US 12,281,190 B2
Bis(phosphino)-phenoxy nickel(II) catalysts for the copolymerization of ethylene and acrylate monomers
Theodor Agapie, Pasadena, CA (US); Shuoyan Xiong, Pasadena, CA (US); Brad C. Bailey, Midland, MI (US); Heather A. Spinney, Midland, MI (US); Alex J. Nett, Midland, MI (US); David R. Wilson, Midland, MI (US); and Jerzy Klosin, Midland, MI (US)
Assigned to Dow Global Technologies LLC, Midland, MI (US); and California Institute of Technology, Pasadena, CA (US)
Appl. No. 17/636,048
Filed by Dow Global Technologies LLC, Midland, MI (US); and California Institute of Technology, Pasadena, CA (US)
PCT Filed Aug. 18, 2020, PCT No. PCT/US2020/046767
§ 371(c)(1), (2) Date Feb. 17, 2022,
PCT Pub. No. WO2021/034809, PCT Pub. Date Feb. 25, 2021.
Claims priority of provisional application 62/889,249, filed on Aug. 20, 2019.
Prior Publication US 2022/0332858 A1, Oct. 20, 2022
Int. Cl. C08F 4/80 (2006.01); B01J 31/24 (2006.01); C08F 4/70 (2006.01); C08F 210/02 (2006.01)
CPC C08F 4/7031 (2013.01) [B01J 31/2409 (2013.01); C08F 4/80 (2013.01); C08F 210/02 (2013.01)] 18 Claims
 
1. A catalyst system comprising a procatalyst having a structure 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, —NH(RC), —N(Si(RC)3)2, —NRCSi(RC)3, —NHSi(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, —N(RC)C(O)RC, —N(RC)C(O)H, —NHC(O)RC, —C(O)N(RC)2, —C(O)NHRC, —C(O)NH2, a halogen, or a hydrogen, wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl, and Q is 0, 1, 2 or 3 and W is 0, 1, or 2;
each Y is a Lewis base, wherein X and Y are optionally linked;
Z1, Z2, Z3 independently are C(RZ) or nitrogen, wherein each RZ is independently substituted (C1-C30)hydrocarbyl, unsubstituted (C1-C30)hydrocarbyl, substituted (C1-C30)heterohydrocarbyl, unsubstituted (C1-C30)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, —NH(RC), —N(Si(RC)3)2, —NRCSi(RC)3, —NHSi(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, —N(RC)C(O) RC, —C(O)N(RC)2, —N(RC)C(O)H, —NHC(O)RC, —C(O)N(RC)2, —C(O)NHRC, —C(O)NH2, a halogen, or a hydrogen, wherein Q is 0, 1, 2 or 3, W is 0, 1 or 2, and each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl, or hydrogen; provided that at least one of Z1, Z2, and Z3 is C(RZ);
R1, R2, R3, and R4 are independently selected from the group consisting of a (C1-C50)hydrocarbyl and (C1-C50)heterohydrocarbyl;
when both Z1 and Z2 are C(RZ), optionally respective groups RZ are linked to form a ring structure;
when both Z2 and Z3 are C(RZ), optionally respective groups RZ are linked to form a ring structure;
when all of Z1, Z2, and Z3 are C(RZ), optionally respective groups RZ are linked to form a multi-ring structure;
optionally, R1 and R2 are linked to form a ring structure; and
optionally, R3 and R4 are linked to form a ring structure.