Biaryl phenoxy group IV transition metal catalysts for olefin polymerization
Embodiments are directed to a catalyst system comprising metal-ligand complexes and processes for polyolefin polymerization using the metal-ligand complex having the following structure:
1. A catalyst system comprising a metal-ligand complex according to formula (I):
where
M is a metal selected from the group consisting of titanium, zirconium, hafnium, the metal 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 20 )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;
m is 1 or 2;
the metal-ligand complex has 6 or fewer metal-ligand bonds;
each Y is independently selected from oxygen or sulfur;
each R 1 , R 2 , R 3 , and R 4 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 5 is independently chosen from (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, (C 6 -C 50 )aryl, (C 4 -C 50 )heteroaryl, —Si(R C ) 3 , and —Ge(R C ) 3 , and, when m is 2, two R 5 are optionally covalently linked;
for each individual ring containing groups z 1 , z 2 , and z 3 , each of z 1 , z 2 , and z 3 is independently selected from the group consisting of sulfur, oxygen, —N(R R )—, or —C(R R )—, provided that at least one and not more than two of z 1 , z 2 , and z 3 are —C(R R )—, where R R is —H or (C 1 -C 30 )hydrocarbyl, wherein any two R R groups bonded to neighboring atoms are optionally linked;
each R C , R N , and R P in formula (I) is independently a (C 1 -C 30 )hydrocarbyl.
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;
each R 1 is independently selected from the group consisting of (C 1 -C 50 )aryl and (C 4 -C 50 )heteroaryl; and
each R 2 , R 3 and R 4 is independently selected from the group consisting of (C 1 -C 50 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, (C 6 -C 40 )aryl, (C 4 -C 50 )heteroaryl, halogen, and —H.
3. The catalyst system according to claim 1 , wherein for each individual ring containing groups z 1 , z 2 , and z 3 , one of z 1 , z 2 , and z 3 is a sulfur atom, and two of z 1 , z 2 , and z 3 are —C(H)—.
4. The catalyst system according to claim 1 , wherein each R 1 is carbazolyl, each R 2 is methyl, and each R 3 is methyl.
5. The catalyst system according to claim 1 , wherein each R 1 is 3,6-di-tert-butylcarbazol-9-yl.
6. The catalyst system according to claim 1 , wherein each R 1 is 3,5-di-tert-butylphenyl.
7. The catalyst system according to claim 1 , wherein R 2 is tert-octyl.
8. The catalyst system according to claim 1 , wherein m is 2 and the metal-ligand complex has a structure according to formula (II):
where R 1 , R 2 , R 3 , R 4 , R 5 , z 1 , z 2 , z 3 , Y, and X are as defined in formula (I); and n is 1 or 2.
9. The catalyst system according to claim 8 , wherein:
M is zirconium or hafnium;
each X is independently selected from the group consisting of (C 6 -C 50 )aryl, (C 6 -C 50 )heteroaryl, (C 4 -C 12 )diene, and halogen;
each Y is oxygen;
each R 1 , R 2 , R 3 and R 4 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, halogen, and hydrogen.
10. The catalyst system according to claim 8 , wherein for each individual ring containing groups z 1 , z 2 , and z 3 , one of z 1 , z 2 , and z 3 is a sulfur atom, and two of z 1 , z 2 , and z 3 are —C(H)—.
11. The catalyst system according to claim 9 , wherein n is 2 and each X is benzyl.
12. The catalyst system according to claim 8 , wherein each R 1 is carbazolyl, each R 2 is methyl, and each R 3 is methyl.
13. The catalyst system according to claim 8 , wherein each R 1 is 3,6-di-tert-butylcarbazol-9-yl or 2,7-di-tert-butylcarbazol-9-yl.
14. The catalyst system according to claim 8 , wherein each R 3 is tert-octyl.
15. The catalyst system according to claim 8 , wherein each R 1 is 3,5-di-tert-butylphenyl.
16. The catalyst system according to claim 8 , wherein the two groups R 5 are covalently linked, whereby the metal-ligand complex comprises a divalent radical Q consisting of the two covalently linked groups R 5 , and the metal-ligand complex has a structure according to formula (III):
where:
Q is (C 1 -C 12 )alkylene, (C 1 -C 12 )heteroalkylene, (—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 —), where R C is (C 1 -C 30 )hydrocarbyl;
R 1-4 , Y, X, M, z 1 , z 2 , and z 3 are defined in formula (I); and
n is 1, or 2.
17. The catalyst system according to claim 16 , wherein Q is —CH 2 Si(CH 3 ) 2 CH 2 —.
18. 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,
wherein the polymer exhibits:
a density from 0.860 g/cm 3 to 0.973 g/cm 3 , measured according to ASTM D792;
a molecular weight distribution from 1 to 20; and
less than 20% octene incorporation.
19. The polymerization process according claim 17 , wherein the density is from 0.880 g/cm 3 to 0.920 g/cm 3 .
20. The polymerization process according claim 17 , wherein the activator comprises MMAO, bis(hydrogenated tallow alkyl)methylammonium, tetrakis(pentafluorophenyl)borate, or tris(pentafluorophenyl)borane.