Polymerizations for olefin-based polymers

A process to form an olefin-based polymer, said process comprising polymerizing at least one olefin, in the presence of at least one catalyst system comprising the reaction product of the following:

• A) at least one cocatalyst;
• and
• B) a procatalyst 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 (C1-C40)hydrocarbyl, a (C1-C40)heterohydrocarbyl, or a halide, and wherein each X, independently, is a monodentate ligand that is neutral, monoanionic, or dianionic;
• or
• wherein two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic;
• and
• wherein X and n are chosen, in such a way, that the metal-ligand complex of Formula (I) is, overall, neutral;
• and
• Each Z independently is an oxygen atom, a sulfur atom, —N[(C1-C40)hydrocarbyl]-, or —P[(C1-C40)hydrocarbyl]-;
• and
• L is a substituted or unsubstituted (C1-C40)hydrocarbylene, or a substituted or unsubstituted (C1-C40)heterohydrocarbylene, and
• wherein, for L, the (C1-C40)hydrocarbylene has a portion that comprises a 1-carbon atom to 10-carbon atom linker backbone linking R21 and R22 in Formula (I) (to which L is bonded), or
• wherein, for L, the (C1-C40)heterohydrocarbylene has a portion that comprises a 1-atom to 10-atom linker backbone linking R21 and R22 in Formula (I), wherein each of the 1 to 10 atoms of the 1-atom to 10-atom linker backbone of the (C1-C40)heterohydrocarbylene, independently, is one of the following:
• i) a carbon atom, ii) a heteroatom, wherein each heteroatom independently is —O— or —S—, or iii) a substituent selected from —S(O)—, —S(O)2—, —Si(RC)2, —Ge(RC)2, —P(RC)—, or —N(RC)—, and wherein each RC is, independently, a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30) heterohydrocarbyl;
• and
• R21 and R22 are each, independently, C or Si;
• and
• R1 through R20 are each, independently, selected from the group consisting of the following:
• a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)hetero-hydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RC)2, —N(RC)2, —ORS, —SRS, —NO2, —CN, —CF3, —S(O)RC, —S(O)2RC, —N═C(RC)2, —OC(O)RC, —C(O)ORC, —N(R)C(O)RC, —C(O)N(RC)2, a halogen atom, and a hydrogen atom;
• and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30) heterohydrocarbyl;
• and
• wherein, when R17 is a hydrogen atom, then R18 is a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RC)2, —N(RC)2, —ORS, —SRS, —NO2, —CN, —CF3, —S(O)RC, —S(O)2RC, —N═C(RC)2, —OC(O)RC, —C(O)ORC, —N(R)C(O)RC, —C(O)N(RC)2, a halogen atom, or a hydrogen atom;
• and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30) heterohydrocarbyl;
• or
• wherein, when R18 is a hydrogen atom, then R17 is a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RC)2, —N(RC)2, —ORS, —SRS, —NO2, —CN, —CF3, —S(O)RB, —S(O)2RC, —N═C(RC)2, —OC(O)RC, —C(O)ORS, —N(R)C(O)RC, —C(O)N(RC)2, a halogen atom, or a hydrogen atom;
• and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30) heterohydrocarbyl;
• and/or
• wherein, when R19 is a hydrogen atom, then R20 is a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RC)2, —N(RC)2, —ORS, —SRS, —NO2, —CN, —CF3, —S(O)RC, —S(O)2RC, —N═C(RC)2, —OC(O)RC, —C(O)ORC, —N(R)C(O)RC, —C(O)N(RC)2, a halogen atom, or a hydrogen atom;
• and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30) heterohydrocarbyl;
• or
• wherein, when R20 is a hydrogen atom, then R19 is a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RC)2, —N(RC)2, —ORS, —SRS, —NO2, —CN, —CF3, —S(O)RC, —S(O)2RC, —N═C(RC)2, —OC(O)RC, —C(O)ORC, —N(R)C(O)RC, —C(O)N(RC)2, a halogen atom, or a hydrogen atom;
• and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30) heterohydrocarbyl;
• and
• wherein, for Formula I, two or more of R1 through R22, optionally, may form one or more ring structures, and wherein each ring structure has from 3 to 50 atoms in the ring, excluding any hydrogen atoms;
• and
• wherein, for Formula I, one or more hydrogen atoms may optionally be substituted with one or more deuterium atoms.