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US 12,466,901 B2Granted
Polymerization of ethylene in solution processes using a Ziegler-Natta catalyst and a hydrogenation procatalyst
AssigneeDow Global Technologies LLC
InventorsLinfeng Chen, David M. Pearson
Life of this patent
Estimating the term…
Abstract
Processes of polymerizing olefin monomers and catalyst systems. The catalyst systems include a non-hydrogen-generating post-metallocene procatalyst; a co-catalyst; and a hydrogenation procatalyst having the formula Cp2TiXnTiCp2 or Cp2TiXn, in which each Cp is cyclopentadienyl substituted with at least one (C1-C10)alkyl; each X is independently monoanionic or neutral, wherein each X is independently (C1-C40)hydrocarbon, (C1-C40)heterohydrocarbon, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, or a halogen atom; and n is 1 or 2.
Claims14
A catalyst system comprising:
- a non-hydrogen-generating post-metallocene procatalyst;
- a co-catalyst;
- and
- a hydrogenation procatalyst having the formula Cp2TiX2TiCp2 or Cp2TiXn, where:
- each Cp is cyclopentadienyl optionally substituted with at least one (C1-C10) alkyl;
- each X is independently (C1-C40)hydrocarbon, (C1-C40)heterohydrocarbon, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, or a halide;
- and
- n is 1 or 2;
- wherein the non-hydrogen-generating post-metallocene procatalyst is a metal-ligand complex according to formula (I):
- where:
- M is a metal selected from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4;
- n is 0, 1, or 2;
- when n is 1, X1 is a monodentate ligand or a bidentate ligand;
- when n is 2, each X1 is independently a monodentate ligand;
- each X1 that is a monodentate ligand is independently halide, unsubstituted (C1-C20)hydrocarbyl, unsubstituted (C1-C20)hydrocarbyl, C(O)O—, or RKRLN—, where each of RK and RL is independently an unsubstituted (C1-C20)hydrocarbyl;
- L is a diradical selected from the group consisting of (C1-C40)hydrocarbylene, (C1-C40)heterohydrocarbylene, —Si(RC)2-, —Si(RC)2OSi(RC)2-, —Si(RC)2C(RC)2-, —Si(RC)2Si(RC)2-, —Si(RC)2C(RC)2Si(RC)2-, —C(RC)2Si(RC)2C(RC)2-, —N(RN)C(RC)2-, —N(RN)N(RN)-, and —C(RC)2N(RN)C(RC)2-,
- each Z is independently selected from —O—, —S—, —N(RN)-, or —P (RP)-;
- R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are independently selected from the group consisting of —H, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RP)2, —N(RN)2, —ORC, —SRC, —NO2, —CN, —CF3, RCS(O)—, RCS(O)2—, —N═C(RC)2, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)—, halide, radicals having formula (XI), radicals having formula (XII), and radicals having formula (XIII):
- where:
- each of R31-R35, R41-R48, and R51-R59 is independently selected from —H, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RP)2, —N(RN)2, —ORC, —SRC, —NO2, —CN, —CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(RN)-, (RC)2NC(O)—, or halide;
- and
- wherein the non-hydrogen-generating post-metallocene procatalyst is unsupported and the hydrogenation procatalyst is unsupported.
19 more elements
A catalyst system comprising:
- a non-hydrogen-generating post-metallocene procatalyst;
- and
- Cp2TiX2 treated with an aluminum alkyl species, where:
- each Cp is cyclopentadienyl substituted with at least one (C1-C10) alkyl;
- each X is independently (C1-C40)hydrocarbon, (C1-C40)heterohydrocarbon, (C1-C40)hydrocarbon anion, (C1-C40)heterohydrocarbon anion, or a halide;
- wherein the non-hydrogen-generating post-metallocene procatalyst is a metal-ligand complex according to formula (I):
- where:
- M is a metal selected from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4;
- n is 0, 1, or 2;
- when n is 1, X1 is a monodentate ligand or a bidentate ligand;
- when n is 2, each X1 is independently a monodentate ligand;
- each X1 that is a monodentate ligand is independently halide, unsubstituted (C1-C20)hydrocarbyl, unsubstituted (C1-C20)hydrocarbyl, C(O)O—, or RKRLN—, where each of RK and RL is independently an unsubstituted (C1-C20)hydrocarbyl;
- L is a diradical selected from the group consisting of (C1-C40)hydrocarbylene, (C1-C40)heterohydrocarbylene, —Si(RC)2-, —Si(RC)2OSi(RC)2-, —Si(RC)2C(RC)2-, —Si(RC)2Si(RC)2-, —Si(RC)2C(RC)2Si(RC)2-, —C(RC)2Si(RC)2C(RC)2-, —N(RN)C(RC)2-, —N(RN)N(RN)-, and —C(RC)2N(RN)C(RC)2-,
- each Z is independently selected from —O—, —S—, —N(RN)-, or —P (RP)-;
- R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are independently selected from the group consisting of —H, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RP)2, —N(RN)2, —ORC, —SRC, —NO2, —CN, —CF3, RCS(O)—, RCS(O)2—, —N═C(RC)2, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)—, halide, radicals having formula (XI), radicals having formula (XII), and radicals having formula (XIII):
- where:
- each of R31-R35, R41-R48, and R51-R59 is independently selected from —H, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RP)2, —N(RN)2, —ORC, —SRC, —NO2, —CN, —CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(RN)-, (RC)2NC(O)—, or halide;
- and
- wherein the non-hydrogen-generating post-metallocene procatalyst is unsupported and the Cp2TiX2 treated with an aluminum alkyl species is unsupported.
16 more elements
Dependencies are inferred from the claim text.