US 12,319,758 B2
Sterically hindered phosphino-urea 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 DJ Froese, Midland, MI (US); and Alejandro J. Garza Gonzalez, Midland, MI (US)
Assigned to Dow Global Technologies LLC, Midland, MI (US)
Appl. No. 17/907,727
Filed by Dow Global Technologies LLC, Midland, MI (US)
PCT Filed Mar. 31, 2021, PCT No. PCT/US2021/025161
§ 371(c)(1), (2) Date Sep. 29, 2022,
PCT Pub. No. WO2021/202722, PCT Pub. Date Oct. 7, 2021.
Claims priority of provisional application 63/002,767, filed on Mar. 31, 2020.
Prior Publication US 2023/0129371 A1, Apr. 27, 2023
Int. Cl. C08F 4/80 (2006.01); B01J 31/18 (2006.01); C07F 15/04 (2006.01); C08F 210/02 (2006.01)
CPC C08F 210/02 (2013.01) [B01J 31/188 (2013.01); C07F 15/04 (2013.01); C08F 4/80 (2013.01)] 20 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, —CH2Si(RC)3-Q(ORC)Q, —Si(RC)3-Q(ORC)Q, —OSi(RC)3-Q(ORC)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, a halogen, or a hydrogen, wherein:
each RC is independently (C1-C30)hydrocarbyl or (C1-C30)heterohydrocarbyl and is optionally substituted with one or more RS,
Q is 0, 1, 2, or 3; and
W is 0, 1, or 2;
Y is a Lewis base optionally covalently connected to X;
R1 and R2 are chosen from (C6-C40) aryl or (C1-C40) heteroaryl and are optionally substituted with one or more R8;
R3 and R4 are independently selected from radicals having formula (II):

OG Complex Work Unit Chemistry
where:
R11, R12, R13, R14, and R15 are independently (C1-C30)hydrocarbyl, (C1-C30)heterohydrocarbyl, —ORN, —NRN2, —SRN, halogen or —H, where each RN is (C1-C30)hydrocarbyl, provided that at least one of R11 and R15 is not-H;
each RC in formula (I) is independently a (C1-C30)hydrocarbyl, (C1-C30)heterohydrocarbyl, or —H; and
each R8 in formula (I) is independently (C1-C20)hydrocarbyl or halogen.