US 12,466,901 B2
Polymerization of ethylene in solution processes using a Ziegler-Natta catalyst and a hydrogenation procatalyst
Linfeng Chen, Missouri City, TX (US); and David M. Pearson, Lake Jackson, TX (US)
Assigned to Dow Global Technologies LLC, Midland, MI (US)
Appl. No. 17/630,802
Filed by Dow Global Technologies LLC, Midland, MI (US)
PCT Filed Jul. 30, 2020, PCT No. PCT/US2020/044208
§ 371(c)(1), (2) Date Jan. 27, 2022,
PCT Pub. No. WO2021/022014, PCT Pub. Date Feb. 4, 2021.
Claims priority of provisional application 62/881,184, filed on Jul. 31, 2019.
Prior Publication US 2022/0306772 A1, Sep. 29, 2022
Int. Cl. C08F 4/64 (2006.01); C08F 4/619 (2006.01); C08F 4/6192 (2006.01); C08F 4/659 (2006.01); C08F 10/02 (2006.01)
CPC C08F 4/6192 (2013.01) [C08F 4/61912 (2013.01); C08F 10/02 (2013.01)] 14 Claims
 
1. A catalyst system comprising:
a non-hydrogen-generating post-metallocene procatalyst;
a co-catalyst; and
a hydrogenation procatalyst having the formula Cp2TiX2TiCp2 or Cp2TiXn, where:
each Cp is cyclopentadienyl optionally substituted with at least one (C1-C10) alkyl;
each X is independently (C1-C40)hydrocarbon, (C1-C40)heterohydrocarbon, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, or a halide; and
n is 1 or 2;
wherein the non-hydrogen-generating post-metallocene procatalyst is a metal-ligand complex according to formula (I):

OG Complex Work Unit Chemistry
where:
M is a metal selected from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4;
n is 0, 1, or 2;
when n is 1, X1 is a monodentate ligand or a bidentate ligand;
when n is 2, each X1 is independently a monodentate ligand;
each X1 that is a monodentate ligand is independently halide, unsubstituted (C1-C20)hydrocarbyl, unsubstituted (C1-C20)hydrocarbyl, C(O)O—, or RKRLN—, where each of RK and RL is independently an unsubstituted (C1-C20)hydrocarbyl;
L is a diradical selected from the group consisting of (C1-C40)hydrocarbylene, (C1-C40)heterohydrocarbylene, —Si(RC)2-, —Si(RC)2OSi(RC)2-, —Si(RC)2C(RC)2-, —Si(RC)2Si(RC)2-, —Si(RC)2C(RC)2Si(RC)2-, —C(RC)2Si(RC)2C(RC)2-, —N(RN)C(RC)2-, —N(RN)N(RN)-, and —C(RC)2N(RN)C(RC)2-,
each Z is independently selected from —O—, —S—, —N(RN)-, or —P (RP)-;
R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are 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—, —N═C(RC)2, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)—, halide, radicals having formula (XI), radicals having formula (XII), and radicals having formula (XIII):

OG Complex Work Unit Chemistry
where:
each of R31-R35, R41-R48, and R51-R59 is independently selected from —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(RN)-, (RC)2NC(O)—, or halide; and
wherein the non-hydrogen-generating post-metallocene procatalyst is unsupported and the hydrogenation procatalyst is unsupported.