| 主权项 |
1. A preparing process for a poly(ethylene alpha-olefin) block copolymer in the presence of an alpha-olefin, the process comprising a step of contacting together a combination of a chain shuttling agent and 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; andeach 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; andwherein 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; andwherein 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-hafinum, (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-hafinum, (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-hafinum, (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-hafinum, (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-hafinum, (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-hafinum, (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). |
