BR112020006332B1 - PRO-CATALYST - Google Patents

Abstract

This is a catalyst system comprising metal-binder complexes and processes for polymerizing polyolefin using the metal-binder complex having the following structure: where X is selected from the group consisting of -ORX or - NRX2.

Description

Cross reference to related order

[0001] The present application claims the benefit of Provisional Patent Application Serial Number U.S. 62/565,780 filed on September 29, 2017, which is incorporated herein by reference.

field of technique

[0002] The embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more specifically to a bis-phenyl-phenoxy polyolefin procatalyst having an amido linker or an alkoxy linker on the metal to enhanced solubility.

Background

[0003] Olefin-based polymers such as ethylene-based polymers and propylene-based polymers 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 such olefin-based polymers.

[0004] Polyethylene and polypropylene are manufactured for various articles. The polyethylene and polypropylene polymerization process can be varied in a number of ways to produce various resulting polyethylene resins that have 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 (such as solvents) such as an alkane or isoalkane, for example isobutene. Hydrogen can also be added to the reactor. Catalyst systems for producing polyethylene may typically comprise a chromium-based catalyst system, a Ziegler-Natta catalyst system, and/or a molecular (either metallocene or non-metallocene (molecular)) catalyst system. The reactants in the diluent in the catalyst system circulate at an elevated polymerization temperature around the reactor, thereby producing polyethylene homopolymer or copolymer. Either periodically or continuously, part of the reaction mixture, including the polyethylene product dissolved in the diluent, together 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 diluent and unreacted reagents, whereupon the diluent and unreacted reagents are typically recycled back to the reactor. Alternatively, the reaction mixture can be sent to a second reactor, connected in series with the first reactor, in which a second polyethylene fraction can be produced. Despite research attempts to develop catalyst systems suitable for olefin polymerization, such as polyethylene or polypropylene polymerization, there is still a need to increase the efficiency of catalyst systems that are capable of producing polymers with high molecular weights and a narrow distribution. of molecular weight.

summary

[0005] 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 caustic solvent, such as toluene or dichlorotoluene, is used in order to dissolve a small amount of catalyst. As a result, there is an increasing need to solubilize a catalyst system with a smaller amount of solvent, while maintaining the efficiency, reactivity and ability of the catalyst to produce polymers with a high or low molecular weight.

[0006] According to some embodiments, a catalyst system may include a metal-ligand complex according to formula (I):

[0007] 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 -ORX or -NRX2; wherein each RX is independently a (C1-C50)hydrocabyl, (C1-C50)heterohydrocabyl or -H and at least one RX is (C1-C50)hydrocabyl or (C1-C50)heterohydrocabyl. When X is -NRX2, optionally two RX are covalently joined; 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)hydrocable, (C1-C40)heterohydrocable, -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 which have the formula (IV):

[0008] In formulas (II), (III), and (IV), each of R31-35, R41-48 and R51-59 is independently chosen from -H, (C1-C40)hydrocable, (C1- C40)heterohydrocabyl, -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).

[0009] In formula (I), each of R2-4, R5-8, R9-12 and R13-15 is independently selected from -H, (C1-C40)hydrocable, (C1-C40)hetero- hydrocable, -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)hydrocabylene or (C2-C40)heterohydrocabylene; and each RC, RP and RN in formula (I) is independently a (C1-C30)hydrocable, (C1-C30)heterohydrocable or -H. The metal-binder complex according to formula (I) has a solubility greater than the solubility of a comparative complex having a structure according to formula (Ia):

[0010] 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 are identical to groups corresponding elements of the metal-ligand complex according to formula (I).

Detailed Description

[0011] Specific embodiments of catalyst systems will now be described. It is to be understood that the catalyst systems of the present disclosure may be incorporated in different forms and are not to be construed as limited to the specific embodiments set forth in the present disclosure. Preferably, embodiments are provided so that the present disclosure is thorough and complete and fully conveys the scope of the matter to those skilled in the art.

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; T-Oct: TERC-octyl (2,4,4-trimethylpentan-2-yl); Tf: trifluoromethane sulfonate; THF: tetrahydrofuran; Et2O: diethyl ether; CH2Cl2: dichloromethane; CV: column volume (used in column chromatography); EtOAc: ethyl acetate; C6D6: deuterated benzene or benzene-D6: CDCl3: deuterated chloroform; Na2SO4: sodium sulfate; MgSO4: magnesium sulfate; HCl: hydrogen chloride; N-BuLi: butyl lithium; T-BuLi: TERC-butyl lithium; Cu2O: Copper (I) oxide; N,N'-DMEDA: N,N'-dimethylethylenediamine; K3PO4: Tribasic Potassium Phosphate; Pd(AmPhos)Cl2: Bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II); Pd(dppf)Cl2: [1,1'-Bis(diphenylphosphino)ferrocene]palladium(II) dichloride; K2CO3: potassium carbonate; Cs2CO3: cesium carbonate; I-PrOBPin: 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane; BrCl2CCCl2Br: 1,2-dibromotetrachloroethane; HfCl4: hafnium(IV) chloride; HfBn4: tetrabenzyl hafnium(IV); ZrCl4: zirconium(IV) chloride; ZrBn4: tetrabenzyl zirconium(IV); ZrBn2Cl2(OEt2): dibenzyl monodiethyl etherate zirconium (IV) dichloride; HfBn2Cl2(OEt2): hafnium(IV) dibenzyl dichloride dibenzyl mono-diethyl etherate; TiBn4: titanium (IV) tetrabenzyl; N2: nitrogen gas; PhMe: toluene; PPR: parallel polymerization reactor; MAO: methylaluminoxane; MMAO: modified methylaluminoxane; TEA: Triethylamine; GC: Gas chromatography; LC: liquid chromatography; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimol; ml: milliliters; M: molar; min: minutes; h: hours; d: days; Rf; retention fraction; TLC; thin layer chromatography; rpm: revolutions per minute.

[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 identical or different (for example, R1, R2, R3, R4 and R5 can all be substituted alkyl, or R1 and R2 can be substituted alkyl, and R3 can be aryl, etc.). A chemical name associated with an R group must convey the chemical structure which is recognized in the art as corresponding to that of the chemical name. As such, chemical names should 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 herein, the terms "cocatalyst" and "activator" are interchangeable terms.

[0015] When used to describe certain chemical groups that contain a carbon atom, a parenteral expression having the form “(Cx-Cy)” means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, a (C1-C50)alkyl is an alkyl group that has from 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be replaced by one or more substituents, such as RS. A chemical group replaced by RS using the parenthetical “(Cx-Cy)” can contain more than y carbon atoms depending on the identity of any RS groups. For example, a “(C1-C50)alkyl exactly substituted by one RS group, where RS is phenyl (-C6H5)”, can contain from 7 to 56 carbon atoms. Thus, in general, when a chemical group defined using the parenthetical “(Cx-Cy)” is replaced by one or more substituents containing an RS carbon atom, the minimum and maximum number of carbon atoms of the chemical group is determined by adding to both x and y the combined sum of the 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 (eg 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 bonded 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)hydrocabyl” means a hydrocarbon radical of 1 to 50 carbon atoms and the term “(C1-C50)hydrocabylene” means a hydrocarbon diradical of 1 to 50 carbon atoms, in which each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (having three carbons or more, and including mono and polycyclic, fused and unfused polycyclic and bicyclic) or acyclic and substituted by a or more RS or not replaced.

[0018] In the present disclosure, a (C1-C50)hydrocable can be a (C1-C50)alkyl, (C3-C50)cycloalkyl, (C3-C20)cycloalkyl-(C1-C20)alkylene, (C6-C40) substituted or unsubstituted 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 straight or branched saturated hydrocarbon radical of 1 to 50 carbon atoms and a straight or branched saturated hydrocarbon radical of 1 to 18 atoms of carbon, respectively, that is substituted or unsubstituted by one or more RS. Examples of unsubstituted (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-decyl. Examples of (C1-C4o)alkyl are substituted (C1-C2o)alkyl, substituted (C1-C10)alkyl, trifluoromethyl and [C45]alkyl. The term "[C45]alkyl" means that there is a maximum of 45 carbon atoms in the radical including substituents and is, for example, a (C27-C40)alkyl substituted by an RS, which is a (CpC5)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 a mono, bi or tricyclic aromatic hydrocarbon radical of 6 to 40 carbon atoms substituted or unsubstituted (by one or more RS), among which at least 6 to 14 of the carbon atoms are aromatic ring 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 radical's rings is aromatic. The other ring or rings of the aromatic radical may be independently fused or unfused and aromatic or non-aromatic. Examples of unsubstituted (C6-C50)aryl include: unsubstituted (C6-C20)aryl, unsubstituted (C6-C18)aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (C6-C40)aryl include: substituted (C1-C20)aryl; substituted (C6-C18)aryl; 2,4-bis([C20]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-one-l-yl.

[0021] The term "(C3-C50)cycloalkyl" means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms which is substituted or unsubstituted 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 which are either unsubstituted or substituted by 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 substituted (C3-C40)cycloalkyl are substituted (C3-C20)cycloalkyl, substituted (C3-C10)cycloalkyl, cyclopentanon-2-yl and 1-fluorocyclohexyl.

[0022] Examples of DE (C1-C50)hydrocabylene include substituted or unsubstituted (C6-C50)arylene, (C3-C50)cycloalkylene, and (C1-C50)alkylene (e.g., (C1-C2o)alkylene). Diradicals can be on the same carbon atom (e.g. -CH2-) or on adjacent carbon atoms (e.g. 1,2-diradicals) or are separated by one, two or more than two intervening carbon atoms (e.g. example, 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 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 (ie, -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 or branched chain diradical (i.e. the radicals are not on ring atoms) of 1 to 50 carbon atoms which is substituted or unsubstituted by a or more RS. Examples of unsubstituted (CpC50)alkylene are (unsubstituted C1 -C4 alkylene, including unsubstituted -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 carbon atom hydrogen is removed to form a secondary or tertiary alkyl radical. Examples of substituted (C1-C50)alkylene are (C1-C20)substituted alkylene, -CF2-, -C(O)-, and -(CH2)14C(CH3) 2(CH2)5- (i.e. a normal-1,20-eicosylene substituted 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 substituted or unsubstituted 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(RC)2, P(RP), N(RN), -N=C(RC )2, -Ge(RC)2- or -Si(RC)-, where each RC and each RP is unsubstituted (C1-C18)hydrocable or -H, and where each RN is (C1-C18)hydrocable not replaced. The term "heterohydrocarbon" refers to a molecule or molecular structure in which one or more carbon atoms of a hydrocarbon are replaced by a heteroatom. The term "(C1-C50)heterohydrocabyl" means a heterohydrocarbon radical of 1 to 50 carbon atoms, and the term "(C1-C50)heterohydrocabylene" means a heterohydrocarbon diradical of 1 to 50 carbon atoms of carbon. (C1-C50)heterohydrocabyl heterohydrocarbon or (C1-C50)heterohydrocabylene has one or more heteroatoms. The heterohydrocabyl radical can be on a carbon atom or a heteroatom. The two heterohydrocabylene radicals can be on a single carbon atom or on a single heteroatom. Additionally, one of the two diradical radicals can be a 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)hetero—hydrocabyl and (C1-C50)hetero—hydrocabylene can be substituted or unsubstituted (by one or more RS), aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic ( including mono and polycyclic, fused and non-fused polycyclic) or acyclic.

[0026] The (C1-C50)hetero—hydrocable can be substituted or unsubstituted. Non-limiting examples of (C1-C50)hetero—hydrocable include (C1-C50)heteroalkyl, (C1-C50)hydrocable-O-, (C1-C50)hydrocable-S-, (C1-C50)hydrocable-S( O)-, (C1-C50)hydrocable-S(O)2-, (C1-C50)hydrocable-Si(RC)2-, (C1-C50)hydrocable-N(RN)-, (C1-C50) hydrocable-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 a mono, bi or tricyclic heteroaromatic hydrocarbon radical of 4 to 50 total carbon atoms substituted or unsubstituted (by one or more RS) and of 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 independently be fused or unfused and aromatic or non-aromatic. Other heteroaryl groups (e.g., (Cx-Cy)heteroaryl generally, 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 substituted or not replaced by one or more than one RS. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered ring or a 6-membered ring.

[0028] 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. Examples of the 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.

[0029] 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. Examples of heteroaromatic hydrocarbon radicals 6-membered ring include pyridin-2-yl; pyrimidin-2-yl and pyrazin-2-yl.

[0030] The bicyclic heteroaromatic hydrocarbon radical may be a 5,6 or 6,6 fused ring system. Examples of the fused-5,6-ring system bicyclic heteroaromatic hydrocarbon radical are indol-1-yl; and benzimidazole-1-yl. Examples of the 6,6-ring 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 system; 5,6,6; 6,5,6 or 6,6,6 fused rings. An example of the 5,6,5 fused ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of the 5,6,6 fused ring system is 1H-benzo[f]indol-1-yl. An example of the 6,5,6 fused ring system is 9H-carbazol-9-yl. An example of the 6,5,6 fused ring system is 9H-carbazol-9-yl. An example of the 6,6,6 fused ring system is acridin-9-yl.

[0031] The term “(C1-C50)heteroalkyl” means a saturated straight or branched chain radical containing one to fifteen 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 heteroatoms. 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.

[0032] Examples of unsubstituted (C2-C40)heterocycloalkyl include unsubstituted (C2-C20)heterocycloalkyl, unsubstituted (C2-C10)heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3 -yl, pyrrolidin-1-yl, tetrahydrothiophen-S,S-dioxido-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa - cyclooctyl, 5-thio-cyclononyl and 2-aza-cyclodecyl.

[0033] 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-).

[0034] The term “saturated” means that there are no carbon-carbon double bonds, carbon-carbon triple bonds and (in heteroatom-containing groups) 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 and/or triple bonds can optionally be present in RS substituents. The term "unsaturated" means containing one or more carbon-carbon double bonds or carbon-carbon triple bonds or (in heteroatom-containing groups) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds or carbon-phosphorus double bonds. carbon-silicon double bonds, without includes double bonds that may be present in RS substituents, if any, or in aromatic rings or heteroaromatic rings, if any.

[0035] Embodiments of the present disclosure include catalyst systems that include a metal-binder complex according to formula (I):

[0036] 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. -ORX or -NRX2; wherein each RX is independently (C1-C50)hydrocable, (C1-C50)heterohydrocable or -H. At least one RX is (C1-C50)hydrocable or (C1-C50)heterohydrocable. When X is -NRX2, the two RX's are optionally covalently linked. The metal-ligand complex has 6 or fewer metal-ligand bonds and can be generally neutrally charged. Each Z is independently chosen from -O-, -S-, -N(RN)- or -P(RP)-.

[0037] In embodiments, the catalyst system may include a metal-binder complex according to formula (I), wherein each of R1 and R16 is independently selected from the group consisting of -H, (C1-C40 )hydrocable, (C1-C40)heterohydrocable, -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):

[0038] In formulas (II), (III) and (IV), each of R31-35, R41-48 and R51-59 is independently chosen from -H, (C1-C40)hydrocable, (C1-C40 )heterohydrocabyl, -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).

[0039] In formula (I), each of R2-4, R5-8, R9-12 and R13-15 is independently selected from -H, (C1-C40)hydrocable, (C1-C40)hetero- hydrocable, -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)hydrocabylene or (C2-C40)heterohydrocabylene; and each RC, RP and RN in formula (I) is independently a (C1-C30)hydrocable, (C1-C30)heterohydrocable or -H.

[0040] In the embodiments, the metal-binder complex according to formula (I) has a solubility greater than the solubility of a comparative complex having a structure according to formula (Ia):

[0041] 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 identical to corresponding groups of metal-ligand complex according to formula (I). Thus, the comparative complex is different from the metal-ligand complex according to formula (I) in that the X group of the metal-ligand complex according to formula (I) is replaced by methyl groups.

[0042] Both the metal-ligand complex of formula (I) and the corresponding comparative complex of formula (Ia) have a solubility in percent by weight (% by weight) in various solvents. In general, as used herein, the weight percent solubility (% by weight) of a solute in a solution is the weight of the solute divided by the weight of the solution, multiplied by 100.

[0043] In the present disclosure, one or more or individual metal-binder complexes according to formula (I) are oils. Solubility measurements of individual metal-binder complexes that are oils (hereinafter "oily solute") are conducted by the following Procedure A: (1) new parts by weight of a solvent such as MCH or Isopar-ETM are added to one part by weight of oily solute (procatalyst); (2) The resulting solution is stored at STP for 48 hours; (3) If the oil solute does not precipitate out of solution, then the weight percent solubility of the oil solute is determined to be at least 10% by weight (or >10% by weight); (4) If the oily solute precipitates out of solution, then steps (1) and (2) are repeated, wherein in step (1) nineteen parts by weight of the solvent are added to one part by weight of the oily solute; (5) If the oil solute does not precipitate out of solution in step (4), then the weight percent solubility of the oil solute is taken to be at least 5% by weight and less than 10% by weight; (6) If the oily solute precipitates out of solution in step (5), then steps (1) and (2) are repeated, where in step (1) 49 parts by weight of the solvent are added to a part by weight of the oil solute; (7) if the oily solute does not precipitate out of solution in step (6), then the weight percent solubility of the oily solute is determined to be at least 2% by weight and less than 5% by weight; (8) if the oil solute precipitates out of solution in step (5), then the weight percent solubility of the oil solute is determined to be less than 2% by weight.

[0044] Solubility measurements of individual metal-ligand complexes that are crystalline are conducted by Procedure B: the solute (procatalyst) is added to a solvent, such as methylcyclohexane (MCH) or Isopar-ETM, so that the amount of added solute is greater than the amount that will dissolve in that amount of solvent. The resulting suspension is stirred for one hour and then allowed to settle overnight. After stirring 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 is removed. Solubility in % 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.

[0045] 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) under room temperature and pressure. All individual values and subranges covered by "from 1.5% by weight to 50% by weight" are disclosed 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 under standard temperature and pressure (STP) (temperature of 22.5 ± 2.5 °C and a pressure of approximately 1 atmosphere).

[0046] In one or more embodiments, the metal-binder complex according to formula (I) has a wt% solubility of 1.5 wt% to 70 wt% in Isopar-ETM at room temperature and pressure. All individual values and subranges covered by "from 1.5% by weight to 70% by weight" are disclosed 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%, of 2.5 wt% to 10% in from 3.0% by weight to 15% by weight or from 10% by weight to 50% by weight in Isopar-ETM and, in other embodiments, the solubility in % by weight is greater than 20% by weight in Isopar -ETM under STP.

[0047] In one or more embodiments, the metal-binder complex according to formula (I) has a weight percent (wt%) solubility of 1.5 wt% to 70 wt% in methylcyclohexane ( MCH) under room temperature and pressure. All individual values and subranges covered by "from 1.5% by weight to 50% by weight" are disclosed 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, from 3, 0% by weight to 15% by weight or from 10% by weight to 50% by weight in MCH. In other embodiments, the solubility is greater than 20% by weight in MCH to STP.

[0048] The metal-ligand complex of formula (I) in MCH under STP has a solubility in wt% W as measured by Procedure A or Procedure B. The corresponding metal-ligand complex of formula (Ia) in MCH under STP has a wt% solubility in MCH under STP of Y, as measured by Procedure B. A wt% solubility ratio (SR) is defined as W divided by Y (W/Y). For example, Complex A, a metal-binder complex of formula (I) which is an oil, has at least a wt% solubility of 10 in MCH under PBS, as measured by Procedure A. Complex B, the complex corresponding metal-linker of (Ia), has a wt% solubility of 2.5 in MCH under STP, as measured by Procedure B. Thus, Complex C has an SR greater than or equal to 4.

[0049] In one or more embodiments of the present 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.

[0050] Industrial scale polymerization processes typically involve the consumption of many liters of solvent. The more soluble the catalyst, the less solvent is used during the polymerization process involving the catalyst, which can make a more soluble catalyst more environmentally friendly than a soluble catalyst. Additionally, the use of less solvent in the polymerization process can decrease chain disturbances in the polymer.

[0051] In some embodiments, any or all chemical groups (eg, L, R1-16, R31-35, R41-48, R51-59) of the metal-ligand complex of formula (I) may be unsubstituted. In other embodiments, none, any 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 from 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 may 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 with RS. In chemical groups that are persubstituted by RS, the individual RS can be the same or can be chosen independently.

[0052] In one or more embodiments, RX of -ORX or -NRX2 is (C5-C5o)alkyl or -H and at least one RX is (C5-C5o)alkyl. In other embodiments, X is chosen from an alkyl having the formula -OCnH2n+1 or NHCnH2n+1, where the subscript n is an integer from 10 to 40; from 15 to 30; or from 15 to 25. In some embodiments, X is -OC22H45, -OC18H37, -N(C18H37)RX, -NH(C18H37) or -N(C22H45)2. Optionally, in some embodiments, the metal-ligand complex according to formula (I), exactly two RX's are covalently bonded.

[0053] 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)hydrocable. In some embodiments, L is -(CH2)m-, where the subscript m is from 2 to 5. In other embodiments, subscript m of -(CH2)m-, is 3 or 4. In some embodiments, L is 1 ,3-bis(methylene)cyclohexane or 1,2-bis(2-ylethyl)cyclohexane.

[0054] In some embodiments, in the metal-ligand complex of formula (I), either one of R1 or R16 or both R1 and R16 are chosen from radicals having formula (II), formula (III) or formula (IV):

[0055] 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-ligand complex of formula (I) are each independently chosen from (C1-C40)hydrocable, (C1-C40)heterohydrocable, 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)hydrocable, (C1-C30)heterohydrocable, or -H.

[0056] 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 (C1-C40)hydrocabyl; 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 the 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 having 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), for which the groups R51-59 are the same or different in R1 and R16.

[0057] In some embodiments, at least one of R1 and R16 is a radical having formula (II), wherein R32 and R34 are TERC-butyl.

[0058] In some embodiments, when at least one of R1 or R16 is a radical having formula (III), one or both of R43 and R46 is TERC-butyl, and each of R41-42, R44-45 and R47 -48 are -H. In other embodiments, one or both of R42 and R47 are TERC-butyl and R41, R43-46 and R48 are -H. In some embodiments, both R42 and R47 are -H.

[0059] In some embodiments, R3 and R14 are TERC-octyl, N-octyl, methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or TERC-butyl). In other embodiments, R6 and R11 are halogen. In some embodiments, R3 and R14 are methyl; and R6 and R11 are halogen.

[0060] In some embodiments of the metal-ligand complex of formula (I), when R5-7 is fluorine, not more than one of R10-12 is fluorine. In other embodiments, when R10-12 are fluorine, no more of R5-7 is fluorine. In other embodiments, less than four 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 out of R5-7 are fluorine and two out of R10-12 are fluorine.

[0061] 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.

[0062] The metal M in the metal-ligand complex of formula (I) may be derived from a metal precursor 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 carrier), 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.

[0063] In the metal-ligand complex of formula (I), each Z independently is O, S, N(C1-C40)hydrocable or P(C1-C40)hydrocable. 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 a Z is S. In another embodiment, a Z is S and a Z is N(C1-C40)hydrokabyl, (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

[0064] The catalyst system comprising a metal-ligand complex of formula (I) can be made catalytically active by any technique known in the art for activating metal-based catalyst of olefin polymerization reactions. For example, the procatalyst according to a metal-ligand complex of formula (I) can be made catalytically active by placing the complex with an active cocatalyst, or by combining the complex therewith. Additionally, 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 aluminum alkyls; 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 cocatalysts and activation techniques are 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, modified triisobutylaluminum methylalumoxane, and isobutylalumoxane.

[0065] Lewis acid activation cocatalysts include Group 13 metal compounds that contain (C1-C2o)hydrocabyl substituents as described herein. In some embodiments, the Group 13 metal compounds are tri((CrC20)hydrocabyl)-substituted aluminum compounds or tri((CrC20)hydrocabyl)-boron compounds. In other embodiments, the Group 13 metal compounds are tri(hydrocabyl)-substituted aluminum, tri((C1-C20)hydrocabyl)-boron compounds, tri((C1-C10)alkyl)aluminum compounds, tri(( C6-C18)aryl)boron and halogenated (including perhalogenated) derivatives thereof. In further 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)hydrocablel borate (e.g., trityl tetrafluoroborate) or a tri((C1-C2o)hydrocable)ammonium tetra((Ci-C2o)hydrocable)borane (e.g., bis(octadecyl)methylammonium tetracis(pentafluorophenyl)borane.) As used herein, the term "ammonium" means a nitrogen cation that is a ((Ci-C2o)hydrocabyl)4N+ to ((Ci- C2o)hydrocable)3N(H)+, a ((C1-C2o)hydrocable)2N(H)2+, (C1-C20)hydrocableN(H)3+ or N(H)4+, where each (CI - C20)hydrocabyl, when two or more are present, can be the same or different.

[0066] Neutral Lewis acid activation cocatalyst combinations 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 mixtures of neutral 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. The mole number ratios of (metal ligand complex):(tris(pentafluorophenylborane):(alumoxane) [e.g., (Group 4 metal ligand complex):(tris(pentafluorophenylborane):(alumoxane) ] are from 1:1:1 to 1:10:30, in other modes from 1:1:1.5 to 1:5:10.

[0067] The catalyst system comprising the metal-ligand complex of formula (I) can be activated to form an active catalyst composition by combination with one or more cocatalysts, for example, a cation-forming catalyst, an acid Strong Lewis or combinations thereof. Suitable activation cocatalysts include polymeric or oligomeric aluminoxanes, especially methyl aluminoxane, as well as inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methyl aluminoxane (MMAO), bis(hydrogenated alkyl tallow)methyl, tetracis(pentafluorophenyl)borate(1-)amine, and combinations thereof.

[0068] In some embodiments, more than one of the activation cocatalysts can be used in combination with each other. A specific example of a cocatalyst combination is a mixture of aluminum tri((C1-C4)hydrocabyl), tri((C1-C4)hydrocabyl)borane or an ammonium borate with an oligomeric or polymeric 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 the activation cocatalyst, preferably the mole number of the alumoxane that is employed is at least 100 times the mole number of the metal-ligand complex of formula (I). When tris(pentafluorophenyl)borane alone is used as the activation cocatalyst, in some embodiments, the number of moles of the tris(pentafluorophenyl)borane that is employed equals the total number of moles of one or more metal-ligand complexes of formula (I) is 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 approximately equal mole amounts to the mole amounts of one or more metal-ligand complexes of formula (I).

[0069] In some embodiments, when more than one or more of the aforementioned cocatalysts are used in combination, 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, reducing efficiency.

polyolefins

[0070] The catalytic systems described in the preceding 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, the 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.

[0071] 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 mol percent (mol %) of ethylene-derived monomer units. All individual values and subranges covered by "at least 50 mol%" are disclosed herein as separate embodiments; for example, 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 mol% of monomer units derived from ethylene; at least 70% by mole of ethylene-derived monomer units; at least 80 percent by weight of ethylene-derived monomer units; or from 50 to 100 mol% monomer units derived from ethylene; or from 80 to 100 mol% of ethylene-derived units.

[0072] In some embodiments, the ethylene-based polymers may comprise at least 90 mole percent of ethylene-derived units. All individual values and subranges of at least 90 mole percent are included herein 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 mole percent units; at least 97 mole percent 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 mole percent of ethylene-derived units.

[0073] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50% by mole; other embodiments include at least 0.5 mol% to 25 mol%; and in further embodiments, the amount of additional α-olefin includes at least 5 mol % to 10 mol %. In some embodiments, the additional α-olefin is 1-octene.

[0074] Any conventional polymerization processes 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 cycle, isothermal reactors, fluidized bed phase reactors, stirred tank reactors, parallel batch reactors, series or any combination thereof, for example.

[0075] In one embodiment, the ethylene-based polymer can be produced by 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 by solution polymerization in a dual reactor system, for example a dual cycle reactor system, in which ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system in the present disclosure and, as described herein, and optionally one or more other catalysts. The catalyst system as described herein can be used in either 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 herein, in both reactors.

[0076] In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single reactor system, for example, a single cycle reactor system, in which ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system, as described in the present disclosure, and optionally one or more cocatalysts, as described, in the preceding paragraphs.

[0077] 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. The ethylene-based polymers can comprise from about 0 to about 10 percent by the combined weight of such additives, based on the weight of the ethylene-based polymers and the 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 weight percent 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. Ethylene-based polymers can be further blended with one or more polymers to form a blend.

[0078] In some embodiments, a polymerization process for producing an ethylene-based polymer may 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 complex metal-binder of formula (I). The polymer resulting from such a catalyst system incorporating the metal-binder complex of formula (I) may have a density according to ASTM D792 (incorporated herein by 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.

[0079] 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 melt index I2 is measured in accordance with ASTM D1238 (incorporated herein by reference in its entirety) at 190 °C and a load of 2.16 kg, and melt index I10 is measured in accordance with ASTM D1238 at 190 ° C and a load of 10 kg. In other embodiments, the melt flow ratio (I10/I2) is 5 to 10, and in others, the melt flow ratio is 5 to 9.

[0080] 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, where Mw is a weight average molecular weight and Mn is a number average molecular weight. All individual values and subranges covered by “from 1.5 to 25” are disclosed in this document as separate modalities; for example, 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.

[0081] The embodiments of the catalyst systems described in the present disclosure general unique polymer properties as a result of the high molecular weights of the formed polymers and the amount of the comonomers incorporated in the polymers.

[0082] All solvents and reagents are obtained from commercial sources and used as received unless otherwise noted. Toluene, hexanes, anhydrous tetrahydrofuran, and diethyl ether are purified by passing through activated alumina and, in some cases, reagent Q-5. Solvents used for experiments performed in a nitrogen filled glove box are further dried by storage over activated 4A molecular sieves. Glass equipment for moisture sensitive reactions is dried in a kiln from one to another for use. NMR spectra are recorded on the Varian 400-MR and VNMRS-500 spectrometers. LC-MS analyzes are performed using a Waters e2695 Separations Module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector and a Waters 3100 ESI mass detector. LC-MS separations are performed on an XBridge C18 3.5 µm 2.1 x 50 mm column using a gradient of acetonitrile to water 5:95 to 100:0 with 0.1% formic acid as the agent of ionization. HRMS analyzes are performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8 µm 2.1 x 50 mm column coupled with an Agilent 6230 TOF Mass Spectrometer with electrospray ionization. 1H NMR data are reported according to the following: 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 the 1H NMR data are reported in ppm downstream of the inner tetramethylsilane (TMS, δ scale) using residual protons in the deuterated solvent as references. 13C NMR data are predetermined with 1H decoupling, and chemical shifts are reported downstream from tetramethylsilane (TMS, δ scale) in ppm versus using residual carbons in the deuterated solvent as references.

SYMRAD HT-GPC Analysis

[0083] Molecular weight data are determined by analysis on a Hybrid Robot Aided Dilution High Temperature Gel 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 by 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 narrow polystyrene (PS) standards is used with clear units adjusted for homopolyethylene (PE) using known Mark-Houwink coefficients for PS and PE in TCB at this temperature.

1-octene incorporation IR analysis

[0084] The execution of the samples for the HT-GPC analysis precedes the IR analysis. For IR analysis, a 48-well HT chip is used for the deposition and 1-octene incorporation analysis of samples. For analysis, samples are heated to 160 °C for 210 minutes or less; samples are reheated to remove magnetic GPC stir bars and are stirred with glass rod stir bars in a J-KEM Scientific heated robotic stirrer. Samples are deposited while being heated using a Tecan MiniPrep 75 deposition station, and the 1,2,4-trichlorobenzene is removed by evaporation 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 E.S.P. FT-IR.

Polymerization procedure in batch reactors

[0085] Batch reactor polymerization reactions are conducted in a 2 L Parr™ Batch Reactor. The reactor is heated by an electrical heating mantle, and is cooled by an internal coil cooling coil containing cooling water. Both the reactor and the heating/cooling system are controlled and monitored by a Camile™ TG process computer. The bottom of the reactor is equipped with a dump valve that empties the reactor content into a stainless steel dump pot. The dampening pot is pre-filled with a catalyst kill solution (typically 5 ml of an Irgafos/Irganox/toluene mixture). The dump pot is vented to a 132.15 l (30 gallon) blowdown tank, with both the pot and tank purged with nitrogen. All solvents used for polymerization or catalyst make-up are passed through solvent purification columns to remove any impurities that may affect polymerization. The 1-octene and Isopar-E are passed through two columns, the first containing A2 alumina, the second containing Q5. The ethylene passes through two columns, in which the first contains alumina A204 and molecular sieves of 4 Å, in which the second contains reagent Q5. The N2, used for transfer, passes through a single column containing A204 alumina, 4A and Q5 molecular sieves.

[0086] The reactor is first charged from an injection tank that may contain the solvent IsoparE and/or 1-octene, depending on the reactor load. The injection tank is charged to the charge set points using a laboratory scale to which the injection tank is mounted. After addition of liquid feed, the reactor is heated to the polymerization temperature set point. If ethylene is used, it is added to the reactor when ethylene is at reaction temperature to maintain the reaction pressure setpoint. The amount of ethylene added is monitored by a micromotion flowmeter. For some experiments, the standard conditions at 120 °C are 46 g ethylene and 303 g 1-octene in 611 g IsoparE, and the standard conditions at 150 °C are 43 g ethylene and 303 g 1-octene in 547 g of IsoparE.

[0087] The pro-catalyst and activators are mixed with the appropriate amount of purified toluene to obtain a molarity solution. The procatalyst and activators are handled in an inert glove box, drawn into a syringe and transferred by pressure to the catalyst injection tank. The syringe is rinsed three times with 5 ml of toluene. Immediately after the catalyst is added, the run timer starts. If ethylene is used, this is used by Camile to maintain the reaction pressure set point in the reactor. Polymerization reactions are run for 10 minutes, then the stirrer is stopped, and the bottom blowdown valve is opened to empty the reactor contents into the blowdown pot. Contents from the unloading pot are poured into trays and placed in a laboratory hood where the solvent has been removed by evaporation overnight. The trays containing the remaining polymer are transferred to a vacuum oven where they are heated to 140°C under vacuum to remove any remaining solvent. After the trays cooled to room temperature, the polymers were weighed for yield to measure efficiencies and submitted for polymer testing.

Procedure for miniplant polymerization

[0088] The raw materials (ethylene, 1-octene) and the process solvent (a high purity isoparaffinic solvent with a narrow boiling range Isopar-ETM, commercially available from ExxonMobil Corporation) are purified with molecular sieves before introduction into the reaction environment. The hydrogen is supplied in pressurized cylinders as a high purity grade and is not further purified. The reactor monomer (ethylene) feed stream is pressurized via a mechanical compressor to a pressure greater than 3.62 MPa (525 psig). The solvent and comonomer (1-octene) feed is pressurized via a mechanical positive displacement pump to a reaction pressure greater than 3.62 MPa (525 psig). MMAO, commercially available from AkzoNobel, was used as an impurity scavenger. The individual catalyst components (procatalyst cocatalyst) were manually batch diluted to specified component concentrations with purified solvent (Isopar E) and pressure above the reaction pressure at 525 psig (3.62 MPa). The cocatalyst is [HNMe(C18H37)2][B(C6F5)4], commercially available from Boulder Scientific, and was used at a 1.2 mol ratio to the procatalyst. Reaction feed flows are measured with mass flowmeters and independently controlled with computer automated valve control systems.

[0089] The continuous solution polymerizations are carried out in a 5 liter (l) continuously stirred tank reactor (CSTR). The reactor has independent control of all vial solvent, monomer, comonomer, hydrogen and catalyst component feeds. The solvent, monomer, comonomer and hydrogen feed is temperature controlled at any point between 5°C to 50°C and typically 25°C. The fresh comonomer feed to the polymerization reactor is fed with the solvent feed. The fresh solvent feed is typically controlled with each injector receiving half of the total fresh feed mass flow. The procatalyst component is fed to the cocatalyst based on a specified calculated mole ratio (1.2 eq.). Immediately following each fresh injection location, the feed streams are mixed to the circulating polymerization reactor grade with static mixing elements. The polymerization reactor effluent (which contains solvent, monomer, comonomer, hydrogen, catalyst component and molten polymer) leaves the first reactor cycle and passes through a control valve (responsible for maintaining the pressure of the first reactor at a specified target ). As the stream exits the reactor, it comes into contact with water to stop the reaction. Furthermore, various additives such as antioxidants could be added at that time. The stream then passed another set of static mixing elements to evenly disperse the kill catalyst and additives.

[0090] After adding the additive, the effluent (which contains solvent, monomer, comonomer, hydrogen, catalyst components and molten polymer) passed through a heat exchanger and in order to raise the temperature of the stream in preparation for the separation of the polymer from other lower boiling point reaction components. The stream then enters a two-stage devolatilization and separation system in which the polymer is removed from the solvent, unreacted hydrogen monomer and comonomer. The separated and devolatilized polymer melt is pumped through a specially designed die for underwater pelletizing, cut into uniform solid pellets, dried and transferred to a bin for storage.

Examples

[0091] Examples 1 to 2 are synthetic procedures for linker intermediates, for the linkers themselves and for isolated procatalysts including the linkers. One or more features of the present disclosure are illustrated in view of the examples as follows: Example 1: Synthesis of Procatalyst 1

[0092] In a glove box, a 40 ml vial was loaded with 20 ml of dry toluene and 264.1 mg of Compound C1. Behenyl alcohol (n-C22H45OH) (81.65 mg, 1 eq.) was added neat at room temperature to the stirred solution of Compound C1 in toluene. The reaction mixture was heated at 60°C for 4 hours (reaction can also be done at room temperature - 1 day). Toluene was evaporated under reduced pressure to give a colorless crystalline oil of procatalyst 1 in quantitative yield as a 2.3/0.7 mixture of stereoisomers.

[0093] 1H NMR (400 MHz, Chloroform-D) δ 8.40 - 8.05 (m, 4H), 7.63 - 6.78 (m, 25H), 5.10 - 2.23 (m , 8H), 2.23 - 2.03 (m, 6H), 1.50 - 0.10 (m, 51H), -1.16 (s, 2.3H); -1.18 (s, 0.7H). Example 2: Synthesis of Procatalyst 3

[0094] In a glove box, a 40 ml vial was loaded with 20 ml of dry toluene and 173.4 mg of Compound C2. Behenyl alcohol (n-C22H45OH) (38.72 mg, 1 eq.) was added neat at room temperature to the stirred solution of Compound C2 in toluene. The reaction mixture was heated at 60 °C for 4 hours (the reaction can also be done at room temperature for approximately 48 hours). Toluene was evaporated under reduced pressure to give a colorless crystalline oil of procatalyst 3 in quantitative yield as a 2.3/0.7 mixture of stereoisomers.

[0095] 1H NMR (400 MHz, Chloroform-d) δ 8.14 - 7.06 (m, 14H), 6.71 (ddd, J = 8.9, 5.6, 3.1 Hz, 2H ), 6.21 (ddd, J = 8.7, 5.7, 3.1 Hz, 2H), 5.99 - 5.77 (m, 2H), 3.73 - 2.23 (m, 7H ), 1.51 - 0.98 (m, 98H), 0.83 - 0.62 (m, 25H), -0.86 (s, 0.7H); - 0.95 (s, 2.3H).

[0096] The synthesis of pro-catalysts 2 and 4 was carried out in a similar way by the corresponding reaction of C1 and C2 with octadecylamine for 6 hours at 60 °C in dry toluene.

Example 3: Solubility study

[0097] The final product for Pro-catalysts 1 to 4 in pure form was an oil that did not crystallize after a week in the freezer. Although each of the solubility limits of Procatalysts 1 to 4 in Isopar-ETM was not specifically investigated, Procatalysts 1 to 4 had a wt% solubility of at least 10 wt%. The wt% solubility of each of Procatalysts 1 to 4 was measured according to Procedure A in Isopar E, described above. No precipitation was observed over a period of two weeks at room temperature.

[0098] The Pro-catalysts 1 to 4 and the Comparative Pro-catalysts C1 and C2 reacted individually using the polymerization conditions in a single reactor system, as described above. The properties for the resulting polymers are reported in Tables 2 and 3. Comparative C1 and Comparative C2 have a structure according to formula (Ia). When compared to Comparative Procatalysts C1 and C2, a significant increase in weight percent solubility was observed for Procatalysts 1 to 4, which are metal-binder complexes according to formula (I). Table 1: Solubility data at 25 °C Table 2: Batch reactor screening of pro-catalysts 1 and comparative 1 *Efficiency is defined in units of 106 grams of polymer per gram of active metal (Hf or Zr). Table 3: Batch reactor screening of pro-catalysts 3 to 4 and comparative C2

[0099] Batch reactor conditions for Tables 2 and 3: reaction temperature was 160 °C; 1.47 kg of Isopar™ E; 100 grams octene, 2.83 MPa (410 psi) ethylene; the RIBS:Catalyst ratio was approximately 1.2; the pro-catalyst:activator ratio was 1:1.2; the activator was [HNMe(C18H37)2][B(C6F5)4]; MMAO-3A was used as an impurity scavenger at a molar ratio of MMAO-3A:procatalyst of approximately 50; MMAO-3A substituted for TEA as the scavenger.

Claims (10)

1. Procatalyst, characterized by the fact that it comprises a metal-ligand complex according to formula (I): where: - M is a metal selected from titanium, zirconium or hafnium, the metal being in a formal oxidation state of +2, +3 or +4; - X is selected from the group consisting of -ORX or -NRX2; wherein each RX is independently a (C1-C50)hydrokabyl, (C1-C50)heterohydrokabyl or -H and at least one RX is (C1—C5o)hydrokabyl, (Ci—C5o)hetero—hydrokabyl and when X is -NRX2, optionally two RX will be covalently linked; - the metal-ligand complex is, in general, neutrally charged; - 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)hydrocable (C1-C40)heterohydrocable -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, radicals having formula (II), radicals having formula (III) and radicals which have the formula (IV): each of R31 35, R41 48 and R51 59 is independently chosen from -H, (C1-C40)hydrocable, (C1-C40)heterohydrocable, -Si(RC)3, -Ge( RC)3, -P(RP)2, -N(RN)2, -N=CHRC, -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), wherein a radical has formula (III) or a radical has formula (IV); - each of R2-4, R5-8, R9-12 and R13-15 is independently selected from -H, (C1-C40)hydrocable, (C1-C40)heterohydrocable, -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)hydrocabylene or (C2-C40)heterohydrocabylene; and - each RC, RP and RN in formula (I) is independently a (C1-C30)hydrocable, (C1-C30)heterohydrocable or -H. 2. Pro-catalyst, according to claim 1, characterized in that RX is chosen from (C5-C50)alkyl or -H. 3. Pro-catalyst, according to claim 1 or 2, characterized by the fact that RX is linear. 4. Pro-catalyst, according to claim 1 or 2, characterized in that the RX is branched. 5. Pro-catalyst, according to claim 1 or 2, characterized in that X is chosen from a linear alkyl that has the formula -OCxHx+1 or - NHCxHx+1, where x is an integer of 10 to 40. 6. Pro-catalyst, according to claim 1, characterized by the fact that: - M is zirconium or hafnium; - each X will be -OC22H45; and - each Z be oxygen. 7. Pro-catalyst, according to any one of claims 1 to 3, characterized by the fact that: - M is zirconium or hafnium; - each X will be -OC18H37; and - each Z be oxygen. 8. Pro-catalyst, according to claim 1, characterized by the fact that: - M is zirconium or hafnium; - each X is -N(CwH37)RX; and - each Z be oxygen. 9. Pro-catalyst, according to claim 1, characterized by the fact that: - M is zirconium or hafnium; - at least one X is -N(C22H45)2; and - each Z be oxygen. 10. Pro-catalyst according to any one of claims 1 to 9, characterized in that the metal-binder complex according to formula (I) has a solubility ratio in % by weight between W/Y equal a at least 1.5, where W is the wt% solubility of the metal-binder complex of formula (I) in MCH under STP; where Y is the % by weight of a corresponding comparative metal-binder complex of formula (Ia) in MCH under STP; and wherein the corresponding comparative complex has a structure according to formula (Ia): wherein M, each Z, each R1 16 and L are identical to corresponding groups of the metal-ligand complex according to formula (I).