	US 11,859,041 B2
	Modulating co-monomer selectivity using non-covalent dispersion interactions in group 4 olefin polymerization catalysts
Steven M. Bischof, Humble, TX (US); Qing Yang, Bartlesville, OK (US); Orson L. Sydora, Sugar Land, TX (US); Graham R. Lief, Bartlesville, OK (US); Richard M Buck, Bartlesville, OK (US); Daniel H. Ess, Provo, UT (US); and Steven M. Maley, Orem, UT (US)
Assigned to Chevron Phillips Chemical Company LP, The Woodlands, TX (US)
Filed by CHEVRON PHILLIPS CHEMICAL COMPANY LP, The Woodlands, TX (US)
Filed on Aug. 16, 2021, as Appl. No. 17/403,527.
Prior Publication US 2023/0098789 A1, Mar. 30, 2023
Int. Cl. C08F 4/76 (2006.01); G16C 10/00 (2019.01); G16C 20/00 (2019.01); G06N 5/00 (2023.01); C08F 10/00 (2006.01); C08F 4/6192 (2006.01)

CPC C08F 4/76 (2013.01) [C08F 10/00 (2013.01); G16C 10/00 (2019.02); G16C 20/00 (2019.02); C08F 4/61925 (2013.01); C08F 4/61927 (2013.01); C08F 2420/10 (2021.01); G06N 5/00 (2013.01)]

23 Claims

1. A method for designing a Group 4 metallocene olefin polymerization catalyst, the method comprising:

(a) selecting a first metallocene catalyst framework comprising a Group 4 metal bonded to a hydrocarbyl ligand and to one or two independently selected substituted or unsubstituted η⁵-cycloalkadienyl ligands, and generating a first ground state model structure (GS^A) derived from the first metallocene catalyst framework;

(b) generating (1) a first transition state model structure (TS^A1) derived from migratory insertion of an ethylene molecule into a metal-hydrocarbyl ligand bond of the first metallocene catalyst framework and (2) a second transition state model structure (TS^A2) derived from migratory insertion of an α-olefin co-monomer molecule into the metal-hydrocarbyl ligand bond of the first metallocene catalyst framework;

(c) determining, by at least one processor of a device, relative energies of each of the first ground state model structure (GS^A), the first transition state model structure (TS^A1), a dispersion energy (Disp E^A1) associated with TS^A1, the second transition state model structure (TS^A2), and a dispersion energy (Disp E^A2) associated with TS^A2, and determining values for ΔG^‡A1(TS^A1−GS^A), ΔG^‡A2(TS^A1−GS^A), ΔΔG^‡A(TS^A2−TS^A1) and an absolute difference in dispersion energies |ΔDisp E^A| calculated as |Δ(Disp E^A2−Disp E^A1)| for migratory insertion of the ethylene molecule versus the α-olefin co-monomer molecule in the first metallocene catalyst framework;

(d) repeating steps (a)-(c) using a second metallocene catalyst framework comprising the Group 4 metal bonded to the hydrocarbyl ligand and to the one or two independently selected η⁵-cycloalkadienyl ligands, wherein at least one of the η⁵-cycloalkadienyl ligands comprises a first test substituent, and generating a corresponding second ground state model structure (GS^B), third transition state model structure (TS^B), and fourth transition state model structure (TS^B2), and determining, by at least one processor of a device, relative energies of each of a GS^B, TS^B1, a dispersion energy (Disp E^B1) associated with TS^B1, TS^B2, and a dispersion energy (Disp E^B2) associated with TS^B2, and determining values for ΔG^‡B1(TS^B1-GS^B), ΔG^‡B2(TS^B2−GS^B), ΔΔG^‡B(TS^B2−TS^B1) and an absolute difference in dispersion energies |ΔDisp E^B| calculated as |Δ(Disp E^B2−Disp E^B1)| for migratory insertion of the ethylene molecule versus the α-olefin co-monomer molecule in the second metallocene catalyst framework; and

(e) identifying the first test substituent of the second metallocene catalyst framework as (1) enhancing α-olefin co-monomer incorporation into a polyethylene co-polymer relative to the first metallocene catalyst framework when ΔΔG^‡B<ΔΔG^‡A, when |ΔDisp E^B|>|ΔDisp E^A|, or a combination thereof, or (2) enhancing ethylene incorporation into a polyethylene co-polymer relative to the first metallocene catalyst framework when ΔΔG^‡B>ΔΔG^‡A, when |ΔDisp E^B|<|ΔDisp E^A|, or a combination thereof.