US 12,319,775 B2
Sterically hindered phosphine-amide supported nickel (II) or palladium (II) catalysts for the copolymerization of ethylene and polar comonomers
Alex J. Nett, Midland, MI (US); Heather A. Spinney, Midland, MI (US); Todd D. Senecal, Midland, MI (US); David R. Wilson, Midland, MI (US); Robert D J Froese, Midland, MI (US); and Alejandro J. Garza Gonzalez, Midland, MI (US)
Assigned to Dow Global Technologies LLC, Midland, MI (US)
Appl. No. 17/907,730
Filed by Dow Global Technologies LLC, Midland, MI (US)
PCT Filed Mar. 31, 2021, PCT No. PCT/US2021/025152
§ 371(c)(1), (2) Date Sep. 29, 2022,
PCT Pub. No. WO2021/202714, PCT Pub. Date Oct. 7, 2021.
Claims priority of provisional application 63/002,760, filed on Mar. 31, 2020.
Prior Publication US 2023/0132484 A1, May 4, 2023
Int. Cl. C08F 4/80 (2006.01); B01J 31/18 (2006.01); C08F 210/02 (2006.01)
CPC C08F 4/80 (2013.01) [B01J 31/188 (2013.01); C08F 210/02 (2013.01)] 18 Claims
 
1. A procatalyst according to formula (I):

OG Complex Work Unit Chemistry
where:
M is nickel (II) or palladium (II);
X is a ligand chosen from (C1-C40) hydrocarbyl, (C1-C40) heterohydrocarbyl, —H, —CH2Si(RC)3-Q (ORC)Q, —Si(RC)3-Q(ORC)Q, —OSi(RC)3-Q(OR)Q, —Ge(RC)3-Q(ORC)Q, —P(RC)2-W(ORC)W, —P(O)(RC)2-W(ORC)W, —N(RC)2, —N(Si(RC)3)2, —NRCSi(RC)3, —ORC, —SRC, —NO2, —CN, —CF3, —OCF3, —S(O)RC, —S(O)2RC, —OS(O)2RC, —N═C(RC)2, —N═CH(RC), —N═CH2, —N═P(RC)3, —OC(O)RC, —C(O)ORC, —C(O)RC, —C(O) H, —N(RC)C(O)RC, —N(RC)C(O)H, —NHC(O)RC, —NHC(O)H, —C(O)N(RC)2, —C(O)NHRC, —C(O)NH2, or a halogen, wherein each RC is independently (C1-C30) hydrocarbyl optionally substituted with one or more RS or (C1-C30) heterohydrocarbyl optionally substituted with one or more RS, wherein subscript Q is 0, 1, 2, or 3, and wherein subscript W is 0, 1, or 2;
Y is a Lewis base;
optionally, Y and X are covalently connected;
R1 is chosen from unsubstituted (C6-C40) aryl, substituted (C6-C40) aryl, unsubstituted (C1-C40) heteroaryl having its radical on a carbon atom, substituted (C1-C40) heteroaryl having its radical on a carbon atom, or substituted (C4-C20)alkyl having at least one tertiary carbon atom and its radical on the tertiary carbon atom of the (C4-C20)alkyl, provided that:
R2 and R3 are independently selected from radicals having formula (II):

OG Complex Work Unit Chemistry
where:
each R11, R12, R13, R14, and R15 are independently, (C1-C30) hydrocarbyl, (C1-C30) heterohydrocarbyl, —ORN, —NRN2, —SRN, halogen, or —H, where RN is (C1-C30) hydrocarbyl;
provided that at least one of R11 and R15 is not-H; and
each RS in formula (I) is independently (C1-C20) hydrocarbyl or halogen.