Multimodal polymerization processes with multi-catalyst systems

A process of producing polyolefin, the process comprising reacting ethylene and optionally one or more olefin monomers in one reactor or multiple reactors in the presence of a catalyst system and optionally hydrogen gas;

• the catalyst comprises two or more catalysts, at least one of which is derived from bis-phenylphenoxy procatalysts according to formula (I) and at least one of which is derived from phosphinimine procatalyst according to formula (V):
• where, in formula (I):
• M1 is titanium, zirconium, hafnium, scandium or yttrium;
• each X is independently a monodentate ligand independently chosen from (C1-C50)hydrocarbyl, (C1-C50)heterohydrocarbyl, —CH2Si(RC)3-Q(ORC)Q, —Si(RC)3-Q(ORC)Q, —OSi(RC)3-Q(ORC)Q, —CH2Ge(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, B(RY)4, Al(RY)4, or Ga(RY)4, or a hydrogen, wherein:
• each RC is independently a (C1-C30)hydrocarbyl, or (C1-C30)heterohydrocarbyl;
• each Q is 0, 1, 2 or 3;
• each W is 0, 1, or 2;
• each RY is —H, (C1-C30)hydrocarbyl, or halogen atom;
• and
• optionally, two X ligands are connected to form a metallacycle ring;
• each Y is independently a Lewis Base;
• optionally, X and Y are linked to form a ring and a bidentate ligand;
• m is 0, 1 or 2;
• n is 0, 1 or 2;
• R1 and R6 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)—, halogen, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):
• where each of R31-35, R41-48, and R51-59 is independently chosen 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 halogen;
• R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15 are 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(R)—, (RC)2NC(O)—, or halogen;
• L is (C1-C40)hydrocarbylene or (C2-C40)heterohydrocarbylene;
• and
• each RC, RP, and RN in formula (I) is independently a (C1-C30)hydrocarbyl, (C1-C30)heterohydrocarbyl, or —H;
• and:
• M2 is titanium, zirconium, or hafnium;
• R61, R62, R63, R64, and R65 are independently H, (C1-C50)hydrocarbyl, or (C1-C50)heterohydrocarbyl, wherein any of the R62, R63, R64, and R65 optionally are connected to form a ring or multi-ring structure;
• R66, R67, and R68 are independently (C1-C20)hydrocarbyl, (C1-C20)heterohydrocarbyl, (C6-C30)aryl, or (C5-C30)heteroaryl, wherein two of R66, R67, and R68 are optionally connected to form a ring.