A modified Ziegler-Natta procatalyst that is a product mixture of modifying an initial Ziegler-Natta procatalyst with a molecular (pro)catalyst, and optionally an activator, the modifying occurring before activating the modified Ziegler-Natta procatalyst with an activator and before contacting the modified Ziegler-Natta procatalyst with a polymerizable olefin. Also, a modified catalyst system prepared therefrom, methods of preparing the modified Ziegler-Natta procatalyst and the modified catalyst system, a method of polymerizing an olefin using the modified catalyst system, and a polyolefin product made thereby.

A modified Ziegler-Natta procatalyst that is a product mixture of modifying an initial Ziegler-Natta procatalyst with a molecular (pro)catalyst, and optionally an activator, the modifying occurring before activating the modified Ziegler-Natta procatalyst with an activator and before contacting the modified Ziegler-Natta procatalyst with a polymerizable olefin. Also, a modified catalyst system prepared therefrom, methods of preparing the modified Ziegler-Natta procatalyst and the modified catalyst system, a method of polymerizing an olefin using the modified catalyst system, and a polyolefin product made thereby.

Embodiments are directed to a metal-ligand complex catalyst precursor, (L.sup.1)(L.sup.2)X(R.sup.1)(R.sup.2), and methods for producing the same from a compound of formula Q.sub.2X(R.sup.1)(R.sup.2). L.sup.1 and L.sup.2 are independently —R.sup.3—Z.sup.1 or —R.sup.4—Z.sup.1. R.sup.1 and R.sup.2 are independently selected from a hydrogen atom, (C.sub.1-C.sub.40)hydrocarbyl and, optionally, R.sup.1 and R.sup.2 are connected to form a ring having from 3 to 50 atoms in the ring, excluding hydrogen atoms. X is Si, Ge, Sn, or Pb. Each Q is independently Ar.sup.1—Y.sup.1R.sup.3— or Ar.sup.2—Y.sup.2—R.sup.4—. R.sup.3 and R.sup.4 are independently selected from —(CR.sup.C.sub.2).sub.m—, where m is 1 or 2, and where each R.sup.c is independently selected from the group consisting of (C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)heterohydrocarbyl, and —H. Y.sup.1 and Y.sup.2 are independently S, Se, or Te. Ar.sup.1 and Ar.sup.2 are independently (C.sub.6-C.sub.50)aryl. Ar.sup.1—Y.sup.1—R.sup.3— and Ar.sup.2—Y.sup.2—R.sup.4— are not identical. Each Z.sup.1 is independently selected from Cl, Br, and I.

Embodiments are directed to a metal-ligand complex catalyst precursor, (L.sup.1)(L.sup.2)X(R.sup.1)(R.sup.2), and methods for producing the same from a compound of formula Q.sub.2X(R.sup.1)(R.sup.2). L.sup.1 and L.sup.2 are independently —R.sup.3—Z.sup.1 or —R.sup.4—Z.sup.1. R.sup.1 and R.sup.2 are independently selected from a hydrogen atom, (C.sub.1-C.sub.40)hydrocarbyl and, optionally, R.sup.1 and R.sup.2 are connected to form a ring having from 3 to 50 atoms in the ring, excluding hydrogen atoms. X is Si, Ge, Sn, or Pb. Each Q is independently Ar.sup.1—Y.sup.1R.sup.3— or Ar.sup.2—Y.sup.2—R.sup.4—. R.sup.3 and R.sup.4 are independently selected from —(CR.sup.C.sub.2).sub.m—, where m is 1 or 2, and where each R.sup.c is independently selected from the group consisting of (C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)heterohydrocarbyl, and —H. Y.sup.1 and Y.sup.2 are independently S, Se, or Te. Ar.sup.1 and Ar.sup.2 are independently (C.sub.6-C.sub.50)aryl. Ar.sup.1—Y.sup.1—R.sup.3— and Ar.sup.2—Y.sup.2—R.sup.4— are not identical. Each Z.sup.1 is independently selected from Cl, Br, and I.

Embodiments of the present application are directed to procatalysts, and catalyst systems including procatalysts, including a metal-ligand complex having the structure of formula (I): [Formula I].

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Embodiments of the present application are directed to procatalysts, and catalyst systems including procatalysts, including a metal-ligand complex having the structure of formula (I): [Formula I].

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Embodiments of a method for producing a multimodal ethylene-based polymer having a first, second, and third ethylene-based component, wherein the multimodal ethylene based polymer results when ethylene monomer, at least one C.sub.3-C.sub.12 comonomer, solvent, and optionally hydrogen pass through a first solution, and subsequently, a second solution polymerization reactor. The first solution polymerization reactor or the second solution polymerization reactor receives both a first catalyst and a second catalyst, and a third catalyst passes through either the first or second solution polymerization reactors where the first and second catalysts are not already present. Each ethylene-based component is a polymerized reaction product of ethylene monomer and C.sub.3-C.sub.12 comonomer catalyzed by one of the three catalysts.

Embodiments of a method for producing a multimodal ethylene-based polymer having a first, second, and third ethylene-based component, wherein the multimodal ethylene based polymer results when ethylene monomer, at least one C.sub.3-C.sub.12 comonomer, solvent, and optionally hydrogen pass through a first solution, and subsequently, a second solution polymerization reactor. The first solution polymerization reactor or the second solution polymerization reactor receives both a first catalyst and a second catalyst, and a third catalyst passes through either the first or second solution polymerization reactors where the first and second catalysts are not already present. Each ethylene-based component is a polymerized reaction product of ethylene monomer and C.sub.3-C.sub.12 comonomer catalyzed by one of the three catalysts.

Embodiments of a method of producing a multimodal ethylene-based polymer comprising a first catalyst and a second catalyst in a first solution polymerization reactor and a third catalyst in a second solution polymerization reactor.

Embodiments of a method of producing a multimodal ethylene-based polymer comprising a first catalyst and a second catalyst in a first solution polymerization reactor and a third catalyst in a second solution polymerization reactor.