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US 8,609,794 B2Granted
Process for selectively polymerizing ethylene and catalyst therefor
AssigneeDow Global Technologies LLC
InventorsJerzy Klosin, Pulikkottil J. Thomas, Robert D. Froese, Xiuhua Cui
Life of this patent
Estimating the term…
Abstract
The present invention generally relates to a process that selectively polymerizes ethylene in the presence of an alpha-olefin, and to a metal-ligand complex (precatalyst) and catalyst useful in such processes, and to related compositions. The present invention also generally relates to ligands and intermediates useful for preparing the metal-ligand complex and to processes of their preparation.
Claims4
A process for selectively polymerizing ethylene in the presence of an alpha-olefin, the process comprising a step of contacting together a catalytic amount of a catalyst, ethylene, and an alpha-olefin, wherein the catalyst comprises a mixture or reaction product of components (a) and (b) that is prepared before the contacting step, wherein component (a) comprises a metal-ligand complex and component (b) comprises an activating co-catalyst;
- ethylene comprises ingredient (c);
- and the alpha-olefin comprises component (d);
- the metal-ligand complex of component (a) being one or more metal-ligand complexes of formula (I):
- wherein:
- M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4;
- n is an integer of from 0 to 3, wherein when n is 0, X is absent;
- each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic;
- or two X are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic;
- X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral;
- each Z independently is O, S, Nhydrocarbyl, or Phydrocarbyl;
- L is hydrocarbylene or heterohydrocarbylene, wherein the hydrocarbylene has a portion that comprises a 1-carbon atom to 6-carbon atom linker backbone linking the Z atoms in formula (I) and the heterohydrocarbylene has a portion that comprises a 1-atom to 6-atom linker backbone linking the Z atoms in formula (I), wherein each atom of the 1-atom to 6-atom linker backbone of the heterohydrocarbylene independently is a carbon atom or a heteroatom, wherein each heteroatom independently is O, S, S(O), S(O)2, Si(RC)2, Ge(RC)2, P(RP), or N(RN), wherein independently each RC is unsubstituted (C1-C18)hydrocarbyl or the two RC are taken together to form a (C2-C19)alkylene, each RP is unsubstituted (C1-C18)hydrocarbyl;
- and each RN is unsubstituted (C1-C18)hydrocarbyl, a hydrogen atom or absent;
- at least one of R1a, R2a, R1b, and R2b independently is a hydrocarbyl, heterohydrocarbyl, or halogen atom;
- and each of the other of R1a, R2a, R1b, and R2b independently is a hydrogen atom, hydrocarbyl, heterohydrocarbyl, or halogen atom;
- each of R3a, R4a, R3b, R4b, R6c, R7c, R8c, R6d, R7d, and R8d independently is a hydrogen atom;
- hydrocarbyl;
- heterohydrocarbyl;
- or halogen atom;
- each of R5c and R5d independently is an aryl or heteroaryl;
- each of the aforementioned aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl, hydrocarbylene, and heterohydrocarbylene groups independently is unsubstituted or substituted with one or more substituents RS;
- and
- each RS independently is a halogen atom, polyfluoro substituted, perfluoro substituted, unsubstituted (C1-C18)alkyl, F3C—, FCH2O—, F2HCO—, F3CO—, R3Si—, R3Ge—, RO—, RS—, RS(O)—, RS(O)2—, R2P—, R2N—, R2C═N—, NC—, RC(O)—, ROC(O)—, RC(O)N(R)—, or R2NC(O)—, or two of the RS are taken together to form an unsubstituted (C1-C18)alkylene, wherein each R independently is an unsubstituted (C1-C18)alkyl;
- wherein the activating co-catalyst of the ingredient (b) comprises one or more activating co-catalysts, or a reaction product thereof, wherein the ratio of total number of moles of the one or more metal-ligand complexes of formula (I) to total number of moles of the one or more activating co-catalysts is from 1:10,000 to 100:1;
- wherein the contacting step is performed under olefin polymerizing conditions and prepares a rich polyethylene in presence of unpolymerized alpha-olefin, wherein the rich polyethylene is a polymeric molecule, or segment thereof, consisting substantially of ethylene repeat units;
- or a mixture or blend of two or more such polymeric molecules;
- and
- wherein the process forms reactive chains and is characterized by a reaction rate constant k11 for adding the ethylene to a first reactive chain end comprising an ethylene residual;
- a reaction rate constant k12 for adding the alpha-olefin to a second reactive chain end comprising an ethylene residual;
- and a reactivity ratio r1 equal to k11 divided by k12 of greater than 14;
- and
- wherein every metal-ligand complex of formula (I) and catalyst based on any one or more of the following ligands (a) to (f) are excluded:
- (a) Each D is anthracen-9-yl;
- (b) Each D is 1,2,3,4,5,6,7,8-octahydroanthracen-9-yl;
- (c) Each D is 9H-carbozol-9-yl;
- or
- (d) Each D is 3,5-bis(1,1-dimethylethyl)phenyl;
- (e) Each E is 1,1-dimethylethyl;
- or
- (f) Each E is methoxy;
- wherein at least one of the one or more than one metal-ligand complexes of formula (I) is any one of metal-ligand complexes (1), (2), (10), (11), (20) to (22), and (23):
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′,5′-difluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (1);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′,5′-dichloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (2);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3′,5′-dimethyl-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (10);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-ethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (11);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5′-fluoro-3′-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (20);
- (2′,2″-(butane-1,4-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (21);
- (2′,2″-(ethane-1,2-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (22);
- and
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-zirconium, (23);
- or
- at least one of the one or more than one metal-ligand complexes of formula (I) is metal-ligand complex (3):
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (3);
- or
- at least one of the one or more than one metal-ligand complexes of formula (I) is metal-ligand complex (13):
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5′-fluoro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (13);
- or
- at least one of the one or more than one metal-ligand complexes of formula (I) is any one of metal-ligand complexes (3a), (6a), (6b), (19a), (4) to (9), (12), (14) to (19), (24), and (25):
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (3a);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-octyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (4);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-chloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (5);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5′-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (6);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (6a);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-(1-methylethyl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (6b);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (7);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-cyano-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (8);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-dimethylamino-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (9);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5′-tert-butyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (12);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(9H-carbazol-9-yl)-5′-chloro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (14);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5′-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (15);
- (2′,2″-(2,2-dimethyl-2-silapropane-1,3-diylbis(oxy))bis(3′,5′-dichloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (16);
- (2′,2″-(2,2-dimethyl-2-silapropane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (17);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3′-bromo-5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (18);
- (2′,2″-(propane-1,3-diylbis(oxy))-(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)-(3″,5″-dichloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (19);
- (2′,2″-(propane-1,3-diylbis(oxy))-(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)-(5″-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (19a);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′,5′-dichloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-titanium, (24);
- and
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-titanium, (25);
- or
- at least one of the one or more than one metal-ligand complexes of formula (I) is any one of metal-ligand complexes (26) to (31):
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-methoxy-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (26);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3′,4′-dimethyl-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (27);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(4′-(tert-butyl)-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (28);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5′-(tert-butyl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (29);
- (2′,2″-(butane-1,4-diylbis(oxy))bis(4′-(tert-butyl)-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (30);
- and
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-4′-(tert-butyl)-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (31);
- or
- at least one of the one or more than one metal-ligand complexes of formula (I) is any one of metal-ligand complexes (32) to (34):
- (2′,2″-(pentane-1,5-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (32);
- (2′,2″-(pentane-2,4-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (33);
- and
- (2′,2″-(hexane-1,6-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (34).
89 more elements
A metal-ligand complex of formula (I)
- wherein:
- M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4;
- n is an integer of from 0 to 3, wherein when n is 0, X is absent;
- each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic;
- or
- two X are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic;
- X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral;
- each Z independently is O, S, Nhydrocarbyl, or Phydrocarbyl;
- L is hydrocarbylene or heterohydrocarbylene, wherein the hydrocarbylene has a portion that comprises a 1-carbon atom to 6-carbon atom linker backbone linking the Z atoms in formula (I) and the heterohydrocarbylene has a portion that comprises a 1-atom to 6-atom linker backbone linking the Z atoms in formula (I), wherein each atom of the 1-atom to 6-atom linker backbone of the heterohydrocarbylene independently is a carbon atom or a heteroatom, wherein each heteroatom independently is O, S, S(O), S(O)2, Si(RC)2, Ge(RC)2, P(RP), or N(RN), wherein independently each RC is unsubstituted (C1-C18)hydrocarbyl or the two RC are taken together to form a (C2-C19)alkylene, each RP is unsubstituted (C1-C18)hydrocarbyl;
- and each RN is unsubstituted (C1-C18)hydrocarbyl, a hydrogen atom or absent;
- at least one of R1a, R2a, R1b, and R2b independently is a hydrocarbyl, heterohydrocarbyl, or halogen atom;
- and each of the other of R1a, R2a, R1b, and R2b independently is a hydrogen atom, hydrocarbyl, heterohydrocarbyl, or halogen atom;
- each of R3a, R4a, R3b, R4b, R6c, R7c, R8c, R6d, R7d, and R8d independently is a hydrogen atom;
- hydrocarbyl;
- heterohydrocarbyl;
- or halogen atom;
- each of R5c and R5d independently is an aryl or heteroaryl;
- each of the aforementioned aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl, hydrocarbylene, and heterohydrocarbylene groups independently is unsubstituted or substituted with one or more substituents RS;
- and
- each RS independently is a halogen atom, polyfluoro substituted, perfluoro substituted, unsubstituted (C1-C18)alkyl, F3C—, FCH2O—, F2HCO—, F3CO—, R3Si—, R3Ge—, RO—, RS—, RS(O)—, RS(O)2—, R2P—, R2N—, R2C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R2NC(O)—, or two of the RS are taken together to form an unsubstituted (C1-C18)alkylene, wherein each R independently is an unsubstituted (C1-C18)alkyl;
- wherein the activating co-catalyst of the ingredient (b) comprises one or more activating co-catalysts, or a reaction product thereof, wherein the ratio of total number of moles of the one or more metal-ligand complexes of formula (I) to total number of moles of the one or more activating co-catalysts is from 1:10,000 to 100:1;
- wherein the contacting step is performed under olefin polymerizing conditions and prepares a rich polyethylene in presence of unpolymerized alpha-olefin, wherein the rich polyethylene is a polymeric molecule, or segment thereof, consisting substantially of ethylene repeat units;
- or
- a mixture or blend of two or more such polymeric molecules;
- and
- wherein the process forms reactive chains and is characterized by a reaction rate constant k11 for adding the ethylene to a first reactive chain end comprising an ethylene residual;
- a reaction rate constant k12 for adding the alpha-olefin to a second reactive chain end comprising an ethylene residual;
- and a reactivity ratio r1 equal to k11 divided by k12 of greater than 14;
- and
- wherein every metal-ligand complex of formula (I) and catalyst based on any one or more of the following ligands (a) to (f) are excluded:
- (a) Each D is anthracen-9-yl;
- (b) Each D is 1,2,3,4,5,6,7,8-octahydroanthracen-9-yl;
- (c) Each D is 9H-carbozol-9-yl;
- or
- (d) Each D is 3,5-bis(1,1-dimethylethyl)phenyl;
- (e) Each E is 1,1-dimethylethyl;
- or
- (f) Each E is methoxy;
- wherein at least one of the one or more than one metal-ligand complexes of formula (I) is any one of metal-ligand complexes (1), (2), (10), (11), (20) to (22), and (23):
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′,5′-difluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (1);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′,5′-dichloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (2);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3′,5′-dimethyl-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (10);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-ethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (11);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5′-fluoro-3′-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (20);
- (2′,2″-(butane-1,4-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (21);
- (2′,2″-(ethane-1,2-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (22);
- and
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-zirconium, (23);
- or
- at least one of the one or more than one metal-ligand complexes of formula (I) is metal-ligand complex (3):
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (3);
- or
- at least one of the one or more than one metal-ligand complexes of formula (I) is metal-ligand complex (13):
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5′-fluoro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (13);
- or
- at least one of the one or more than one metal-ligand complexes of formula (I) is any one of metal-ligand complexes (3a), (6a), (6b), (19a), (4) to (9), (12), (14) to (19), (24), and (25):
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (3a);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-octyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (4);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-chloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (5);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5′-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (6);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (6a);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-(1-methylethyl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (6b);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (7);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-cyano-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (8);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-dimethylamino-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (9);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5′-tert-butyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (12);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(9H-carbazol-9-yl)-5′-chloro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (14);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5′-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (15);
- (2′,2″-(2,2-dimethyl-2-silapropane-1,3-diylbis(oxy))bis(3′,5′-dichloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (16);
- (2′,2″-(2,2-dimethyl-2-silapropane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (17);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3′-bromo-5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (18);
- (2′,2″-(propane-1,3-diylbis(oxy))-(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)-(3″,5″-dichloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (19);
- (2′,2″-(propane-1,3-diylbis(oxy))-(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)-(5″-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (19a);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′,5′-dichloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-titanium, (24);
- and
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-titanium, (25);
- or
- at least one of the one or more than one metal-ligand complexes of formula (I) is any one of metal-ligand complexes (26) to (31):
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-methoxy-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (26);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3′,4′-dimethyl-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (27);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(4′-(tert-butyl)-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (28);
- (2′,2″-(propane-1,3-diylbis(oxy))bis(3′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5′-(tert-butyl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (29);
- (2′,2″-(butane-1,4-diylbis(oxy))bis(4′-(tert-butyl)-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (30);
- and
- (2′,2″-(propane-1,3-diylbis(oxy))bis(5′-chloro-4′-(tert-butyl)-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (31);
- or
- at least one of the one or more than one metal-ligand complexes of formula (I) is any one of metal-ligand complexes (32) to (34):
- (2′,2″-(pentane-1,5-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (32);
- (2′,2″-(pentane-2,4-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (33);
- and
- (2′,2″-(hexane-1,6-diylbis(oxy))bis(5′-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol))dimethyl-hafnium, (34).
88 more elements
Dependencies are inferred from the claim text.