Biaryl phenoxy group IV transition metal catalysts for olefin polymerization

1. A catalyst system comprising a metal-ligand complex according to formula (I):

where

M is titanium, zirconium, or hafnium having a formal oxidation state of +2, +3, or +4;

each X is a monodentate or bidentate ligand independently selected from the group consisting of unsaturated (C 2 -C 50 )hydrocarbon, unsaturated (C 2 -C 50 )heterohydrocarbon, (C 1 -C 50 )hydrocarbyl, (C 6 -C 50 )aryl, (C 6 -C 50 )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C 4 -C 12 )diene, halogen, —N(R N ) 2 , and —NCOR C ;

n is 1, 2, or 3;

the metal-ligand complex has 6 or fewer metal-ligand bonds;

each Y is independently oxygen or sulfur;

each R 1 is independently selected from the group consisting of (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, —P(O)(R P ) 2 , R C S(O) 2 —, (R c ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R c ) 2 NC(O)—, halogen, and —H;

Q is (C 2 -C 12 )alkylene, (C 2 -C 12 )heteroalkylene, (C 6 -C 50 )arylene, (C 4 -C 50 )heteroarylene, (—CH 2 Si(R C ) 2 CH 2 —), (—CH 2 CH 2 Si(R C ) 2 CH 2 CH 2 —), (—CH 2 Ge(R C ) 2 CH 2 —), or (—CH 2 CH 2 Ge(R C ) 2 CH 2 CH 2 —);

for each individual ring containing groups z 1 and z 2 , each of z 1 and z 2 is independently selected from the group consisting of sulfur, oxygen, —N(R R )—, ═N—, and —C(R R )—, provided that at least one of z 1 or z 2 is —C(R R )—;

each A is independently selected from the group consisting of -z 3 -z 4 -z 5 - and —C(R 3 )C(R 4 )C(R 5 )C(R 6 )—, where:

each of z 3 , z 4 , and z 5 is selected from the group consisting of sulfur, oxygen, —N(R R )—, and —C(R R )—, provided that exactly one of z 3 , z 4 , or z 5 is —C(R R )—or that exactly two of z 3 , z 4 , or z 5 are —C(R R )—; and

each R 3 , R 4 , R 5 , and R 6 is independently selected from the group consisting of (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R c ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R c ) 2 NC(O)—, halogen, and —H;

each R C , R N , and R P in formula (I) is independently a (C 1 -C 50 )hydrocarbyl; and

each R R is independently selected from the group consisting of (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, halogen, and —H, wherein any two R R groups bonded to neighboring atoms are optionally linked.

2. The catalyst system according to claim 1 , wherein:

M is zirconium or hafnium;

each X is independently selected from the group consisting of (C 6 -C 20 )aryl, (C 4 -C 20 )heteroaryl, (C 4 -C 12 )diene, and a halogen;

each Y is oxygen; and

each R 1 is independently selected from the group consisting of (C 1 -C 50 )aryl and (C 4 -C 50 )heteroaryl.

3. The catalyst system according to claim 1 , wherein for each individual ring containing groups z 1 and z 2 , one of z 1 and z 2 is sulfur, and the other is —C(H) —.

4. The catalyst system according to claim 1 , wherein each A is —C(R 3 )C(R 4 )C(R 5 )C(R 6 )— each R 3 , R 4 , R 5 , and R 6 is —H.

5. The catalyst system according to claim 1 , wherein each R 1 is carbazolyl.

6. The catalyst system according to claim 1 , wherein each R 1 is phenyl or a substituted phenyl.

7. The catalyst system according to claim 1 , wherein R 1 is independently selected from the group consisting of carbazole; 3,6-di-tert-butylcarbazole; 3,6-bis-(2,4,6-trimethylphenyl)carbazole; 3,6-bis-(2,4,6-triisopropylphenyl)carbazole; 3,6-bis-(3,5-di-tert-butylphenyl)carbazole; 2,4,6-tri-iso-propylphenyl; 3,5-di-iso-propylphenyl; m-terphenyl; 3,5-bis-(2,4,6-trimethylphenyl)phenyl; 3,5-bis-(2,4,6-triisopropylphenyl)phenyl; and 3,5-bis-(3,5-di-tert-butylphenyl)phenyl groups.

8. The catalyst system according to claim 1 , wherein each R 1 is a substituted phenyl selected from the group consisting of 2,4,6-trimethylphenyl; 2,4,6-tri(iso-propyl)phenyl; 3,5-di-tert-butylphenyl, and 3,5-diphenylphenyl.

9. The catalyst system according to claim 1 , wherein each R 1 is independently 3,6-di-tert-butylcarbazol-9-yl or 2,7-di-tert-butylcarbazol-9-yl.

10. The catalyst system according to claim 1 , wherein each R 1 is 3,5-di-tert-butylphenyl.

11. The catalyst system according to claim 1 , wherein each R 1 is 2,4,6-trimethylphenyl.

12. The catalyst system according to claim 1 , where Q is (C 2 -C 12 )alkylene, (C 2 -C 12 )heteroalkylene, (C 6 -C 50 )arylene, (C 4 -C 50 )heteroarylene, (—CH 2 Si(R C ) 2 CH 2 —), (—CH 2 CH 2 Si(R C ) 2 CH 2 CH 2 —), (—CH 2 Ge(R C ) 2 CH 2 —), or (—CH 2 CH 2 Ge(R C ) 2 CH 2 CH 2 —).

13. The catalyst system according to claim 1 , wherein Q is chosen from —(CH 2 ) x —, where x is from 2 to 5.

14. The catalyst system according to claim 1 , wherein Q is —(CH 2 ) 4 —.

15. A polymerization process for producing an ethylene-based polymer, the polymerization process comprising:

polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system according to claim 1 and at least one activator to form a polymer.

16. A polymerization process for producing a propylene-based polymer, the polymerization process comprising:

polymerizing propylene and optionally one or more additional α-olefin in the presence of a catalyst system according to claim 1 and at least one activator to form a polymer.

17. The polymerization process according claim 16 , wherein the activator comprises MMAO, bis(hydrogenated tallow alkyl)methylammonium, tetrakis(pentafluorophenyl)borate, or tris(pentafluorophenyl)borane.