IP Library › Granted Patent US 8,609,794

Granted Patent B2

US 8,609,794 · App. 13/105,018 · Granted Dec 17, 2013

Process for selectively polymerizing ethylene and catalyst therefor

Inventors: Jerzy Klosin (Midland, MI); Pulikkottil J. Thomas (Midland, MI); Robert D. Froese (Midland, MI); Xiuhua Cui (Pearland, TX)

Assignee: Dow Global Technologies, LLC.

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Quick Facts

Patent No.: US 8,609,794
App. No.: 13/105,018
Granted: Dec 17, 2013
Kind: B2

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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.

Claims (181)

1. 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(R C ) 2 , Ge(R C ) 2 , P(R P ), or N(R N ), wherein independently each R C is unsubstituted (C 1 -C 18 )hydrocarbyl or the two R C are taken together to form a (C 2 -C 19 )alkylene, each R P is unsubstituted (C 1 -C 18 )hydrocarbyl; and each R N is unsubstituted (C 1 -C 18 )hydrocarbyl, a hydrogen atom or absent;

at least one of R 1a , R 2a , R 1b , and R 2b independently is a hydrocarbyl, heterohydrocarbyl, or halogen atom; and each of the other of R 1a , R 2a , R 1b , and R 2b independently is a hydrogen atom, hydrocarbyl, heterohydrocarbyl, or halogen atom;

each of R 3a , R 4a , R 3b , R 4b , R 6c , R 7c , R 8c , R 6d , R 7d , and R 8d independently is a hydrogen atom; hydrocarbyl; heterohydrocarbyl; or halogen atom;

each of R 5c and R 5d 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 R S ; and

each R S independently is a halogen atom, polyfluoro substituted, perfluoro substituted, unsubstituted (C 1 -C 18 )alkyl, F 3 C—, FCH 2 O—, F 2 HCO—, F 3 CO—, R 3 Si—, R 3 Ge—, RO—, RS—, RS(O)—, RS(O) 2 —, R 2 P—, R 2 N—, R 2 C═N—, NC—, RC(O)—, ROC(O)—, RC(O)N(R)—, or R 2 NC(O)—, or two of the R S are taken together to form an unsubstituted (C 1 -C 18 )alkylene, wherein each R independently is an unsubstituted (C 1 -C 18 )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 k 11 for adding the ethylene to a first reactive chain end comprising an ethylene residual; a reaction rate constant k 12 for adding the alpha-olefin to a second reactive chain end comprising an ethylene residual; and a reactivity ratio r 1 equal to k 11 divided by k 12 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;

(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).

2. 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;

each of R 3a , R 4a , R 3b , R 4b , R 6c , R 7c , R 8c , R 6d , R 7d , and R 8d independently is a hydrogen atom; hydrocarbyl; heterohydrocarbyl; or halogen atom;

each of R 5c and R 5d independently is an aryl or heteroaryl;

each R S independently is a halogen atom, polyfluoro substituted, perfluoro substituted, unsubstituted (C 1 -C 18 )alkyl, F 3 C—, FCH 2 O—, F 2 HCO—, F 3 CO—, R 3 Si—, R 3 Ge—, RO—, RS—, RS(O)—, RS(O) 2 —, R 2 P—, R 2 N—, R 2 C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R 2 NC(O)—, or two of the R S are taken together to form an unsubstituted (C 1 -C 18 )alkylene, wherein each R independently is an unsubstituted (C 1 -C 18 )alkyl;

a mixture or blend of two or more such polymeric molecules; and