Process for the polymerization of olefins using a catalyst containing a novel catalyst component

Claim 2

A process for polymerization of at least one compound selected from the group consisting of α-olefins, linear diolefins, cyclic olefins, cyclic polyenes and aromatic vinyl compounds, comprising polymerizing or copolymerizing said at least one compound in the presence of a polymerization catalyst comprising the following components (A) and (B): (A) a catalyst component comprising a transition metal compound represented by the general formula (1) or (2): (R a Cp) m (R′ b Cp) n M(—X—Ar—Y c ) 4−(m+n) (1) wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and R′ each represents a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, X represents an oxygen or a sulphur atom, Ar represents an aromatic ring, Y represents a hydrogen atom, a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, each of a and b is an integer of 0 to 5, each of m and n is an integer of 0 to 3 and m+n is an integer of 1 to 3, and c is an integer of 1 to 5, with a proviso that Y is not a hydrogen atom when Ar is a benzene ring; R″(R d Cp)(R′ e Cp)M(—X—Ar—Y c ) 2 (2) wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and R′ each represents a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, R″ represents a divalent radical which links (R d Cp) and (R′ e Cp) and is selected from the group consisting of an alkylene, an arylalkylene, a dialkylsilylene, a dialkylgermylene, an alkylphosphindiyl or an alkylimino radical, X represents an oxygen or a sulphur atom, Ar represents an aromatic ring, Y represents a hydrogen atom, a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, each of d and e is an integer of 0 to 4, and c is an integer of 1 to 5, with a proviso that Y is not a hydrogen atom when Ar is a benzene ring, and (B) an organic aluminum oxy compound or a cation generator.

Claim 3

A process for polymerization according to the claim 1 , comprising polymerizing an α-olefin or copolymerizing an α-olefin and another α-olefin or copolymerizing an α-olefin and at least one said compound other than an α-olefin.

Claim 4

A process for polymerization according to the claim 1 , wherein Ar in the general formula (1) and (2) represents a benzene or naphthalene ring.

Claim 5

A process for polymerization according to the claim 1 , wherein Y in the general formula (1) and (2) is a radical selected from the group consisting of a hydrogen atom, an alkyl radical having 1 to 10 carbon atoms, an aryl radical having 6 to 10 carbon atoms, an alkenyl radical having 2 to 10 carbon atoms, an alkynyl radical having 2 to 10 carbon atoms, an arylalkyl radical having 7 to 20 carbon atoms, an arylalkenyl radical having 8 to 20 carbon atoms, an alkylaryl radical having 7 to 20 carbon atoms, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, cyano, nitro, nitroso, isocyanide, cyanate, isocyanate, amino, amido, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl and arylsulfonyl radical, with a proviso that Y is not a hydrogen atom when Ar is a benzene ring.

Claim 6

A process for polymerization according to claim 1 , wherein, in the general formula (1) and (2), said hydrocarbon radical is a hydrocarbon radical other than a methyl group.

Claim 7

A process for polymerization according to claim 1 , wherein, in the general formula (1) and (2), said hydrocarbon radical is a hydrocarbon radical other than a methyl or ethyl group.

Claim 8

A process for polymerization according to claim 1 , wherein, in the general formula (1) and (2), said hydrocarbon radical is selected from the group consisting of an aryl radical having 6 to 10 carbon atoms, an alkenyl radical having 2 to 10 carbon atoms, an alkynyl radical having 2 to 10 carbon atoms, an arylalkyl radical having 7 to 20 carbon atoms, an arylalkenyl radical having 8 to 20 carbon atoms and an alkylaryl radical having 7 to 20 carbon atoms.

Claim 9

A process for polymerization according to claim 1 , wherein said catalyst component (A) is represented by the general formula (1).

Claim 10

A process for polymerization according to claim 8 , wherein, in the general formula (1), said hydrocarbon radical is a hydrocarbon radical other than a methyl group.

Claim 11

A process for polymerization according to claim 8 , wherein, in the general formula (1), said hydrocarbon radical is a hydrocarbon radical other than a methyl or ethyl group.

Claim 12

A process for polymerization according to claim 8 , wherein, in the general formula (1), said hydrocarbon radical is selected from the group consisting of an aryl radical having 6 to 10 carbon atoms, an alkenyl radical having 2 to 10 carbon atoms, an alkynyl radical having 2 to 10 carbon atoms, an arylalkyl radical having 7 to 20 carbon atoms, an arylalkenyl radical having 8 to 20 carbon atoms and an alkylaryl radical having 7 to 20 carbon atoms.

Claim 13

A process for polymerization according to claim 1 , wherein said catalyst component (A) is represented by the general formula (2).

Claim 14

A process for polymerization according to claim 1 , wherein said catalyst component (A) is represented by the general formula (1) or (2): (R a Cp) m (R′ b Cp) n M(—X—Ar—Y c ) 4−(m+n) (1) wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and R′ each represents a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, X represents an oxygen or a sulphur atom, Ar represents an aromatic ring, Y represents a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, each of a and b is an integer of 0 to 5, each of m and n is an integer of 0 to 3 and m+n is an integer of 1 to 3, and c is an integer of 1 to 5; R″(R d Cp)(R′ e Cp)M(—X—Ar—Y c ) 2 (2) wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and R′ each represents a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, R″ represents a divalent radical which links (R d Cp) and (R′ e Cp) and is selected from the group consisting of an alkylene, an arylalkylene, a dialkylsilylene, a dialkylgermylene, an alkylphosphindiyl or an alkylimino radical, X represents an oxygen or a sulphur atom, Ar represents an aromatic ring, Y represents a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, each of d and e is an integer of 0 to 4, and c is an integer of 1 to 5.

Claim 15

A process for the polymerization of at least one compound selected from the group consisting of α-olefins, linear diolefins, cyclic olefins, cyclic polyenes and aromatic vinyl compounds, comprising polymerizing or copolymerizing said at least one compound in the presence of a polymerization catalyst comprising the following components (A), (B), and (C): (A) a catalyst component comprising a transition metal compound represented by the general formula (1) or (2): (R a Cp) m (R′ b Cp) n M(—X—Ar—Y c ) 4−(m+n) (1) wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and R′ each represents a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, X represents an oxygen or a sulphur atom, Ar represents an aromatic ring, Y represents a hydrogen atom, a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, each of a and b is an integer of 0 to 5, each of m and n is an integer of 0 to 3 and m+n is an integer of 1 to 3, and c is an integer of 1 to 5, with a proviso that Y is not a hydrogen atom when Ar is a benzene ring; R″(R d Cp)(R′ e Cp)M(—X—Ar—Y c ) 2 (2) wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and R′ each represents a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, R″ represents a divalent radical which links (R d Cp) and (R′ e Cp) and is selected from the group consisting of an alkylene, an arylalkylene, a dialkylsilylene, a dialkylgermylene, an alkylphosphindiyl or an alkylimino radical, X represents an oxygen or a sulphur atom, Ar represents an aromatic ring, Y represents a hydrogen atom, a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, each of d and e is an integer of 0 to 4, and c is an integer of 1 to 5, with a proviso that Y is not a hydrogen atom when Ar is a benzene ring, (B) an organic aluminum oxy compound or a cation generator, and (C) an organic aluminum compound.

Claim 16

A process for the polymerization of at least one compound selected from the group consisting of α-olefins, linear diolefins, cyclic olefins, cyclic polyenes and aromatic vinyl compounds, comprising polymerizing or copolymerizing said at least one compound in the presence of a polymerization catalyst comprising the following components (A), (B), and (C): (A) a catalyst component comprising a transition metal compound represented by the general formula (1) or (2): (R a Cp) m (R′ b Cp) n M(—X—Ar—Y c ) 4−(m+n) (1) wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and R′ each represents a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, X represents an oxygen or a sulphur atom, Ar represents an aromatic ring, Y represents a hydrogen atom, a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, each of a and b is an integer of 0 to 5, each of m and n is an integer of 0 to 3 and m+n is an integer of 1 to 3, and c is an integer of 1 to 5, with a proviso that Y is not a hydrogen atom when Ar is a benzene ring; R″(R d Cp)(R′ e Cp)M(—X—Ar—Y c ) 2 (2) wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and R′ each represents a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, R″ represents a divalent radical which links (R d Cp) and (R′ e Cp) and is selected from the group consisting of an alkylene, an arylalkylene, a dialkylsilylene, a dialkylgermylene, an alkylphosphindiyl or an alkylimino radical, X represents an oxygen or a sulphur atom, Ar represents an aromatic ring, Y represents a hydrogen atom, a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, each of d and e is an integer of 0 to 4, and c is an integer of 1 to 5, with a proviso that Y is not a hydrogen atom when Ar is a benzene ring, (B) an organic aluminum oxy compound or a cation generator, and (C) an organic aluminum compound.

Claim 17

A process for polymerization according to the claim 14 , comprising polymerizing an α-olefin or copolymerizing an α-olefin and another α-olefin or copolymerizing an α-olefin and at least one said compound other than an α-olefin.

Claim 18

A process for polymerization according to the claim 14 , wherein Ar in the general formula (1) and (2) represents a benzene or naphthalene ring.

Claim 19

A process for polymerization according to the claim 14 , wherein Y in the general formula (1) and (2) is a radical selected from the group consisting of a hydrogen atom, an alkyl radical having 1 to 10 carbon atoms, an aryl radical having 6 to 10 carbon atoms, an alkenyl radical having 2 to 10 carbon atoms, an alkynyl radical having 2 to 10 carbon atoms, an arylalkyl radical having 7 to 20 carbon atoms, an arylalkenyl radical having 8 to 20 carbon atoms, an alkylaryl radical having 7 to 20 carbon atoms, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, cyano, nitro, nitroso, isocyanide, cyanate, isocyanate, amino, amido, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl and arylsulfonyl radical, with a proviso that Y is not a hydrogen atom when Ar is a benzene ring.

Claim 20

A process for polymerization according to claim 14 , wherein, in the general formula (1) and (2), said hydrocarbon radical is a hydrocarbon radical other than a methyl group.

Claim 21

A process for polymerization according to claim 14 , wherein, in the general formula (1) and (2), said hydrocarbon radical is a hydrocarbon radical other than a methyl or ethyl group.

Claim 22

A process for polymerization according to claim 14 , wherein, in the general formula (1) and (2), said hydrocarbon radical is selected from the group consisting of an aryl radical having 6 to 10 carbon atoms, an alkenyl radical having 2 to 10 carbon atoms, an alkynyl radical having 2 to 10 carbon atoms, an arylalkyl radical having 7 to 20 carbon atoms, an arylalkenyl radical having 8 to 20 carbon atoms and an alkylaryl radical having 7 to 20 carbon atoms.

Claim 23

A process for polymerization according to claim 14 , wherein said catalyst component (A) is represented by the general formula (1).

Claim 24

A process for polymerization according to claim 21 , wherein, in the general formula (1), said hydrocarbon radical is a hydrocarbon radical other than a methyl group.

Claim 25

A process for polymerization according to claim 21 , wherein, in the general formula (1), said hydrocarbon radical is a hydrocarbon radical other than a methyl or ethyl group.

Claim 26

A process for polymerization according to claim 21 , wherein, in the general formula (1), said hydrocarbon radical is selected from the group consisting of an aryl radical having 6 to 10 carbon atoms, an alkenyl radical having 2 to 10 carbon atoms, an alkynyl radical having 2 to 10 carbon atoms, an arylalkyl radical having 7 to 20 carbon atoms, an arylalkenyl radical having 8 to 20 carbon atoms and an alkylaryl radical having 7 to 20 carbon atoms.

Claim 27

A process for polymerization according to claim 14 , wherein said catalyst component (A) is represented by the general formula (2).

Claim 28

A process for polymerization according to claim 14 , wherein said catalyst component (A) is represented by the general formula (1) or (2): (R a Cp) m (R′ b Cp) n M(—X—Ar—Y c ) 4−(m+n) (1) wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and R′ each represents a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, X represents an oxygen or a sulphur atom, Ar represents an aromatic ring, Y represents a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, each of a and b is an integer of 0 to 5, each of m and n is an integer of 0 to 3 and m+n is an integer of 1 to 3, and c is an integer of 1 to 5; R″(R d Cp)(R′ e Cp)M(—X—Ar—Y c ) 2 (2) wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and R′ each represents a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, R″ represents a divalent radical which links (R d Cp) and (R′ e Cp) and is selected from the group consisting of an alkylene, an arylalkylene, a dialkylsilylene, a dialkylgermylene, an alkylphosphindiyl or an alkylimino radical, X represents an oxygen or a sulphur atom, Ar represents an aromatic ring, Y represents a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, each of d and e is an integer of 0 to 4, and c is an integer of 1 to 5.