Polymerization of olefinic compounds
AssigneesE. I. Du Pont de Nemours and Company, The University of North Carolina at Chapel Hill
InventorsMaurice S. Brookhart, Keith Kunitsky, Weijun Liu, Jon M. Malinoski, Lin Wang, Ying Wang, Lynda Kaye Johnson, Kristina A. Kreutzer, Steven Dale Ittel
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Abstract
Certain complexes containing ligands having a phosphino group, amino group or an imino group, and a second functional group such as amide, ester or ketone, when complexed to transition metals, catalyze the (co)polymerization of olefinic compounds such as ethylene, α-olefins and/or acrylates. A newly recognized class of ligands for making copolymer containing polar monomers using late transition metal complexes is described.
Claims26
A Group 3 through 11 (IUPAC) transition metal or lanthamide metal complex of a ligand of the formula (I)
- 22
- wherein:
- Z is nitrogen or oxygen;
- and
- Q is nitrogen or phosphorous;
- provided that:
- when Q is phosphorous and Z is nitrogen:
- R1 and R2 are each independently hydrocarbyl, silyl, or substituted hydrocarbyl having an Es of about −0.90 or less;
- R3, R4, R5, and R6 are each independently hydrogen, hydrocarbyl, a functional group, or substituted hydrocarbyl;
- R7 is hydrogen, hydrocarbyl, substituted hydrocarbyl or silyl;
- and R8 is hydrocarbyl, substituted hydrocarbyl, or silyl;
- provided that any two of R3, R4, R5, R6, R7 and R8 vicinal or geminal to one another together may form a ring;
- when Q is phosphorous and Z is oxygen:
- R1 and R2 are each independently hydrocarbyl, silyl, or substituted hydrocarbyl having an Es of about −0.90 or less;
- R3 and R4 are each independently hydrogen, hydrocarbyl, a functional group, or substituted hydrocarbyl;
- R5 and R7 taken together form a double bond;
- R8 is not present;
- and R6 is —OR9, —NR1OR11, hydrocarbyl or substituted hydrocarbyl, wherein R9 is hydrocarbyl or substituted hydrocarbyl, and R10 and R11 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
- and provided that any two of R3, R4, and R6 vicinal or geminal to one another may form a ring;
- or
- R1 and R2 are each independently hydrocarbyl, silyl, or substituted hydrocarbyl having an Es of about −0.90 or less;
- R3, R4, R5 and R6 are each independently hydrogen, hydrocarbyl, a functional group, or substituted hydrocarbyl;
- R7 is hydrocarbyl, silyl, or substituted hydrocarbyl;
- and R8 is not present;
- and provided that any two of R3, R4, R5, R6, and R7 vicinal or geminal to one another may form a ring;
- when Q is nitrogen:
- R1 is hydrocarbyl, silyl, or substituted hydrocarbyl having an Es of about −0.90 or less;
- R2 and R3 are each independently hydrogen, hydrocarbyl, a functional group, or substituted hydrocarbyl, or taken together form a double bond;
- R4 is hydrogen, hydrocarbyl, a functional group, or substituted hydrocarbyl;
- Z is oxygen;
- R6 and R7 taken together form a double bond;
- R8 is not present;
- R5 is —OR12, —R13 or —NR14R15, wherein R12 and R13 are each independently hydrocarbyl or substituted hydrocarbyl, and R14 and R15 are each hydrogen, hydrocarbyl or substituted hydrocarbyl;
- provided that when R2 and R3 taken together form an aromatic ring, R1 and R4 are not present;
- and further provided that any two of R2, R3, R4 and R5 vicinal or germinal to one another taken together may form a ring.
A process for the manufacture of a polar copolymer by contacting, under polymerizing conditions, a hydrocarbon olefin, a polar olefin, and a polymerization catalyst comprising a nickel complex of a bidentate ligand which is an active ligand.
An improved process for the manufacture of a polar copolymer by contacting, under polymerizing conditions, a hydrocarbon olefin, a polar olefin, and a polymerization catalyst comprising a nickelcomplex, wherein the improvement comprises that the polymerization catalyst comprises a nickel complex of a bidentate ligand which is an active ligand.
Dependencies are inferred from the claim text.