Titanium(II) or zirconium(II) complexes and addition polymerization catalysts therefrom
AssigneeThe Dow Chemical Company
InventorsDavid D. Devore, Francis J. Timmers, David R. Wilson, Robert K. Rosen
Life of this patent
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Abstract
Novel titanium or zirconium complexes containing one and only one cyclic delocalized, anionic, .pi.-bonded group wherein the metal is in the +2 formal oxidation state and having a bridged ligand structure, also referred to as constrained geometry complexes; catalytic derivatives of such complexes; methods of preparation; and the use thereof as catalysts for polymerizing olefins, diolefins and/or acetylenically unsaturated monomers.
Claims14
A metal complex containing one and only one cyclic delocalized, anionic, .pi.-bonded group, said complex corresponding to the formula:
- ##STR10## wherein:
- M is titanium or zirconium in the +2 formal oxidation state;
- L is a group containing a cyclic, delocalized, anionic, .pi.-system through which the group is bound to M, and which group is also bound to Z;
- Z is a moiety bound to M via a .sigma.-bond, comprising boron, and the members of Group 14 of the Periodic Table of the Elements, and also comprising an element selected from the groups consisting of an element selected from the groups consisting of nitrogen, phosphorus, sulfur and oxygen, said moiety having up to 60 nonhydrogen atoms;
- and
- X is a neutral, conjugated or nonconjugated diene, optionally substituted with one or more groups selected from hydrocarbyl or trimethylsilyl groups, said X having up to 40 carbon atoms and forming a .pi.-complex with M.
A process for preparing a metal complex containing one and only one cyclic delocalized .pi.-bonded group, said complex corresponding to the formula:
- ##STR14## wherein:
- M is titanium or zirconium in the +2 formal oxidation state;
- L is a group containing a cyclic, delocalized .pi.-system through which the group is bound to M, and which group is also bound to Z;
- Z is a moiety bound to M via a .sigma.-bond, comprising an element selected from the groups consisting of boron, and the members of Group 14 of the Periodic Table of the Elements, and also comprising an element selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen, said moiety having up to 60 nonhydrogen atoms;
- and
- X is a neutral, conjugated or nonconjugated diene, optionally substituted with one or more groups selected from hydrocarbyl or trimethylsilyl groups, said X having up to 40 carbon atoms and forming a .pi.-complex with M, the steps of the process comprising:
- 1) a) contacting a conjugated or nonconjugated C.sub.4-40 diene compound with a metal complex corresponding to the formula:
- ##STR15## wherein, M* is titanium or zirconium in the +3 formal oxidation state;
- M** is titanium or zirconium in the +4 formal oxidation state;
- and
- X* is halo;
- G* is a neutral Lewis base selected from the group consisting of amines, phosphines and ethers said G having from 3 to 20 nonhydrogen atoms;
- Z and L are as previously defined;
- and
- g is a number from 0 to 3, in a suitable, noninterfering solvent;
- and
- b) contacting the resulting mixture with a reducing agent, or
- 2) a) contacting a conjugated or nonconjugated C.sub.4-40 diene compound with a reducing agent in a suitable noninterfering solvent;
- and
- b) contacting the resulting mixture with a metal complex corresponding to the formula:
- ##STR16## wherein, M* is titanium or zirconium in the +3 formal oxidation state;
- M** is titanium or zirconium in the +4 formal oxidation state;
- and
- X* is halo;
- G* is a neutral Lewis base selected from the group consisting of amines, phosphines and ethers said G having from 3 to 20 nonhydrogen atoms;
- Z and L are as previously defined;
- and
- g is a number from 0 to 3.
A process for preparing a metal complex containing one and only one cyclic, delocalized .pi.-bonded group, said complex corresponding to the formula:
- ##STR17## wherein:
- M is titanium or zirconium in the +2 formal oxidation state;
- L is a group containing a cyclic, delocalized .pi.-system through which the group is bound to M, and which group is also bound to Z;
- Z is a moiety bound to M via a .sigma.-bond, comprising an element selected from the groups consisting of boron, and the members of Group 14 of the Periodic Table of the Elements, and also comprising an element selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen, said moiety having up to 60 nonhydrogen atoms;
- and
- X is a stable, neutral, conjugated or nonconjugated diene, optionally substituted with one or more groups selected from hydrocarbyl or trimethylsilyl groups, said X having up to 40 carbon atoms and forming a .pi.-complex with M;
- said process comprising contacting a compound according to the formula M(X*).sub.2 or a solvated adduct thereof
- wherein X* is halo;
- and
- M is as previously defined,
- with a conjugated or nonconjugated C.sub.4-40 diene compound corresponding to X and a source of a dianion ligand:
- (Z--L).sup.-2.
Dependencies are inferred from the claim text.