Productivity catalysts and microstructure control
AssigneeEastman Chemical Company
InventorsPeter Borden MacKenzie, Leslie Shane Moody, James Allen Ponasik JR., Amy Kathryn Farthing
Life of this patent
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Abstract
Improved Group 3-11 transition-metal based catalysts and processes for the polymerization of olefins are described. Some of the ligands are characterized by a preferred substitution pattern which allows for higher productivities of highly branched olefins; substitution patterns which boost productivity or alter the polymer microstructure are also described.
Claims41
A catalyst for olefin polymerization, comprising a Group 3-11 metal complex of a bidentate, tridentate, or tetradentate ligand, wherein said complex comprises at least one N-donor fragment of formula 1a or 1b;
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- wherein:
- M is a Group 3-11 transition metal;
- R3a-d are each, independently, H, F, Cl, Br, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl, nitro, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl;
- and
- Ar1a is an aryl or heteroaryl group substituted at one or both ortho positions by a group Q2;
- wherein Q2 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl.
A bidentate, tridentate, or tetradentate ligand of Set 1, Set 2, or Set 3.
A process for the polymerization of olefins, comprising contacting one or more olefins with a catalyst comprising a Group 8-10 metal complex of a bidentate, N,N-donor ligand, wherein the first of said donor nitrogens, N1, is substituted by an aromatic or heteroaromatic ring wherein the ortho substituents are aryl or heteroaryl groups, and the second of said donor nitrogens, N2, is substituted by an aromatic or heteroaromatic ring wherein one or both of the ortho substituents are other than aryl or heteroaryl;
- wherein said catalyst is capable of homopolymerizing ethylene to produce a polymer with a number average molecular weight of at least 20,000 g/mole and at least 20 branch points per 1000 carbons with a catalyst productivity of at least 500 kg polyethylene per g of Group 8-10 metal at a temperature of at least 60° C. at a partial pressure of ethylene of at least 350 psia at a partial pressure of hydrogen of at least 2 psia.
A process for the polymerization of olefins, comprising contacting one or more olefins with a catalyst comprising a Group 8-10 metal complex of a bidentate, tridentate or multidentate ligand, wherein said catalyst is activated using an alkylaluminum compound, wherein said alkylaluminum compound is subsequently selectively deactivated before the bulk of said polymerization has occurred.
A catalyst for the polymerization of olefins, comprising a nickel complex of a ligand of formula 2a;
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- wherein:
- R2x,y are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or silyl;
- in addition, R2x and R2y may be linked by a bridging group;
- R3a-f are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, iodo, cyano, or nitro;
- R3x,y are each independently halo or fluoroalkyl;
- and
- Ar2a,b are each independently aryl or heteroaryl.
An ethylene homopolymer having a number average molecular weight of at least 10,000 g/mole, total branching of less than about 70 branches per 1000 carbons, at least 10% saturated hydrocarbon polymer chains, and a ratio of C5 and longer branches to methyl branches of at least 0.35.
Dependencies are inferred from the claim text.