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US5627117A Expired / Lapsed US ⏱️ 0.0 years remaining

Olefin polymerization catalyst and process for olefin polymerization

Assignee: Mitsui Chemicals Inc
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Filing: 1994-12-27
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Granted: 1997-05-06
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Expires: 2014-12-27
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Abstract

Abstract Disclosed in an olefin polymerization catalyst comprising a transition metal compound having at least two transition metals in which at least one of said metals is bonded to a ligand having a cyclopentadienyl skeleton, at least one of said metals is selected from Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and lanthanoid metals and at least on of the others is selected from the specific transition metals; and an organoaluminum oxy-compound or an organoboron compound. Corresponding to the kind of the metal combined with said metal selected from Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and lanthanoid metals, the olefin polymerization catalyst exhibit a property to give polymers having a wide molecular weight distribution in spite of the catalyst system using one kind of a transition metal compound, or to give polymers having high molecular weight and be excellent in the polymerization activity at low polymerization temperature.

Inventors

  • 👤 Teruaki Mukaiyama
  • 👤 Makoto Mitani
  • 👤 Kunihiro Oouchi

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-01 11:11
CPC Classifications
C; C08; C08F; C08F4/00; C08F4/28; C08F4/32; C08F10/00; C08F4/42; C08F4/44; C08F4/52; C08F110/00; C08F110/02; C08F210/00; C08F210/16; C08F2410/00; C08F2410/03; C08F4/60; C08F4/619; C08F4/61908; C08F4/61912; C08F4/6192; C08F4/61922

Claims Analysis

Total Claims: 27
Claim 1
Independent Claim 330 words
An olefin polymerization catalyst comprising (A- 1) a transition metal compound and (B) an organoaluminum oxy-compound selected from the group consisting of an aluminoxane compound and a benzene-insoluble organoaluminum oxy-compound or an organoboron compound, said transition metal compound being represented by the following formula (I): ##STR30## wherein M 1 , M 2 and M 3 are the same metals as each other and are each one metal selected from Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and lanthanoid metals; Cp 1 , Cp 2 , Cp 3 and Cp 4 are each one group having a cyclopentadienyl skeleton, which may have a substituent, and the groups having a cyclopentadienyl skeleton may be the same as or different from each other; R 1 and R 2 are each one bond group selected from the group consisting of an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, a divalent tin-containing group and a divalent germanium-containing group or a single bond and the groups may be the same as or different from each other; and X, Y and Z are each one group selected from a hydrocarbon group, a nitrogen-containing group, an oxygen-containing group, a silicon-containing group, a phosphorus-containing group and a sulfur-containing group, or an atom selected from a halogen atom and a hydrogen atom, the groups or atoms indicated by X, Y and Z may be the same as or different from each other, and a pair of X and Y, a pair of Y and Z, or a pair of X and Z may form a bond group selected from --O-- and --S--, or may form a divalent bond group containing at least one atom selected from an oxygen atom, a carbon atom, a silicon atom, a germanium atom, a phosphorus atom and a sulfur atom; and n is an integer of 1-5; m is an integer of 1-5; p is an integer of 1-5; and q is 0 or 1.
Claim 2
Dependent Claim 330 words
An olefin polymerization catalyst comprising (A- 1) a transition metal compound and (B) an organoaluminum oxy-compound selected from the group consisting of an aluminoxane compound and a benzene-insoluble organoaluminum oxy-compound or an organoboron compound, said transition metal compound being represented by the following formula (I): ##STR30## wherein M 1 , M 2 and M 3 are the same metals as each other and are each one metal selected from Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and lanthanoid metals; Cp 1 , Cp 2 , Cp 3 and Cp 4 are each one group having a cyclopentadienyl skeleton, which may have a substituent, and the groups having a cyclopentadienyl skeleton may be the same as or different from each other; R 1 and R 2 are each one bond group selected from the group consisting of an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, a divalent tin-containing group and a divalent germanium-containing group or a single bond and the groups may be the same as or different from each other; and X, Y and Z are each one group selected from a hydrocarbon group, a nitrogen-containing group, an oxygen-containing group, a silicon-containing group, a phosphorus-containing group and a sulfur-containing group, or an atom selected from a halogen atom and a hydrogen atom, the groups or atoms indicated by X, Y and Z may be the same as or different from each other, and a pair of X and Y, a pair of Y and Z, or a pair of X and Z may form a bond group selected from --O-- and --S--, or may form a divalent bond group containing at least one atom selected from an oxygen atom, a carbon atom, a silicon atom, a germanium atom, a phosphorus atom and a sulfur atom; and n is an integer of 1-5; m is an integer of 1-5; p is an integer of 1-5; and q is 0 or 1.
Claim 3
Dependent Claim 218 words
The olefin polymerization catalyst as claimed in claim 1, wherein said transition metal compound is a transition metal compound represented by the following formula (I'): ##STR31## wherein M 1 and M 2 are the same metals as each other and are each one metal selected from Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and lanthanoid metals; Cp 1 and Cp 2 are each a group having a cyclopentadienyl skeleton, which may have a substituent, and the groups having a cyclopentadienyl skeleton may be the same as or different from each other; X and Y are each a group selected from a hydrocarbon group, a nitrogen-containing group, an oxygen-containing group, a silicon-containing group, a phosphorus-containing group and a sulfur-containing group, or an atom selected from a halogen atom and a hydrogen atom, the groups or atoms indicated by X and y may be the same as or different from each other, and a pair of X and Y may form a bond group selected from --O-- and --S--, or may form a divalent bond group containing at least one atom selected from an oxygen atom, a carbon atom, a silicon atom, a germanium atom, a phosphorus atom and a sulfur atom; and n is an integer of 1-5; and m is an integer of 1-5.
Claim 4
Dependent Claim 45 words
The olefin polymerization catalyst as claimed in claim 2, wherein the transition metal compound is represented by the formula [I'] in which M 1 and M 2 are each selected from Zr, Ti, Hf, V, Nb and Ta, and are the same as each other.
Claim 5
Dependent Claim 107 words
The olefin polymerization catalyst as claimed in claim 2, wherein the transition metal compound is represented by the formula [I'] in which M 1 and M 2 are each Zr, Ti or Hf; R 1 is one bond group selected from an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group and a divalent germanium-containing group, or a single bond; at least one of the groups indicated by X is a group having a cyclopentadienyl skeleton, which may have a substituent; and at least one of the groups indicated by Y is a group having a cyclopentadienyl skeleton, which may have a substituent.
Claim 6
Dependent Claim 118 words
The olefin polymerization catalyst as claimed in claim 2, wherein the transition metal compound is represented by the formula [I'] in which M 1 and M 2 are each Zr or Ti; R 1 is one bond group selected from an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group and a divalent germanium-containing group, or a single bond; at least one of the groups indicated by X is a group having a cyclopentadienyl skeleton, which may have a substituent, while the others are halogen atoms; and at least one of the groups indicated by Y is a group having a cyclopentadienyl skeleton, which may have a substituent, while the others are halogen atoms.
Claim 7
Dependent Claim 214 words
A olefin polymerization catalyst comprising (A-2) a transition metal compound and (B) an organoaluminum oxy-compound selected from the group consisting of an aluminoxane compound and a benzene-insoluble organoaluminum oxy-compound or an organoboron compound, said transition metal compound being represented by the following formula (II): ##STR32## wherein M 1 , M 2 and M 3 are each one metal selected from Sc, Y, Ti, Zr, Ef, V, Nb, Ta, Cr, Mo, W and lanthanoid metals, and at least two of M 1 , M 2 and M 3 are different from each other; Cp 1 , Cp 2 , Cp 3 and Cp 4 are each a group having a cyclopentadienyl skeleton, which may have a substituent, and the groups having a cyclopentadienyl skeleton may be the same as or different from each other; R 1 and R 2 are each one bond group selected from the group consisting of an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, a divalent tin-containing group and a divalent germanium-containing group or a single bond and the groups may be the same as or different from each other; and n is an integer of 1-5; m is an integer of 1-5; P is an integer of 1-5; and q is 0 or 1.
Claim 8
Dependent Claim 214 words
A olefin polymerization catalyst comprising (A-2) a transition metal compound and (B) an organoaluminum oxy-compound selected from the group consisting of an aluminoxane compound and a benzene-insoluble organoaluminum oxy-compound or an organoboron compound, said transition metal compound being represented by the following formula (II): ##STR32## wherein M 1 , M 2 and M 3 are each one metal selected from Sc, Y, Ti, Zr, Ef, V, Nb, Ta, Cr, Mo, W and lanthanoid metals, and at least two of M 1 , M 2 and M 3 are different from each other; Cp 1 , Cp 2 , Cp 3 and Cp 4 are each a group having a cyclopentadienyl skeleton, which may have a substituent, and the groups having a cyclopentadienyl skeleton may be the same as or different from each other; R 1 and R 2 are each one bond group selected from the group consisting of an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, a divalent tin-containing group and a divalent germanium-containing group or a single bond and the groups may be the same as or different from each other; and n is an integer of 1-5; m is an integer of 1-5; P is an integer of 1-5; and q is 0 or 1.
Claim 9
Dependent Claim 239 words
The olefin polymerization catalyst as claimed in claim 6, wherein said transition metal compound is a transition metal compound represented by the following formula (II'): ##STR33## wherein M 4 and M 5 are each one metal selected from Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and lanthanoid metals, and are different from each other; Cp 1 and Cp 2 are each a group having a cyclopentadienyl skeleton, which may have a substituent, and the groups having a cyclopentadienyl skeleton may be the same as or different from each other; R 1 is a divalent group containing carbon atom, silicone atom, tin atom, germanium atom, phosphorus atom or sulfur atom, or a single bond; X an Y are each a group selected from a hydrocarbon group, a nitrogen-containing group, an oxygen-containing group, a silicon-containing group, a phosphorus-containing group and a sulfur-containing group, or an atom selected from a halogen atom and a hydrogen atom, the groups or atoms indicated by X and Y may be the same as or different from each other, and a pair of X and Y may form a bond group selected from --O-- and --S--, or may form a divalent bond group containing at least one atom selected from an oxygen atom, a carbon atom, a silicon atom, a germanium atom, a phosphorus atom and a sulfur atom; n is an integer of 1-5; and m is an integer of 1-5.
Claim 10
Dependent Claim 46 words
The olefin polymerization catalyst as claimed in claim 7, wherein the transition metal compound is represented by the formula [II'] in which M 4 and M 5 are each one metal selected from Zr, Ti, Hf, V, Nb and Ta, and are different from each other.
Claim 11
Dependent Claim 116 words
The olefin polymerization catalyst as claimed in claim 7, wherein the transition metal compound is represented by the formula [II'] in which M 4 and M 5 are each one metal selected from Zr, Ti and Hf, and are different from each other; R 1 is one bond group selected from an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, a divalent germanium-containing group, or a single bond; at least one of the groups indicated by X is a group having a cyclopentadienyl skeleton, which may have a substituent; and at least one of the groups indicated by Y is a group having a cyclopentadienyl skeleton, which may have a substituent.
Claim 12
Dependent Claim 116 words
The olefin polymerization catalyst as claimed in claim 7, wherein the transition metal compound is represented by the formula [II'] in which M 4 is Zr; M 5 is Ti; R 1 is one bond group selected from an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group and a divalent germanium-containing group, or a single bond; at least one of the groups indicated by X is a group having a cyclopentadienyl skeleton, which may have a substituent, while the rest are halogen atoms; and at least one of the groups indicated by Y is a group having a cyclopentadienyl skeleton, which may have a substituent, while the rest are halogen atoms.
Claim 13
Dependent Claim 240 words
A olefin polymerization catalyst comprising (A-3) a transition metal compound and (B) an organoaluminum oxy-compound selected from the group consisting of an aluminoxane compound and a benzene-insoluble organoaluminum oxy-compound or an organoboron compound, said transition metal compound being represented by the following formula (III): ##STR34## wherein M 7 is a transition metal selected from Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and lanthanoid metals, M 8 is a transition metal selected from Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd and Hg, and M 9 is a transition metal, and M 7 and M 9 , M 8 and M 9 are the same as or different from each other; Cp 1 , Cp 2 , Cp 3 and Cp 4 are each a group having a cyclopentadienyl skeleton, which may have a substitutent, and the groups having a cyclopentadienyl skeleton may be the same as or different from each other; R 1 and R 2 are each one bond group selected from the group consisting of an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, a divalent tin-containing group and a divalent germanium-containing group or a single bond and the groups may be the same as or different from each other; and n is an integer of 1-4; m is an integer of 1-5; and p is an integer of 1-5.
Claim 14
Dependent Claim 240 words
A olefin polymerization catalyst comprising (A-3) a transition metal compound and (B) an organoaluminum oxy-compound selected from the group consisting of an aluminoxane compound and a benzene-insoluble organoaluminum oxy-compound or an organoboron compound, said transition metal compound being represented by the following formula (III): ##STR34## wherein M 7 is a transition metal selected from Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and lanthanoid metals, M 8 is a transition metal selected from Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd and Hg, and M 9 is a transition metal, and M 7 and M 9 , M 8 and M 9 are the same as or different from each other; Cp 1 , Cp 2 , Cp 3 and Cp 4 are each a group having a cyclopentadienyl skeleton, which may have a substitutent, and the groups having a cyclopentadienyl skeleton may be the same as or different from each other; R 1 and R 2 are each one bond group selected from the group consisting of an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, a divalent tin-containing group and a divalent germanium-containing group or a single bond and the groups may be the same as or different from each other; and n is an integer of 1-4; m is an integer of 1-5; and p is an integer of 1-5.
Claim 15
Dependent Claim 68 words
The olefin polymerization catalyst as claimed in claim 11, wherein the transition metal compound is represented by the formula [III] in which M 7 is one metal selected from Ti, Zr, Hf, V, Nb and Ta, M 8 and M 9 are a transition metals selected from Mn, Re, Fe, Ru, Co, Rh, Ir, Ni and Pd and may be the same as or different from each other.
Claim 16
Dependent Claim 137 words
The olefin polymerization catalyst as claimed in claim 11, wherein the transition metal compound is represented by the formula [III] in which M 7 is one metal selected from Zr, Ti and Hf, M 8 and M 9 are each one metal selected from Mn, Fe, Ru and Rh and may be the same as or different from each other; R 1 and R 2 are each one bond group selected from an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, a divalent germanium-containing group, or a single bond; at least one of the groups indicated by Y is a group having a cyclopentadienyl skeleton, which may have a substituent; and at least one of the groups indicated by Z is a group having a cyclopentadienyl skeleton, which may have a substituent.
Claim 17
Dependent Claim 135 words
The olefin polymerization catalyst as claimed in claim 11, wherein the transition metal compound is represented by the formula [III] in which M 7 is one metal selected from Zr, Ti and Hf, M 8 and M 9 are each Fe; R 1 and R 2 are each one bond group selected from an alkylene group, a substituted alkylene group, a silylene group and a substituted silylene group, or a single bond; the groups indicated by X are halogen atoms at least one of the groups indicated by Y is a group having a cyclopentadienyl skeleton, which may have a substituent, while the rest are halogen atoms; and at least one of the groups indicated by X is a group having a cyclopentadienyl skeleton, which may have a substituent, while the rest are halogen atoms.
Claim 18
Dependent Claim 257 words
The olefin polymerization catalyst as claimed in claim 11, wherein said transition metal compound is a transition metal compound represented by the following formula [III']: ##STR35## wherein M 7 is a transition metal selected from Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, MO, W and lanthanoid metals and M 8 is a transition metal selected from Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd and Hg; Cp 1 and Cp 2 are each a group having a cyclopentadienyl skeleton, which may have a substituent, and the groups having a cyclopentadienyl skeleton are the same as or different from each other; R 1 is a divalent group containing carbon atom, silicone atom, tin atom, germanium atom, phosphorus atom or sulfur atom, or a single bond; X and Y are each a group selected from a hydrocarbon group, a nitrogen-containing group, an oxygen-containing group, a silicon-containing group, a phosphorus-containing group and a sulfur-containing group, or an atom selected from a halogen atom and a hydrogen atom, the groups or atoms indicated by X and Y may be the same as or different from each other, and a pair of X and Y may form a bond group selected from --O-- and --S--, or may form a divalent bond group containing at least one atom selected from an oxygen atom, a carbon atom, a silicon atom, a germanium atom, a phosphorus atom and a sulfur atom; n is an integer of 1-5; and m is an integer of 1-5.
Claim 19
Dependent Claim 54 words
The olefin polymerization catalyst as claimed in claim 15, wherein the transition metal compound is represented by the formula [III'] in which M 7 is one metal selected from Tin, Zr, Hf, V, Nb and Ta, M 8 is a transition metal selected from Mn, Re, Fe, Ru, Co, Rh, Ir, Ni and Pd.
Claim 20
Dependent Claim 118 words
The olefin polymerization catalyst as claimed in claim 15, wherein the transition metal compound is represented by the formula [III'] in which M 7 is one metal selected from Zr, Ti and Hf, M 8 is one metal selected from Mn, Fe, Ru and Rh; R 1 is one bond group selected from an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, a divalent germanium-containing group, or a single bond; at least one of the groups indicated by X is a group having a cyclopentadienyl skeleton, which may have a substituent; and at least one of the groups indicated by Y is a group having a cyclopentadienyl skeleton, which may have a substituent.
Claim 21
Dependent Claim 119 words
The olefin polymerization catalyst as claimed in claim 15, wherein the transition metal compound is represented by the formula [III'] in which M 7 is one metal selected from Zr, Ti and Hf, M 8 is Fe; R 1 is one bond group selected from an alkylene group, a substituted alkylene group, a silylene group and a substituted silylene group, or a single bond; at least one of the groups indicated by X is a group having a cyclopentadienyl skeleton, which may have a substituent, while the others are halogen atoms; and at least one of the groups indicated by Y is a group having a cyclopentadienyl skeleton, which may have a substituent, while the others are halogen atoms.
Claim 22
Dependent Claim 17 words
The olefin polymerization catalyst as claimed in claim 1, wherein the organoaluminum oxy-compound is an aluminoxane compound.
Claim 23
Dependent Claim 17 words
The olefin polymerization catalyst as claimed in claim 6, wherein the organoaluminum oxy-compound is an aluminoxane compound.
Claim 24
Dependent Claim 17 words
The olefin polymerization catalyst as claimed in claim 11, wherein the organoaluminum oxy-compound is an aluminoxane compound.
Claim 25
Dependent Claim 48 words
The olefin polymerization catalyst as claimed in claim 1, wherein the organoaluminum oxy-compound is a benzene-insoluble organoaluminum oxy-compound selected from a benzene-insoluble organoaluminum oxy-compound obtained by contacting aluminoxane with water or an active hydrogen-containing compound, and a benzene-insoluble organoaluminum oxy-compound obtained by contacting an organoaluminum compound with water.
Claim 26
Dependent Claim 48 words
The olefin polymerization catalyst as claimed in claim 6, wherein the organoaluminum oxy-compound is a benzene-insoluble organoaluminum oxy-compound selected from a benzene-insoluble organoaluminum oxy-compound obtained by contacting aluminoxane with water or an active hydrogen-containing compound, and a benzene-insoluble organoaluminum oxy-compound obtained by contacting an organoaluminum compound with water.
Claim 27
Dependent Claim 48 words
The olefin polymerization catalyst as claimed in claim 11, wherein the organoaluminum oxy-compound is a benzene-insoluble organoaluminum oxy-compound selected from a benzene-insoluble organoaluminum oxy-compound obtained by contacting aluminoxane with water or an active hydrogen-containing compound, and a benzene-insoluble organoaluminum oxy-compound obtained by contacting an organoaluminum compound with water.

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