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US 12,686,731 B2Granted
Catalyst systems and processes for producing polyethylene using the same
AssigneeDow Global Technologies LLC
InventorsRhett A. Baillie, Hien Q. Do, Andrew M. Camelio, Johnathan E. Delorbe, Mari S. Rosen, Philip P. Fontaine, David M. Pearson
Life of this patent
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Abstract
Embodiments of the present application are directed to procatalysts, and catalyst systems including procatalysts including a metal-ligand complex having the structure of formula (1): [Formula I].
Claims20
A procatalyst comprising a metal-ligand complex disposed on one or more support materials, wherein the metal-ligand complex has a structure according to formula (I):
- wherein:
- M is titanium, zirconium, or hafnium;
- N is 1, 2, or 3;
- each X is a monodentate ligand independently chosen from unsaturated (C2-C50)hydrocarbon, unsaturated (C2-C50)heterohydrocarbon, (C1-C50)hydrocarbyl, (C1-C50)heterohydrocarbyl, (C6-C50)aryl, (C4-C50)heteroaryl, halogen, —N(RN)2, and —N(RN)CORC;
- the metal-ligand complex is overall charge-neutral;
- each Z is independently chosen from —O—, —S—, (C6-C50)aryl, (C4-C50)heteroaryl, N(C1-C50)hydrocarbyl, and P(C1-C50)hydrocarbyl;
- R1 and R16 are independently chosen from (C6-C50)aryl, (C4-C50)heteroaryl, (C1-C50)alkyl, (C3-C40)heteroalkyl, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):
- wherein R31-35, R41-48, and R51-59 are independently chosen from —H, (C1-C50)hydrocarbyl, (C1-C50)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)—, and halogen;
- R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15 are independently chosen from —H, (C1-C50)hydrocarbyl, (C1-C50)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(R)—, (RC)2NC(O)—, and halogen;
- R23 and R24 are independently chosen from —(CRC2)m—, wherein subscript m is from 1 to 10;
- R17 and R18 are independently chosen from linear or branched (C1-C20)alkyl;
- and
- each RC, RP, and RN are independently chosen from —H, (C1-C50)hydrocarbyl, and (C1-C50)heterohydrocarbyl.
10 more elements
A method for producing a catalyst system, the method comprising:
- contacting one or more support materials, one or more activators, and a metal-ligand complex in an inert hydrocarbon solvent to produce the catalyst system, wherein the metal-ligand complex has a structure according to formula (Ia):
- wherein:
- A− is an anion;
- M is titanium, zirconium, or
- hafnium;
- n is 1, 2, or 3;
- each X is a monodentate ligand independently chosen from unsaturated (C2-C50)hydrocarbon, unsaturated (C2-C50)heterohydrocarbon, (C1-C50)hydrocarbyl, (C1-C50)heterohydrocarbyl, (C6-C50)aryl, (C4-C50)heteroaryl, halogen, —N(RN)2, and —N(RN)CORC;
- each Z is independently chosen from —O—, —S—, (C6-C50)aryl, (C4-C50)heteroaryl, N(C1-C40)hydrocarbyl, and P(C1-C40)hydrocarbyl;
- R1 and R16 are independently chosen from (C6-C50)aryl, (C4-C50)heteroaryl, (C1-C40)alkyl, (C3-C40)heteroalkyl, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):
- wherein R31-35, R41-48, and R51-59 are independently chosen from —H, (C1-C50)hydrocarbyl, (C1-C50)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)—, and halogen;
- R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15 are independently chosen from —H, (C1-C50)hydrocarbyl, (C1-C50)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(R)—, (RC)2NC(O)—, and halogen;
- R23 and R24 are independently chosen from —(CRC2)m—, wherein subscript m is from 1 to 10;
- R17 and R18 are independently chosen from linear or branched (C1-C20)alkyl;
- and
- each RC, RP, and RN are independently chosen from —H, (C1-C50)hydrocarbyl, and (C1-C50)heterohydrocarbyl.
12 more elements
A process for producing polyethylene, the process comprising contacting ethylene and, optionally, one or more (C3-C12)α-olefin comonomers with a catalyst system in a gas-phase polymerization reactor, wherein the catalyst system comprises a metal-ligand complex disposed on one or more support materials;
- and the metal-ligand complex has a structure according to formula (Ia):
- wherein:
- A− is an anion;
- M is titanium, zirconium, or
- hafnium;
- subscript n of (X)n is 1, 2, or 3;
- each X is a monodentate ligand independently chosen from unsaturated (C2-C50)hydrocarbon, unsaturated (C2-C50)heterohydrocarbon, (C1-C50)hydrocarbyl, (C1-C50)heterohydrocarbyl, (C6-C50)aryl, (C4-C50)heteroaryl, halogen, —N(RN)2, and —N(RN)CORC;
- each Z is independently chosen from —O—, —S—, (C6-C50)aryl, (C4-C50)heteroaryl, N(C1-C40)hydrocarbyl, and P(C1-C40)hydrocarbyl;
- R1 and R16 are independently chosen from (C6-C50)aryl, (C4-C50)heteroaryl, (C1-C40)alkyl, (C3-C40)heteroalkyl, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):
- wherein R31-35, R41-48, and R51-59 are independently chosen from —H, (C1-C50)hydrocarbyl, (C1-C50)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)—, and halogen;
- R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15 are independently chosen from —H, (C1-C50)hydrocarbyl, (C1-C50)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(R)—, (RC)2NC(O)—, and halogen;
- R23 and R24 are independently chosen from —(CRC2)m—, wherein subscript m is from 1 to 10;
- R17 and R18 are independently chosen from linear or branched (C1-C20)alkyl;
- and
- each RC, RP, and RN are independently chosen from —H, (C1-C50)hydrocarbyl, and (C1-C50)heterohydrocarbyl.
12 more elements
Dependencies are inferred from the claim text.