BR112020005874B1 - CATALYST SYSTEM - Google Patents

Abstract

Embodiments are directed to a catalyst system comprising metal-binder complexes and the complex processes for polyolefin polymerization, using the metal-binder complex having the following structure: (I) where each X is selected from the group consisting of ?(CH2)SiRX3.

Description

TECHNICAL FIELD

[0001] Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more specifically to the bis-phenyl-phenoxy polyolefin procatalyst which has two methylenetrialkylsilicon linkers on the metal for improved solubility in non-aromatic hydrocarbons.

BACKGROUND

[0002] Olefin-based polymers such as polyethylene, ethylene-based polymer, polypropylene and propylene-based polymer are produced through various catalyst systems. The selection of such catalyst systems used in the polymerization process of olefin-based polymers is an important factor contributing to the characteristics and properties of these olefin-based polymers.

[0003] Polyethylene and polypropylene are manufactured for a wide variety of articles. The polyethylene and polypropylene polymerization process can be varied in many respects to produce a wide variety of resulting polyethylene resins with different physical properties that make the various resins suitable for use in different applications. Ethylene monomers and optionally one or more comonomers are present in liquid diluents (as solvents) such as an alkane or isoalkane, for example isobutene. Hydrogen can also be added to the reactor. Catalyst systems for polyethylene production may typically comprise a chromium-based catalyst system, a Ziegler-Natta catalyst system and/or a molecular catalyst system (metallocene or non-metallocene (molecular)). The reactants in the diluent and catalyst system are circulated at an elevated polymerization temperature around the reactor shell, thereby producing polyethylene homopolymer or copolymer. Periodically or continuously, part of the reaction mixture, including the polyethylene product dissolved in the diluent, along with unreacted ethylene and one or more optional comonomers, is removed from the reactor. The reaction mixture, when removed from the reactor, can be processed to remove the polyethylene product from the unreacted diluent and reagents, with the unreacted diluent and reagents typically being recycled back to the reactor. Alternatively, the reaction mixture can be sent to a second reactor, connected in series to the first reactor, where a second polyethylene fraction can be produced. Despite research efforts in developing catalyst systems suitable for the polymerization of olefins, such as polymerization of polyethylene or polypropylene, there is still a need to increase the efficiencies of catalyst systems capable of producing polymers with high molecular weights and a narrow molecular weight distribution.

SUMMARY

[0004] Molecular catalyst systems are not easily solubilized in nonpolar solvents. Since ethylene and other olefins are polymerized in nonpolar solvents, a large amount of solvent (or an undesirable solvent, ie toluene) is used to dissolve a small amount of catalyst. As a result, there is an ongoing need to solubilize a catalyst system with a smaller amount of solvent, while maintaining catalyst effectiveness, reactivity and the ability to produce high or low molecular weight polymers.

[0005] According to some embodiments, a catalyst system may include a metal-ligand complex according to formula (I):

[0006] In formula (I), M is a metal chosen from titanium, zirconium or hafnium, wherein the metal is in a formal oxidation state of +2, +3 or +4. Each X is selected from the group consisting of -(CH2)SiR3, where each Rx is independently a (C1-C30)hydrocarbyl group and at least one RX is (C2-C30)hydrocarbyl, where any two RX or all three RX's are optionally covalently linked; each Z is independently chosen from -O-, -S-, -N(RN)- or -P(RP)-; R1 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)-, halogen, radicals of formula (II), radicals of formula (III) and radicals of formula (IV) ):

[0007] In formulas (II), (III) and (IV), each of R31-35, R41-48 and R51-59 is independently chosen from -H, 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, provided that at least one of R1 or R16 is a radical having formula (II), a radical having formula (III) or a radical having formula (IV).

[0008] In formula (I), each of R2-4, R5-8, R9-12 and R13-15 is independently selected from -H, (C1-C40)hydrocarbyl, (C1-C40)hetero- hydrocarbyl, -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)- and halogen. L is (C2-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. The metal-ligand complex according to formula (I) has a solubility greater than the solubility of a comparative complex having a structure according to formula (Ia):

[0009] In formula (Ia), M, each Z, each R1-16, each R31-35, each R41-48, each R51-59, L, each RC, each RP and each RN are all identical to the corresponding groups of the metal-ligand complex according to formula (I).

DETAILED DESCRIPTION

[0010] Specific embodiments of catalyst systems will now be described. It is to be understood that the catalyst systems of this disclosure may be incorporated in different forms and are not to be construed as limited to the specific embodiments set forth in this disclosure. Rather, modalities are provided for this disclosure to be thorough and complete and fully convey the scope of the matter to those skilled in the art.

[0011] Common abbreviations are listed below:

[0012] R, Z, M, X and n: as defined above; Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl; I-Pr: ISO-propyl; T-Bu: TERC-butyl; THF: tetrahydrofuran; Et2O: diethyl ether; CH2Cl2: dichloromethane; C6D6: deuterated benzene or benzene-D6: CDCl3: deuterated chloroform; Na2SO4: sodium sulfate; MgSO4: magnesium sulfate; HCl: hydrogen chloride; N-BuLi: butyllithium; HfCl4: hafnium(IV) chloride; HfBn4: tetrabenzyl hafnium(IV); ZrCl4: zirconium(IV) chloride; ZrBn4: tetrabenzyl zirconium (IV); ZrBn2Cl2(OEt2): zirconium (IV) dibenzyl dichloride monodiethyl etherate; HfBn2Cl2(OEt2): hafnium (IV) dibenzyl dichloride monodiethyl etherate; N2: nitrogen gas; PhMe: toluene; PPR: parallel polymerization reactor; MAO: methylaluminoxane; MMAO: modified methylaluminoxane; NMR: nuclear magnetic resonance; mmol: millimoles; ml: milliliters; M: molar; min or mins: minutes; h: hours; d: days; rpm: rotation per minute; STP: standard pressure and temperature.

[0013] The term “independently selected” is used in this document to indicate that the R groups, such as, R1, R2, R3, R4 and R5, can be the same or different (for example, R1, R2, R3, R4 and R5 can be all substituted alkyls or R1 and R2 can be substituted alkyl and R3 can be aryl, etc.). A chemical name associated with an R group is intended to convey the chemical structure which is recognized in the art as corresponding to the chemical name. Thus, chemical names are intended to complement and illustrate, not exclude, structural definitions known to those skilled in the art.

[0014] The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with a procatalyst in a manner that converts the procatalyst into a catalytically active catalyst. As used in this document, the terms "cocatalyst" and "activator" are interchangeable terms.

[0015] When used to describe certain chemical groups that contain a carbon atom, an expression in parentheses having the form “(Cx-Cy)” means that the unsubstituted form of the chemical group has from x carbon atoms to y atoms of carbon, inclusive of x and y. For example, a (C1-C50)alkyl group is an alkyl group having from 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted by one or more substituents, such as RS. A substituted chemical group RS defined using the "(Cx-Cy)" in parentheses can contain more than y carbon atoms, depending on the identity of any RS groups. For example, a “(C1-C50)alkyl substituted with exactly one RS group, where R is phenyl (-C6H5)” can contain from 7 to 56 carbon atoms. Thus, in general, when a chemical group defined using the "(Cx-Cy)" in parentheses is replaced by one or more substituents containing an RS carbon atom, the minimum and maximum number of carbon atoms in the chemical group is determined by adding to both x and y the sum of the combined number of carbon atoms of all substituents containing an RS carbon atom.

[0016] The term “substitution” means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g. RS ). The term "persubstitution" means that every hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (eg, RS). The term "polysubstitution" means that at least two, but less than all, hydrogen atoms attached to carbon atoms or heteroatoms of a corresponding unsubstituted compound or functional group are replaced by a substituent. The term “-H” means a hydrogen or hydrogen radical that is covalently bonded to another atom. “Hydrogen” and “-H” are interchangeable and, unless clearly specified, have identical meanings.

[0017] The term "(C1-C50)hydrocarbyl" means a hydrocarbon radical of 1 to 50 carbon atoms and the term "(C1-C50)hydrocarbylene" means a hydrocarbon diradical of 1 to 50 carbon atoms, in the of which each hydrocarbon radical and each hydrocarbon radial is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (having three carbons or more and including mono and polycyclic, fused and unfused polycyclic and bicyclic) or acyclic, and replaced by one or more RS or not replaced.

[0018] In this disclosure, a (C1-C50)hydrocarbyl can be an unsubstituted or substituted (C1-C50)alkyl, (C3-C50)cycloalkyl, (C3-C20)cycloalkyl-(C1-C20)alkylene, (C6 -C40)aryl or (C6-C20)aryl-(C1-C20)alkylene (such as benzyl (-CH2-C6H5)).

[0019] The terms “(C1-C50)alkyl” and “(C1-C18)alkyl” mean a linear or branched saturated hydrocarbon radical of 1 to 50 carbon atoms and a linear or branched saturated hydrocarbon radical of 1 to 18 atoms of carbon, respectively, that is unsubstituted or substituted by one or more RS. Examples of (C1-C50)alkyl are unsubstituted (C1-C20)alkyl; unsubstituted (C1-C10)alkyl; unsubstituted (C1-C5)alkyl; methyl; ethyl; 1- propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1- hexyl; 1-heptyl; 1-nonyl; and 1-decile. Examples of substituted (C1-C40)alkyl are substituted (C1-C20)alkyl, substituted (C1-C10)alkyl, trifluoromethyl and [C45]alkyl. The term "[C45]alkyl" means that there are a maximum of 45 carbon atoms in the radical including substituents and is, for example, a (C27-C40)alkyl group replaced by an RS, which is a (C1-C5) group ) alkyl, respectively. Each (C1-C5)alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0020] The term “(C6-C50)aryl” means an unsubstituted or substituted (by one or more RS) mono, bi or tricyclic aromatic hydrocarbon radical having between 6 and 40 carbon atoms, of which at least 6 to 14 of the carbon atoms are aromatic ring carbon atoms. A monocyclic aromatic hydrocarbon radical includes an aromatic ring; a bicyclic aromatic hydrocarbon radical has two rings; and a tricyclic aromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may be independently fused or unfused and aromatic or non-aromatic. Examples of (C6-C50)alkylaryl include: unsubstituted (C6-C20)aryl, (C6-C18)aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of (C6-C40)aryl include: (C1-C20)aryl; (C6-C18)aryl; 2,4-bis([C20]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-one-1-yl.

[0021] The term "(C3-C50)cycloalkyl" means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms that is unsubstituted or substituted by one or more RS. Other cycloalkyl groups (e.g., (Cx-Cy)cycloalkyl) are similarly defined as having from x to y carbon atoms and being unsubstituted or substituted with one or more RS. Examples of unsubstituted (C3-C40)cycloalkyl are unsubstituted (C3-C20)cycloalkyl, unsubstituted (C3-C10)cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl . Examples of (C3-C40)cycloalkyl are substituted (C3-C20)cycloalkyl, substituted (C3-C10)cycloalkyl, cyclopentanon-2-yl and 1-fluorocyclohexyl.

[0022] Examples of (C1-C50)hydrocarbylene include unsubstituted or substituted (C6-C50)arylene, (C3-C50)cycloalkylene, and (C1-C50)alkylene (eg, (C1-C20)alkylene). Diradicals can be on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (e.g., 1,2-diradicals), or are spaced apart by one, two, or more than two atoms intervening carbon atoms (eg 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include a 1,2-, 1,3-, 1,4- or an α,w-diradical and others a 1,2-diradical. The α,w-diradical is a diradical that has maximum carbon backbone spacing between the radical carbons. Some examples of (C2-C20)alkylene α,w-diradicals include ethan-1,2-diyl (i.e. -CH2CH2-), propan-1,3-diyl (i.e. -CH2CH2CH2-), 2-methylpropan -1,3-diyl (i.e. -CH2CH(CH3)CH2-). Some examples of (C6-C50)arylene α,w-diradicals include phenyl-1,4-diyl, naphthalen-2,6-diyl, or naphthalen-3,7-diyl.

[0023] The term "(C1-C50)alkylene" means a saturated straight chain or diradical branched chain (i.e. radicals are not on the ring atoms) of 1 to 50 carbon atoms which is unsubstituted or substituted by one or more RS. Examples of (C1-C50)alkylene are unsubstituted (C1-C20)alkylene, including -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6- , -(CH2)7-, -(CH2)8-, -CH2C*HCH3 and -(CH2)4C*(H)(CH3), where "C*" denotes a carbon atom of which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (C1-C50)alkylene are substituted (C1-C20)alkylene, -CF2-, -C(O)-, and -(CH2)14C(CH3)2(CH2)5- (i.e. a 1, Normal 20-eicosylene replaced by 6,6-dimethyl). Since, as mentioned earlier, two RS can be taken together to form a (C1-C18)alkylene, examples of substituted (C1-C50)alkylene also include 1,2-bis(methylene)cyclopentane, 1,2- bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0024] The term "(C3-C50)cycloalkylene" means a cyclic diradical (ie, the radicals are on the ring atoms) of 3 to 50 carbon atoms which is unsubstituted or substituted by one or more RS.

[0025] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more than one heteroatom include O, S, S(O), S(O)2, Si(R C )2, P(RP), N(RN), -N=C(RC)2, -Ge(RC)2-, or -Si(RC)-, where each RC and each RP is (Ci-Ci8 )unsubstituted hydrocarbyl or -H, and where each RN is unsubstituted (C1-C18)hydrocarbyl. The term "heterohydrocarbon" refers to a molecule or molecular structure in which one or more carbon atoms of a hydrocarbon are substituted with a heteroatom. The term "(C1-C50)heterohydrocarbyl" means a heterohydrocarbon radical of 1 to 50 carbon atoms, and the term "(C1-C50)heterohydrocarbylene" means a heterohydrocarbylene diradical. hydrocarbon of 1 to 50 carbon atoms. The heterohydrocarbon of (C1-C50)heterohydrocarbyl or (C1-C50)heterohydrocarbylene has one or more heteroatoms. The heterohydrocarbyl radical may be on a carbon atom. carbon or on a heteroatom.The two heterohydrocarbylene radicals can be on a single carbon atom or on a single heteroatom. Additionally, one of the two diradical radicals can be on one carbon atom and the other radical can be on a different carbon atom; one of the two radicals can be on a carbon atom and the other on a heteroatom; or one of the two radicals may be on one heteroatom and the other radical on a different heteroatom. Each (C1-C50)heterohydrocarbyl and (C1-C50)heterohydrocarbylene can be unsubstituted or substituted (by one or more RS), aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including monocyclic and polycyclic, fused and unfused polycyclic) or acyclic.

[0026] The (C1-C50)heterohydrocarbyl can be unsubstituted or substituted. Non-limiting examples of (C1-C50)heterocarbyl include (C1-C50)heteroalkyl, (C1-C50)hydrocarbyl-O-, (C1-C50)hydrocarbyl-S-, (C1-C50)hydrocarbyl-S(O)-, ( C1C50) hydrocarbyl-S(O)2-, (C1-C50)hydrocarbyl-Si(RC)2-, (C1-C50)hydrocarbyl-N(RN)-, (C1-C50)hydrocarbyl-P(RP)- , (C2-C50)heterocycloalkyl, (C2-C19)heterocycloalkyl-(C1-C20)alkylene, (C3-C20)cycloalkyl-(C1-C19)heteroalkylene, (C2-C19)heterocycloalkyl-(C1-C20)heteroalkylene, (C1-C50)heteroaryl, (C1-C19)heteroaryl-(C1-C20)alkylene, (C6-C20)aryl-(C1-C19)heteroalkylene, or (C1-C19)heteroaryl-(C1-C20)heteroalkylene.

[0027] The term "(C4-C50)heteroaryl" means an unsubstituted or substituted (by one or more RS) mono, bi or tricyclic hydrocarbon radical of 4 to 50 carbon atoms in total and 1 to 10 heteroatoms. A monocyclic heteroaromatic hydrocarbon radical includes a heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon radical has two rings; and a tricyclic heteroaromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring or rings of the heteroaromatic radical may be independently fused or unfused and aromatic or non-aromatic. Other heteroaryl groups (e.g., (Cx-Cy)heteroaryl in general, such as (C4-C12)heteroaryl) are similarly defined as having from x to y carbon atoms (such as 4 to 12 carbon atoms) and being unsubstituted or replaced by one or more than one RS. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered ring or a 6-membered ring. The 5-membered ring monocyclic heteroaromatic hydrocarbon radical has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2 or 3; and each heteroatom can be O, S, N or P.

[0028] Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol-1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring monocyclic heteroaromatic hydrocarbon radical has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2 and the heteroatoms can be N or P.

[0029] Examples of 6-membered ring heteroaromatic hydrocarbon radicals include pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radical may be a fused 5,6 or 6,6 ring system. Examples of the 5,6-fused ring system bicyclic heteroaromatic hydrocarbon radical are indol-1-yl; and benzimidazole-1-yl. Examples of the 6,6-fused ring system bicyclic heteroaromatic hydrocarbon radical are quinolin-2-yl; and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radical may be a 5,6,5 ring system; 5,6,6; 6,5,6; or 6,6,6 cast. An example of the fused 5,6,5 ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of the fused 5,6,6 ring system is 1H-benzo[f]indol-1-yl. An example of the fused 6,5,6 ring system is 9H-carbazol-9-yl. An example of the fused 6,5,6 ring system is 9H-carbazol-9-yl. An example of the fused 6,6,6 ring system is acryldin-9-yl.

[0030] The term "(C1-C50)heteroalkyl" means a saturated straight or branched chain radical containing one to fifty carbon atoms and one or more heteroatoms. The term "(C1-C50)heteroalkylene" means a saturated straight or branched chain diradical containing from 1 to 50 carbon atoms and one or more than one heteroatom. Heteroalkyl heteroatoms or heteroalkylenes may include Si(RC)3, Ge(RC)3, Si(RC)2, Ge(RC)2, P(RP)2, P(RP), N(RN)2, N(RN), N, O, ORC, S, SRC, S(O) and S(O) 2 , wherein each of the heteroalkyl and heteroalkylene groups are unsubstituted or are substituted by one or more RS.

[0031] Examples of unsubstituted (C2-C40)heterocycloalkyl include unsubstituted (C2-C20)heterocycloalkyl, (C2-C10)heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophen-S, S-2-yl dioxide, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxacyclooctyl, 5-thio-cyclononyl and 2-aza-cyclodecyl.

[0032] The term "halogen atom" or "halogen" means the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br) or iodine atom (I). The term "halide" means the anionic form of the halogen atom: fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-).

[0033] The term "saturated" means that it lacks carbon-carbon double bonds, carbon-carbon triple bonds and (in groups containing heteroatoms) carbon-nitrogen, carbon-phosphorus and carbon-silicon double bonds. When a saturated chemical group is replaced by one or more RS substituents, one or more double bonds and/or triple bonds, optionally, can be present in the RS substituents. The term "unsaturated" means containing one or more carbon-carbon double bonds or carbon-carbon triple bonds, or (in groups containing heteroatoms) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds or carbon-silicon double bonds , not including double bonds which may be present in R S substituents, if any, or in aromatic rings or heteroaromatic rings, if any.

[0034] Embodiments of this disclosure include catalyst systems that include a metal-binder complex according to formula (I):

[0035] In formula (I), M is a metal chosen from titanium, zirconium or hafnium, wherein the metal is in a formal oxidation state of +2, +3 or +4. Each X is selected from the group consisting of -(CH2)SiRX3, where each Rx independently represents a (C1-C30)hydrocarbyl group or a (C1-C30)hetero group and at least one RX is (C2-C30 )hydrocarbyl, where any two of RX or all three of RX are optionally covalently linked. The metal-ligand complex has 6 or fewer metal-ligand bonds and can be overall neutral charge or it can have a positive charge associated with the metal center. Each Z is independently chosen from -O-, -S-, -N(RN)- or -P(RP)-; selected from oxygen or sulfur.

[0036] In embodiments, the catalyst system may include a metal-ligand complex according to formula (I), wherein each of R1 and R16 is 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):

[0037] In formulas (II), (III) and (IV), each of R 31-35, R41-48, 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, provided that at least one of R1 or R16 is a radical having formula (II), a radical having formula (III) or a radical having formula (IV).

[0038] In formula (I), each of R2-4, R5-8, R9-12 and R13-15 is independently selected from -H, (C1-C40)hydrocarbyl, (C1-C40)hetero- hydrocarbyl, -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)- and halogen. In one or more embodiments, L is (C2-C40)hydrocarbylene or (C2-C40)heterohydrocarbylene; and each RC, RP and RN in formula (I) independently represents a (C1-C30)hydrocarbyl, (C1-C30)heterohydrocarbyl, or -H.

[0039] In embodiments, the metal-ligand complex according to formula (I) has a solubility greater than the solubility of a corresponding comparative complex having a structure according to formula (Ia):

[0040] In formula (Ia), M, n, each Z, each R1-16 each R31-35, each R41-48, each R51-59, L, each RC, each RP and each RN all are identical to the groups corresponding elements of the metal-ligand complex according to formula (I). Thus, the corresponding comparative complex differs from the metal-ligand complex according to formula (I) in that all X groups of the metal-ligand complex according to formula (I) are replaced by methyl groups.

[0041] The metal-binder complex of formula (I) and the corresponding comparative complex of formula (Ia) both have a percentage by weight (% by weight) of solubility in various solvents. In general, as used herein, the weight percent (wt%) solubility of a solute in a solution is the weight of the solute divided by the weight of the solution, multiplied by 100. Solubility measurements of individual metal complexes -ligand are carried out as follows: The solute (procatalyst) is added to a solvent, such as methylcyclohexane (MCH) or Isopar-ETM, such that the amount of solute added is greater than the amount that will be dissolved in that amount of solvent. The resulting suspension is stirred for one hour and then allowed to stand overnight. After standing overnight (approximately 16 hours), the suspension is filtered through a 0.2 µm PTFE syringe filter into a tared vial. The amount of solution in the tared flask is weighed out and the solvent is removed under reduced pressure. The residual solid weight is measured after all solvent has been removed. Solubility by weight is determined by dividing the weight of the residual solid by the weight of the solution in the tared flask and multiplying by 100.

[0042] In one or more embodiments, the metal-binder complex according to formula (I) has a weight percent (wt%) solubility of 1.5 wt% to 50 wt% in methylcyclohexane (MCH) at ambient temperature and pressure. All values and subranges encompassed by individual "from 1.5% by weight to 50% by weight" are described herein as separate embodiments. For example, in some embodiments, the solubility of the metal-binder complex according to formula (I) is from 2.5% by weight to 15% by weight, from 1.5% by weight to 10% by weight or from 3.0% by weight to 15% by weight in MCH and in other embodiments, the solubility is greater than 20% by weight in MCH at standard temperature and pressure (STP) (temperature of 22.5 ± 2.5 °C and a pressure of approximately 1 atmosphere).

[0043] In one or more embodiments, the metal-binder complex according to formula (I) has a wt% solubility of 1.5 wt% to 50 wt% in Isopar-ETM at ambient temperature and pressure . All values and subranges encompassed by individual "from 1.5% by weight to 50% by weight" are described herein as separate embodiments. For example, in some embodiments, the metal-binder complex according to formula (I) has a wt% solubility of 2.5 wt% to 15 wt%, from 2.5 wt% to 10 wt% by weight or from 3.0% by weight to 15% by weight in Isopar-ETM and in other embodiments, the % by weight solubility is greater than 20% by weight in Isopar-ETM in STP.

[0044] The metal-binder complex of formula (I) in MCH in STP has a wt% solubility of W, as measured by the previously described procedure. The corresponding metal-ligand complex of formula (Ia) in MCH in PBS has a solubility by weight in MCH in STP of Y, as measured by the same procedure as the corresponding metal-ligand complex of formula (I). A solubility ratio in % by weight (SR) is defined as W divided by Y (W/Y). For example, Complex A, a metal-binder complex of formula (I), has a solubility by weight of 10% by weight in MCH in PBS, as measured by the procedure in the preceding paragraphs. Complex B, the corresponding metal-ligand complex of formula (Ia), has a solubility of 2 wt% MCH in PBS, as measured by the same procedure as complex A. Thus, complex A has a SR of 5.

[0045] In one or more embodiments of this disclosure, the SR of the metal-ligand complex of formula (I) is at least 1.5, at least 2, or at least 3. In some embodiments, the SR is 1.5 to 50, 2 to 50, 2 to 10, 3 to 15 or 1.5 to 100. All individual values and subranges covered by “from 2 to 100” are disclosed in this document as separate modalities.

[0046] Polymerization processes on an industrial scale generally involve large volumes of procatalyst solutions in non-aromatic hydrocarbon solvents. When procatalyst solubility is low in non-aromatic hydrocarbons, very dilute solutions should be used. This requires larger volumes of solvent to transport the procatalyst. Increasing the solubility of the procatalyst can therefore lead to a more environmentally friendly process, as smaller volumes of solvent can be used. Diluted solutions can also lead to process interruptions. In some cases, the procatalyst is so insoluble in non-aromatic hydrocarbons that even dilute solutions cannot be used and undesirable aromatic hydrocarbon solvents are needed.

[0047] In some embodiments, any or all of the chemical groups (e.g., L, R1-16, R31-35, R41-48, R51-59) of the metal-binder complex of formula (I) may be non- replaced. In other embodiments, none, some, or all of the chemical groups, L, R1-16, R31-35, R41-48, R51-59, of the metal-ligand complex of formula (I) may be replaced by one or more of the that an RS. When two or more than two RS are attached to the same chemical group of the metal-ligand complex of formula (I), the individual RS of the chemical group can be attached to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, none, any or all of the chemical groups L, R1-16, R31-35, R41-48, R51-59 may be persubstituted by RS. In chemical groups that are persubstituted by RS, the individual RS can be the same or can be independently chosen.

[0048] In one or more embodiments, each X is independently -(CH2)SiRX3, wherein each Rx is independently a (C1-C30)alkyl or a (C1-C30)heteroalkyl and at least one RX is (C2 -C30)alkyl. In some embodiments, when one of RX is a (C1-C30)heteroalkyl, the heteroatom is silica. In some embodiments, RX is methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or TERC-butyl), pentyl, hexyl, heptyl, n-octyl, TERC-octyl, or nonyl.

[0049] In one or more embodiments, X is -(CH2)Si(CH3)2(CH2CH3); -(CH2)Si(CH3)(CH2CH3)2, -(CH2)Si(CH2CH3)3, -(CH2)Si(CH3)2(n-butyl), -(CH2)Si(CH3)2(n- hexyl), -(CH2)Si(CH3)(n-Oct)RX, -(CH2)Si(n-Oct)RX2, -(CH2)Si(CH3)2(2-ethylhexyl), -(CH2 )Si(CH3)2(dodecyl), -CH2Si(CH3)2CH2Si(CH3)3 (also referred to as -CH2Si(CH3)2CH2TMS). Optionally, in some embodiments, the metal-ligand complex according to formula (I), exactly two RX's are covalently bonded or exactly three RX's are covalently bonded.

[0050] In one or more embodiments, L is chosen from (C2-C12)alkylene, (C2-C12)heteroalkylene, (C6-C50)arylene, (C5-C50)heteroarylene, (-CH2Si(RC)2CH2 -), (-CH2CH2Si(RC)2CH2CH2-), (-CH2CH2Ge(RC)2CH2CH2-), or (-CH2Ge(RC)2CH2-), where RC is (C1-C30)hydrocarbyl. In some embodiments, L is -(CH2)x-, where the x subscript is from 2 to 5. In other embodiments, the x subscript, of -(CH2)x-, is 3 or 4. In some embodiments, L is 1 ,3-bis(methylene)cyclohexane or 1,2-bis(2-ylethyl)cyclohexane.

[0051] In some embodiments, in which the metal-binder complex of formula (I), or one of R1 or R16, or both R1 and R 16, are chosen from radicals having formula (II), formula (III) , or formula (IV):

[0052] When present in the metal-ligand complex of formula (I) as part of a radical having formula (II), formula (III) or formula (IV), the groups R31-35, R41-48 and R51-59 of the metal-binder complex of formula (I) are each independently chosen from (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, Si(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)-, (RN)2NC(O)-, halogen, hydrogen (-H), or combinations thereof. Independently, each RC, RP, and RN is unsubstituted (C1-C18)hydrocarbyl, (C1-C30)heterohydrocarbyl, or -H.

[0053] The groups R1 and R16 in the metal-ligand complex of formula (I) are chosen independently of one another. For example, R1 can be chosen from a radical having formula (II), (III) or (IV) and R16 can be a (C1-C40)hydrocarbyl group; or R1 can be chosen from a radical having formula (II), (III), or (IV) and R16 can be chosen from a radical having formula (II), (III), or (IV) equal to or different from that of R1. Both R1 and R16 can be radicals having formula (II), for which the groups R31-35 are the same or different in R1 and R16. In other examples, both R1 and R16 can be radicals of formula (III), for which the groups R41-48 are the same or different in R1 and R16; or both R1 and R16 can be radicals having the formula (IV), in which the groups R51-59 are the same or different in R1 and R16.

[0054] In some embodiments, at least one of R1 and R16 is a radical having formula (II), wherein R32 and R34 are TERC-butyl.

[0055] In some embodiments, when at least one of R1 or R16 represents a radical having formula (III), one of or both R43 and R46 is TERC-butyl and each of R41 -42, R44 -45 and R47- 48 are -H. In other embodiments, one of or both R42 and R47 is TERC-butyl and R41, R43 -46 and R48 are -H. In some embodiments, both R42 and R47 are -H.

[0056] In one or more embodiments, R3 and R14 are (C1-C12)alkyl. In some embodiments, R3 and R14 are TERC-octyl, N-octyl, methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or TERC-butyl). In one or more embodiments, R6 and R11 are halogen. In some embodiments, R3 and R14 are methyl; and R6 and R11 are halogen.

[0057] In some embodiments, the metal-ligand complex of formula (I), when R5-7 are fluorine, at most one of R10 -12 is fluorine. In other embodiments, when R10-12 is fluorine, at most one of R5-7 is fluorine. In other embodiments, less than four of R5-7 and R10-12 are fluorine. In one or more embodiments, R7, R8, R9 and R10 are -H. In some embodiments, R7 and R10 are halogen. In some embodiments, two of R5-7 are fluorine and two of R10-12 are fluorine.

[0058] The M in the metal-ligand complex of formula (I) may be a transition metal such as titanium (Ti), zirconium (Zr) or hafnium (Hf), and the transition metal may have a formal oxidation state of + 2, +3 or +4.

[0059] The metal M in the metal-ligand complex of formula (I) may be derived from a precursor metal which is subsequently subjected to single-step or multi-step synthesis to prepare the metal-ligand complex. Suitable metal precursors can be monomeric (one metal center), dimeric (two metal centers) or can have a plurality of metal centers greater than two, such as 3, 4, 5 or more than 5 metal centers. Specific examples of suitable hafnium and zirconium precursors, for example, include, but are not limited to, HfCl4, HfMe4, Hf(CH2Ph)4, Hf(CH2CMe3)4, Hf(CH2SiMe3)4, Hf(CH2Ph)3Cl, Hf(CH2CMe3 )3Cl, Hf(CH2SiMe3)3Cl, Hf(CH2Ph)2Cl2, Hf(CH2CMe3)2Cl2, Hf(CH2SiMe3)2Cl2, Hf(NMe2)4, Hf(NEt2)4 and Hf(N(SiMe3)2)2Cl2; ZrCl4, ZrMe4, Zr(CH2Ph)4, Zr(CH2CMe3)4, Zr(CH2SiMe3)4, Zr(CH2Ph)3Cl, Zr(CH2CMe3)3Cl, Zr(CH2SiMe3)3Cl, Zr(CH2Ph)2Cl2, Zr(CH2CMe3) 2Cl2, Zr(CH2SiMe3)2Cl2, Zr(NMe2)4, Zr(NEt2)4, Zr(NMe2)2Cl2, Zr(NEt2)2Cl2, Zr(N(SiMe3)2)2Cl2, TiBn4, TiCl4 and Ti(CH2Ph) 4. The Lewis base adducts from these examples are also suitable as metal precursors, for example ethers, amines, thioethers and phosphines are suitable as Lewis bases. Specific examples include HfCl4(THF)2, HfCl4(SMe2)2 and Hf(CH2Ph)2Cl2(OEt2). Activated metal precursors can be ionic or zwitterionic compounds, such as (M(CH2Ph)3+)(B(C6F5)4-) or (M(CH2Ph)3+) (PhCH2B(C6F5)3-), where M is defined above as either Hf or Zr.

[0060] In the metal-binder complex of formula (I), each Z is independently O, S, N(C1-C40)hydrocarbyl, or P(C1-C40)hydrocarbyl. In some embodiments, each Z is different. For example, one Z is O and the other Z is NCH3. In some embodiments, a Z is O and Z is an S. In another embodiment, a Z is S and Z is N(C1-C40)hydrocarbyl, (e.g., NCH3). In a further embodiment, each Z is equal. In still another embodiment, each Z is O. In another embodiment, each Z is S.

COCATALYST COMPONENT

[0061] The catalyst system comprising a metal-binder complex of formula (I) may be rendered catalytically active by any technique known in the art for activating metal-based catalysts of olefin polymerization reactions. For example, the procatalyst according to a metal-ligand complex of formula (I) can be made catalytically active by contacting the complex or by combining the complex with an activating cocatalyst. Furthermore, the metal-ligand complex according to formula (I) includes both a procatalyst form, which is neutral, and a catalytic form, which can be positively charged, due to the loss of a monoanionic ligand, such as benzyl or phenyl . Activation cocatalysts suitable for use herein include alkyl aluminums; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the aforementioned cocatalysts and activation techniques are also contemplated. The term "aluminum alkyl" means a monoalkyl aluminum dihydride or monoalkyl aluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0062] Lewis acid activation cocatalysts include Group 13 metal compounds that contain (C1-C2o)hydrocarbyl substituents as described herein. In some embodiments, the Group 13 metal compounds are tri((C1-C20)hydrocarbyl)-substituted aluminum or tri((C1-C20)hydrocarbyl)-boron compounds. In other embodiments, the Group 13 metal compounds are tri(hydrocarbyl)-substituted-aluminium, tri((C1-C20)hydrocarbyl)-boron, tri((C1-C10)alkyl)aluminium, tri((C6- C18)aryl)boron and the halogenated (including perhalogenated) derivatives thereof. In other embodiments, the Group 13 metal compounds are tris(fluoro-substituted phenyl)boranes, tris(pentafluorophenyl)borane. In some embodiments, the activation cocatalyst is a tris((C1-C20)hydrocarbyl borate (e.g., trityl tetrafluoroborate) or a tri((C1-C20)hydrocarbyl)ammonium tetra((C1-C2o)hydrocarbyl)borane (e.g., bis(octadecyl)methylammonium tetracis(pentafluorophenyl)borane.) As used herein, the term "ammonium" means a nitrogen cation that is a ((C1-C20)hydrocarbyl)4N+, a ((C1- C20)hydrocarbyl)3N(H)+, a ((C1-C2o)hydrocarbyl)2N(H)2+, (C1-C2o)hydrocarbylN(H)3+ or N(H)4+, where each (Ci - C20)hydrocarbyl, when two or more are present, may be the same or different.

[0063] Combinations of a neutral Lewis acid that activate cocatalysts include mixtures comprising a combination of an aluminum tri((C1-C4)alkyl) and a halogenated tri((C6-C18)aryl)boron compound, especially a tris (pentafluorophenyl)borane. Other embodiments are combinations of such neutral mixtures of Lewis acid with a polymeric or oligomeric alumoxane and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane. Mole number ratios of (metal-ligand complex):(tris(pentafluoro-phenylborane):(alumoxane) [eg, (Group 4 metal-ligand complex): (tris(pentafluoro-phenylborane):(alumoxane)] are from 1:1:1 to 1:10:30, in other modes from 1:1:1.5 to 1:5:10.

[0064] The catalyst system comprising the metal-ligand complex of formula (I) may be activated to form an active catalyst composition by combination with one or more cocatalysts, for example, a cation-forming cocatalyst, a Lewis acid strength, or combinations thereof. Suitable activation cocatalysts include polymeric or oligomeric aluminoxanes, especially methyl aluminoxane, as well as inert, compatible, non-coordinating and ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetracis(pentafluorophenyl)borate(1-)amine, and combinations thereof.

[0065] In some embodiments, more than one of the aforementioned activation cocatalysts may be used in combination with each other. A specific example of a cocatalyst combination is a mixture of an aluminum tri((C1-C4)hydrocarbyl) compound, tri((C1-C4)hydrocarbyl)borane, or an ammonium borate with either a polymeric or oligomeric alumoxane compound. . The ratio between the total number of moles of one or more metal-ligand complexes of formula (I) and the total number of moles of one or more of the activation cocatalysts is from 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments, at least 1:1000; and 10:1 or less, and in some other embodiments 1:1 or less. When an alumoxane alone is used as an activation cocatalyst, preferably the number of moles of the alumoxane that is employed is at least 100 times the number of moles of the metal-ligand complex of formula (I). When tris(pentafluorophenyl)borane alone is used as an activation cocatalyst, in some other embodiments, the number of moles of tris(pentafluorophenyl)borane that is employed in the total number of moles of one or more metal-ligand complexes of formula (I ) from 0.5:1 to 10:1, from 1:1 to 6:1 or from 1:1 to 5:1. The remaining activation cocatalysts are generally employed in mole amounts approximately equal to the total mole amounts of one or more metal-ligand complexes of formula (I).

[0066] In some embodiments, when more than one of the aforementioned cocatalysts is used in combination with a second cocatalyst, one of the cocatalysts may function as a scavenger. The purpose of the scavenger is to react with any water or other impurities present in the system that would otherwise react with the catalyst, leading to reduced effectiveness.

POLYOLEFINS

[0067] The catalytic systems described in the previous paragraphs are used in the polymerization of olefins, primarily ethylene and propylene. In some embodiments, there is only a single type of olefin or α-olefin in the polymerization scheme, creating a homopolymer. However, additional α-olefins can be incorporated into the polymerization procedure. Additional α-olefin comonomers typically have no more than 20 carbon atoms. For example, α-olefin comonomers can have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, one or more α-olefin comonomers can be selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene; or, alternatively, from the group consisting of 1-hexene and 1-octene.

[0068] Ethylene-based polymers, for example, homopolymers and/or interpolymers (including copolymers) of ethylene and, optionally, one or more comonomers, such as α-olefins, may comprise at least 50 mole % (% by mol) of ethylene-derived monomer units. All individual values and subranges covered by "of at least 50 mole%" are disclosed herein as separate embodiments; for example, the ethylene-based polymers, homopolymers and/or interpolymers (including copolymers) of ethylene and, optionally, one or more comonomers, such as α-olefins, may comprise at least 60 mole % of ethylene-derived monomer units ; at least 70% by moles of monomer units derived from ethylene; at least 80% by moles of monomer units derived from ethylene; or from 50 to 100 mole percent of ethylene-derived monomer units; or from 80 to 100 mole percent of ethylene-derived monomer units.

[0069] In some embodiments, the ethylene-based polymers may comprise at least 90 mole% of ethylene-derived units. All individual values and subranges of at least 90 mole % are included and disclosed herein as separate embodiments. For example, ethylene-based polymers can comprise at least 93 mole percent of ethylene-derived units; at least 96 percent in moles of units; at least 97% by moles of ethylene-derived units; or, alternatively, from 90 to 100 mole percent of ethylene-derived units; from 90 to 99.5 mole percent of ethylene-derived units; or from 97 to 99.5% by moles of ethylene-derived units.

[0070] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50 mole percent (mole %); other embodiments include at least 1 mol% to 25 mol%; and in other embodiments the additional amount of α-olefin includes at least 5 mole % to 103 mole %. In some embodiments, the additional α-olefin is 1-octene.

[0071] Any conventional polymerization process can be employed to produce the ethylene-based polymers. Such conventional polymerization processes include, but are not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof using one or more conventional reactors, such as loop reactors. closed reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, parallel batch reactors, series or any combination thereof, for example.

[0072] In one embodiment, the ethylene-based polymer can be produced by means of solution polymerization in a dual reactor system, for example, a dual loop reactor system, wherein ethylene and, optionally, one or more α-olefins are polymerized in the presence of the catalyst system as described herein and, optionally, one or more cocatalysts. In another embodiment, the ethylene-based polymer can be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system, in which ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system in this disclosure, and as described herein, and optionally one or more other catalysts. The catalyst system as described herein can be used in the first reactor, or the second reactor, optionally in combination with one or more other catalysts. In one embodiment, the ethylene-based polymer can be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system, in which ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system, as described in this document, in both reactors.

[0073] In another embodiment, the ethylene-based polymer can be produced by means of solution polymerization in a single reactor system, for example, a single loop reactor system, in which ethylene and, optionally, one or more further α-olefins are polymerized in the presence of the catalyst system as described in this disclosure and, optionally, one or more cocatalysts as described in the preceding paragraphs.

[0074] The ethylene-based polymers may additionally comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers and combinations thereof. Ethylene-based polymers can contain any amount of additives. Ethylene-based polymers can comprise from about 0 to about 10% by weight combined of such additives, based on the weight of the ethylene-based polymers and one or more additives. Ethylene-based polymers can further comprise fillers, which can include, but are not limited to, organic or inorganic fillers. The ethylene-based polymers can contain from about 0 to about 20% by weight of fillers, such as, for example, calcium carbonate, talc, or Mg(OH)2, based on the combined weight of the ethylene-based polymers. and any additives or fillers. The ethylene-based polymers can be further blended with one or more polymers to form a blend.

[0075] In some embodiments, a polymerization process for producing an ethylene-based polymer can include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, wherein the catalyst system incorporates at least one metal-olefin complex binder of formula (I). The polymer resulting from such a catalyst system that incorporates the metal-binder complex of formula (I) can have a density according to ASTM D792 standard (incorporated into this document by way of reference in its entirety), of 0.850 g/ cm3 to 0.950 g/cm3, from 0.880 g/cm3 to 0.920 g/cm3, from 0.880 g/cm3 to 0.910 g/cm3, or from 0.880 g/cm3 to 0.900 g/cm3, for example.

[0076] In another embodiment, the polymer resulting from the catalyst system that includes the metal-binder complex of formula (I) has a melt flow ratio (I10/I2) of 5 to 15, where the index melt index I2 is measured in accordance with ASTM D1238 (incorporated herein by reference in its entirety) at 190 °C and 2.16 kg load, and melt index I10 is measured in accordance with ASTM D1238 at 190 °C and 10 kg load. In other embodiments, the melt flow rate (I10/I2) is 5 to 10, and in others, the melt flow rate is 5 to 9.

[0077] In some embodiments, the polymer resulting from the catalyst system that includes the metal-binder complex of formula (I) has a molecular weight distribution (MWD) of 1.5 to 25, where MWD is defined as Mw/Mn with Mw being a weight average molecular weight and Mn being a number average molecular weight. In other embodiments, the polymers resulting from the catalyst system have an MWD of 1.5 to 6. Another embodiment includes an MWD of 1.5 to 3; and other embodiments include MWD from 2 to 2.5.

[0078] Modalities of the catalyst systems described in this disclosure produce unique polymeric properties as a result of the high molecular weights of the polymers formed and the amount of comonomers incorporated into the polymers.

[0079] All solvents and reagents are obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexanes, tetrahydrofuran, and diethyl ether are purified by passage through activated alumina and, in some cases, reagent Q-5. Solvents used for experiments performed in a nitrogen-charged glove box are further dried by storage on activated 4A molecular sieves. Glassware for moisture sensitive reactions is dried in an oven overnight before use. NMR spectra are recorded on the Varian 400-MR and VNMRS-500 spectrometers. 1H NMR data are recorded as follows: chemical shift (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sex = sextet, sept = septet, and m = multiplet), integration and assignment). Chemical shifts for 1H NMR data are reported in ppm downstream of the internal tetramethylsilane (TMS, δ scale) using residual protons in the deuterated solvent as references. 13C NMR data are determined with 1H dissociation, and chemical shifts are reported with reference to downstream tetramethylsilane (TMS, δ scale) in ppm versus the residual carbons in use in the deuterated solvent as references.

SYMRAD HT-GPC ANALYSIS

[0080] Molecular weight data are determined by analysis on a Robot Aided Dilution High Temperature Permeation Chromatograph (Sym-RAD-GPC) built by Symyx/Dow. Polymer samples are dissolved by heating for 120 minutes at 160 °C in 1,2,4-trichlorobenzene (TCB) at a concentration of 10 mg/ml stabilized at 300 parts per million (ppm) butylated hydroxyl toluene (BHT ). Each sample was diluted to 1 mg/ml immediately before injecting a 250 μl aliquot of the sample. The GPC is equipped with two Polymer Labs PLgel 10 µm MIXED-B columns (300 x 10 mm) at a flow rate of 2.0 ml/minute at 160 °C. Sample detection is performed using a PolyChar IR4 detector in concentration mode. A conventional calibration of polystyrene (PS) narrow standards is used with apparent units adjusted to homopolyethylene (PE) using known Mark-Houwink coefficients for PS and PE in TCB at this temperature.

ANALYSIS OF IR BY INCORPORATION OF 1-OCTENE

[0081] Running samples for HT-GPC analysis precedes IR analysis. For IR analysis, a 48-well HT silicon wafer is used for deposition and incorporation analysis of 1-octene samples. For analysis, samples are heated to 160 °C for less than or equal to 210 minutes; samples are reheated to remove the magnetic GPC stir bars and stirred with glass rod stir bars in a heated J-KEM Scientific robotic stirrer. Samples are deposited while heated using a Tecan MiniPrep 75 deposition station, and the 1,2,4-trichlorobenzene is evaporated from the pellet deposit wells at 160 °C under nitrogen purge. 1-octene analysis is performed on the HT silicon wafer using a NEXUS 670 ESP FT-IR.

BATCH REACTOR POLYMERIZATION PROCEDURE

[0082] The batch reactor polymerization reactions are conducted in a one gallon (3.79 L) stirred autoclave reactor charged with ca. 1.35 kg Isopar™ E and 1-octene mixed alkanes solvent (250 g). The reactor is then heated to the desired temperature and charged with hydrogen (if desired), followed by an amount of ethylene to bring the total pressure to ca. 450 psig (2.95 MPa). The ethylene feed was passed through an additional purification column before entering the reactor. The catalyst composition was prepared in a dry box, under inert atmosphere, by mixing the desired procatalyst and a cocatalyst (a mixture of 1.2 equiv of tetracis(pentafluorophenyl)borate(1-)amine and 50 equiv of triisobutylaluminum-modified alumoxane ( MMAO-3A)), with additional solvent, to give a total volume of about 17 ml. The activated catalyst mixture was then rapidly injected into the reactor. The reactor pressure and temperature were kept constant by feeding ethylene during polymerization and cooling the reactor as necessary. After 10 minutes, the ethylene feed was turned off and the solution transferred to a nitrogen purged resin kettle. The polymer was completely dried in a vacuum oven and the reactor was thoroughly washed with hot Isopar™ E between polymerization tests.

EXAMPLES

[0083] Example 1 comprises synthetic procedures for procatalyst intermediates, for reagents used to produce procatalysts, and for isolated procatalysts themselves. One or more features of the present disclosure are illustrated in view of the examples as follows: EXAMPLE 1 - SYNTHESIS OF PROCATALYST 1

[0084] A solution of Intermediate 1 (2.271 g, 1.84 mmol) in a mixture of benzene (40 ml) and toluene (40 ml) was chilled in a glove box freezer (-35 °C). A solution of 14 ml of dimethyloctylsilylmethyllithium in hexane (0.13 M, 1.84 mmol) was added to the solution and the reaction mixture was stirred over the weekend at room temperature to give a clear colorless solution. At this time, the solution was cooled in the glove box freezer, dimethyloctylylsilmethyllithium (5.26 ml, 0.69 mmol) was added, and the reaction mixture was stirred overnight at 60 °C. Three more times the reaction mixture was chilled in the glove box freezer plus dimethyloctylylsilmethyllithium (4.5 ml, 0.59 mmol; 2.8 ml, 0.36 mmol; 2.2 ml, 0.29 mmol ) was added and the reaction mixture was stirred overnight. The reaction mixture was filtered and volatiles were removed under reduced pressure. The residue was extracted with hot (50 °C) hexanes, the extract was filtered and the volatiles were removed under reduced pressure. The residue was extracted a second time with hot (50 °C) hexanes, the extract was filtered from a small amount of insoluble material and the volatiles were removed under reduced pressure to give the product as a slightly sticky beige solid. This reaction gave a yield of 2.13 g, 83.6% yield.

[0085] 1H NMR (400 MHz, Benzene-d6) δ 8.37 - 8.26 (m, 1.5H), 8.17 (ddt, J = 7.8, 6.8, 1.3 Hz , 1.7H), 8.14 - 7.82 (m, 3.5H), 7.69 - 7.17 (m, 13.3H), 7.13 - 6.64 (m, 10.4H) , 4.93 (dd, J = 8.3, 1.2 Hz, 0.9H), 4.68 (dd, J = 8.2, 1.2 Hz, 0.8H), 4.19 (dd , J = 12.4, 8.6 Hz, 1.3H), 3.85 (d, J = 11.0 Hz, 1.1H), 3.76 (d, J = 10.8 Hz, 0, 7H), 3.38 (d, J = 12.4 Hz, 1.3H), 3.19 (d, J = 10.9 Hz, 1.1H), 2.21 - 2.00 (m, 6H ), 1.85 - 0.33 (m, 73H), 0.32 - 0.25 (m, 4.6H), 0.22 - 0.04 (m, 5.4H), 0.02 (s , 1H), 0.00 - -0.13 (m, 2.3H), -0.15 (d, J = 2.5 Hz, 2.6H), -0.33 (s, 1.3H) , -0.38 (s, 1.6H), -1.70 (dd, J = 372.3, 13.0 Hz, 1.7H), -1.73 (dd, J = 272.4, 13 .1Hz, 1.8H).

[0086] Procatalyst 1, Comparative Procatalyst C1 and Comparative Procatalyst C2 were reacted individually using the polymerization conditions in a single reactor system, as previously described. The properties for the resulting polymers are reported in Table 2. Comparative procatalyst C1 has a structure according to formula (Ia). In comparison with Comparative Procatalyst C1 and Comparative Procatalyst C2, a significant increase in the percentage of solubility by weight of Procatalyst 1, which is a metal-ligand complex according to formula (I), was observed. TABLE 1: SOLUBILITY DATA AT 25 °C TABLE 2: PROCATALYST 1 AND C1 COMPARATIVE BATCH REACTOR SCREENING *Efficacy is defined in units of 106 grams of polymer per gram of active metal (Hf or Zr). **H2 (% in moles) is defined as: the molar fraction of hydrogen in relation to ethylene supplied to the reactor. TABLE 3: SCREENING OF PROCATALYST BATCH REACTOR 1 AND COMPARATIVE C1 *Efficacy is defined in units of 106 grams of polymer per gram of active metal (Hf or Zr). **H2 (% in moles) is defined as: the molar fraction of hydrogen in relation to ethylene supplied to the reactor.

[0087] Batch reactor conditions for Table 3: 1.47 kg of Isopar™ E; 100 grams of octene; 105 grams of ethylene was added at 160°C or 88 grams of ethylene at 190°C; the RIBS:catalyst ratio was approximately 1.2; Procatalyst: activator ratio was 1:1.2; the activator was [HNMe(C18H37)2][B(C6F5)4]; MMAO-3A was used as an impurity scavenger at an MMAO-3A:procatalyst molar ratio of about 50; total pressure was initially 410 psig.

Claims (5)

1. Catalyst system, characterized by the fact that it comprises a metal-binder complex according to formula (I): where: M is a metal chosen from titanium, zirconium or hafnium, the metal being in a formal oxidation state of +2, +3 or +4; each X is selected from the group consisting of -(CH2)SiRX3, each RX is independently a (C1-C30)hydrocarbyl group or a (C1-C30)heterohydrocarbyl group, and at least one RX is (C2 -C30)hydrocarbyl, and any two RX or all three RX are optionally covalently linked; n is 1 or 2; each Z is independently chosen from -O-, -S-, -N(RN)-, or -P(RP)-; R1 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)-, halogen, radicals having formula (II), radicals having formula (III), and radicals having formula (IV ): each of R31-R35, R41-R48, R51-R59 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, provided that at least one of R1 or R16 is a radical having formula (II), a radical having formula (III) or a radical having formula (IV); each of R2-4, R5-8, R9-12 and R13-15 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(R)-, (RC)2NC(O)- and halogen; L is (C2-C40)hydrocarbylene or (C2-C40)heterohydrocarbylene; and each RC, RP and RN in formula (I) independently represents a (C1-C30)hydrocarbyl, (C1-C30)heterohydrocarbyl, or -H, the metal-ligand complex according to formula ( I) has a wt% solubility ratio W/Y of at least 1.5, where W is the wt% solubility of the metal-binder complex of formula (I) in methylcyclohexane (MCH) at temperature and pressure standard (STP); wherein Y is the % by weight of a corresponding comparative metal-binder complex of formula (Ia) in MCH in STP; and wherein the corresponding comparative complex has a structure according to formula (Ia): wherein M, each Z, each R1-16 and L are all identical to the corresponding groups of the metal-ligand complex according to formula (I). 2. Catalyst system, according to claim 1, characterized by the fact that: M is zirconium or hafnium; each X is -(CH2)Si(CH2CH3)3; and each Z be oxygen. 3. Catalyst system, according to claim 1, characterized by the fact that: M is zirconium or hafnium; each X is selected from the group consisting of -(CH2)Si(CH3)(n-Oct)RX; and each Z be oxygen. 4. Catalyst system, according to claims 1, characterized by the fact that exactly two RX are covalently linked or exactly three RX are covalently linked. 5. Catalyst system, characterized by the fact that it comprises a metal-binder complex according to formula (I): where: M is a metal chosen from zirconium or hafnium, the metal being in a formal oxidation state of +2, +3 or +4; each X is selected from the group consisting of -(CH2)Si(n-Oct)RX2, where each RX is independently a (C1-C30)hydrocarbyl or a (C1-C30)heterohydrocarbyl, and any two RX are optionally covalently linked; n is 1 or 2; each Z is -O-; R1 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)-, halogen, radicals having formula (II), radicals having formula (III), and radicals having formula (IV): each of R31-R35, R41-R48, R51-R59 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, provided that at least one of R1 or R16 is a radical having formula (II), a radical having formula (III) or a radical having formula (IV); each of R2-4, R5-8, R9-12 and R13-15 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(R)-, (RC)2NC(O)- and halogen; L is (C2-C40)hydrocarbylene or (C2-C40)heterohydrocarbylene; and each RC, RP and RN in formula (I) independently represents a (C1-C30)hydrocarbyl, (C1-C30)heterohydrocarbyl, or -H, the metal-ligand complex according to formula ( I) has a wt% solubility ratio W/Y of at least 1.5, where W is the wt% solubility of the metal-binder complex of formula (I) in methylcyclohexane (MCH) at temperature and pressure standard (STP); wherein Y is the % by weight of a corresponding comparative metal-binder complex of formula (Ia) in MCH in STP; and wherein the corresponding comparative complex has a structure according to formula (Ia): wherein M, each Z, each R1-R16, and L are all identical to the corresponding groups of the metal-ligand complex according to formula (I).