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US 6,074,977 AGranted
Olefin addition polymerization catalyst composition
AssigneeThe Dow Chemical Company
InventorsRobert K. Rosen, James C. Stevens, John C. Tracy
Life of this patent
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Abstract
Catalyst compositions that are highly tolerant of catalyst poisons comprising a cationic or zwitterionic Group 4 metal complex of the constrained geometry type and an organoaluminum hydrocarbyloxide compound according to the formula R.sup.1.sub.2 Al(OR.sup.2), wherein R.sup.1 and R.sup.2 independently each ocurrence are C.sub.1-30 hydrocarbyl, the molar ratio of complex to organoaluminum hydrocarbyloxide compound being from 1:0.1 to 1:100.
Claims8
A catalyst composition comprising in combination:
- a1) a metal complex corresponding to the formula:
- Z L MX.sub.p X'.sub.q, wherein:
- M is a metal of Group 4 of the Periodic Table of the Elements having an oxidation state of +2, +3 or +4, bound in an .eta..sup.5 bonding mode to L;
- L is a cyclopentadienyl-, indenyl-, tetrahydroindenyl-, fluorenyl-, tetrahydrofluorenyl-, or octahydrofluorenyl-group covalently substituted with at least a divalent moiety, Z, and L further may be substituted with from 1 to 8 substituents independently selected from the group consisting of hydrocarbyl, halo, halohydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, dihydrocarbylphosphino or silyl groups containing up to 20 non-hydrogen atoms, or two such substituents may together form a divalent derivative;
- Z is a divalent moiety bound to both L and M via .sigma.-bonds, said Z comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally, also comprising nitrogen, phosphorus, sulfur or oxygen;
- X is an anionic or dianionic ligand group having up to 60 atoms, exclusive of the class of ligands that are cyclic, delocalized, .pi.-bound ligand groups;
- X' independently each occurrence is a neutral ligating compound, having up to 20 atoms;
- p is 0, 1 or 2, and is two less than the formal oxidation state of M, with the proviso that when X is a dianionic ligand group, p is 1;
- and
- q is 0, 1 or 2;
- a1') trispentafluorophenylborane;
- and
- b) an organoaluminum hydrocarbyloxide compound according to the formula R.sup.1.sub.2 Al (OR.sup.2),
- wherein R.sup.1 and R.sup.2 independently each occurrence are C.sub.1-30 hydrocarbyl, the molar ratio of a1):
- b) being torn 1:0.1 to 1:100.
12 more elements
A catalyst composition comprising in combination:
- a1) a metal complex corresponding to the formula:
- Z L MX.sub.p X'.sub.q, wherein:
- M is a metal of Group 4 of the Periodic Table of the Elements having an oxidation state of +2 or +3, bound in an .eta..sup.5 bonding mode to L;
- L is a cyclopentadienyl-, indenyl-, tetrahydroindenyl-, fluorenyl-, tetrahydrofluorenyl-, or octahydrofluorenyl-group covalently substituted with at least a divalent moiety, Z, and L further may be substituted with from 1 to 8 substituents independently selected from the group consisting of hydrocarbyl, halo, halohydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, dihydrocarbylphosphino or silyl groups containing up to 20 non-hydrogen atoms, or two such substituents may together form a divalent derivative;
- Z is a divalent moiety bound to both L and M via .sigma.-bonds, said Z comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally, also comprising nitrogen, phosphorus, sulfur or oxygen;
- X is an anionic ligand group having up to 60 atoms, exclusive of the class of ligands that are cyclic, delocalized .pi.-bound ligand groups;
- X' independently each occurrence is a neutral ligating compound, having up to 20 atoms;
- p is 0 or 1, and is two less than the formal oxidation state of M, and
- q is 0, 1 or 2;
- a1') an activating cocatalyst which forms a cationic derivative of a1);
- and
- b) an organoaluminum hydrocarbyloxide compound according to the formula R.sup.1.sub.2 Al(OR.sup.2),
- wherein R.sup.1 and R.sup.2 independently each occurrence are C.sub.1-30 hydrocarbyl,
- the molar ratio of a1):
- b) being from 1:0.1 to 1:100;
- or
- a catalyst composition comprising in combination a cationic complex,
- a2) corresponding to the formula:[Z L M*X*.sub.p* ].sup.+ A.sup.-,
- wherein:
- M* is a metal of Group 4 of the Periodic Table of the Elements having an oxidation state of +3, bound in an .eta..sup.5 bonding mode to L;
- L is a cyclopentadienyl-, indenyl-, tetrahydroindenyl-, fluorenyl-, tetrahydrofluorenyl-, or octahydrofluorenyl-group covalently substituted with at least a divalent moiety, Z, and L further may be substituted with from 1 to 8 substituents independently selected from the group consisting of hydrocarbyl, halo, halohydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, dihydrocarbylphosphino or silyl groups containing up to 20 non-hydrogen atoms, or two such substituents may together form a divalent derivative;
- Z is a divalent moiety bound to both L and M* via .sigma.-bonds, said Z comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and also optionally comprising nitrogen, phosphorus, sulfur or oxygen;
- X* is an anionic ligand group having up to 60 atoms, exclusive of the class of ligands that are cyclic, delocalized, .pi.-bound ligand groups;
- p* is 0;
- and
- A.sup.- is an noncoordinating, compatible anion, and
- b) an organoaluminum hydrocarbyloxide compound according to the formula R.sup.1.sub.2 Al(OR.sup.2),
- wherein R.sup.1 and R.sup.2 independently each occurrence are C.sub.1-30 hydrocarbyl
- the molar ratio of a2):
- b) being from 1:0.1 to 1:100.
27 more elements
Dependencies are inferred from the claim text.