Process for producing multimodal polyethylene using at least one group III or lanthanide biphenylphenoxy catalyst

Abstract

Embodiments of the present disclosure are directed to catalyst systems comprising metal-ligand complexes according to formula (I). [Formula 1] JPEG2025529770000031.jpg48170

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Application No. 63 / 401,924, filed August 29, 2022, the entire disclosure of which is incorporated herein by reference.

[0002] FIELD OF THE INVENTION FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more specifically to bis-phenylphenoxy metal-ligand complexes having Group III or lanthanide metal centers. [Background technology]

[0003] Olefin-based polymers, such as polyethylene, ethylene-based polymers, polypropylene, and propylene-based polymers, are produced by a variety of catalyst systems. The selection of such catalyst system used in the polymerization process of an olefin-based polymer is an important factor that contributes to the characteristics and properties of such an olefin-based polymer.

[0004] Ethylene-based and propylene-based polymers are produced for a wide variety of articles. Polyethylene and polypropylene polymerization processes can be varied in several ways 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 monomer, and optionally one or more comonomers, are present in a liquid diluent or solvent, such as an alkane or isoalkane, of which hexane and isobutane are particular examples. Hydrogen may also be added to the reactor. Catalyst systems for producing ethylene-based polymers typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (metallocene or nonmetallocene) catalyst systems. The reactants in the catalyst system and diluent are circulated within the reactor at elevated polymerization temperatures, thereby producing an ethylene-based homopolymer or copolymer. Periodically or continuously, a portion of the reaction mixture, including the polyethylene product dissolved in the diluent, is removed from the reactor along with unreacted ethylene and one or more optional comonomers. After being removed from the reactor, the reaction mixture may be treated to remove the polyethylene product from the diluent and unreacted reactants, which are typically recycled back into the reactor. Alternatively, the reaction mixture may be sent to a second reactor connected in series with the first reactor, where a second polyethylene fraction may be produced. Despite research efforts to develop catalyst systems suitable for olefin polymerization, such as polyethylene polymerization, there remains a need for improved efficiency of catalyst systems with high selectivity for ethylene. Summary of the Invention

[0005] There is a continuing need to create catalyst systems or metal-ligand complexes that have high selectivity for ethylene during the copolymerization reaction of ethylene and α-olefins. Furthermore, the metal-ligand complexes should have high catalytic efficiency and the versatile ability to produce high or low molecular weight polymers at high temperatures (e.g., above 140°C or around 190°C).

[0006] Embodiments of the present disclosure include a polymerization process. The polymerization process comprises polymerizing ethylene and optionally one or more olefins in the presence of a catalyst system. The catalyst system comprises at least one metal-ligand complex of Formula (I), at least one Group IV catalyst, at least one additive, and optionally a Lewis acid. The polymerization process is conducted in a solution polymerization reactor under olefin polymerization conditions to form an ethylene-based polymer.

[0007] In one or more embodiments, the metal-ligand complex of formula (I) has a structure according to the following:

[0008] [ka]

[0009] In formula (I), M is scandium, yttrium, a lanthanide metal, or an actinide metal. n The subscript n is 0, 1, or 2. T is a Lewis base. X k The subscript k is 1 or 2. X is (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -CH2Ge(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C )2-W (OR C ) W , -N(R C )2, -NH(R C ), -N(Si(R C )3)2, -NR C Si(R C )3, -NHSi(R C )3, -OR C , -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C , -S(O)2R C , -OS(O)2R C , -N=C(R C )2, -N=CH(R C ), -N=CH2, -N=P(R C ) 3、 -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -C(O)N(R C )2, -C(O)NHR C , —C(O)NH, or hydrogen; C are independently substituted or unsubstituted (C1 to C 30 ) hydrocarbyl, or substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl. The subscript Q is 0, 1, 2, or 3, and the subscript W is 0, 1, or 2. T n When the subscript n in is 1, X and T are optionally joined to form a bidentate ligand. n The subscript n of is 1, and X k When k is 2, each X and T are optionally connected to form a bidentate or tridentate ligand. The metal-ligand complex is overall charge neutral.

[0010] In formula (I), R 1 and R 16 are independently -H, (C1 to C 40 ) hydrocarbyl, (C1-C40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, -N=C(R C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV).

[0011] [ka]

[0012] In formulas (II), (III), and (IV), R 31~35 , R 41~48 , and R 51~59 Each of the groups independently represents -H, (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or halogen.

[0013] In formula (I), R2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 are independently -H, (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2-OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, and halogen.

[0014] In formula (I), L is (C1 to C 40 ) hydrocarbylene or (C1-C 40 ) heterohydrocarbylene, and each Z is independently —O—, —S—, —N(R N )-, or -P(R P )- is selected from.

[0015] In formulas (I), (II), (III), and (IV), each R C , R P , and R N are independently (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H. DETAILED DESCRIPTION OF THE INVENTION

[0016] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure.

[0017] Common abbreviations are listed below.

[0018] R, Z, M, X, and n: as defined above, Me: methyl, Et: ethyl, Ph: phenyl, Bn: benzyl, i-Pr: isopropyl, t-Bu: tert-butyl, t-Oct: tert-octyl(2,4,4-trimethylpentan-2-yl), Tf: trifluoromethanesulfonate, CV: column volume (if used in column chromatography), EtOAc: ethyl acetate, TEA: triethylaluminum, MAO: methylaluminoxane, MMAO: modified methylaluminoxane, LiCH2TMS: (trimethylsilyl)methyllithium, TMS: trimethylsilyl, Pd(AmPhos)Cl2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II), Pd(AmPhos): chloro(crotyl)(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II), Pd(dpp f) Cl2: [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride, ScCl3: scandium(III) chloride, PhMe: toluene, THF: tetrahydrofuran, CHCl2: dichloromethane, DMF: N,N-dimethylformamide, EtOAc: ethyl acetate, Et2O: diethyl ether, MeOH: methanol, NHCl: ammonium chloride, MgSO4: magnesium sulfate, NaSO4: sodium sulfate, NaOH: sodium hydroxide, Brine: saturated aqueous sodium chloride solution, SiO2: silica, CDCl3: chloroform-D, GC: gas chromatography, LC: liquid chromatography, NMR: nuclear magnetic resonance, MS: mass spectrometry, mmol: millimole, mL: milliliter, M: molar concentration, min or mins: minute, h or hrs: hour, d: day, TLC: thin layer chromatography, rpm: revolutions per minute, rt: room temperature.

[0019] The term "independently selected" refers to 1 , R 2 , R 3 , R 4 , and R 5 and the R groups may be the same or different (e.g., R 1 , R 2 , R 3 , R 4 , and R 5 may all be substituted alkyl, or R 1 and R 2 may be substituted alkyl, R 3 The R group is used herein to indicate that the R group may be an aryl group, etc. Chemical names associated with R groups are intended to convey chemical structures recognized in the art as corresponding to the chemical structure of the chemical name. Thus, the chemical names are intended to supplement and illustrate, not preclude, structural definitions known to those of skill in the art.

[0020] When used to describe certain carbon atom-containing chemical groups, x ~C y A bracketed expression having the form "(C1-C)" means that the unsubstituted form of the chemical group has x to y carbon atoms, inclusive, including x and y. For example, (C1-C 50 ) Alkyl, in its unsubstituted form, is an alkyl group having 1 to 50 carbon atoms. In some embodiments and general structures, certain chemical groups are R S The parenthesized "(C x ~C y )" S The substituted chemical group can be any group R S For example, "R S exactly one group R is phenyl (-C6H5) S (C1~C 50A "(C ) alkyl" can contain 7 to 56 carbon atoms. Thus, in general, the parenthesized "(C x ~C y )" is a group defined using one or more carbon atom-containing substituents R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group is the sum of all carbon atom-containing substituents R S It is determined by adding the total number of carbon atoms from

[0021] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S The term "hypersubstituted" means that all hydrogen atoms (H) bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group are replaced by a substituent (e.g., R S ) The term "polysubstituted" means that at least two, but fewer than all, hydrogen atoms bonded to a carbon atom or heteroatom of the corresponding unsubstituted compound or functional group are replaced by substituents. The term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0022] "(C1~C 50 The term "(C1-C)hydrocarbyl" means a hydrocarbon radical of 1 to 50 carbon atoms. 50 The term "hydrocarbylene" means a hydrocarbon diradical of 1 to 50 carbon atoms, each hydrocarbon radical and each hydrocarbon diradical being aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (having 3 or more carbons, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and containing one or more R S is or is not replaced by

[0023] In this disclosure, (C1 to C 50) hydrocarbyl is unsubstituted or substituted (C1-C 50 ) Alkyl, (C3-C 50 ) cycloalkyl, (C3-C 20 )Cycloalkyl-(C1-C 20 ) Alkylene, (C6-C 40 ) aryl, or (C6-C 20 )Aryl-(C1-C 20 ) alkylene (such as benzyl (—CH2 to C6H5)).

[0024] "(C1~C 50 ) alkyl" and "(C1-C 18 The term "alkyl" refers to an unsubstituted or alkyl group containing one or more R S and saturated straight-chain or branched-chain hydrocarbon radicals of 1 to 50 carbon atoms and 1 to 18 carbon atoms, respectively, substituted by unsubstituted (C1 to C 50 Examples of alkyl are unsubstituted (C1-C 20 ) Alkyl, unsubstituted (C1-C 10 ) 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. 40 Examples of substituted (C1-C 20 ) Alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "alkyl" refers to a group having up to 45 carbon atoms in the radical, including the substituents, e.g., one R that is (C1-C5) alkyl. S replaced by (C 27 ~C 40 Each (C1-C5) alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0025] "(C6~C50 The term "aryl" refers to an unsubstituted or (one or more R S "Aromatic hydrocarbon radicals" refers to monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radicals substituted (by C6-C), where at least 6 to 14 of the carbon atoms are aromatic ring carbon atoms. A monocyclic aromatic hydrocarbon radical contains one aromatic ring, a bicyclic aromatic hydrocarbon radical has two rings, and a tricyclic aromatic hydrocarbon radical has three rings. When a 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 independently be fused or non-fused, and aromatic or non-aromatic. Unsubstituted (C6-C 50 Examples of aryl include unsubstituted (C6-C 20 )Aryl, unsubstituted (C6-C 18 )aryl, 2-(C1-C5)alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. 40 Examples of aryl include substituted (C1-C 20 ) Aryl, substituted (C6-C 18 )aryl, 2,4-bis([C 20 ]alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0026] "(C3~C 50 The term "cycloalkyl" refers to an unsubstituted or substituted group having one or more R S means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms substituted with other cycloalkyl groups, such as (C x ~C y )cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S Unsubstituted (C3 to C 40 Examples of cycloalkyl are unsubstituted (C-C 20) Cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C3-C 20 ) Cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0027] (C1~C 50 Examples of hydrocarbylene include unsubstituted or substituted (C-C 50 ) arylene, (C3-C 50 ) cycloalkylene, and (C1-C 50 ) alkylene (e.g., (C1-C 20 ) alkylene). Diradicals can be on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or three or more intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or α,ω-diradicals, while others include 1,2-diradicals. α,ω-diradicals are diradicals with the greatest carbon backbone spacing between the radical carbons. (C2-C 20 Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CHCH-), propane-1,3-diyl (i.e., -CHCHCH-), and 2-methylpropane-1,3-diyl (i.e., -CHCH(CH)CH-). (C6-C 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0028] "(C1~C 50 The term "alkylene" refers to an unsubstituted or substituted group having one or more R Smeans a saturated straight or branched chain diradical of 1 to 50 carbon atoms (i.e., the radical is not on a ring atom) substituted by 50 Examples of alkylene are unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C * HCH3 and -(CH2)4C * Unsubstituted (C1-C, including (H)(CH3) 20 ) alkylene, wherein "C * " denotes a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical. 50 Examples of alkylene are substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosylene). As mentioned above, the two R S are combined together (C1~C 18 ) alkylene, so that the substituted (C1-C 50 Examples of )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.

[0029] "(C3~C 50 The term "cycloalkylene" refers to a group that is unsubstituted or has one or more R S means a cyclic diradical (i.e., the radicals are on ring atoms) of 3 to 50 carbon atoms substituted by

[0030] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include O, S, S(O), S(O), Si(R C )2, P(R P ), N(R N ), -N=C(RC )2, -Ge(R C )2-, -Si(R C )-, boron (B), aluminum (Al), gallium (Ga), or indium (In), and each R C and each R P is unsubstituted (C1 to C 18 ) hydrocarbyl or —H, and each R N is unsubstituted (C1 to C 18 The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. 50 The term "(C1-C)heterohydrocarbyl" means a heterohydrocarbon radical having 1 to 50 carbon atoms. 50 The term "heterohydrocarbylene" means a heterohydrocarbon diradical having 1 to 50 carbon atoms. (C1-C 50 ) heterohydrocarbyl or (C1-C 50 The heterohydrocarbon of the heterohydrocarbylene has one or more heteroatoms. The heterohydrocarbyl radical can be on a carbon atom or a heteroatom. The two radicals of the heterohydrocarbylene can be on a single carbon atom or a single heteroatom. Additionally, one of the two radicals of the diradical can be on 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 can be on a heteroatom and the other radical on a different heteroatom. Each (C1-C 50 ) heterohydrocarbyl and (C1-C 50 ) heterohydrocarbylene is unsubstituted or (one or more R S and may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0031] (C1~C 50 ) Heterohydrocarbyl can be unsubstituted or substituted. (C1-C50 Non-limiting examples of heterohydrocarbyls include (C1-C 50 ) heteroalkyl, (C1-C 50 ) hydrocarbyl-O-, (C1-C 50 ) hydrocarbyl-S-, (C1-C 50 ) hydrocarbyl-S(O)-, (C1-C 50 ) hydrocarbyl-S(O)2-, (C1-C 50 ) Hydrocarbyl-Si(R C )2-, (C l ~C 50 )hydrocarbyl-N(R N )-, (C l ~C 50 ) hydrocarbyl-P(R P )-, (C2~C 50 ) heterocycloalkyl, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 )Cycloalkyl-(C1-C 19 ) heteroalkylene, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) heteroalkylene, (C1-C 50 ) heteroaryl, (C1-C 19 )Heteroaryl-(C1-C 20 ) alkylene, (C6-C 20 )Aryl-(C1-C 19 ) heteroalkylene, or (C1-C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene.

[0032] "(C1~C 50 The term "heteroaryl" refers to an unsubstituted or heteroaryl group having a total of 1 to 50 carbon atoms and 1 to 10 heteroatoms (one or more R S(C1-C4) means a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical substituted with a cyclic or cyclic heteroaromatic group. A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring, a bicyclic heteroaromatic hydrocarbon radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring(s) of the heteroaromatic radical may independently be fused or non-fused, and aromatic or non-aromatic. Other heteroaryl groups (e.g., (C1-C4) 12 ) heteroaryl, etc. x ~C y ) heteroaryl (general) has x to y carbon atoms (e.g., 1 to 12 carbon atoms) and is unsubstituted or has one or more R SThe monocyclic heteroaromatic hydrocarbon radical is defined in the same manner as being substituted with . The monocyclic heteroaromatic hydrocarbon radical is a 5-membered or 6-membered ring. The 5-membered monocyclic heteroaromatic hydrocarbon radical has 5 minus h carbon atoms, where h is the number of heteroatoms, which may be 1, 2, 3, or 4, and each heteroatom may be O, S, N, or P. Examples of 5-membered 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. A 6-membered monocyclic heteroaromatic hydrocarbon radical has 6 minus h carbon atoms, where h is the number of heteroatoms, which may be 1 or 2, and the heteroatom may be N or P. Examples of 6-membered heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. A bicyclic heteroaromatic hydrocarbon radical may be a fused 5,6- or 6,6-ring system. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl and isoquinolin-1-yl. A tricyclic heteroaromatic hydrocarbon radical may be a fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring system. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridine-9-yl.

[0033] "(C1~C 50The term "(C1-C)heteroalkyl" means a saturated straight or branched chain radical containing 1 to 50 carbon atoms and one or more heteroatoms. 50 The term "heteroalkylene" refers to a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of a heteroalkyl or heteroalkylene include Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C , S, S.R. C , S(O), and S(O)2, each of the heteroalkyl and heteroalkylene groups may be unsubstituted or may contain one or more R S has been replaced by

[0034] Unsubstituted (C2~C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 ) Heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0035] The term "halogen atom" or "halogen" refers to a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to the anionic form of a halogen atom, fluoride (F - ), chloride (Cl - ), bromide (Br - ), or iodide (I - ) means

[0036] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S When substituted by, one or more double and / or triple bonds may optionally be replaced by a substituent R S The term "unsaturated" refers to a group 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-silicon double bonds, and the substituent R S This means that the aromatic ring or heteroaromatic ring does not contain any double bonds that may be present in the ring (if present), or in the aromatic or heteroaromatic ring (if present).

[0037] The term "lanthanide metals" includes elements 57-71 (lanthanum (La) through lutetium (Lu)).

[0038] Embodiments of the present disclosure include a polymerization process. The polymerization process comprises polymerizing ethylene and optionally one or more olefins in the presence of a first catalyst system and a second catalyst system. The catalyst systems comprise at least one metal-ligand complex of Formula (I), at least one Group IV catalyst, at least one additive, and optionally a Lewis acid. The polymerization process is conducted in a solution polymerization reactor under olefin polymerization conditions to form an ethylene-based polymer.

[0039] In one or more embodiments, the metal-ligand complex of formula (I) has a structure according to the following:

[0040] [ka]

[0041] In formula (I), M is scandium, yttrium, a lanthanide metal, or an actinide metal. n The subscript n is 0, 1, or 2, and Xk The subscript k is 1 or 2, and X is (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -CH2Ge(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -NH(R C ), -N(Si(R C )3)2, -NR C Si(R C )3, -NHSi(R C )3, -OR C , -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C , -S(O)2R C , -OS(O)2R C , -N=C(R C )2, -N=CH(R C ), -N=CH2, -N=P(R C ) 3、 -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -C(O)N(RC )2, -C(O)NHR C , —C(O)NH, or hydrogen. C are independently substituted or unsubstituted (C1 to C 30 ) hydrocarbyl, or substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl. The subscript Q is 0, 1, 2, or 3, and the subscript W is 0, 1, or 2. T is a Lewis base. T n When the subscript n in is 1, X and T are optionally joined to form a bidentate ligand. n The subscript n of is 1, and X k When k is 2, each X and T are optionally connected to form a bidentate or tridentate ligand. The metal-ligand complex is overall charge neutral.

[0042] In formula (I), R 1 and R 16 are independently -H, (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, -N=C(R C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV).

[0043] [ka]

[0044] In some embodiments, in the metal-ligand complex of formula (I), R 1 or R 16 Either of the above or R 1 and R 16 and R are both selected from radicals having formula (II), formula (III), or formula (IV), provided that M is yttrium or a lanthanide metal. 1 is not -H, phenyl, or tert-butyl, and R 16 is not -H, phenyl, or tert-butyl.

[0045] When present in a metal-ligand complex of formula (I) as part of a radical having formula (II), formula (III), or formula (IV), the group R 31~35 , R 41~48 , and R 51~59 are each independently (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, Si(R C )3, P(R P )2, N(R N )2, OR C , S.R. C , NO2, CN, CF3, R C S(O)-, R C S(O) 2- , (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R N )NC(O)-, halogen, hydrogen (-H), or a combination thereof. C , R P , and R N is unsubstituted (C1 to C 18 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H.

[0046] R in the metal-ligand complex of formula (I) 1 Groups and R 16The groups are selected independently of each other. For example, R 1 may be selected from radicals having formula (II), (III), or (IV), and R 16 is (C1~C 40 ) hydrocarbyl, or R 1 may be selected from radicals having formula (II), (III), or (IV), and R 16 may be selected from radicals having formula (II), (III), or (IV), and R 1 R 1 and R 16 may both be radicals having formula (II), in which case R 31~35 The group is R 1 and R 16 In another embodiment, R 1 and R 16 may both be radicals having formula (III), in which case R 41~48 The group is R 1 and R 16 are the same or different in R 1 and R 16 may both be radicals having formula (IV), in which case R 51~59 The group is R 1 and R 16 are the same or different.

[0047] In some embodiments, R 1 and R 16 at least one of R is a radical having formula (II) 32 and R 34 is tert-butyl. In one or more embodiments, R 32 and R 34 is (C1~C 16 ) hydrocarbyl, -Si[(C1-C 16 ) hydrocarbyl]3.

[0048] In some embodiments, R 1 or R 16is a radical having the formula (III), then R 43 and R 46 one or both of R 41~42 , R 44~45 , and R 47~48 is —H. In other embodiments, R 42 and R 47 one or both of R 41 , R 43~46 , and R 48 is —H. In some embodiments, R 42 and R 47 and R are —H. In various embodiments, R 42 and R 47 is (C1~C 20 ) hydrocarbyl or -Si[(C 16 )hydrocarbyl]3. In other embodiments, R 43 and R 46 is (C1~C 20 ) hydrocarbyl or -Si(C 16 ) alkyl]3. In some embodiments, R 42 and R 43 are linked to form a ring structure, and R 46 and R 47 are linked to form a ring structure.

[0049] In some embodiments, R 1 or R 16 When at least one of R is a radical having formula (IV), then each R 52 , R 53 , R 55 , R 57 , and R 58 is -H, (C1~C 20 ) hydrocarbyl, -Si[(C1-C 20 ) hydrocarbyl]3, or -Ge[(C1-C 20 )hydrocarbyl]3. In some embodiments, R 52 , R 53 , R 55 , R 57 , and R 58At least one of (C3~C 10 ) alkyl, -Si[(C3~C 10 ) alkyl]3, or -Ge[(C3-C 10 ) alkyl]3. In one or more embodiments, R 52 , R 53 , R 55 , R 57 , and R 58 At least two of them are (C3~C 10 ) alkyl, -Si[(C3~C 10 ) alkyl]3, or -Ge[(C3-C 10 ) alkyl]3. In various embodiments, R 52 , R 53 , R 55 , R 57 , and R 58 At least three of them (C3-C 10 ) alkyl, -Si[(C3~C 10 ) alkyl]3, or -Ge[(C3-C 10 ) alkyl]3.

[0050] In some embodiments, R 1 or R 16 is a radical having the formula (IV), then R 52 , R 53 , R 55 , R 57 , and R 58 At least two of them (C1~C 20 ) hydrocarbyl or -C(H)2Si[(C1-C 20 ) hydrocarbyl]3.

[0051] (C3~C 10Examples of alkyl include, but are not limited to, propyl, 2-propyl (also called isopropyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl.

[0052] In some embodiments of the metal-ligand catalyst according to Formula (I), R 1 and R 16are 3,5-di-tert-butylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, 3,5-diisopropylphenyl, carbazolyl, carbazol-9-yl, 1,2,3,4-tetrahydrocarbazolyl, 1,2,3,4,5,6,7,8-octahydrocarbazolyl, 3,6-bis-(3,5-di-tert-butylphenyl)carbazol-9-yl, 3,6-bis-(2,4,6-trimethylphenyl)carbazol-9-yl), 3,6-bis-(2,4 ,6-triisopropylphenyl)carbazol-9-yl, 2,7-di(tertiary butyl)-carbazol-9-yl, 2,7-di(tertiary octyl)-carbazol-9-yl, 2,7-diphenylcarbazol-9-yl, 2,7-bis(2,4,6-trimethylphenyl)-carbazol-9-ylanthracenyl, 2,7-di(triisobutylsilyl)-carbazol-9-yl, 2,7-di(dimethylphenylsilyl)-carbazol-9-yl, 2,7-di(methyldiphenylsilyl)-carbazol n-octyl, 2,7-di(diisopropyl-n-octylsilyl)-carbazol-9-yl, 1,2,3,4-tetrahydroanthracenyl, 1,2,3,4,5,6,7,8-octahydroanthracenyl, phenanthrenyl, 1,2,3,4,5,6,7,8-octahydrophenanthrenyl, 1,2,3,4-tetrahydronaphthyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 3,5-diphenylphenyl, 1-naphthyl, 2-methyl-1-naphthyl, 2-naphthyl, 1,2 ,3,4-tetrahydronaphth-5-yl, 1,2,3,4-tetrahydronaphth-6-yl, anthracen-9-yl, 1,2,3,4-tetrahydroanthracen-9-yl, 1,2,3,4,5,6,7,8-octahydroanthracen-9-yl, 1,2,3,4,5,6,7,8-octahydrophenanthrene-9-yl, indolyl, indolinyl, quinolinyl, 1,2,3,4-tetrahydroquinolinyl, isoquinolinyl, or 1,2,3,4-tetrahydroisoquinolinyl.

[0053] In formula (I), R 2 , R 3 , R4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 are independently -H, (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, and halogen.

[0054] In one or more embodiments, R 2 , R 4 , R 5 , R 12 , R 13 , and R 15 is hydrogen and each Z is oxygen.

[0055] In embodiments, the dotted lines are optionally coordinate bonds between the metal center, M, and group Z. In some embodiments, one of the dotted lines connecting Z and M does not form a coordinate bond between Z and M. In various embodiments, both dotted lines form coordinate bonds between groups Z and M.

[0056] In various embodiments, R 3 and R 14 is (C1~C 24 ) alkyl. In one or more embodiments, R 3 and R14 (C4~C 24 ) alkyl. In some embodiments, R 3 and R 14 is 1-propyl, 2-propyl (also called isopropyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. 3 and R 14 -OR C and R C is (C1~C 20 ) hydrocarbon, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), or 1,1-dimethylethyl.

[0057] In one or more embodiments, R 8 and R 9 In various embodiments, one of R 8 and R 9 At least one of (C1~C 24 ) alkyl. In some embodiments, R 8 and R 9 Both of (C1~C 24 ) alkyl. In some embodiments, R 8 and R 9 is methyl. In another embodiment, R 8 and R 9 is a halogen.

[0058] In some embodiments, R 3 and R 14 is methyl. In one or more embodiments, R 3 and R 14 (C4~C 24 ) alkyl. In some embodiments, R 8 and R 9are 1-propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-l-butyl, hexyl, 4-methyl-l-pentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl.

[0059] In various embodiments, in the metal-ligand complex of formula (I), R 6 and R 11 is halogen. In some embodiments, R 6 and R 11 is (C1~C 24 ) alkyl. In various embodiments, R 6 and R 11 is independently selected from 1-propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. 6 and R 11 is tert-butyl. In some embodiments, R 6 and R 11 -OR C and R C is (C1~C 20 ) hydrocarbyl, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), or 1,1-dimethylethyl. 6 and R 11 -SiR C 3, and each R C are independently (C1~C 20 ) hydrocarbyl, and in some embodiments, R Cis methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), or 1,1-dimethylethyl.

[0060] In some embodiments, the chemical groups (e.g., X and R) of the metal-ligand complex of formula (I) 1~59 Any or all of the chemical groups X and R of the metal-ligand complex of formula (I) may be unsubstituted. 1~59 Any of the following may contain one or more R S Even if they are not substituted with one or more R S It may be substituted with two or more R S are attached to the same chemical group of the metal-ligand complex of formula (I), the individual R S may be attached to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, the chemical groups X and R 1~59 Any of the above is R S Even if they are not over-substituted with R, any or all of them may be S It may also be oversubstituted with R S In chemical groups that are over-substituted with S may all be the same or may be independently selected. In one or more embodiments, R S is (C1~C 20 ) hydrocarbyl, (C1-C 20 ) alkyl, (C1-C 20 ) heterohydrocarbyl, or (C1-C 20 ) heteroalkyl.

[0061] In formula (I), L is (C1 to C 40 ) hydrocarbylene or (C1-C 40 ) heterohydrocarbylene, and each Z is independently —O—, —S—, —N(R N )-, or -P(R P )- In one or more embodiments, L contains 1 to 10 atoms.

[0062] In formulas (I), (II), (III), and (IV), each R C , R P , and R N are independently (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H.

[0063] In some embodiments of Formula (I), L is a (C-C) alkyl 1,3-diradical, such as, for example, —CHCHCH—, —CH(CH)CHC * H(CH3), -CH(CH3)CH(CH3)C * In some embodiments, L may be selected from (C4-C 10 ) alkyl 1,4-diradicals, such as -CH2CH2CH2CH2-, -CH2C(CH3)2C(CH3)2CH2-, cyclohexane-1,2-diyldimethyl, and bicyclo[2.2.2]octane-2,3-diyldimethyl. In some embodiments, L is selected from (C5-C 12 ) alkyl 1,5-diradicals, such as —CH2CH2CH2CH2CH2—, and 1,3-bis(methylene)cyclohexane. In some embodiments, L is (C6-C 14 ) alkyl 1,6-diradicals, such as -CH2CH2CH2CH2CH2CH2-, or 1,2-bis(ethylene)cyclohexane.

[0064] In one or more embodiments, L is (C2-C 40 ) heterohydrocarbylene, where at least one of the 2 to 10 atoms comprises a heteroatom. In some embodiments, L is —CHGe(R C )2CH2-, and each R C is (C1~C 30) hydrocarbyl. In some embodiments, L is —CHGe(CH3)2CH2—, —CH2Ge(ethyl)2CH2—, —CH2Ge(2-propyl)2CH2—, —CH2Ge(t-butyl)2CH2—, —CH2Ge(cyclopentyl)2CH2—, or —CH2Ge(cyclohexyl)2CH2—.

[0065] In one or more embodiments, L is —CH—, —CHCH—, —CH(CH) m CH2- (m is 1 to 3), -CH2Si(R C )2CH2-, -CH(CH3)CH2CH * (CH3)(C * indicates the configuration of the radical (this group can also be written as -CH(CH3)CH2CH(CH3)-), and -CH2(phen-1,2-di-yl)CH2-, and each R in L is selected from C is (C1~C 20 ) hydrocarbyl.

[0066] It takes (C1~C 12 Examples of alkyl include, but are not limited to, methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), 1,1-dimethylethyl, cyclopentyl or cyclohexyl, butyl, tert-butyl, pentyl, hexyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpent-2-yl), nonyl, decyl, undecyl, and dodecyl.

[0067] In some embodiments, in the metal-ligand complex according to formula (I), R 8 and R 9 and R are both methyl. 8 and R 9 one of R 8 and R 9 The other is -H.

[0068] In the metal-ligand complex according to formula (I), X is bonded to M through a covalent or ionic bond. In some embodiments, X can be a monoanionic ligand having a net formal oxidation state of -1. Each monoanionic ligand can independently be a hydride ion, (C1-C 40 ) hydrocarbyl carbanions, (C1-C 40 ) Heterohydrocarbyl carbanions, halides, nitrates, carbonates, phosphates, sulfates, HC(O)O - , HC(O)N(H) - , (C1~C 40 ) Hydrocarbyl C(O)O - , (C1~C 40 ) Hydrocarbyl C(O)N((C1-C 20 )hydrocarbyl) - , (C1~C 40 ) Hydrocarbyl C(O)N(H) - , R K R L B - , R K R L N - , R K O - , R K S - , R K R L P - , or R M R K R L Si - Each R may be K , R L , and R M are independently hydrogen, (C1 to C 40 ) hydrocarbyl, or (C1-C 40 ) heterohydrocarbyl, or R K and R L Together, (C2~C 40 ) hydrocarbylene or (C1-C 20 ) form a heterohydrocarbylene, and R M is as defined above.

[0069] In some embodiments, X is unsubstituted (C1-C 20 ) Hydrocarbyl, unsubstituted (C1-C 20 ) hydrocarbyl C(O)O—, or R K R L N- and R K and R L each independently is unsubstituted (C1 to C 20 In some embodiments, each monodentate ligand X is a chlorine atom, (C1-C 10 ) hydrocarbyl (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C 10 ) hydrocarbyl C(O)O—, or R K R L N-, where R K and R L each independently is unsubstituted (C1 to C 10 ) hydrocarbyl.

[0070] In some embodiments, n is 1 and X and T are linked and are selected from the group consisting of:

[0071] [ka]

[0072] In further embodiments, X is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, or chloro. In one embodiment, k is 2. In certain embodiments, when k is 2, two X groups are linked to form a bidentate ligand.

[0073] In one or more embodiments, each X is independently —(CH 2 )SiR X 3, and each R X are independently (C1~C 30 ) alkyl or (C1-C 30 ) heteroalkyl, and at least one R X is (C1~C 30) alkyl. In some embodiments, R X One of them is (C1~C 30 ) heteroalkyl, the heteroatom is a silica or oxygen atom. In some embodiments, R X is methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl.

[0074] In one or more embodiments, X is —(CH)Si(CH), —(CH)Si(CH)(CHCH); —(CH)Si(CH)(CHCH), —(CH)Si(CHCH), —(CH)Si(CH)(n-butyl), —(CH)Si(CH)(n-hexyl), —(CH)Si(CH)(n-Oct)R X , -(CH2)Si(n-Oct)R X 2, —(CH2)Si(CH3)2(2-ethylhexyl), —(CH2)Si(CH3)2(dodecyl), —CH2Si(CH3)2CH2Si(CH3)3 (referred to herein as —CH2Si(CH3)2CH2TMS). Optionally, in some embodiments, the metal-ligand complex according to Formula (I) contains exactly two R X are covalently bonded or exactly three R X are covalently bonded.

[0075] In some embodiments, X is —CHSi(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q where the subscript Q is 0, 1, 2, or 3, and each R C are independently substituted or unsubstituted (C1 to C 30) hydrocarbyl, or substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl.

[0076] In some embodiments, X is B(R Y )4, Al(R Y )4, or Ga(R Y )4, and each R Y is -H, (C1~C 30 In certain embodiments, when k is 2, the two X groups are R Y are linked to form a bidentate ligand such that two of them are both independently attached to the metal M.

[0077] In the metal-ligand complex according to Formula (I), each T is bonded to M via a coordinate bond or an ionic bond. In one or more embodiments, T is a Lewis base. A Lewis base can be a compound or ionic species capable of donating an electron pair to an acceptor compound. For purposes of this description, the acceptor compound is M, the metal of the metal-ligand complex of Formula (I). A Lewis base can be neutral or anionic. In some embodiments, a Lewis base can be a heterohydrocarbon or hydrocarbon. Examples of neutral heterohydrocarbon Lewis bases include, but are not limited to, amines, trialkylamines, ethers, cycloethers, or sulfides. Examples of anionic hydrocarbons include, but are not limited to, cyclopentadiene. Examples of neutral hydrocarbons include, but are not limited to, 1,3-butadiene.

[0078] In one or more embodiments, the Lewis base may be a monodentate ligand, which may be a neutral ligand. In some embodiments, the neutral ligand may contain a heteroatom. In certain embodiments, the neutral ligand may be R T NR K R L , R K OR L , R K SR L , or R T PR K R Land each R T are independently hydrogen, [(C1-C 10 )hydrocarbyl]3Si(C1-C 10 ) hydrocarbyl, (C1-C 40 ) hydrocarbyl, [(C1-C 10 )hydrocarbyl]Si, or (C1-C 40 ) heterohydrocarbyl, and each R K and R L are independently as previously defined.

[0079] In some embodiments, the Lewis base is (C1-C 20 ) hydrocarbon. In some embodiments, the Lewis base is cyclopentadiene or 1,3-buta-diene.

[0080] In various embodiments, the Lewis base is (C1-C 20 ) heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is oxygen. In some embodiments, T is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

[0081] In the metal-ligand complex of formula (I), each Z is independently O, S, N (C1-C 40 ) hydrocarbyl, or P(C1-C 40 ) hydrocarbyl. In some embodiments, each Z is different. For example, one Z is O and the other Z is NCH3. In some embodiments, one Z is O and one Z is S. In other embodiments, one Z is S and one Z is N(C1-C 40 ) hydrocarbyl (e.g., NCH3). In a further embodiment, each Z is the same. In yet another embodiment, each Z is O. In another embodiment, each Z is S.

[0082] In Formula (I), each Z is connected to M via a dotted line. The dotted lines define optional coordinate bonds. In some embodiments, one of the dotted lines forms a coordinate bond between Z and M, and the second dotted line is not directly connected or bonded from Z to M. In various embodiments, each Z forms a coordinate bond with M. In other embodiments, each Z is not directly connected or bonded to M. Without intending to be bound by theory, it is believed that the number of ZM coordinate bonds depends on the atomic radius of the metal, as defined by M.

[0083] In certain embodiments of the catalyst system, the metal-ligand complex according to formula (I) may include, but is not limited to, a complex having the structure of any of Metal-Ligand Complexes 1-3 (US2021 / 015723).

[0084] [ka]

[0085] Olefin Propagation Although a cocatalyst is not required to initiate olefin propagation for the metal-ligand complex of formula (I), it is believed that the metal-ligand complex is not efficient when a Lewis base, T, is coordinated to the metal center, M, of formula (I). Thus, without intending to be bound by theory, during olefin propagation, the Lewis base dissociates from the metal center, M, and the metal-ligand complex has a structure according to formula (Ia).

[0086] [ka]

[0087] In formula (Ia), R 1 ~R 16 , M, Z, and L are as defined in formula (I). P is a hydrocarbyl, the hydrocarbyl having at least 30 carbon atoms and being branched or unbranched. More specifically, X P is the propagating olefin chain.

[0088] Additive ingredients An additive is a chemical agent present in the polymerization reaction that does not inhibit olefin propagation. In one or more embodiments, the catalyst system further comprises an additive. In some embodiments, the additive functions as a co-catalyst. In other embodiments, the additive functions as a scavenger or scavenger. In some embodiments, the additive functions as an alkylating agent. In one or more embodiments, the additive may have more than one function, or may function as a scavenger, alkylating agent, and co-catalyst.

[0089] The cocatalyst is a reagent that reacts with the procatalyst to form the active catalyst. Without intending to be bound by theory, it is believed that the Lewis base T of formula (I) dissociates in the absence of the cocatalyst. However, it is also believed that the cocatalyst may facilitate the dissociation of the Lewis base from the metal center of the metal-ligand complex.

[0090] Suitable additives may include, but are not limited to, alkylaluminums, 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). Combinations of one or more of the foregoing additives and techniques are also contemplated. The term "alkylaluminum" refers to monoalkylaluminum dihydrides or dihalides, dialkylaluminum hydrides or halides, or trialkylaluminums. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0091] In some embodiments, the additive is a compound selected from the group consisting of (C1-C6) 20 In some embodiments, the additive is a Lewis acid Group 13 metal compound containing a tri((C1-C) hydrocarbyl substituent. 20)hydrocarbyl)-substituted aluminum or tri((C1-C 20 In another embodiment, the additive comprises a tri(hydrocarbyl)-substituted aluminum, tri((C-C 20 )hydrocarbyl)-boron compounds, tri((C1-C 10 ) alkyl) aluminum, tri((C6-C 18 )aryl)boron compounds and their halogenated (including perhalogenated) derivatives.

[0092] In one or more embodiments, the polymerization process further comprises a borate-based additive. In some embodiments, the borate-based additive is selected from tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the co-catalyst is a tri((C1-C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)borates (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" refers to a ((C1-C 20 ) Hydrocarbyl) 4N + , ((C1~C 20 )hydrocarbyl)3N(H) + , ((C1~C 20 )hydrocarbyl)2N(H)2 + , (C1~C 20 ) Hydrocarbyl N(H)3 + , or N(H)4 + Each of the nitrogen cations (C1 to C 20 When two or more hydrocarbyls are present, they may be the same or different.

[0093] In one or more embodiments, the additive may be selected from polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, and inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable additives include, but are not limited to, modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)ammonium, triethylaluminum, butylated hydroxytoluene diethylaluminum, bis-(butylated hydroxytoluene)ethylaluminum, tris-(butylated hydroxytoluene)aluminum, and combinations thereof.

[0094] Additives such as aluminoxanes and alkylaluminums can have multiple functions: they can function as cocatalysts, scavengers, and alkylating agents in the polymerization process.

[0095] In some embodiments, the additive is AlR A1 R B1 R C1 wherein R is an alkylaluminum having the formula A1 , R B1 , and R C1 are independently (C1~C 40 ) alkyl. In one or more embodiments, R A1 , R B1 , and R C1 are independently (C1~C 10 ) alkyl. In one or more embodiments, R A1 , R B1 , and R C1 is independently methyl, ethyl, propyl, 2-propyl, butyl, tert-butyl, or octyl. A1 , R B1 , and R C1 are the same. In another embodiment, R A1 , R B1 , and R C1 At least one of the other R A1, R B1 , and R C1 is different from.

[0096] In some embodiments, the alkylaluminum species is triisobutylaluminum (TiBAl) or an aluminoxane. The alkylaluminoxane may be any of (C1-C 10 ) alkylaluminoxane or the polymeric form of polymethylaluminoxane (PMAO). The PMAO may be performance-improved polymethylaluminoxane (PMAO-IP) commercially available from Nouryon. (C1-C 10 The alkylaluminoxane can be methylaluminoxane (MAO), modified methylaluminoxane (MMAO), such as modified methylaluminoxane, type 3A (MMAO-3A), type 7 (MMAO-7), or type 12 (MMAO-12), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, n-pentylaluminoxane, neopentylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane, 2-ethylhexylaluminoxane, cyclohexylaluminoxane, or 1-methylcyclopentylaluminoxane. The arylaluminoxane can be (C6-C 10 ) arylaluminoxane, which may be phenylaluminoxane, 2,6-dimethylphenylaluminoxane, or naphthylaluminoxane.

[0097] In some embodiments, one or more cocatalysts can be used in combination with each other. Specific examples of cocatalyst combinations include tri((C1-C8)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, tri((C6-C 18(aryl)borane or ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of the total moles of one or more metal-ligand complexes of Formula (I) to the total moles of one or more of the cocatalysts is 1:10,000 to 100:1. In some embodiments, this ratio is at least 1:5000; in some other embodiments, it is at least 1:1000 and 10:1 or less; and in some other embodiments, it is 1:1 or less. When alumoxane alone is used as the cocatalyst, preferably the ratio of Al of the alumoxane to the metal of the metal-ligand complex of Formula (I) (Al / M) is at least 20. When tris(pentafluorophenyl)borane is used alone as the co-catalyst, in some other embodiments, the number of moles of tris(pentafluorophenyl)borane used relative to 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.

[0098] Catalyst System Components In embodiments, the second catalyst system comprises at least one Group IV catalyst. The at least one Group IV catalyst may be selected from a Group IV metal-ligand complex, such as a titanium (Ti) metal-ligand complex, a zirconium (Zr) metal-ligand complex, or a hafnium (Hf) metal-ligand complex. In one or more embodiments, the Group IV metal-ligand complex comprises a bis-biphenylphenoxy Group IV metal-ligand complex, which is a procatalyst that can become catalytically active when contacted with an activator of the present disclosure.

[0099] In one or more embodiments, the Group IV metal-ligand complex may include a -biphenylphenoxy Group IV metal-ligand complex, a constrained geometry catalyst, or a phosphine imide Group IV complex.

[0100] According to some embodiments, the bis-biphenylphenoxy Group IV metal-ligand complex has a structure according to formula (X):

[0101] [ka]

[0102] In formula (X), M 1 is a metal selected from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4. (X x ) n The subscript n is 1, 2, or 3. When the subscript n is 1, X x is a monodentate or bidentate ligand, and when the subscript n is 2, each X is a monodentate ligand. In formula (X), each Z is independently -O-, -S-, -N(R N )-, or -P(R P )-, and L x is (C1~C 40 ) hydrocarbylene or (C1-C 40 ) heterohydrocarbylene, and R 2x~4x , R 5x~8x , R 9x~12x and R 13x~15x are independently -H, (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, -N=C(R C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )NC(O)-, and halogen. 1x and R 16x is selected from a radical having formula (XI), a radical having formula (XII), and a radical having formula (XIII),

[0103] [ka]

[0104] In formulas (XI), (XII), and (XIII), R 31~35 , R 41~48 , and R 51~59 Each of the groups independently represents -H, (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or halogen.

[0105] In some embodiments of Formula (X), L x is a (C3-C7) alkyl 1,3-diradical, for example, -CH2CH2CH2-, -CH(CH3)CH2C * H(CH3), -CH(CH3)CH(CH3)C * H(CH), —CHC(CH)CH—, cyclopentane-1,3-diyl, or cyclohexane-1,3-diyl, and the like. In some embodiments, L x (C4~C 10 ) alkyl 1,4-diradicals, such as -CH2CH2CH2CH2-, -CH2C(CH3)2C(CH3)2CH2-, cyclohexane-1,2-diyldimethyl, and bicyclo[2.2.2]octane-2,3-diyldimethyl. In some embodiments, L is selected from (C5-C 12) alkyl 1,5-diradicals, such as —CHCHCHCHCHCH—, and 1,3-bis(methylene)cyclohexane. In some embodiments, L x (C6~C 14 ) alkyl 1,6-diradicals, such as, for example, —CH2CH2CH2CH2CH2CH2— or 1,2-bis(ethylene)cyclohexane.

[0106] In one or more embodiments, L is (C2-C 40 ) heterohydrocarbylene, where at least one of the 2 to 10 atoms comprises a heteroatom. In some embodiments, L is —CHGe(R C )2CH2-, and each R C is (C1~C 30 ) hydrocarbyl. In some embodiments, L is —CHGe(CH3)2CH2—, —CH2Ge(ethyl)2CH2—, —CH2Ge(2-propyl)2CH2—, —CH2Ge(t-butyl)2CH2—, —CH2Ge(cyclopentyl)2CH2—, or —CH2Ge(cyclohexyl)2CH2—.

[0107] In one or more embodiments, in formula (X), each X x is any other ligand X x Independently from halogen, unsubstituted (C1-C 20 ) hydrocarbyl, unsubstituted [(C1-C 20 )hydrocarbyl]C(O)O—, or R K R L N-, wherein R K and R L each independently is unsubstituted (C1 to C 20 ) hydrocarbyl. In some embodiments, X x benzyl, phenyl, chloro, (C 1~ C 10 ) alkyl, or -CH2Si(R x ) and each R x is (C1~C 20 ) alkyl.

[0108] Exemplary metal-ligand complexes according to formula (X) include, for example, the following:

[0109] [ka]

[0110] Other bis-biphenylphenoxy Group IV metal-ligand complexes that may be used in combination with additives in the catalyst systems of the present disclosure will be apparent to those skilled in the art.

[0111] In one or more embodiments, the Group IV metal-ligand complex comprises a constrained geometry Group IV complex having a structure according to formula (XV).

[0112] [ka]

[0113] In formula (XV), M 2 is titanium, hafnium or zirconium. (X) b The subscript b in is 1, 2, or 3. C is unsaturated (C2 to C 50 ) Hydrocarbons, unsaturated (C2-C 50 ) Heterohydrocarbons, saturated (C2-C 50 ) Heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (C6-C 50 ) Aryl, (C6-C 50 ) Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 ) Diene, halogen, -N(R N )2, and -NCOR C The metal-ligand complex is generally charge neutral.

[0114] In one or more embodiments, in formula (XV), each X C is any other ligand X CIndependently from halogen, unsubstituted (C1-C 20 ) hydrocarbyl, unsubstituted [(C1-C 20 )hydrocarbyl]C(O)O—, or R K R L N-, wherein R K and R L each independently is unsubstituted (C1 to C 20 ) hydrocarbyl. In some embodiments, X C benzyl, phenyl, chloro, (C 1~ C 10 ) alkyl, or -CH2Si(R x ) and each R x is (C1~C 20 ) alkyl.

[0115] In formula (XV), Cp is cyclopentadienyl and R S substituted cyclopentadienyl, Cp is selected from the group consisting of η 5 is bonded to M in a bonding manner, and R S are independently (C1~C 20 ) alkyl, (C1-C 20 ) heteroalkyl, (C1-C 20 ) aryl, or R S Substituents (C1~C 20 ) aryl, (C1-C 20 ) heteroaryl, or R S Substituents (C1~C 20 ) heteroaryl, wherein two adjacent R S The groups are optionally linked to form a ring.

[0116] In formula (XV), N is nitrogen, Y is carbon or silicon, Y is covalently bonded to Cp, and R 1 and R 2 are independently -H, (C1 to C 40 ) hydrocarbyl, and (C1-C 40 ) heterohydrocarbyl, R 3 are independently (C1~C 40 ) hydrocarbyl, and (C1-C40 ) heterohydrocarbyl.

[0117] Other catalysts, particularly catalysts containing one or more other Group IV metal complexes not specifically listed above, will be apparent to those skilled in the art.

[0118] Catalytic system characteristics Procatalysts comprising the metal-ligand complex of Formula (I) and one or more cocatalysts described herein have a reactivity ratio r1, as further defined below, in the range of greater than 100, e.g., greater than 150, greater than 200, greater than 300, or greater than 500.

[0119] For random copolymers, where the properties of the last monomer inserted determine the rate of insertion of subsequent monomers, the terminal copolymerization model is used. In this model, the following types of insertion reactions occur:

[0120]

number

[0121]

number

[0122] The mole fraction of comonomer (i=2) in the reaction medium is defined by the following equation:

[0123]

number

[0124] As disclosed in George Odian, Principles of Polymerization, Second Edition, John Wiley and Sons, 1970, a simple equation for comonomer composition can be derived as follows:

[0125]

number

[0126] From this equation, the mole fraction of comonomer in the polymer depends only on the mole fraction of comonomer in the reaction medium and two temperature-dependent reactivity ratios defined in terms of the insertion rate constant as follows:

[0127]

number

[0128] Alternatively, in the penultimate copolymerization model, the properties of the last two monomers inserted into a growing polymer chain dictate the rate of subsequent monomer insertions. The polymerization reaction is of the form:

[0129]

number

[0130]

number

[0131] The comonomer content can be calculated as follows (also disclosed in George Odian, supra):

[0132]

number

[0133]

number

[0134]

number

[0135] In this model, the polymer composition is also a function of only the temperature-dependent reactivity ratio and the comonomer mole fraction in the reactor, even if reversed comonomer or monomer insertion can occur, or in the case of copolymerization of more than two monomers.

[0136] Reactivity ratios for use in the above-mentioned models can be predicted using well-known theoretical methods or empirically derived from actual polymerization data. Suitable theoretical methods are disclosed, for example, in BG Kyle, Chemical and Process Thermodynamics, Third Addition, Prentice-Hall, 1999, and Redlich-Kwong-Soave (RKS) Equation of State, Chemical Engineering Science, 1972, pp. 1197-1203. Commercially available software programs may be used to assist in the derivation of reactivity ratios from empirically derived data. One example of such software is Aspen Plus from Aspen Technology, Inc., Ten Canal Park, Cambridge, MA 02141-2201 USA.

[0137] Thus, a process for producing an ethylene-based polymer according to the present invention selectively provides a rich polyethylene (e.g., high-density polyethylene) or rich polyethylene segment of a poly(ethylene alpha-olefin) copolymer in the presence of an alpha-olefin, thereby substantially unpolymerized. The process for producing an ethylene-based polymer employs olefin polymerization conditions. In some embodiments, the olefin polymerization conditions independently generate an in situ catalyst formed by the reaction of a procatalyst comprising a metal-ligand complex of Formula (I) with one or more cocatalysts in the presence of one or more other components. Such other components include, but are not limited to, (i) an olefin monomer, (ii) another metal-ligand complex of Formula (I), (iii) one or more of a catalyst system, (iv) one or more chain shuttling agents, (v) one or more catalyst stabilizers, (vi) one or more solvents, and (vii) a mixture of any two or more thereof.

[0138] In particular, the catalyst of the present invention is useful in processes for producing ethylene-based polymers (C3 to C 40 ) high selectivity for polymerizing ethylene in the presence of alpha-olefins can be achieved, the high selectivity being characterized by the aforementioned reactivity ratio r1. Preferably, for the process of the present invention, the reactivity ratio r1 is greater than 50, more preferably greater than 100, even more preferably greater than 150, and even more preferably greater than 200. As the reactivity ratio r1 for the process of the present invention approaches infinity, the incorporation of alpha-olefins into (or onto) the rich polyethylene produced thereby approaches 0 mole percent (mol%).

[0139] Polyolefin The catalyst systems described in this disclosure can be utilized in the polymerization of olefins, primarily ethylene, propylene, α-olefins such as octene, and dienes. In some embodiments, there is only one type of olefin or α-olefin in the polymerization scheme, resulting in the production of a homopolymer. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin comonomer typically has 20 or fewer carbon atoms. For example, the α-olefin comonomer may 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 may 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.

[0140] An ethylene-based polymer, e.g., a homopolymer and / or an interpolymer (including a copolymer) of ethylene and, optionally, one or more comonomers such as an α-olefin, can comprise at least 50 mole percent (mol %) of monomer units derived from ethylene. All individual values ​​and subranges encompassed by "at least 50 mole percent" are disclosed herein as separate embodiments; for example, an ethylene-based polymer, a homopolymer and / or an interpolymer (including a copolymer) of ethylene and, optionally, one or more comonomers such as an α-olefin can comprise at least 60 mole percent of monomer units derived from ethylene, at least 70 mole percent of monomer units derived from ethylene, at least 80 mole percent of monomer units derived from ethylene, or from 50 to 100 mole percent of monomer units derived from ethylene, or from 80 to 100 mole percent of monomer units derived from ethylene.

[0141] In some embodiments, the catalyst system can produce an ethylene-based polymer comprising at least 90 mole percent units derived from ethylene. All individual values ​​and subranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer can comprise at least 93 mole percent units derived from ethylene, at least 96 mole percent units, at least 97 mole percent units derived from ethylene, or alternatively, 90 to 100 mole percent units derived from ethylene, 90 to 99.5 mole percent units derived from ethylene, or 97 to 99.5 mole percent units derived from ethylene.

[0142] In some embodiments, the catalyst system produces an ethylene-based polymer having an amount of additional α-olefin less than 50 mole percent (mol %), in other embodiments, the amount of additional α-olefin comprises at least 0.01 mol % to 25 mol %, and in further embodiments, the amount of additional α-olefin comprises at least 0.1 mol % to 10 mol %. In some embodiments, the additional α-olefin is 1-octene.

[0143] Ethylene-based polymers can be produced by other conventional polymerization processes incorporating catalyst systems according to embodiments of the present disclosure, including, but 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, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, and the like, in parallel, series, or any combination thereof.

[0144] In one embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of a catalyst system described herein and, optionally, one or more cocatalysts. In another embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of a catalyst system described herein and herein and, optionally, one or more other catalysts. The catalyst system described herein, optionally in combination with one or more other catalysts, can be used in the first reactor or the second reactor. In one embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in both reactors in the presence of a catalyst system described herein.

[0145] In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single reactor system, for example a single loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized as described in the previous paragraph in the presence of a catalyst system described within this disclosure and optionally one or more cocatalysts.

[0146] The ethylene-based polymer may further 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. The ethylene-based polymer may comprise any amount of additives. The ethylene-based polymer may comprise from about 0 to about 10 percent by weight of such additives, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further comprise a filler, including, but not limited to, an organic or inorganic filler. The ethylene-based polymer may contain from about 0 to about 20 percent by weight of a filler, such as calcium carbonate, talc, or Mg(OH)2, based on the total weight of the ethylene-based polymer and all additives or fillers. The ethylene-based polymer may be further blended with one or more polymers to form a blend.

[0147] In some embodiments, a polymerization process for producing an ethylene-based polymer comprises 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-ligand complex of Formula (I). Polymers obtained from such catalyst systems incorporating a metal-ligand complex of Formula (I) have a densitometric value of, for example, 0.850 g / cm according to ASTM D792, which is incorporated herein by reference in its entirety. 3 ~0.970g / cm 3 , 0.870g / cm 3 ~0.950g / cm 3 , 0.870g / cm 3 ~0.920g / cm 3 , or 0.870 g / cm 3 ~0.900g / cm 3 The density may be

[0148] In embodiments, the polymers obtained from catalyst systems comprising metal-ligand complexes of formula (I) have a melt flow ratio (I 10 / I2), where the melt index I2 is measured at 190°C and a load of 2.16 kg in accordance with ASTM D1238 (which is incorporated herein by reference in its entirety), and the melt index I 10 is measured according to ASTM D1238 at 190°C and a 10 kg load. In other embodiments, the melt flow ratio (I 10 / I2) is 5-10, and in another embodiment the melt flow ratio is 5-9.

[0149] In some embodiments, the polymer obtained from the catalyst system comprising the metal-ligand complex of Formula (I) has a melt index (I2) of 0.1 to 100, wherein the melt index I2 is measured at 190°C and a 2.16 kg load according to ASTM D1238, which is incorporated herein by reference in its entirety.

[0150] In some embodiments, the polymer obtained from the catalyst system comprising the metal-ligand complex of formula (I) has a molecular weight distribution (MWD) of 1.0 to 25, w / M n is defined as M w is the weight average molecular weight, and M n is the number average molecular weight. In another embodiment, the polymer resulting from the catalyst system has an MWD of 1.5 to 6. Another embodiment includes an MWD of 1.5 to 3, and another embodiment includes an MWD of 2 to 2.5.

[0151] SymRAD HT-GPC analysis Molecular weight data were determined by analysis on a hybrid robot-assisted dilution high-temperature gel permeation chromatography system (Sym-RAD-GPC) built by Symyx / Dow. Polymer samples were dissolved in 1,2,4-trichlorobenzene (TCB) at a concentration of 10 mg / mL, stabilized with 300 parts per million (ppm) butylated hydroxyl toluene (BHT), by heating at 160 °C for 120 min. Each sample was diluted to 1 mg / mL immediately before injection of a 250 μL aliquot. The GPC was equipped with two Polymer Labs PLgel 10 μm MIXED-B columns (300 × 10 mm) at a flow rate of 2.0 mL / min at 160 °C. Sample detection was performed using a PolyChar IR4 detector in concentration mode. Conventional calibration of narrow polystyrene (PS) standards utilizes apparent units adjusted to homopolyethylene (PE) using the known Mark-Houwink coefficients for PS and PE in TCB at this temperature.

[0152] 1-Octene Incorporated IR Analysis Samples run for HT-GPC analysis precede IR analysis. For IR analysis, a 48-well HT silicon wafer is utilized for sample deposition and analysis of 1-octene incorporation. For analysis, the sample is heated to 160 °C for 210 min or less, reheated to remove the magnetic GPC stir bar, and shaken with a glass rod stir bar on a J-KEM Scientific heated robotic shaker. Samples are deposited with heating using a Tecan MiniPrep 75 deposition station, and 1,2,4-trichlorobenzene is evaporated from the wafer's deposition wells at 160 °C under a nitrogen purge. Analysis of 1-octene is performed on the HT silicon wafer using a NEXUS 670 ESP FT-IR. [Example]

[0153] Examples 1-5 are synthetic procedures for the ligand intermediates, the ligands themselves, and isolated metal-ligand complexes containing the ligands. It should be understood, of course, that the synthetic procedures for catalysts 1-5 are provided to illustrate embodiments described in this disclosure and are not intended to limit the scope of this disclosure or the claims appended hereto.

[0154] The synthetic protocols for catalyst 1 (catalyst-1) are published in WO 2021 / 155158.

[0155] The synthesis protocol for catalyst 2 (catalyst-2) is published in WO 2021 / 155158.

[0156] The synthesis protocol for catalyst 3 (catalyst-3) is published in WO 2021 / 155158.

[0157] The synthesis protocol for catalyst 4 (catalyst-4) is published in WO2021243213.

[0158] The synthesis protocol for catalyst 5 (catalyst-5) can be found in International Application No. US11208503(B2) and published as WO 2018 / 183056.

[0159] Example 1 - Continuous Process Polymerization Results Preparation of Examples All raw materials (monomers and comonomers) and process solvents (high-purity narrow-boiling range paraffinic and cycloparaffinic solvents) were purified with molecular sieves before being introduced into the reaction environment. High-purity hydrogen was supplied through a shared pipeline and dried with molecular sieves. The monomer feed stream to the reactor was pressurized to a pressure higher than the reaction pressure by a mechanical compressor. The solvent feed was pressurized to a pressure higher than the reaction pressure by a pump. The comonomer feed was pressurized to above the reaction pressure via a pump. The individual catalyst components were manually batch diluted with purified solvent to the specified component concentrations and pressurized to a pressure higher than the reaction pressure. All reaction feed streams were measured with mass flow meters and independently controlled with metering pumps.

[0160] The comonomer feed can be mechanically pressurized and injected into the process at several potential locations depending on the reactor configuration, including the first reactor feed only, the second reactor feed only, or both the first and second reactor feeds independently. Some comonomer injection combinations are only possible when implementing a dual reactor configuration.

[0161] Reactor configuration options include single reactor operation, dual reactors in series, or dual reactors in parallel.

[0162] The continuous solution polymerization reactor consists of a liquid-filled, adiabatic, continuous stirred tank reactor (CSTR). Independent control of all solvent, monomer, comonomer, hydrogen, and catalyst component feeds is possible. All feed streams to the reactor (solvent, monomer, comonomer, and hydrogen) are temperature controlled by passing the feed streams through heat exchangers. All feeds to the polymerization reactor are injected into the reactor at one location. Catalyst components are injected into the polymerization reactor separately from the other feeds. An agitator within the reactor provides continuous mixing of the reactants. An oil bath provides some fine control of the reactor temperature.

[0163] In a dual reactor in series configuration, the effluent from the first polymerization reactor exits the first reactor and is added to the second reactor separately from the other feeds to the second reactor.

[0164] In a dual parallel reactor configuration, the effluent streams from the first and second polymerization reactors are combined before any additional processing.

[0165] In all reactor configurations, the final reactor effluent (the second reactor effluent in the case of dual series, the combined effluent in the case of dual parallel, or the single reactor effluent) enters a zone where it is deactivated by adding and reacting with a suitable reagent (usually water). At the outlet of this same reactor, other additives may also be added for polymer stabilization (octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, tetrakis(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))methane, and tris(2,4-di-tert-butyl-phenyl)phosphite).

[0166] After catalyst deactivation and addition of any additives, the reactor effluent enters a devolatilization system where the polymer is removed from the non-polymer stream. The non-polymer stream is removed from the system. The isolated polymer melt is pelletized and recovered.

[0167] [Table 1]

[0168] H2 (mol%) is defined as the mole fraction of hydrogen relative to the ethylene fed to the reactor. Ethylene conversion is measured as the difference between the ethylene fed to the reactor and the amount exiting the reactor, expressed as a percentage. C8 / olefins is the fresh C8 feed divided by the sum of the fresh C8 feed and the fresh C2 feed. The cocatalyst ratio is the total molar ratio of Al from MMAO or MMAO-3a to the sum of catalyst A and B metals or C metal, or the molar ratio of bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)ammonium (RIBS-2) to catalyst A metal. The catalyst A / B ratio is the metal molar ratio of two catalysts in the same reactor.

[0169] MMAO-3a is commercially available from Nouryon and has a CAS# of 146905-79-5. MMAO is modified with n-octyl substituents, resulting in a methyl:n-octyl ratio of approximately 6:1.

[0170] Equipment standards All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passage through activated alumina and, in some cases, Q-5 reactants. Solvents used in experiments conducted in a nitrogen-filled glovebox were further dried by storage over activated 4 Å molecular sieves. Glassware for moisture-sensitive reactions was dried overnight in an oven before use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. 1 Chemical shifts for H NMR data are reported in ppm downfield from internal tetramethylsilane (tetramethylsilane, TMS, δ scale) using residual protons in the deuterated solvent as the reference. 13 C NMR data is 1 Determined using H decoupling, chemical shifts are reported in ppm downfield from tetramethylsilane (TMS, δ scale) using residual carbon in the deuterated solvent as the reference.

Claims

1. 1. A polymerization process comprising: Polymerizing ethylene, and optionally one or more olefins, in a solution polymerization reactor under olefin polymerization conditions in the presence of a catalyst system comprising at least one metal-ligand complex of Formula (I), at least one Group IV procatalyst, at least one additive, and optionally a Lewis acid to form an ethylene-based polymer, wherein said metal-ligand complex (pre-catalyst) of Formula (I) 【Chemical 1】 wherein: M is scandium, yttrium, or a lanthanide metal; Each X is (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —CH ２ Si(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -Si(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -OSi(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -CH ２ Ge(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -Ge(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -P(R Ｃ ) ２－Ｗ (OR Ｃ ) Ｗ , -P(O)(R Ｃ ) ２－Ｗ (OR Ｃ ) Ｗ , -N(R Ｃ ) ２ , -NH(R Ｃ ), —N(Si(R Ｃ ) ３ ) ２ , -NR Ｃ Si(R Ｃ ) ３ , -NHSi(R Ｃ ) ３ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , -OCF ３ , -S(O)R Ｃ , -S(O) ２ R Ｃ , -OS(O) ２ R Ｃ , -N=C(R Ｃ ) ２ , -N=CH(R Ｃ ), -N=CH ２ , -N=P(R Ｃ ) ３ , -OC(O)R Ｃ , -C(O)OR Ｃ , -N(R Ｃ ) C(O)R Ｃ , -N(R Ｃ )C(O)H, -NHC(O)R Ｃ , -C(O)N(R Ｃ ) ２ , —C(O)NHR Ｃ , —C(O)NH ２ , B(R Ｙ ) ４ , Al(R Ｙ ) ４ , or Ga(R Ｙ ) ４ or hydrogen, and each R Ｃ are independently substituted or unsubstituted (C １ ~C ３０ ) hydrocarbyl, or substituted or unsubstituted (C １ ~C ３０ ) heterohydrocarbyl, each Q is 0, 1, 2, or 3, each W is 0, 1, or 2, and each R Ｙ is -H, (C １ ~C ３０ ) a hydrocarbyl or halogen atom; k is 1 or 2; each T is independently a Lewis base; n is 0, 1, or 2, and when n is 1, X and T are optionally linked, and when n is 2, X and one of T are optionally linked; The metal-ligand complex is overall charge neutral; Each Z is independently —O—, —S—, —N(R Ｎ ) - or -P(R Ｐ )—, where the dotted lines optionally define coordinate bonds; R １ and R １６ are independently １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, -N=C(R Ｃ ) ２ , R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ NC(O)—, or halogen; R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , and R １５ are independently —H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, (R Ｃ ) ２ P=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ NC(O)— and halogen; However, when M is yttrium or a lanthanide metal, R １ is not —H, phenyl, or tert-butyl, and R １６ is not —H, phenyl, or tert-butyl; L is (C １ ~C ４０ ) hydrocarbylene or (C １ ~C ４０ ) heterohydrocarbylene; Each R in formula (I) Ｃ , R Ｐ , and R Ｎ are independently １ ~C ３０ ) hydrocarbyl, (C １ ~C ３０ ) heterohydrocarbyl, or —H.

2. 10. The polymerization process of claim 1, wherein the polymerization reactor is a single reactor.

3. the polymerization reactor is a double reactor, the metal-ligand catalyst of formula (I) is in a first reactor and the Group (IV) catalyst is in a second reactor; or the Group (IV) catalyst is in a first reactor and the metal-ligand catalyst of formula (I) is in a second reactor; or the metal-ligand catalyst of formula (I) and the Group (IV) catalyst are in the first reactor, and a second metal-ligand catalyst of formula (I) or a second Group (IV) catalyst is in the second reactor; or 2. The polymerization process of claim 1, wherein the metal-ligand catalyst of formula (I) and the Group (IV) catalyst are in the second reactor, and a second metal-ligand catalyst of formula (I) or a second Group (IV) catalyst is in the first reactor.

4. 10. The polymerization process of claim 1, wherein the polymerization reactor is a multi-zone reactor.

5. The polymerization process of any one of claims 1 to 4, wherein the additive is an alkylating agent, a cocatalyst, or a scavenger.

6. The polymerization process of any one of claims 1 to 5, wherein the additive is an alkylaluminoxane compound, an alkyl-modified aluminoxane, or an alkylaluminum.

7. The polymerization process of any one of claims 1 to 6, wherein the Lewis acid is an alkyl-modified aluminoxane.

8. The Lewis acid is AlR Ａ ３ wherein each R Ａ But independently, (C １ ~C ４０ 8. The polymerization process of claim 1, wherein the alkyl group is a methyl group.

9. Each R Ａ But independently, (C １ ~C ４０ 10. The polymerization process of claim 9, wherein:

10. The additive is (A) at least one cocatalyst selected from the group consisting of aluminoxanes, or (B) a compound of the formula AlR Ａ１ R Ｂ１ R Ｃ１ or (C) at least one cocatalyst selected from the group consisting of an aluminoxane and an alkylaluminum of the formula AlR １ R ２ R ３ wherein R Ａ１ , R Ｂ１ , and R Ｃ１ But independently, (C １ ~C ４０ 5. The polymerization process of claim 1, wherein the alkyl is 2-(2-methyl-2-propanol).

11. The polymerization process according to any one of claims 1 to 10, wherein the additive is a borate compound.

12. 10. The polymerization process of claim 1, wherein the at least one Lewis acid is selected from a mixture of alkylaluminum compounds and boron-based Lewis acids.

13. R １ and R １６ is selected from a radical having formula (II), a radical having formula (III), and a radical having formula (IV), 【Chemistry 2】 In the formula, R ３１～３５ , R ４１～４８ and R ５１～５９ Each of the groups independently represents —H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ ) -, (R Ｃ ) ２ NC(O)—, or halogen, with the proviso that R １ and R １６ is formula (II), R ３１ ~R ３５ The polymerization process of any one of claims 1 to 12, provided that at least one of

14. The polymerization process of any one of claims 1 to 13, wherein M is scandium.

15. When M is yttrium or a lanthanide metal, R ５～８ At least one of the groups is not —H and is R ９～１２ The polymerization process of any one of claims 1 to 14, wherein at least one of

16. R １ and R １６ is a radical having the formula (III) R ４２ and R ４７ However, (C １ ~C ２０ ) hydrocarbyl, —Si[(C １ ~C ２０ ) hydrocarbyl] ３ , or -Ge[(C １ ~C ２０ ) hydrocarbyl] ３ or R ４３ and R ４６ However, (C １ ~C ２０ ) hydrocarbyl, —Si[(C １ ~C ２０ ) hydrocarbyl] ３ , or -Ge[(C １ ~C ２０ ) hydrocarbyl] ３ The polymerization process according to any one of claims 1 to 15, wherein

17. R １ and R １６ is a radical having the formula (II), R ３１ ~R ３５ is not —H, or R ３２ and R ３４ However, (C １ ~C ２０ ) hydrocarbyl, —Si[(C １ ~C ２０ ) hydrocarbyl] ３ , or -Ge[(C １ ~C ２０ ) hydrocarbyl] ３ The polymerization process according to any one of claims 1 to 15, wherein

18. R １ and R １６ is a radical having the formula (IV), R ５２ , R ５３ , R ５５ , R ５７ , and R ５８ At least two of (C １ ~C ２０ ) hydrocarbyl, —Si[(C １ ~C ２０ ) hydrocarbyl] ３ , or -Ge[(C １ ~C ２０ ) hydrocarbyl] ３ and Optionally, R ５２ and R ５３ are linked to form a cyclic structure, and optionally, R ５７ and R ５８ The polymerization process of any one of claims 1 to 15, wherein

19. L is -CH ２ -, -CH, where m is 0 to 3 ２ (CH ２ ) ｍ CH ２ -, -CH ２ Si(R Ｃ ) ２ CH ２ -, -CH ２ Ge(R Ｃ ) ２ CH ２ -, -CH(CH ３ ) CH ２ CH (CH ３ ), and -CH ２ (phen-1,2-diyl)CH ２ -, and each R in L is selected from Ｃ However, (C １ ~C ２０ 19. The polymerization process of claim 1, wherein the alkyl group is a methyl group.

20. X is (C ６ ~C ２０ ) aryl, benzyl, -CH ２ Si[(C １ ~C ２０ ) alkyl] ３ , (C １ ~C １２ 20. The polymerization process of claim 1, wherein the alkyl is .

21. n is 1 or 2, and at least one T is (C １ ~C ２０ 21. The polymerization process of claim 1, wherein the heteroatom is oxygen.

22. 22. The polymerization process of any one of claims 1 to 21, wherein n is 1 or 2 and at least one T is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

23. R ２ , R ４ , R ５ , R １２ , R １３ , and R １５ is hydrogen, The polymerization process of any one of claims 1 to 22, wherein each Z is oxygen.

24. the Group (IV) metal-ligand complex is a bis-biphenylphenoxy Group IV metal-ligand complex having a structure according to formula (X); 【Chemistry 3】 In the formula, M １ is a metal selected from titanium, zirconium, or hafnium; Each X ｘ is unsaturated (C ２ ~C ５０ ) hydrocarbons, unsaturated (C ２ ~C ５０ ) heterohydrocarbon, saturated (C ２ ~C ５０ ) heterohydrocarbons, (C １ ~C ５０ ) hydrocarbyl, (C ６ ~C ５０ ) aryl, (C ６ ~C ５０ ) heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C ４ ~C １２ ) diene, halogen, -N(R Ｎ ) ２ , and -NCOR Ｃ are monodentate or bidentate ligands independently selected from n is 1, 2, or 3, and when n is 1, X ｘ is a monodentate or bidentate ligand, and when the subscript n is 2, each X ｘ is a monodentate ligand, the metal-ligand complex is overall charge neutral; Each Z is independently —O—, —S—, —N(R Ｎ ) - or -P(R Ｐ ) - is selected from L ｘ is (C １ ~C ４０ ) hydrocarbylene or (C １ ~C ４０ ) heterohydrocarbylene; R ２ｘ～４ｘ , R ５ｘ～８ｘ , R ９ｘ～１２ｘ and R １３ｘ～１５ｘ are independently —H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, -N=C(R Ｃ ) ２ , R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ selected from the group consisting of NC(O)— and halogen; R １ｘ and R １６ｘ is selected from a radical having formula (XI), a radical having formula (XII), and a radical having formula (XIII), 【Chemistry 4】 In the formula, R ３１～３５ , R ４１～４８ , and R ５１～５９ each independently represents —H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ ) -, (R Ｃ ) ２ 24. The polymerization process of any one of claims 1 to 23, wherein the alkyl group is selected from NC(O)-, or halogen.

25. the Group (IV) metal-ligand complex is a constrained geometry Group IV complex having a structure according to formula (XV); 【Chemistry 5】 M ２ is titanium, hafnium or zirconium, b is 1, 2, or 3; Each X is an unsaturated (C ２ ~C ５０ ) hydrocarbons, unsaturated (C ２ ~C ５０ ) heterohydrocarbon, saturated (C ２ ~C ５０ ) heterohydrocarbons, (C １ ~C ５０ ) hydrocarbyl, (C ６ ~C ５０ ) aryl, (C ６ ~C ５０ ) heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C ４ ~C １２ ) diene, halogen, -N(R Ｎ ) ２ , and -NCOR Ｃ are monodentate or bidentate ligands independently selected from the metal-ligand complex is overall charge neutral; Cp is cyclopentadienyl and R Ｓ substituted cyclopentadienyl, wherein Cp is selected from the group consisting of η ５ The binding mode is M ２ is bonded to R Ｓ are independently １ ~C ２０ ) alkyl, (C １ ~C ２０ ) heteroalkyl, (C １ ~C ２０ ) aryl, or R Ｓ Substituent (C １ ~C ２０ ) aryl, (C １ ~C ２０ ) heteroaryl, or R Ｓ Substituent (C １ ~C ２０ ) heteroaryl, wherein two adjacent R Ｓ the groups are optionally linked to form a ring; N is nitrogen; Y is carbon or silicon, and Y is covalently bonded to Cp; R １ and R ２ are independently —H, (C １ ~C ４０ ) hydrocarbyl, and (C １ ~C ４０ ) heterohydrocarbyl; R ３ are independently １ ~C ４０ ) hydrocarbyl, and (C １ ~C ４０ 24. The polymerization process of any one of claims 1 to 23, wherein the heterohydrocarbyl is selected from:

26. 1. A polymerization process comprising: Polymerizing ethylene and optionally one or more olefins in a solution polymerization reactor under olefin polymerization conditions to form an ethylene-based polymer in the presence of a catalyst system comprising at least one olefin propogating catalyst species according to formula (Ia): at least one Group IV catalyst olefin propogating catalyst species, at least one additive, and optionally a Lewis acid, wherein said olefin propogating catalyst species of (Ia) 【Chemistry 6】 wherein: M is scandium, yttrium, or a lanthanide metal; X Ｐ is a ligand selected from hydrocarbyls, said hydrocarbyls having at least 30 carbon atoms and being branched or unbranched; Each Z is independently —O—, —S—, —N(R Ｎ ) - or -P(R Ｐ )—, and the dotted line optionally defines a coordinate bond; R １ and R １６ But independently, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, -N=C(R Ｃ ) ２ , R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ NC(O)—, or halogen; R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , and R １５ are independently -H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, (R Ｃ ) ２ P=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ NC(O)— and halogen, When M is yttrium or a lanthanide metal, R １ is not —H, phenyl, or tert-butyl, and R １６ is not —H, phenyl, or tert-butyl; L is (C １ ~C ４０ ) hydrocarbylene or (C １ ~C ４０ ) heterohydrocarbylene; Each R in formula (I) Ｃ , R Ｐ , and R Ｎ But independently, (C １ ~C ３０ ) hydrocarbyl, (C １ ~C ３０ ) heterohydrocarbyl, or —H.

27. M is yttrium or a lanthanide metal; R ５～８ At least one of the groups is not —H and is R ９～１２ 27. The polymerization process of claim 26, wherein at least one of

28. R １ and R １６ is selected from a radical having formula (II), a radical having formula (III), and a radical having formula (IV), 【Chemistry 7】 In the formula, R ３１～３５ , R ４１～４８ and R ５１～５９ Each of the groups independently represents —H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ ) -, (R Ｃ ) ２ NC(O)—, or halogen, with the proviso that R １ and R １６ is formula (II), R ３１ ~R ３５ 28. The olefin propogating catalyst species of claim 26 or claim 27, provided that at least one of: is not —H.

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