US 12,221,507 B2
Monobidentate, bis-bidentate, and tetrabidentate guanidine Group IV transition metal olefin copolymerization catalysts
Andrew M. Camelio, Midland, MI (US); Brad C. Bailey, Midland, MI (US); Robert D. J. Froese, Midland, MI (US); and Sukrit Mukhopadhyay, Midland, MI (US)
Assigned to Dow Global Technologies LLC, Midland, MI (US)
Appl. No. 17/615,440
Filed by Dow Global Technologies LLC, Midland, MI (US)
PCT Filed May 28, 2020, PCT No. PCT/US2020/034832
§ 371(c)(1), (2) Date Nov. 30, 2021,
PCT Pub. No. WO2020/243241, PCT Pub. Date Dec. 3, 2020.
Claims priority of provisional application 62/855,306, filed on May 31, 2019.
Prior Publication US 2022/0235154 A1, Jul. 28, 2022
Int. Cl. C08F 4/64 (2006.01); C08F 4/659 (2006.01); C08F 210/14 (2006.01); C08F 210/16 (2006.01)
CPC C08F 4/64044 (2013.01) [C08F 4/65904 (2013.01); C08F 210/14 (2013.01); C08F 210/16 (2013.01); C08F 2410/01 (2013.01)] 14 Claims
OG exemplary drawing
 
1. A process for polymerizing polyolefin, the process comprising contacting ethylene and optionally one or more (C3-C12) α-olefin in the presence of a catalyst system, wherein the catalyst system comprises a metal-ligand structure according to formula (I):

OG Complex Work Unit Chemistry
where:
M is a metal chosen from zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4;
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, (C4-C12)diene, halogen, —ORX, —N(RX)2, or —NCORX, wherein each RX is (C1-C30) hydrocarbyl or —H;
n is 1, 2, or 3;
m is 1 or 2;
m+n=3 or 4;
each R1 is R1a or R1b;
each R4 is R4a or R4b;
R1a, R1b, R4a, and R4b are independently chosen from −H, (C1-C40) hydrocarbyl, (C1-C40) heterohydrocarbyl, (C1-C40) aryl, (C1-C40) heteroaryl, −P(RP)2, —N(RN)2, RCS(O)—, RCS(O)2—, or (RC)2C═N—, where each RC and each RP is unsubstituted (C1-C18) hydrocarbyl or —H, and where each RN is unsubstituted (C1-C18) hydrocarbyl;
each A is selected from the group consisting of:

OG Complex Work Unit Chemistry