Polymerization process for producing ethylene based polymers

A polymerization process for producing ethylene based polymers comprising:

• polymerizing ethylene and optionally one or more α-olefins in the presence of one or more first catalyst systems and optionally one or more second catalyst systems in a single reactor, wherein first catalyst system comprises;
• (a) one or more procatalysts comprising a metal-ligand complex of formula (I):
• wherein:
• M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4;
• and n is an integer of from 0 to 3, and wherein when n is 0, X is absent;
• and each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic;
• or two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic;
• and X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral;
• and L is (C3-C40)hydrocarbylene or (C3-C40)heterohydrocarbylene;
• and
• each R1a and each R1b is independently (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)—, halogen atom,
• R3, R6, R8, R9, R11, and R14 are independently selected from the group consisting of a (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)—, halogen atom, hydrogen atom, and combinations thereof;
• when R8 is H, R9 is a (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 atom;
• or
• when R9 is H, R8 is a (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 atom;
• wherein each RC, each RN, and each RP is independently (C1-C30)hydrocarbyl, and
• optionally two or more the R3, R6, R8, R9, R11, and R14 groups can combine together into ring structures, with such ring structures having from 3 to 50 atoms in the ring excluding any hydrogen atoms;
• each of the hydrocarbyl, heterohydrocarbyl, Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)—, hydrocarbylene, and heterohydrocarbylene groups independently is unsubstituted or substituted with one or more RS substituents;
• each RS independently is a halogen atom, polyfluoro substitution, perfluoro substitution, unsubstituted (C1-C18)alkyl, F3C—, FCH2O—, F2HCO—, F3CO—, R3Si—, R3Ge—, RO—, RS—, RS(O)—, RS(O)2—, R2P—, R2N—, R2C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R2NC(O)—, or two of the RS are taken together to form an unsubstituted (C1-C18)alkylene, wherein each R independently is an unsubstituted (C1-C18)alkyl;
• and
• (b) one or more cocatalysts;
• wherein the ratio of total number of moles of the one or more metal-ligand complexes of formula (I) to total number of moles of the one or more cocatalysts is from 1:10,000 to 100:1.