorotris (triethylphosphine) (2,6-dimethylpyridine) tungsten] (μ ₂ − Dinitrogen)} titanium, chlorotris {[chlorotris (triphenylphosphine) (2,6-dimethylpyridine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chlorotris (dimethylphenylphosphine) (2,6-dimethyl Pyridine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chlorotris (trimethylphosphine) (quinoline) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chlorotris (triethylphosphine) (quinoline) tungsten] (Μ ₂ -dinitrogen)} titanium, chlorotris {[chlorotris (triphenylphosphine) (quinoline) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chlorotris (dimethylphenylphosphine) (quinoline) tungsten] (μ _2- dinitrogen)} titanium, chlorotris {[chloro (tetrahydrofuran) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chloro (tetrahydrofuran) tris (triethylphosphine) tungsten] (μ ₂ − dinitrogen)} titanium, chlorotris {[chloro (tetrahydrofuran) tris (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, chlorotris {[chloro (tetrahydrofuran) tris (dimethylphenylphosphine) Tan Sten] (μ ₂ - dinitrogen)} titanium,

Chlorotris {[chloro (diethylether) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chloro (diethylether) tris (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, Chlorotris {[Chloro (diethylether) tris (triphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[Chloro (diethylether) tris (dimethylphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chloro (acetonitrile) tris (trimethylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, chlorotris {[chloro (acetonitrile) tris (triethylphosphine) tungsten] (mu ₂ - dinitrogen)} inch Emissions, chlorotris {[chloro (acetonitrile) tris (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, chlorotris {[chloro (acetonitrile) tris (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen)} Titanium, chlorotris {[chloro (benzonitrile) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chloro (benzonitrile) tris (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chloro (benzonitrile) tris (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, chlorotris {[chloro (benzonitrile) tris (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen } Titanium,

Chlorotris {[chloro (carbonyl) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chloro (carbonyl) tris (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris { [Chloro (carbonyl) tris (triphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[Chloro (carbonyl) tris (dimethylphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris { [Chloro (dimethoxyethane) bis (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[Chloro (dimethoxyethane) bis (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris { [K B (dimethoxyethane) bis (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, chlorotris {[chloro (dimethoxyethane) bis (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, chlorotris {[Chloro (dimethoxyethane) bis (methyldiphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[Chloro (diphenylphosphinoethane) (dimethoxyethane) tungsten] (μ ₂ -dinitrogen)} titanium Chlorotris {[chloro (diphenylphosphinopropane) (dimethoxyethane) tungsten] (μ ₂ -dinitrogen)} titanium,

Chlorotris {[Chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[Chloro (N, N, N ′, N ′ - tetramethylethylenediamine) bis (triethylphosphine) tungsten] (mu ₂ - dinitrogen)} titanium, chlorotris {[chloro (N, N, N ', N'-tetramethylethylenediamine) bis (triphenyl phosphine) tungsten] ( μ ₂ -dinitrogen)} titanium, chlorotris {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (dimethylphenylphosphine) tungsten] (μ ₂ -dinitrogen)} titanium, chlorotris {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (methyldiphenylphosphine) Tungsten] (mu ₂ - dinitrogen)} titanium, chlorotris {[chloro (N, N, N ', N'-tetramethylethylenediamine) (diphenylphosphino ethane) tungsten] (mu ₂ - dinitrogen)} titanium, chlorotris {[Chloro (N, N, N ′, N′-tetramethylethylenediamine) (diphenylphosphinopropane) tungsten] (μ ₂ -dinitrogen)} titanium,
These compounds are compounds in which tungsten is changed to molybdenum, chromium, ruthenium, rhodium or palladium, compounds in which titanium is changed to zirconium or hafnium, chloro is fluoro, bromo, iodo, methyl, benzyl, methoxy, phenoxy, azide Transition metal compounds such as compounds changed to groups, cyano groups or isothiocyanate groups.

Also, dichlorotris {[chlorotetrakis (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chlorotris (trimethylphosphine) (pyridine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris { [chloro tetrakis (triethylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chlorotris (triethylphosphine) (pyridine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chloro tetrakis ( triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chlorotris (triphenylphosphine) (pyridine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[Kurorote Rakisu (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chlorotris (dimethylphenylphosphine) (pyridine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chloro tetrakis ( methyl diphenyl phosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chlorotris (methyl diphenylphosphine) (pyridine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chlorobis {1,2 -Bis (dimethylphosphino) ethane} tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chlorobis {1,2-bis (diethylphosphino) ethane} tungsten] (μ ₂ -dinitrogen)} vanadium , Dichlorotris { Chlorobis {1,2-bis (diphenylphosphino) ethane} tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chlorobis {1,3-bis (diphenylphosphino) propane} tungsten] (mu ₂ - Dinitrogen)} vanadium,

Dichlorotris {[chlorotris (trimethylphosphine) (2,6-dimethylpyridine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chlorotris (triethylphosphine) (2,6-dimethylpyridine) tungsten] (μ _2- dinitrogen)} vanadium, dichlorotris {[chlorotris (triphenylphosphine) (2,6-dimethylpyridine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chlorotris (dimethylphenylphosphine) (2 , 6-dimethylpyridine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chlorotris (trimethylphosphine) (quinoline) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chlorotris (triethylphosphine ) (Quinoline) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chlorotris (triphenylphosphine) (quinoline) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chlorotris (dimethyl) Phenylphosphine) (quinoline) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chloro (tetrahydrofuran) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chloro (tetrahydrofuran) ) tris (triethylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chloro (tetrahydrofuran) tris (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris [click B (tetrahydrofuran) tris (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium,

Dichlorotris {[Chloro (diethylether) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[Chloro (diethylether) tris (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} Vanadium, dichlorotris {[chloro (diethylether) tris (triphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chloro (diethylether) tris (dimethylphenylphosphine) tungsten] (μ ₂ − Dinitrogen)} vanadium, dichlorotris {[chloro (acetonitrile) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chloro (acetonitrile) tris (triethylphosphine) ta Ngsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chloro (acetonitrile) tris (triphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chloro (acetonitrile) tris (dimethylphenyl) Phosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chloro (benzonitrile) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chloro (benzonitrile) tris (triethylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chloro (benzonitrile) tris (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chloro (Benzonitori ) Tris (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium,

Dichlorotris {[chloro (carbonyl) tris (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chloro (carbonyl) tris (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, Dichlorotris {[Chloro (carbonyl) tris (triphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[Chloro (carbonyl) tris (dimethylphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichloro-tris {[chloro (dimethoxyethane) bis (trimethylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chloro (dimethoxyethane) bis (triethylphosphine) tungsten] (mu ₂ - two nitrogen )} Vanadium, dichloro-tris {[chloro (dimethoxyethane) bis (triphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chloro (dimethoxyethane) bis (dimethylphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chloro (dimethoxyethane) bis (methyl diphenyl phosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chloro (diphenylphosphinoethane) (dimethoxyethane) Tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chloro (diphenylphosphinopropane) (dimethoxyethane) tungsten] (μ ₂ -dinitrogen)} vanadium,

Dichlorotris {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (trimethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (triethylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (triphenylphosphine) Tungsten] (μ ₂ -dinitrogen)} vanadium, dichlorotris {[chloro (N, N, N ′, N′-tetramethylethylenediamine) bis (dimethylphenylphosphine) tungsten] (μ ₂ -dinitrogen)} vanadium, Dichlorotris {[Chloro (N, N, N ′, N′-tetramethylethylenediamine) bis ( Chill diphenylphosphine) tungsten] (mu ₂ - dinitrogen)} vanadium, dichloro-tris {[chloro (N, N, N ', N'-tetramethylethylenediamine) (diphenylphosphino ethane) tungsten] (mu ₂ - dinitrogen )} Vanadium, dichlorotris {[chloro (N, N, N ′, N′-tetramethylethylenediamine) (diphenylphosphinopropane) tungsten] (μ ₂ -dinitrogen)} vanadium,
These compounds are compounds in which tungsten is changed to molybdenum, chromium, ruthenium, rhodium or palladium, compounds in which vanadium is changed to niobium or tantalum, chloro is fluoro, bromo, iodo, methyl, benzyl, methoxy, phenoxy, azide Transition metal compounds such as compounds changed to groups, cyano groups or isothiocyanate groups.

  In addition, these transition metal compounds include tetrahydrofuran, diethyl ether, dimethoxyethane, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, pyridine, 2,6-dimethylpyridine, trimethylphosphine, triphenylphosphine, dimethylphenyl. Compounds such as phosphine, acetonitrile, benzonitrile and carbon monoxide may be coordinated.

The transition metal compound of the present invention is suitably used as a catalyst component for addition polymerization. The addition polymerization catalyst using the transition metal compound of the present invention is obtained by bringing the transition metal compound of the present invention (hereinafter referred to as component (A)) into contact with the activating cocatalyst component. Preferably, the activating cocatalyst component is preferably the following component (B) and / or the following component (C).
(B): One or more aluminum compounds selected from the following (B1) to (B3) (B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) General formula {-Al (E ² ) -O-} cyclic aluminoxane having a structure represented by _b (B3) a linear aluminoxane having a structure represented by the general formula E ³ {-Al (E ³ ) -O—} _c AlE ³ ₂ (the above ( In B1) to (B3), a represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, c represents an integer of 1 or more, and E ¹ , E ^2, and E ³ are carbonized. It represents a hydrogen group, if E ¹ is more, each E ¹ may be different be the same as each other. in addition, E ² each may be different, even the same as each other, respectively E ³ is optionally different from one another identical .Z represents a hydrogen atom or Ha It represents a Gen atom, if Z is a plurality, Z each may be different, even the same as each other.)
(C): One or more boron compounds selected from the following (C1) to (C3) (C1) Boron compounds represented by the general formula BQ ¹ Q ² Q ³ (C2) General formula G ⁺ (BQ ⁴ Q ⁵ Boron compound represented by Q ⁶ Q ⁷ ) ^- (C3) Boron compound represented by general formula (L-H) ⁺ (BQ ⁸ Q ⁹ Q ¹⁰ Q ¹¹ ) ^- (in the above (C1) to (C3) , B represents a trivalent boron atom, Q ^{1 to} Q ¹¹ represent a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, and Q ^{1 to} Q ¹¹ represent G ⁺ represents an inorganic or organic cation, L represents a neutral Lewis base, and (L—H) ⁺ represents a Bronsted acid.

In the general formula E ¹ _a AlZ _3-a of (B1), E ¹ is a hydrocarbon group, preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl having 1 to 8 carbon atoms. When there are a plurality of E ¹ groups, each E ¹ may be the same as or different from each other. Z is a hydrogen atom or a halogen atom, and when there are a plurality of Z, each Z may be the same as or different from each other. a is a number satisfying 0 <a ≦ 3, and preferably 2 or 3.

Specific examples of (B1) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexyl. Dialkylaluminum chlorides such as aluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum hydride, dipropiol Aluminum hydride, diisobutylaluminum hydride, there can be mentioned dialkyl aluminum hydride such as dihexyl aluminum hydride.
Trialkylaluminum is preferable, and triethylaluminum or triisobutylaluminum is more preferable.

In the general formula {—Al (E ² ) —O—} _b of (B2), E ² is a hydrocarbon group, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal Examples of the alkyl group include a pentyl group and a neopentyl group, and a methyl group or an isobutyl group is preferable. Each E ² may be the same as or different from each other. Moreover, b is an integer greater than or equal to 2, Preferably b is an integer of 2-40.

In general formula E ³ {-Al (E ³ ) —O—} _c AlE ³ ₂ in (B3), E ³ is a hydrocarbon group, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group. An alkyl group such as an isobutyl group, a normal pentyl group, or a neopentyl group can be exemplified, and a methyl group or an isobutyl group is preferable. Each E ³ may be the same as or different from each other. C is an integer of 1 or more, and preferably c is an integer of 1 to 40.

  There is no restriction | limiting in particular about the manufacturing method of (B2) and (B3), A well-known method is used. For example, a method in which a solution in which a trialkylaluminum (such as trimethylaluminum) is dissolved in an appropriate organic solvent (such as benzene or aliphatic hydrocarbon) is contacted with water, or a metal salt (copper sulfate) containing crystal water Examples thereof include a method of producing a product by bringing a hydrate and the like into contact with a trialkylaluminum (such as trimethylaluminum).

In the general formula BQ ¹ Q ² Q ³ of (C1), B is a trivalent boron atom, and Q ^{1 to} Q ³ are halogen atoms, hydrocarbon groups (including halogenated hydrocarbon groups), substituted silyl groups , An alkoxy group or a disubstituted amino group, and Q ^{1 to} Q ³ may be the same or different. In Q ^{1 to} Q ³ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-butyl group, a sec-butyl group, Phenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 2,6-di-tert-butylphenyl group, 2,4,6-trimethylphenyl group, trifluoromethyl group, 2,3,4, Examples include 5,6-pentafluorophenyl group and 2,6-bis (trifluoromethyl) phenyl group. The substituted silyl group is a silyl group substituted with a hydrocarbon group, and examples thereof include a trimethylsilyl group and a triethylsilyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a t-butoxy group. The disubstituted amino group is an amino group substituted with two hydrocarbon groups, and examples thereof include a dimethylamino group and a diethylamino group. Q ^{1 to} Q ³ are preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 2 to 2 carbon atoms. 20 is an amino group, more preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and further preferably a fluorinated hydrocarbon having 1 to 20 carbon atoms having at least one fluorine atom. And particularly preferably a fluorinated aryl group having 6 to 20 carbon atoms and having at least one fluorine atom.

  Specific examples of (C1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane, and tris. (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane and the like are mentioned, but most preferably, tris (pentafluorophenyl) ) Borane.

In the general formula G ⁺ (BQ ⁴ Q ⁵ Q ⁶ Q ⁷ ) ⁻ of (C2), B is a trivalent boron atom, and Q ^{4 to} Q ⁷ are each a halogen atom or a hydrocarbon group (halogenated hydrocarbon group). A substituted silyl group, an alkoxy group or a disubstituted amino group, and Q ^{4 to} Q ⁷ may be the same or different. Specific examples of Q ^{4 to} Q ⁷ include those described as specific examples of Q ^{1 to} Q ³ in (C1) above. Preferred groups of Q ^{4 to} Q ⁷ include the above (C1 ) In Q ^{1 to} Q ³ can be mentioned. Specific examples of (BQ ⁴ Q ⁵ Q ⁶ Q ⁷ ) ⁻ include tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5). -Tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis [3 5-bis (trifluoromethyl) phenyl] borate and the like. G ⁺ is an inorganic or organic cation. Examples of the inorganic cation include ferrocenium cation, alkyl-substituted ferrocenium cation, and silver cation. Examples of the organic cation include triphenylmethyl cation. . G ⁺ is preferably a carbenium cation, particularly preferably a triphenylmethyl cation.

  Specific examples of the component (C2) include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylmethyl. Examples thereof include tetrakis (pentafluorophenyl) borate and triphenylmethyltetrakis [3,5-bis (trifluoromethyl) phenyl] borate, and preferably triphenylcarbenium tetrakis (pentafluorophenyl) borate (triphenyl). Methyl tetrakis (pentafluorophenyl) borate).

In the general formula (LH) ⁺ (BQ ⁸ Q ⁹ Q ¹⁰ Q ¹¹ ) ⁻ of (C3), B is a trivalent boron atom, and Q ^{8 to} Q ¹¹ are each a halogen atom or a hydrocarbon group (halogen) A substituted silyl group, an alkoxy group, or a disubstituted amino group, and Q ^{4 to} Q ⁷ may be the same or different. Specific examples of Q ^{8 to} Q ¹¹ include those described as specific examples of Q ^{1 to} Q ³ in (C1) above. Preferred groups of Q ^{8 to} Q ¹¹ include the above (C1 ) In Q ^{1 to} Q ³ can be mentioned. Specific examples of (BQ ⁸ Q ⁹ Q ¹⁰ Q ¹¹ ) ⁻ include those described as specific examples of (BQ ⁴ Q ⁵ Q ⁶ Q ⁷ ) ^{− in} the above component (C2). Preferable groups for ⁸ Q ⁹ Q ¹⁰ Q ¹¹ ) ⁻ include those described as the preferred groups for (BQ ⁴ Q ⁵ Q ⁶ Q ⁷ ) ^{− in} the above component (C2). L is a neutral Lewis base, (LH) ⁺ is a Bronsted acid, and specific examples of the Bronsted acid include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, And triarylphosphonium.

  Specific examples of the component (C3) include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n- Butyl) ammonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N , N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate Diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) Phosphonium tetrakis (pentafluorophenyl) borate and the like, preferably tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate is there.

  When a compound obtained by bringing the component (A) and the component (B) into contact with each other as a catalyst for addition polymerization using the transition metal compound of the present invention, the component (B) includes (B2) and / or (B3) is preferred. Moreover, when using the compound obtained by making a component (A), a component (B), and a component (C) contact, (B1) is easy to use as a component (B).

  As a method of bringing the component (A) into contact with the component (B) and / or the component (C), the component (A) is brought into contact with the component (B) and / or the component (C), and the addition polymerization catalyst is used. As long as it is formed, any means may be used. A method in which the component (A) and the component (B) and / or the component (C) are mixed and brought into contact with each other after being diluted with a solvent in advance or not, or separately. The method of supplying to a polymerization tank and making it contact in a polymerization tank can be taken. Here, the component (A) to the component (C) may be used in combination of a plurality of types of compounds, respectively, but some of them may be mixed in advance or used separately. You may use by supplying to a tank.

  As the usage ratio of the component (A) to the component (C), [number of moles of Al atom contained in component (B)] / [number of moles of metal atom M contained in component (A)] is preferably 0. 0.1 to 10000, more preferably 5 to 2000, and [number of moles of component (C)] / [number of moles of metal atom M contained in component (A)] is preferably 0.01 to 100. More preferably, it is 0.5-10.

  The concentration of each component when the component (A) to the component (C) are used in a solution state, a state suspended in a solvent, or a slurry state depends on conditions such as the performance of an apparatus for supplying each component to the polymerization reactor. It is selected appropriately. In general, the concentration of the component (A) is usually 0.001 to 200 mmol / liter, more preferably 0.001 to 100 mmol / liter, in terms of the molar concentration of the metal atom M contained in the component (A), More preferably, it is 0.05-50 mmol / liter. The concentration of the component (B) is usually 0.01 to 5000 mmol / liter, more preferably 0.1 to 2500 mmol / liter, more preferably in terms of the molar concentration of Al atoms contained in the component (B). Is 0.1 to 2000 mmol / liter. The density | concentration of a component (C) is 0.001-500 mmol / liter normally, More preferably, it is 0.01-250 mmol / liter, More preferably, it is 0.05-100 mmol / liter.

  An addition polymer is produced by using the catalyst for addition polymerization using the transition metal compound of the present invention for polymerization of an addition polymerizable unsaturated monomer. Examples of the addition polymerizable unsaturated monomer include olefins, dienes, alicyclic vinyl compounds, vinyl aromatic hydrocarbons, and the like.

  Examples of the olefin include linear olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene; 3-methyl-1-butene Branched olefins such as 3-methyl-1-pentene, 4-methyl-1-pentene, and 5-methyl-1-hexene, and olefins having 2 to 20 carbon atoms are preferable. These may be used alone or in combination of two or more. Examples of the combination of olefins when two or more are used include, for example, ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, and ethylene and 1-octene. Propylene and 1-butene.

  Examples of the diene include conjugated dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene; dicyclopentadiene, Non-conjugated dienes such as 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5-dicyclooctadiene, 7-methyl-1,6-octadiene, 5-vinyl-2-norbornene, etc. A diene having 4 to 20 carbon atoms is preferred. These may be used alone or in combination of two or more.

  Examples of the alicyclic vinyl compound include vinylcyclopentane, vinylcyclohexane, and vinylcycloheptane. These may be used alone or in combination of two or more.

  Examples of the addition polymer produced by the addition polymerization catalyst of the present invention include ethylene homopolymer, propylene homopolymer, 1-butene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, Ethylene-1-hexene copolymer, propylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer, ethylene-propylene-5-ethylidene-2- Norbornene copolymer, ethylene-propylene-5-vinyl-2-norbornene copolymer, styrene-ethylene copolymer, styrene-propylene copolymer, styrene-2-methyl-1,3-butadiene copolymer, vinyl Examples thereof include a cyclohexane homopolymer and an ethylene-vinylcyclohexane copolymer.

  There are no particular limitations on the method for producing the addition polymer using the catalyst for addition polymerization using the transition metal compound of the present invention. For example, the gas phase polymerization method, the bulk polymerization method, the solution polymerization method using an appropriate solvent, Any method such as a slurry polymerization method can be used. When a solvent is used, various solvents can be used under the condition that the catalyst is not deactivated. Examples of such solvents include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane; benzene, toluene Aromatic hydrocarbons such as; halogenated hydrocarbons such as methylene dichloride. In these production methods, either continuous polymerization or batch polymerization may be used.

  There is no restriction | limiting in particular about the polymerization temperature at the time of addition polymerization, Usually, it is -50-300 degreeC, Preferably it is -20-200 degreeC. Moreover, there is no restriction | limiting in particular about superposition | polymerization pressure, Usually, it is 6 MPa or less. The polymerization time is appropriately determined depending on the kind of the target addition polymer and the reaction apparatus, and is usually 1 minute to 20 hours. In the polymerization, a chain transfer agent such as hydrogen may be used to adjust the molecular weight of the addition polymer.

Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to these.
The properties of the polymers in the examples were measured by the following methods.

(1) Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn): Measured by gel permeation chromatography (GPC) under the following conditions. A calibration curve was prepared using standard polystyrene. The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
Model Millipo Outers 150CV type column Shodex M / S 80
Measurement temperature 145 ° C, solvent orthodichlorobenzene,
Sample concentration 5mg / 8ml

(2) Content of repeating structural unit derived from α-olefin in copolymer of ethylene and α-olefin: using infrared spectrophotometer (IR-810, manufactured by JASCO Corporation), ethylene and α -It calculated | required from the characteristic absorption of the olefin, and represented it as the number of short chain branches (SCB) per 1000 carbons.

(3) Melting | fusing point of polymer It calculated | required on condition of the following using Seiko SSC-5200.
Temperature rise: 40 ° C to 150 ° C (10 ° C / min), hold for 5 minutes Cooling: 150 ° C to 10 ° C (5 ° C / min), hold for 10 minutes Measurement: 10 ° C to 160 ° C (5 ° C / min)

¹H NMR (C₆D₆) δ: -2.2 (W-CH₃, m, 6H), 0.1 (T-CH₃, s, 6H), 1.0 (m, 48H), 1.3 (m, 32H), 1.5 (m, 8H), 2.1 (m, 8H)． [Example 1]
(1) Synthesis of dimethylbis {[methylbis (diethylphosphinoethane) tungsten] (μ ₂ -dinitrogen)} titanium;
All operations were performed under a nitrogen atmosphere. The raw material complex [chlorobis (diethylphosphinoethane) tungsten] (μ ₂ -dinitrogen) [dichloro (cyclopentadienyl) titanium] was synthesized according to a known method (Japanese Patent Laid-Open No. 2002-206004). Methyl lithium in diethyl ether was purchased from Kanto Chemical. Dehydrated solvents (tetrahydrofuran and hexane) were purchased from Kanto Chemical and used after degassing.
114 mg (0.17 mmol) of [chlorobis (diethylphosphinoethane) tungsten] (μ ₂ -dinitrogen) [dichloro (cyclopentadienyl) titanium] was dissolved in 5 ml of tetrahydrofuran and cooled to −78 ° C. Methyl lithium in diethyl ether (1.02 mol / L, 0.93 ml; 0.95 mmol) was added dropwise, and the mixture was stirred at -78 ° C for 1 hour, then returned to room temperature and further stirred for 1 hour, and then the solvent was distilled off. A black solid was obtained. The black solid was extracted with n-hexane, and the obtained extract was recrystallized using an n-hexane solvent to obtain 39.6 mg of black brown plate-like crystals. Yield 34%.

¹ H NMR (C ₆ D ₆ ) δ: -2.2 (W-CH ₃ , m, 6H), 0.1 (T-CH ₃ , s, 6H), 1.0 (m, 48H), 1.3 (m, 32H), 1.5 (m, 8H), 2.1 (m, 8H).

(2) polymerization;
An autoclave with a stirrer having an internal volume of 0.4 liter was vacuum-dried and replaced with argon. Then, 198 ml of toluene was charged as a solvent, 2 ml of 1-hexene was charged as an α-olefin, and the reactor was heated to 60 ° C. After the temperature rise, the feed was carried out while adjusting the ethylene pressure to 0.6 MPa. After the system was stabilized, 0.25 mmol of triisobutylaluminum was added, followed by [chlorobis (diethylphosphinoethane) tungsten] (μ ₂ − Dinitrogen) [dichloro (cyclopentadienyl) titanium] 0.025 μmol was added, and subsequently also called triphenylmethyltetrakis (pentafluorophenyl) borate ([triphenylcarbenium] [tetrakis (pentafluorophenyl) borate]. .) 1.0 μmol was charged. Polymerization was carried out for 60 minutes while adjusting the temperature to 60 ° C.
As a result of polymerization, a copolymer of ethylene and 1-hexene having SCB = 17.9, M _w = 2.9 × 10 ⁵ , M _w / M _n = 3.2, and a melting point of 110.0 ° C. 1.2 × 10 ⁶ g was produced per hour per 1 mol of the complex.

Claims (7)

A transition metal compound represented by the following general formula [1].
(L _p X _o M) [(N ₂ ) _n M′X ′ _m L ′ _l ] _q X ″ _k [1]
(In the formula, M and M ′ each independently represent a transition metal atom of Groups 3 to 10 of the periodic table of elements, and X and X ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an aralkyl group. An aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, a disubstituted amino group, an azide group, a cyano group, an isothiocyanate group, an oxo group or a group having a cyclopentadiene type anion skeleton, and L and L ′ each independently represents a group bonded to M or M ′ by a lone pair or π electron. X ″ is a counter anion, k, o and p are each independently an integer of 0 to 5; Is an integer of 2 to 5, m is an integer of 0 to 2, n is an integer of 1 to 3, and q is 2 or 3.)   The transition metal compound according to claim 1, wherein M is a group 3-5 transition metal atom.   The transition metal compound according to claim 1 or 2, wherein M 'is a group 6-10 transition metal atom.   The transition metal compound according to claim 1, wherein l is 4, m is 1, and q is 2.   A catalyst component for addition polymerization comprising the transition metal compound according to any one of claims 1 to 4. The catalyst for addition polymerization obtained by making the transition metal compound (A) in any one of Claims 1-4 and the following (B) and / or the following (C) contact.
(B): One or more aluminum compounds selected from the following (B1) to (B3) (B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) General formula {-Al (E ² ) -O-} cyclic aluminoxane having a structure represented by _b (B3) a linear aluminoxane having a structure represented by the general formula E ³ {-Al (E ³ ) -O—} _c AlE ³ ₂ (the above ( In B1) to (B3), a represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, c represents an integer of 1 or more, and E ¹ , E ^2, and E ³ are carbonized. It represents a hydrogen group, if E ¹ is more, each E ¹ may be different be the same as each other. in addition, E ² each may be different, even the same as each other, respectively E ³ is optionally different from one another identical .Z represents a hydrogen atom or Ha It represents a Gen atom, if Z is a plurality, Z each may be different, even the same as each other.)
(C): one or more boron compounds selected from the following (C1) to (C3) (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ ,
(C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^-
(C3) A boron compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (in the above (C1) to (C3), B represents a trivalent boron atom, ¹ to Q ¹¹ represents a halogen atom, a hydrocarbon group, halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, Q ¹ to Q ¹¹ good be different even in the same .G ⁺ Represents an inorganic or organic cation, L represents a neutral Lewis base, and (LH) ⁺ represents a Bronsted acid.) A method for producing an addition polymer, which comprises addition polymerization of an addition polymerizable unsaturated monomer using the addition polymerization catalyst according to claim 6.