Transition metal compound, coordinative compound, catalyst for polymerization of olefin, and process for polymerization of olefin using the catalyst

Abstract

A transition metal compound having a ligand with an azaferrocene structure or a ferrocene structure. The transition metal compound is used in combination with an activating cocatalyst, as a catalyst for polymerization of olefins.

1 - 12 . (canceled)  
     
     
         13 . A process for polymerization of an olefin, which comprises polymerizing an olefin in the present of a catalyst comprising a transition metal compound selected from the group consisting of a first transition metal compound, a second transition metal compound, a third transition metal compound and a fourth transition metal compound, 
 wherein the first transition metal compound is represented by the following formula (1):                          wherein M represents a transition metal atom selected from the group consisting of metal atoms of group 3 to group 12 of the periodic table;    X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxygroup having 1 to 20 carbon atoms, an amino group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, a sulfonate group having an organic residue with 1 to 20 carbon atoms, or a non-coordinative anion containing an element selected from the group consisting of B, Al, P and Sb, and, when q is an integer of at least 2, Xs may be the same as or different from each other;    A represents a carbon atom, a nitrogen atom or a phosphorus atom;    R 1  represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing at least one halogen atom, or a ferrocenyl group or a substituted ferrocenyl group;    R 2  represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of halogen, silicon, nitrogen, oxygen and sulfur atoms, or a ferrocenyl group or a substituted ferrocenyl group; and R and R may form together a ring;    Q represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, an amino group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, an oxy group having a hydrocarbon group with 1 to 20 carbon atoms, a thio group having a hydrocarbon group with 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur atoms, or oxygen or sulfur; and, when Q contains a coordinative atom, Q can be coordinatively bound to M;    R 3  represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of nitrogen, oxygen, halogen and sulfur atoms and one of R 3 s adjacent to Q may form a ring together with Q; and, when m is an integer of at least 2, R 3 s may be the same as or different from each other, and adjacent R 3 s may form together a ring;    R 4  represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, an oxy group having a hydrocarbon group with 1 to 20 carbon atoms, a thio group having a hydrocarbon group with 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of nitrogen, phosphorus, oxygen, halogen and sulfur atoms; and, when n is an integer of at least 2, R 4 s may be the same as or different from each other, and adjacent R 4 s may form together a ring; and R 3  and R 4  may form together a ring; and, when R 4  contains a heteroatom, R 4  can coordinate with the transision metal atom M;    L is a coordinate bond-forming compound selected from the group consisting of J electron, ethers, nitrites, amines and phosphines, and L may be bound to X;    m is an integer of 1 to 3, n is an integer of 1 to 5, and p is an integer of 0 or 1;    when Q is sulfur or oxygen, the bond between Q and M is a sigma bond;    when p is 0 and A is a nitrogen atom or a phosphorus atom, A can be coordinatively bound to M; and    q is an integer of 1 to 3 and r is an integer of 0 to 3,    wherein the second transition metal compound is represented by the following formula (2):                          wherein M represents a transition metal atom selected from the group consisting of metal atoms of group 3 to group 12 of the periodic table;    X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a sulfonate group having an organic residue with 1 to 20 carbon atoms, or a non-coordinative anion containing an element selected from the group consisting of B, Al, P and Sb, and, when q is an integer of at least 2, Xs may be the same as or different from each other;    R 1  represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing at least one halogen atom, or a ferrocenyl group or a substituted ferrocenyl group;    R 2  represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of halogen, silicon, nitrogen, oxygen and sulfur atoms, or a ferrocenyl group or a substituted ferrocenyl group; and R and R may form together a ring;    R 3  represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of nitrogen, oxygen, halogen and sulfur atoms and, when m is an integer of at least 2, R 3 s may be the same as or different from each other, and adjacent R 3 s may form together a ring;    R 4  represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, an oxy group having a hydrocarbon group with 1 to 20 carbon atoms, a thio group having a hydrocarbon group with 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of nitrogen, phosphorus, oxygen, halogen and sulfur atoms; and, when n is an integer of at least 2, R 4 s may be the same as or different from each other, and adjacent R 4 s may form together a ring; and R 3  and R 4  may form together a ring;    L is a coordinate bond-forming compound selected from the group consisting of n electron, ethers, nitrites, amines and phosphines, and L may be bound to X;    m is an integer of 1 to 3, n is an integer of 1 to 5, q is an integer of 1 to 3 and r is an integer of 0 to 3,    wherein the third transition metal compound is represented by the following formula (3):                          wherein M represents a transition metal atom selected from the group consisting of metal atoms of group 3 to group 12 of the periodic table;    X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxygroup having 1 to 20 carbon atoms, an amino group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, a sulfonate group having an organic residue with 1 to 20 carbon atoms, or a non-coordinative anion containing an element selected from the group consisting of B, Al, P and Sb, and, when q is an integer of at least 2, Xs may be the same as or different from each other;    R 1  represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing at least one halogen atom, or a ferrocenyl group or a substituted ferrocenyl group;    R 2  represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of halogen, silicon, nitrogen, oxygen and sulfur atoms, or a ferrocenyl group or a substituted ferrocenyl group; and R and R may form together a ring;    Q represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, an amino group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, an oxy group having a hydrocarbon group with 1 to 20 carbon atoms, a thio group having a hydrocarbon group with 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur atoms, or oxygen or sulfur; and, when Q contains a coordinative atom, Q can be coordinatively bound to M;    R 3  represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of nitrogen, oxygen, halogen and sulfur atoms, and one of R 3 s adjacent to Q may form a ring together with Q; and, when m is an integer of at least 2, R 3 s may be the same as or different from each other, and adjacent R 3 s may form together a ring;    R 4  represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, an oxy group having a hydrocarbon group with 1 to 20 carbon atoms, a thio group having a hydrocarbon group with 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of nitrogen, phosphorus, oxygen, halogen and sulfur atoms; and, when n is an integer of at least 2, R 4 s may be the same as or different from each other, and adjacent R 4 s may form together a ring; and R 3  and R 4  may form together a ring; and, when R 4  contains a heteroatom, R 4  can coordinate with the transition metal atom M;    L is a coordinate bond-forming compound selected from the group consisting of a electron, ethers, nitrites, amines and phosphines, and L may be bound to X;    m is an integer of 1 to 3 and n is an integer of 1 to 5;    when Q is sulfur or oxygen, the bond between Q and M is a sigma bond; and    q is an integer of 1 to 3 and r is an integer of 0 to 3, and    wherein the fourth transition metal compound is represented by the following formula                          wherein M represents a transition metal atom selected from the group consisting of metals of group 3 to group 12 of the periodic table;    X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a sulfonate group having an organic residue with 1 to 20 carbon atoms, or a non-coordinative anion containing an element selected from the group consisting of B, Al, P and Sb, and, when q is an integer of at least 2, Xs may be the same as or different from each other;    R 1  represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a trifluoromethyl group, a ferrocenyl group or a substituted ferrocenyl group;    R 2  represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of silicon, nitrogen, oxygen and sulfur atoms, or a ferrocenyl group or a substituted ferrocenyl group; and R 1  and R 2  may form together a ring;    R 3  represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a silyl group having one or more hydrocarbon groups each with 1 to 20 carbon atoms; and, when m is an integer of at least 2, R 3 s may be the same as or different from each other;    R 4  represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino group having one or more hydrocarbon groups each with 1 to 20 carbon atoms, an oxy group having a hydrocarbon group with 1 to 20 carbon atoms, a thio group having a hydrocarbon group with 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from the group consisting of nitrogen, phosphorus, oxygen, halogen and sulfur atoms; and, when n is an integer of at least 2, R 4 s may be the same as or different from each other, and adjacent R 4 s may form together a ring;    R 5  represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an amino group having one or more hydrocarbon groups each with 1 to 20 carbon atoms;    L is a coordinate bond-forming compound selected from the group consisting of π electron, ethers, nitrites, amines and phosphines, and L may be bound to X;    m is an integer of 1 or 2, n is an integer of 1 to 5, q is an integer of 1 to 3 and r is an integer of 0 to 3.    
     
     
         14 . The process according to  claim 13 , wherein the olefin is selected from the group consisting of α-olefins, styrene and styrene derivatives, conjugated dienes, non-conjugated dienes, cycloolefins, α,β-unsaturated carboxylic acids, metal salts of α,β-unsaturated carboxylic acids, esters of α,β-unsaturated carboxylic acids, vinyl esters, unsaturated glycidyl esters, vinyl ketones, and α,β-unsaturated nitriles.  
     
     
         15 . The process according to  claim 13 , wherein M in the formula (1) to (4) represents a transition metal atom selected from the group consisting of metal atoms of group 8 to group 12 of the periodic table.  
     
     
         16 . The process according to  claim 15 , wherein the olefin is selected from the group consisting of α-olefins, styrene and styrene derivatives, conjugated dienes, non-conjugated dienes, cycloolefins, α,β-unsaturated carboxylic acids, metal salts of α,β-unsaturated carboxylic acids, esters of α,β-unsaturated carboxylic acids, vinyl esters, unsaturated glycidyl esters, vinyl ketones, and α,β-unsaturated nitriles.  
     
     
         17 . The process according to  claim 13 , wherein M in the formula (1) to (4) represents a transition metal atom selected from the group consisting of Ni, Pd, Fe and Cu.  
     
     
         18 . The process according to  claim 17 , wherein the olefin is selected from the group consisting of α-olefins, styrene and styrene derivatives, conjugated dienes, non-conjugated dienes, cycloolefins, α,β-unsaturated carboxylic acids, metal salts of α,β-unsaturated carboxylic acids, esters of α,β-unsaturated carboxylic acids, vinyl esters, unsaturated glycidyl esters, vinyl ketones, and α,β-unsaturated nitriles.  
     
     
         19 . The process according to  claim 13 , wherein the polymerization of an olefin is carried out further in the presence of an activating cocatalyst.  
     
     
         20 . The process according to  claim 19 , wherein the olefin is selected from the group consisting of α-olefins, styrene and styrene derivatives, conjugated dienes, non-conjugated dienes, cycloolefins, α,β-unsaturated carboxylic acids, metal salts of α,β-unsaturated carboxylic acids, esters of α,β-unsaturated carboxylic acids, vinyl esters, unsaturated glycidyl esters, vinyl ketones, and α,β-unsaturated nitriles.