US 12,221,508 B2
Biaryl phenoxy group IV transition metal catalysts for olefin polymerization
Andrew M. Camelio, Midland, MI (US); Brad C. Bailey, Midland, MI (US); Robert D J Froese, Midland, MI (US); Sukrit Mukhopadhyay, Midland, MI (US); David D. Devore, Midland, MI (US); and Jerzy Klosin, Midland, MI (US)
Assigned to Dow Global Technologies LLC, Midland, MI (US)
Appl. No. 17/413,780
Filed by Dow Global Technologies LLC, Midland, MI (US)
PCT Filed Dec. 12, 2019, PCT No. PCT/US2019/065966
§ 371(c)(1), (2) Date Jun. 14, 2021,
PCT Pub. No. WO2020/131566, PCT Pub. Date Jun. 25, 2020.
Claims priority of provisional application 62/782,855, filed on Dec. 20, 2018.
Prior Publication US 2022/0041764 A1, Feb. 10, 2022
This patent is subject to a terminal disclaimer.
Int. Cl. C08F 4/659 (2006.01); C08F 210/02 (2006.01)
CPC C08F 4/65908 (2013.01) [C08F 210/02 (2013.01); C08F 2800/10 (2013.01)] 20 Claims
OG exemplary drawing
 
1. A catalyst system comprising:
a metal-ligand complex according to formula (I):

OG Complex Work Unit Chemistry
where:
M is a metal chosen from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4;
each X is a monodentate or bidentate ligand independently chosen from unsaturated (C2-C20)hydrocarbon, unsaturated (C2-C50)heterohydrocarbon, (C1-C50)hydrocarbyl, (C6-C50)aryl, (C6-C50)heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C12)diene, halogen, —ORC, —N(RN)2, and —NCORC;
n is 1 or 2;
Y is oxygen, sulfur, or —N(RN)—;
each R1 is independently selected from the group consisting of —H, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RP)2, —N(RN)2, —ORC, —SRC, —NO2, —CN, —CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)—, halogen, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):

OG Complex Work Unit Chemistry
where each of R31-35, R41-48 and R51-59 is independently chosen from (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RP)2, —N(RN)2, —N═CHRC, —ORC, —SRC, —NO2, —CN, —CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(RN)—, (RC)2NC(O)—, halogen, or —H, provided at least one R1 in formula (I) is a radical having formula (II), a radical having formula (III), or a radical having formula (IV);
Q is (C1-C12)alkylene, (C1-C12)heteroalkylene, (—CH2Si(RQ)2CH2—), (—CH2CH2Si(RQ)2CH2CH2—), (—CH2Ge(RQ)2CH2—), or (—CH2CH2Ge(RQ)2CH2CH2—), where each RQ is (C1-C20)hydrocarbyl;
each z1 and z2 is independently selected from the group consisting of sulfur, oxygen, —N(RC)—, and —C(RC)—, provided at least one of z1 and z2 in each individual ring containing groups z1 and z2 is sulfur;
R4a, R5a, R6a, R7a, R4b, R5b, R6b, and R7b are independently chosen from (C1-C50)hydrocarbyl, (C1-C50)heterohydrocarbyl, (C6-C50)aryl, (C4-C50)heteroaryl, —Si(RC)3, —Ge(RC)3, —P(RP)2, —N(RN)2, —ORC, —SRC, —NO2, —CN, —CF3, RCS(O)—, —P(O)(RP)2, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)—, halogen, and —H, in which optionally R4a and R5a, or R5a and R6a, or R6a and R7a, or R4b and R5b, or R5b and R6b, or R6b and R7b are covalently connected to form an aromatic ring or a non-aromatic ring;
each RC, RN, and RP in formula (I) is independently selected from the group consisting of (C1-C20)hydrocarbyl, (C1-C20)heterohydrocarbyl, and —H; and
provided that when Q is —CH2CH2CH2CH2—:
(1) when each R1 is 3,6-di-tert-butylcarbazol-9-yl and z2 is sulfur and each X is benzyl, R5a and R5b are not —OMe, fluorine, or tert-octyl; or
(2) at least one of R4a, R5a, R6a, and R7a is halogen, and at least one of R4b, R5b, R6b, and R7b is halogen; or
(3) at least one of R4a, R5a, R6a, R7a, R4b, R5b, R6b, and R7b is selected from the group consisting of (C1-C50)hydrocarbyl, (C1-C50)heterohydrocarbyl, (C6-C50)aryl, (C4-C50)heteroaryl, —Si(RC)3, —Ge(RC)3, —P(RP)2, —N(RN)2, —ORC, —SRC, —NO2, —CN, —CF3, RCS(O)—, —P(O)(RP)2, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, and (RC)2NC(O)—.