Monodentate / bidentate aminopyridine group 4 transition metal olefin copolymerization catalysts with ultra-high molecular weight tolerance and ultra-low comonomer incorporation

Abstract

The process for polymerizing polyolefins comprises reacting ethylene and any one or more (C3-C 12 ) an α-olefin, wherein the catalyst system comprises a metal-ligand complex having a structure according to formula (I). [Formula 1] JPEG2022525889000048.jpg130170

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 825,264, filed March 28, 2019, the disclosure of which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate broadly to olefin polymerization catalyst systems and processes, and more specifically to olefin polymerization catalyst systems that include monobidentate aminopyridine Group 4 transition metal catalysts, and olefin polymerization processes incorporating the catalyst systems. [Background technology]

[0003] Olefin-based polymers, such as polyethylene, ethylene-based polymers, polypropylene, and propylene-based polymers, are produced by various 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 polymers are produced for a wide variety of articles. The polyethylene polymerization process can be modified in many ways to produce a wide variety of resulting polyethylene resins with different physical properties that make the various resins suitable for use in a variety of applications. The ethylene monomer and optionally one or more comonomers are present in a liquid diluent (such as a solvent), such as an alkane or isoalkane, e.g., isobutene. Hydrogen can also be added to the reactor. Catalyst systems for producing ethylene-based polymers can typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (either metallocene or non-metallocene) catalyst systems. The diluent and reactants in the catalyst system are circulated in the reactor at elevated polymerization temperatures, thereby producing an ethylene-based homopolymer or copolymer. Periodically or continuously, a portion of the reaction mixture containing the polyethylene product dissolved in the diluent is removed from the reactor, along with unreacted ethylene and one or more optional comonomers. The reaction mixture upon removal from the reactor 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 to the first reactor, where a second polyethylene fraction may be produced. Summary of the Invention [Problem to be solved by the invention]

[0005] Despite the numerous homogeneous solution olefin polymerization catalyst systems available today, a need exists for high temperature polymerization catalysts with improved molecular properties that facilitate the production of high molecular weight (Mw) polymers with narrow polydispersity (PDI), and / or high molecular weight (Mw) ethylene / comonomer copolymers with defined comonomer incorporation ranges (i.e., 0-20 mol % 1-hexene or 1-octene), and / or high molecular weight (Mw) polymers that can be chain transferred with a chain transfer agent (CSA) to produce olefin block copolymers (OBCs).

[0006] Embodiments of the present disclosure include polymerization processes. These polymerization processes produce ethylene-based polymers. The polymerization processes comprise a process for producing ethylene and any one or more (C3-C 12 ) an α-olefin, the catalyst system comprising a metal-ligand complex having a structure according to formula (I). [ka]

[0007] In formula (I), M is titanium, zirconium or hafnium. Each X is independently an unsaturated (C2-C 20 ) Hydrocarbons, unsaturated (C2-C 50 ) Heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (C1-C 50 )heterohydrocarbyl, (C6-C 50 )Aryl, (C6-C 50 )Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 )Diene, halogen, -OR X , -N(R X )2 or -NCOR X and each R is a monodentate or bidentate ligand selected from X is (C1-C 30 ) hydrocarbyl or -H.

[0008] In formula (I), R 1 , R 2 , R 3 and R 4 are independently -H, (C1-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-, (RC )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)- or halogen, and each R C , each R N and each R P is (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl or -H, R 5 is -H, (C1-C 40 ) hydrocarbyl or (C1-C 40 ) heterocyclocarbyl, where R 5 is not phenyl or substituted phenyl.

[0009] In various embodiments, R 1 is selected from the group consisting of a radical having formula (II), a radical having formula (III) and a radical having formula (IV). [ka]

[0010] In formulas (II), (III) and (IV), R 31 -R 35 , R 41 -R 48 and R 51 -R 59 is (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R T )3, -Ge(R T )3, -P(R T )2, -N(R T )2, -N=CHR T , -OR T , -SR T , -NO2, -CN, -CF3, R T S(O)-, R T S(O)2-, (R T )2C=N-, R T C(O)O-, R TOC(O)-, R T C(O)N(R T )-, (R T )2NC(O)-, halogen or -H, and each R T (C1-C 30 ) hydrocarbyl or -H. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 shows Ligand 1 to Ligand 8. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Here, specific embodiments of the catalyst system are described. It is understood that the catalyst system of the present disclosure may be implemented in different forms and should not be construed as being limited to the specific embodiments described in this disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0013] Common abbreviations are listed below.

[0014] R, Z, M, X, and n are as defined above, Me: methyl, Et: ethyl, Ph: phenyl, Bn: benzyl, i-Pr: iso-propyl, t-Bu: tert-butyl, t-Oct: tert-octyl (2,4,4-trimethylpentan-2-yl), Tf: trifluoromethanesulfonate, 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: hydrochloric acid. n-BuLi: butyl lithium, t-BuLi: tert-butyl lithium, Cu2O: copper oxide (I), N,N'-DMEDA: N,N'-dimethylethylenediamine, K3PO4: potassium tribasic phosphate, Pd(AmPhos)Cl2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II), Pd(dppf)Cl2: [1,1'-bis(diphenylphosphino)ferrocene]dichloridepalladium(II), 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: Hafnium(IV) tetrabenzyl, ZrCl4: Zirconium(IV) chloride, ZrBn4: Zirconium(IV) tetrabenzyl, ZrBn2Cl2(OEt2): Zirconium(IV) dibenzyl dichloride mono-diethyl etherate, HfBn2Cl2(OEt2): Hafnium(IV) dibenzyl dichloride mono-diethyl etherate, TiBn4: Titanium(IV) tetrabenzyl, Zr(CH2SiMe3)4: Zirconium(IV) tetrakis-trimethylsilylmethyl, Hf(CH2SiMe3)4: Hafnium(IV) tetrakis-trimethylmethyl, N2: Nitrogen gas, PhMe: Toluene, PPR: Parallel polymerization reactor, MAO: Methylaluminoxane, MMAO: Modified methylaluminoxane, GC: Gas chromatography, LC: Liquid chromatography, NMR: Nuclear magnetic resonance, MS: Mass spectrometry, mmol: Millimole, mL: Milliliter, M: Mole, min or mins: Minute, h or hrs: Hours, d: Days, R, f : Retained fraction, TLC: Thin layer chromatography, rpm: Revolutions per minute.

[0015] The term "independently selected" followed by multiple options is 1 , R 2 , R 3 , R 4 and R 5 etc. are used herein to indicate that the individual R groups appearing before the term may be the same or different and there is no dependency as to the identity of the other groups appearing before the term.

[0016] 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 to convert the procatalyst into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms.

[0017] When used to describe certain carbon atom-containing chemical groups, "(Cx -C y A parenthetical expression having the form "(C1-C2)" means that the unsubstituted form of the chemical group has x carbon atoms to y carbon atoms, inclusive. For example, (C1-C2) 50 ) Alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups are R S The parenthetical "(C x -C y )" for the chemical group R S The substituted form can be any group R S Depending on the identity of "R", the group may contain more than y carbon atoms. For example, "R S is phenyl (-C6H5), then exactly one group R S (C1-C 50 "(C)alkyl" can contain from 7 to 56 carbon atoms. Thus, the parenthetical "(C)alkyl" can generally be used. x -C y )" is a group defined as 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 determined by the sum of all carbon atom-containing substituents R S It is determined by adding the total number of carbon atoms from

[0018] The term "substituted" refers to the replacement of at least one hydrogen atom (-H) bonded to a carbon or heteroatom or functional group of the corresponding unsubstituted compound with a substituent (e.g., R S The term "persubstituted" means that all hydrogen atoms (H) attached to carbon 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 or heteroatom of the 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 have the same meaning unless otherwise specified.

[0019] "(C1-C 50 The term "(C1-C)hydrocarbyl" means a hydrocarbon radical having 1 to 50 carbon atoms. 50 The term "hydrocarbylene" means a hydrocarbon diradical having from 1 to 50 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is 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 contains one or more R S or not replaced by

[0020] In this disclosure, (C 1-C50 ) Hydrocarbyl is unsubstituted or substituted (C1-C 50 )Alkyl, (C3-C 50 ) cycloalkyl, (C 3- C 20 )Cycloalkyl-(C1-C20)alkylene, (C6-C 40 ) aryl, or (C6-C 20 )Aryl-(C1-C 20 ) alkylene, such as benzyl (-CH2-C6H5).

[0021] "(C1-C 50 ) alkyl" and "(C1-C 18 The terms "alkyl" and "alkyl-alkyl" refer to saturated linear or branched hydrocarbon radicals of 1 to 50 carbon atoms and 1 to 18 carbon atoms, respectively, unsubstituted or substituted with one or more R SIt means that the unsubstituted (C1-C 50 Examples of alkyl are unsubstituted (C1-C20) 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. 1- C 40 Examples of substituted (C-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, each of which is (C-C) alkyl. S Replaced by (C 27 -C 40 )alkyl. Each (C1-C5)alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0022] "(C6-C 50 The term "aryl" refers to an unsubstituted or substituted aryl group having 6 to 40 carbon atoms, of which at least 6 to 14 carbon atoms are aromatic ring carbon atoms. S (by C6-C8) means a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical substituted with a cyclic or cyclic aromatic ring. 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, aromatic or non-aromatic. Unsubstituted (C6-C8) means a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical substituted with a cyclic or cyclic aromatic ring. 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, aromatic or non-aromatic. 50 Examples of aryl include unsubstituted (C6-C20)aryl, unsubstituted (C6-C 18)aryl, 2-(C1-C5)alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. C40 Examples of aryl include substituted (C 1- C 20 )Aryl, Substituted (C6-C 18 )aryl, 2,4-bis([C 20 ]alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl and fluoren-9-one-l-yl.

[0023] "(C3-C 50 The term "cycloalkyl" refers to an unsubstituted or substituted cycloalkyl group that is substituted with 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 is defined in a similar manner as being either unsubstituted (C 3- 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. 3- C 40 Examples of cycloalkyl include substituted (C3-C20)cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0024] (C1-C 50 Examples of hydrocarbylenes include unsubstituted or substituted (C 6- C 50 )Arylene, (C3-C 50) cycloalkylene, and (C1-C 50 ) alkylene (e.g., (C1-C 20 ) alkylene). The diradicals may 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 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 the 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-), 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.

[0025] "(C1-C 50 The term "alkylene" refers to an unsubstituted or substituted alkylene with one or more R S means a saturated straight or branched diradical of 1 to 50 carbon atoms (i.e., the radical is not a ring atom) substituted by 50 ) Examples of alkylene are: 非置換- CH2CH2-, -(CH2)3-, - (CH2 )4 - , -(CH2)5-, -(CH2)6- 、- Unsubstituted (C1-C, including (CH2)7-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3). 20 ) alkylene, and "C*" refers to the carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. C50Examples of alkylenes 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 shown above, the two R S can be taken together to form a (C1-C18) alkylene, and the substituted (C1-C 50 Examples of alkylenes 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.

[0026] "(C3-C 50 The term "cycloalkylene" refers to an unsubstituted or substituted cycloalkylene with one or more R S "R" means a cyclic diradical (i.e., the radical is on a ring atom) of 3 to 50 carbon atoms substituted with

[0027] 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(R C )2, -Ge(RC)2-, or -Si(RC)-, where each RC and each R P is unsubstituted (C1-C 18 ) hydrocarbyl or -H, and each R N is unsubstituted (C1-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. The term "(C1-C50)heterohydrocarbyl" refers to a heterohydrocarbon radical of 1 to 50 carbon atoms, and ... 50The term "(C1-C50)heterohydrocarbylene" means a heterohydrocarbon diradical of 1 to 50 carbon atoms. 50 The heterohydrocarbon of the (C1-C50)heterohydrocarbylene has one or more heteroatoms. The radical of the heterohydrocarbyl can be present on a carbon atom or on a heteroatom. The two radicals of the heterohydrocarbylene can be present on a single carbon atom or on a single heteroatom. Furthermore, one of the two radicals of the diradical can be present on a carbon atom and the other radical can be present on a different carbon atom, one of the two radicals can be present on a carbon atom and the other radical can be present on a heteroatom, or one of the two radicals can be present on a heteroatom and the other radical can be present on a different heteroatom. Each of the (C1-C50)heterohydrocarbyl and (C1-C 50 ) Heterohydrocarbylene is unsubstituted or (one or more R S They may be substituted (by) aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0028] (C1-C 50 ) Heterohydrocarbyl may be unsubstituted or substituted. (C1-C 50 Non-limiting examples of heterohydrocarbyls include (C-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-, (C1-C 50 )hydrocarbyl-N(R N )-, (C1-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.

[0029] "(C4-C 50 The term "heteroaryl" refers to unsubstituted or heteroaryl groups having a total of 4 to 50 carbon atoms and 1 to 10 heteroatoms. S (C) means a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical substituted with a heteroaromatic ring. 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 or rings of the heteroaromatic radical can independently be fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., generally (C) x -C y )heteroaryl, (C4-C 12 ) heteroaryl, etc., has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or substituted with one or more R SThe monocyclic heteroaromatic hydrocarbon radical is a 5- or 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms, which can be 1, 2 or 3, and each heteroatom can 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. The six-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms, which can be 1 or 2, and the heteroatoms can be N or P. Examples of six-membered heteroaromatic hydrocarbon radicals are pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radicals can be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals include indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon radicals include quinolin-2-yl and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radicals can be fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. 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 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridine-9-yl.

[0030] "(C1-C 50The term "(C1-C2)heteroalkyl" means a saturated straight or branched chain radical containing 1 to 50 carbon atoms or fewer 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), each of the heteroalkyl and heteroalkylene groups being unsubstituted or containing one or more R S has been replaced by

[0031] 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.

[0032] 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 a radical of a fluoride atom (F - ), chloride (Cl - ), bromide (Br - ) or iodide (I -) means the anionic form of a halogen atom.

[0033] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S When substituted with, one or more double and / or triple bonds may be optionally substituted with a substituent R S The term "unsaturated" refers to a group that contains one or more carbon-carbon double bonds, 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 is not limited to the substituent R S It is meant to exclude any double bonds that may be present in the (hetero)aromatic ring (if present) or in the (hetero)aromatic ring (if present).

[0034] An embodiment of the present disclosure includes a process for polymerizing olefin monomers. The process comprises the polymerization of ethylene and any one or more (C3-C 12 ) an α-olefin. The catalyst system comprises a metal-ligand complex having a structure according to formula (I). [ka]

[0035] In formula (I), M is titanium, zirconium or hafnium. Each X is independently an unsaturated (C2-C 20 ) Hydrocarbons, unsaturated (C2-C 50 ) Heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (C1-C 50 )heterohydrocarbyl, (C6-C 50 )Aryl, (C6-C 50 )Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 )Diene, halogen, -OR X , -N(R X )2 or -NCOR Xand each R is a monodentate or bidentate ligand selected from X is (C1-C 30 ) hydrocarbyl or -H.

[0036] R 1 are independently -H, (C1-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)- or halogen. C 、 Each R N , and each R P is (C1-C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl or -H.

[0037] In formula (I), R 2 , R 3 and R 4 are independently -H, (C1-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-, RC OC(O)-, R C C(O)N(R)-, (R C )2NC(O)- or halogen, and each R C 、 Each R N and each R P is (C1-C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl or -H. 5 is -H, (C1-C 40 ) hydrocarbyl or (C1-C 40 ) heterohydrocarbyl, where R 5 is not phenyl or substituted phenyl.

[0038] In various embodiments, R 1 is selected from the group consisting of a radical having formula (II), a radical having formula (III) and a radical having formula (IV). [ka]

[0039] In formulas (II), (III) and (IV), R 31 ~R 35 , R 41 ~R 48 and R 51 ~R 59 is (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R T )3, -Ge(R T )3, -P(R T )2, -N(R T )2, -N=CHR T , -OR T , -SR T , -NO2, -CN, -CF3, R T S(O)-, R T S(O)2-, (R T )2C=N-, R T C(O)O-, R T OC(O)-, R T C(O)N(RT )-, (R T )2NC(O)-, halogen or -H, and each R T (C1-C 30 ) hydrocarbyl or -H.

[0040] In one or more embodiments of formula (I), R 1 is a radical having the formula (II), R 31 , R 33 and formula R 35 are independent, (C1-C 12 ) alkyl or (C1-C 20 ) aryl. In some embodiments, R 1 is selected from radicals having the formula (II) 32 and R 34 are independent, (C1-C 12 ) alkyl or (C1-C 20 ) aryl.

[0041] In various embodiments of formula (I), R 1 is a radical having the formula (IV), R of formula (IV) 52 and R 58 are independent, (C1-C 12 ) alkyl or (C1-C 20 ) aryl. In one or more embodiments, R 1 is a radical having the formula (IV), R of formula (IV) 53 and R 58 are independent, (C1-C 12 ) alkyl or (C1-C 20 ) aryl. In some embodiments, R 1 is a radical having the formula (IV), R of formula (IV) 53 and R 57 are independent, (C1-C 12 ) alkyl or (C1-C 20 ) aryl. In some embodiments, R 1 is a radical having the formula (IV), R of formula (IV) 53 , R 55 and R 57are independent, (C1-C 12 ) alkyl or (C1-C 20 ) aryl.

[0042] R 31 ~R 35 , R 41 ~R 48 and R 51 ~R 59 (C1-C 12 In any embodiment where the alkyl is (C-C 12 ) Alkyl can be methyl, ethyl, propyl, 2-propyl, n-butyl, tert-butyl, 2-methylpropyl, pentyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, n-octyl, tert-octyl, nonyl, decyl, undecyl or dodecyl.

[0043] In some embodiments of Formula (I), R 5 is benzyl, (C1-C 20 ) alkyl, or -CH2SiR R 3, R R is (C1-C 12 ) alkyl. In one or more embodiments, R 5 is methyl, ethyl, propyl, 2-propyl, n-butyl, tert-butyl, 2-methylpropyl, pentyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, n-octyl, tert-octyl, nonyl, decyl, undecyl or dodecyl.

[0044] The metal-ligand complex has six or fewer metal-ligand bonds and may be neutral in overall charge or may have a positive charge associated with the metal center. In some embodiments, the catalyst system comprises a metal-ligand complex according to formula (I), wherein M is zirconium or hafnium, and each X is independently selected from the group consisting of (C6-C 20 )Aryl, (C4-C 20 )heteroaryl, (C4-C 12 ) a diene, or a halogen, and each R 1 are independent, (C1-C 50 )Aryl, (C4-C50 ) heteroaryl.

[0045] In the metal-ligand complex according to formula (I), each X is bonded to M via a covalent bond, a coordinate bond, or an ionic bond. Generally, the metal-ligand complex according to formula (I) is overall charge neutral. In some embodiments, the monodentate ligand can be a monoanionic ligand. The monoanionic ligand has a net formal oxidation state of -1. Each monoanionic ligand can independently be a hydride, (C1-C 40 ) hydrocarbyl carbanion, (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- C20 )hydrocarbyl) - , (C1-C 40 ) Hydrocarbyl C(O)N(H) - , RKRLB-, RKRLN - , RKO-, R.K.S. - , R.K.R. L P - , or R M R K R L S - Each R may be K , R L , and R M are independently hydrogen, (C1-C 40 ) hydrocarbyl, or (C1-C 40 ) heterohydrocarbyl, or R K and R L Together, (C2-C 40 ) hydrocarbylene or (C1-C 20 ) forms a heterohydrocarbylene, R M is as defined above.

[0046] In other embodiments, at least one monodentate ligand X, independently of any other ligand X, may be a neutral ligand. In certain embodiments, a neutral ligand is R Q NR K R L , R K OR L , R K S.R. L , or R Q PR K R L and each R Q are independently hydrogen, [(C1-C 10 )hydrocarbyl]3Si(C1-C 10 ) hydrocarbyl, (C1-C 40 ) hydrocarbyl, [(C1-C 10 )hydrocarbyl]3Si, or (C1-C 40 ) heterohydrocarbyl, each R K and R L are independently as defined above.

[0047] Additionally, each X may be, independently of any other ligand X, a halogen, an unsubstituted (C C20 ) Hydrocarbyl, unsubstituted (C1-C 20 ) may be a monodentate ligand which is a hydrocarbyl C(O)O-, or RKRLN-; K and R L Each of is independently unsubstituted (C-C 20 In some embodiments, each monodentate ligand X is a chlorine atom, (C1- C10 ) hydrocarbyl (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C 10 ) Hydrocarbyl C(O)O - , or R K RLN- and R K and R L Each of is independently unsubstituted (C-C 10 ) hydrocarbyl.

[0048] In exemplary embodiments including a bidentate ligand, the bidentate ligand may be a neutral bidentate ligand. In one embodiment, the neutral bidentate ligand has the formula (R D )2C=C(R D )-C(R D )=C(R D )2 dienes, wherein each R D are independently H, unsubstituted (C1-C6) alkyl, phenyl, or naphthyl. In some embodiments, the bidentate ligand is a monoanionic-mono (Lewis base) ligand. In some embodiments, the bidentate ligand is a dianionic ligand. The dianionic ligand has a net formal oxidation state of -2. In one embodiment, each dianionic ligand is independently a carbonate, an oxalate (i.e., -O2CC(O)O-), (C2-C 40 ) hydrocarbylene dicarbanion, (C1-C 40 ) heterohydrocarbylene dicarbanion, phosphate, or sulfate.

[0049] In further embodiments, X is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, or chloro. In some embodiments, each X is benzyl. In some cases, at least two X are different from each other. In embodiments where at least two X are different from at least one X, X is different from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, and chloro. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

[0050] In certain embodiments, X is benzyl, -CHSiR R 3, or -(CH2) n (SiR C ) 3, the subscript n is an integer from 1 to 10, and R R (C1-C 12 ) alkyl, R C (C1-C30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl or -H. In more particular embodiments, X is benzyl, -CHSiR R 3, or -(CH2) n (SiR C ) 3, the subscript n is an integer from 1 to 10, and R R (C1-C 12 ) alkyl, R C (C1-C 20 ) alkyl.

[0051] In some embodiments, the chemical groups (e.g., X, R 1 ~R 5 , R 31 ~R 35 , R 41 ~R 48 and R 51 ~R 59 In other embodiments, any or all of the chemical groups X, R of the metal-ligand complex of formula (I) may be unsubstituted. 1 ~R 5 , R 31 ~R 35 , R 41 ~R 48 and R 51 ~R 59 Any or all of the following may be used: S or none of the 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, R 1 ~R 5 , R 31 ~R 35 , R 41 ~R 48 and R 51 ~R 59 Any or all of R Sor either may be unsubstituted or unsubstituted. S In chemical groups that are over-substituted with S may all be the same or may be independently selected.

[0052] In an exemplary embodiment, the catalyst system can include a metal-ligand complex according to formula (I) having the structure of any of the procatalysts 1-16 listed below, which are synthesized from the corresponding ligands 1-8 shown in FIG. [ka] [ka]

[0053] Chain shuttle and / or chain transfer agents In one or more embodiments, the polymerization process of the present disclosure comprises the polymerization of ethylene and / or one or more (C3-C4) olefins in a reactor in the presence of a catalyst system and a chain transfer or chain shuttle agent. 12 ) contacting an α-olefin with a procatalyst and a cocatalyst having a metal-ligand complex having the structure of formula (I), (B) an olefin polymerization catalyst characterized by having a comonomer selectivity different from that of the procatalyst (A), and (C) a mixture of chain transfer or chain shuttle agents.

[0054] As used herein, the term "chain transfer agent" refers to a molecule that can transfer a polymer chain between two separate catalysts in a single polymerization reactor. Each catalyst in the reactor may have a different monomer selectivity. The term "chain transfer agent" is similar to the term "chain shuttle agent", but those skilled in the art will recognize that a chain transfer agent may be used as a chain shuttle agent depending on the type of reactor and catalyst system. For example, chain shuttle occurs in a continuous reactor with a dual catalyst system. In this scenario, a chain shuttle agent is added to the catalyst system of the polymerization reaction. In contrast, chain transfer occurs in a batch reactor with either a single catalyst or a dual catalyst system, so a chain transfer agent is added to the catalyst system. However, the same molecule may be used as a chain transfer agent or a chain transfer agent.

[0055] Typically, the chain transfer agent comprises a metal that is Al, B, or Ga in a formal oxidation state of +3, or a metal that is Zn or Mg in a formal oxidation state of +2. Chain transfer agents suitable for the process of the present disclosure are described in U.S. Patent Application Publication No. US2007 / 0167315, which is incorporated herein by reference in its entirety.

[0056] In one or more embodiments of the polymerization process, the chain transfer agent, if present, is selected from the group consisting of diethyl zinc, di(isobutyl) zinc, di(n-hexyl) zinc, triethyl aluminum, trioctylaluminum, triethylgallium, isobutylaluminum bis(dimethyl(t-butyl)siloxane), isobutylaluminum bis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxy), bis(n-octadecyl)isobutylaluminum, isobutylaluminum bis(di(n-pentyl)amide), n-octylaluminum bis(2,6-di-t-butylphenoxide, n-octylaluminum di (ethyl(l-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminum bis(2,3,6,7-dibenzo-l-azacycloheptanamide), n-octylaluminum bis(2,3,6,7-dibenzo-l-azacycloheptanamide), n-octylaluminum bis(dimethyl(dimethyl)t-butyl)siloxide, ethylzinc(2,6-diphenylphenoxide), ethylzinc(t-butoxide), dimethylmagnesium, dibutylmagnesium and n-butyl-sec-butylmagnesium. Cocatalyst Component

[0057] The catalyst system comprising the metal-ligand complex of formula (I) can be made catalytically active by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, the procatalyst according to the metal-ligand complex of formula (I) can be made catalytically active by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. Furthermore, the metal-ligand complex according to formula (I) includes both a procatalyst form that is neutral and a catalyst form that can be positively charged by loss of a monoanionic ligand such as benzyl or phenyl. Activating cocatalysts suitable for use herein include alkylaluminum, polymeric or oligomeric alumoxanes (also known as aluminoxanes), neutral Lewis acids, and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the aforementioned activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means a monoalkylaluminum dihydride or dihalide, a dialkylaluminum hydride or halide, or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum modified methylalumoxane, and isobutylalumoxane.

[0058] The Lewis acid activating cocatalyst may be any of the Lewis acid activating cocatalysts described herein (C1-C 20 In some embodiments, the Group 13 metal compound contains a tri((C1-C2) hydrocarbyl substituent. 20 )hydrocarbyl)-substituted aluminum or tri((C1-C 20 In other embodiments, the Group 13 metal compound is 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. In further embodiments, the Group 13 metal compound is tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tris((C1-C 20 ) hydrocarbyl borates (e.g., trityl tetrafluoroborate) or tri((C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)boranes (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to any of the ((C 20 )Hydrocarbyl)4N + , ((C1-C 20 )hydrocarbyl)3N(H) + , ((C1-C 20 )hydrocarbyl)2N(H)2 + , (C1-C 20 ) HydrocarbylN(H)3 + , or N(H)4 + Each of the nitrogen cations (C1-C 20 ) Hydrocarbyls, when present in two or more occurrences, may be the same or different.

[0059] A combination of neutral Lewis acid activating cocatalysts is tri((C1-C4) alkyl)aluminum and tri((C6-C 18)aryl)boron compounds, particularly tris(pentafluorophenyl)borane. Other embodiments are combinations of such neutral Lewis acid mixtures with polymeric or oligomeric alumoxanes, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymeric or oligomeric alumoxanes. The ratio of the number of moles of (metal-ligand complex):(tris(pentafluorophenylborane):(alumoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluorophenylborane):(alumoxane)] is 1:1:1 to 1:10:30, and in other embodiments is 1:1:1.5 to 1:5:10.

[0060] The catalyst system comprising the metal-ligand complex of formula (I) can be activated to form an active catalyst composition by combining with one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, as well as inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, and combinations thereof.

[0061] In some embodiments, two or more of the aforementioned activating cocatalysts can be used in combination with each other. Specific examples of cocatalyst combinations are mixtures of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate with oligomeric or polymeric alumoxane compounds. The ratio of the total number of moles of the one or more metal-ligand complexes of formula (I) to the total number of moles of the one or more activating cocatalysts is 1:10,000 to 100:1. In some embodiments, this ratio is at least 1:5000, in some other embodiments, at least 1:1000 and not more than 10:1, and in some other embodiments, not more than 1:1. When alumoxane is used alone as the activating cocatalyst, it is preferred that the number of moles of alumoxane used is at least 100 times the number of moles of the metal-ligand complexes of formula (I). When tris(pentafluorophenyl)borane is used alone as the activating cocatalyst, 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 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1. The remaining activating cocatalysts are generally used in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of formula (I).

[0062] Polyolefin The catalyst system described in the previous paragraph is utilized for the polymerization of olefins, primarily ethylene and propylene. In some embodiments, only a single type of olefin or α-olefin is present in the polymerization scheme to produce 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-l-pentene. For example, the 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.

[0063] An ethylene-based polymer, e.g., a homopolymer and / or interpolymer (including copolymer) of ethylene, and optional one or more comonomers, such as an α-olefin, can include at least 50 weight percent of monomer units derived from ethylene. All individual values ​​and subranges encompassed by "from at least 50 weight percent" are disclosed herein as separate embodiments, for example, an ethylene-based polymer, a homopolymer and / or interpolymer (including copolymer) of ethylene, and optional one or more comonomers, such as an α-olefin, can include at least 60 weight percent of monomer units derived from ethylene, at least 70 weight percent of monomer units derived from ethylene, at least 80 weight percent of monomer units derived from ethylene, from 50 to 100 weight percent of monomer units derived from ethylene, or from 80 to 100 weight percent of monomer units derived from ethylene.

[0064] In some embodiments, the ethylene-based polymer can include at least 90 mole percent of monomeric 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 include at least 93 mole percent units derived from ethylene, at least 96 mole percent units derived from ethylene, at least 97 mole percent units derived from ethylene, or alternatively, from 90 to 100 mole percent units derived from ethylene, from 90 to 99.5 mole percent units derived from ethylene, or from 97 to 99.5 mole percent units derived from ethylene.

[0065] In some embodiments of the ethylene-based polymer, the amount of the additional α-olefin is less than 50%, other embodiments include at least 0.5 mole percent (mol%) to 25 mol%, and in further embodiments the amount of the additional α-olefin includes at least 5 mol% to 10 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0066] Any conventional polymerization process may be used to produce the ethylene-based polymers, including, but not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and any combination 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, in series, or any combination thereof.

[0067] In one embodiment, the 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 the catalyst system 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, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of the catalyst system described herein and, optionally, one or more other catalysts. The catalyst system described herein can be used in the first reactor or the second reactor, optionally in combination with one or more other catalysts. In one embodiment, the ethylene-based polymer can be produced 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 the catalyst system described herein.

[0068] In another embodiment, the ethylene-based polymer can be produced in a solution polymerization in a single reactor system, such as a single loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized in the presence of a catalyst system described within this disclosure and optionally one or more cocatalysts, as described in the previous paragraph.

[0069] The ethylene-based polymer may further include 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 include any amount of additives. The ethylene-based polymer may include from about 0 to about 10 weight percent of such additives, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further include a filler, which may include, but is not limited to, organic or inorganic fillers. The ethylene-based polymer may include from about 0 to about 20 weight percent of a filler, such as, for example, 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 compounded with one or more polymers to form a blend.

[0070] In some embodiments, a polymerization process for producing an ethylene-based polymer can include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, the catalyst system incorporating at least one metal-ligand complex of formula (I). Polymers obtained from such catalyst systems incorporating a metal-ligand complex of formula (I) can have a molecular weight of, for example, 0.850 g / cm or less according to ASTM D792, which is incorporated herein by reference in its entirety. 3 ~0.950g / cm 3 , 0.880g / cm 3 ~0.920g / cm 3 , 0.880g / cm 3 ~0.910g / cm 3 , or 0.880 g / cm 3 ~0.900g / cm 3 The density of the sintered body may be 0.01 to 0.01.

[0071] In another embodiment, the polymer obtained from the catalyst system comprising the metal-ligand complex of formula (I) has a melt flow ratio (I 10 / I2), where melt index I2 is measured at 190° C. and a load of 2.16 kg according to ASTM D1238, which is incorporated herein by reference in its entirety, and melt index I 10 is measured at 190° C. and a load of 10 kg according to ASTM D1238. In another embodiment, the melt flow ratio (I 10 / I2) is 5-10, and in others, the melt flow ratio is 5-9.

[0072] 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 to 25, w / M n is defined as M w is the weight average molecular weight, M n is the number average molecular weight. In another embodiment, the polymer resulting from the catalyst system has an MWD of 1 to 6. Another embodiment includes an MWD of 1 to 3, and another embodiment includes an MWD of 1.5 to 2.5.

[0073] Embodiments of the catalyst systems described in this disclosure result in unique polymer properties as a result of the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer.

[0074] All solvents and reagents were obtained from commercial sources and used as received unless otherwise stated. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether are purified by passing through activated alumina and, in some cases, Q-5 reactants. Solvents used in experiments performed in a nitrogen-filled glove box are further dried by storage over activated 4 Å molecular sieves. Moisture-sensitive reaction glassware is dried overnight in an oven before use. NMR spectra are recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analysis is performed using a Waters e2695 separation module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separation is performed on an XBridge C18 3.5 μm 2.1 × 50 mm column using a 5:95 to 100:0 gradient of acetonitrile and water (with 0.1% formic acid as the ionizing agent). HRMS analysis is performed using an Agilent 1290 Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm 2.1 × 50 mm column coupled to an Agilent 6230 TOF mass spectrometer equipped with electrospray ionization. 1 H NMR data are reported as follows: chemical shifts (multiplicities (br=broadline, s=singlet, d=doublet, t=triplet, q=quartet, p=quintet, sex=sexet, sept=septet, and m=multiplet), integrals, and assignments) using residual protons in deuterated solvents as standards. 1 Chemical shifts for H NMR data are reported in ppm downfield from internal tetramethylsilane (TMS, δ scale). 13 C NMR data is 1 Determined with 1 H decoupling and chemical shifts are reported as ppm downfield from tetramethylsilane (TMS, δ scale) using residual carbon in the deuterated solvent as the reference.

[0075] General procedure for PPR screening experiments Polyolefin catalyst screening is performed in a high-throughput parallel polymerization reactor (PPR) system. The PPR system consists of an array of 48 single-cell (6 × 8 matrix) reactors in an inert atmosphere glovebox. Each cell is equipped with a glass insert with an internal working liquid volume of approximately 5 mL. Each cell has independent pressure control, which continuously stirs the liquids in the cells at 800 rpm. Catalyst solutions are prepared by dissolving the appropriate amount of procatalyst in toluene, unless otherwise noted. All liquids (e.g., solvent, 1-octene, chain shuttling agent solution appropriate for the experiment, and catalyst solution) are added to the single-cell reactor via robotic syringes. Gaseous reagents (i.e., ethylene, H2) are added to the single-cell reactor via gas injection ports. Before each run, the reactor is heated to 80 °C, purged with ethylene, and vented.

[0076] A portion of Isopar-E is added to the reactor. The reactor is heated to the run temperature and pressurized with ethylene to the appropriate psig. Toluene solutions of the reagents are added in the following order: (1) 1-octene along with 500 nmol of scavenger MMAO-3A, ​​(2) activators (Cocatalyst-1, Cocatalyst-2, etc.), and (3) catalyst.

[0077] A small amount of Isopar-E is added after each liquid addition so that the total reaction volume is 5 mL after the final addition. Once the catalyst is added, the PPR software begins monitoring the pressure in each cell. The pressure (within approximately 2-6 psig) is maintained by the addition of additional ethylene gas by opening the valve at set point minus 1 psi and closing the valve when the pressure rises above 2 psi. All pressure drops are recorded cumulatively as ethylene "uptake" or "conversion" over the duration of the run or until the uptake or conversion requirement is reached, whichever comes first. Each reaction is quenched by the addition of 10% carbon monoxide in argon for 4 minutes at a pressure of 40-50 psi above the reactor pressure. A shorter "quench time" means a more active catalyst. To prevent the formation of excess polymer in any given cell, the reactions are quenched when a predetermined uptake level (50 psig for the 120°C run, 75 psig for the 150°C run) is reached. After all reactions are quenched, the reactor is cooled to 70° C. The reactor is vented and purged with nitrogen for 5 minutes to remove carbon monoxide, and the tube is removed. The polymer sample was dried in a centrifugal evaporator at 70° C. for 12 hours, weighed to determine the polymer yield, and submitted for IR (1-octene incorporation) and GPC (molecular weight) analysis.

[0078] SymRAD HT-GPC analysis Molecular weight data are determined by analysis on a hybrid Symyx / Dow built robot-assisted dilution high temperature gel permeation chromatography instrument (Sym-RAD-GPC). Polymer samples are dissolved by heating at 160° C. for 120 minutes in 1,2,4-trichlorobenzene (TCB) at a concentration of 10 mg / mL stabilized with 300 parts per million (ppm) butylated hydroxyl toluene (BHT). Each sample was diluted to 1 mg / mL immediately prior to injection of a 250 μL aliquot of sample. The GPC is 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 is performed using a PolyChar IR4 detector in concentration mode. Conventional calibration of narrow polystyrene (PS) standards is utilized with apparent units adjusted to homopolyethylene (PE) using known Mark-Houwink coefficients for PS and PE in TCB at this temperature.

[0079] 1-Octene Incorporation IR Analysis A sample run for HT-GPC analysis precedes the 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 up to 210 minutes, the sample is reheated to remove the magnetic GPC stir bar, and shaken with a glass rod stir bar in a J-KEM Scientific heated robotic shaker. The sample is deposited with heating using a Tecan MiniPrep 75 deposition station, and 1,2,4-trichlorobenzene is evaporated from the deposition wells of the wafer at 160°C under a nitrogen purge. Analysis of 1-octene is performed on the HT silicon wafer using a NEXUS 670 ESPFT-IR.

[0080] Batch Reactor Polymerization Procedure The polymerization reaction in the batch reactor is carried out in a 4 L Parr™ batch reactor. The reactor is heated by an electric heating mantle and cooled by an internal serpentine 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 fitted with a dump valve that transfers the reactor contents to a stainless steel dump pot. The dump pot is pre-filled with a catalyst deactivation solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). Both the pot and the tank are purged with nitrogen and the dump pot is vented to a 30 gallon blowdown tank. All solvents used for the polymerization or catalyst make-up are passed through a solvent purification column to remove any impurities that may affect the polymerization. The 1-octene and IsoparE are passed through two columns, the first containing A2 alumina and the second containing Q5. Ethylene is passed through two columns, the first containing A204 alumina and 4 Å molecular sieves, the second containing the Q5 reactant. The N2 used for transport is passed through a single column containing A204 alumina, 4 Å molecular sieves, and Q5.

[0081] The reactor is first loaded from a shot tank which may contain IsoparE solvent and / or 1-octene depending on the reactor load. The shot tank is filled to the load set point using a lab scale attached to the shot tank. After the liquid feed is added, the reactor is heated to the polymerization temperature set point. If ethylene is used, it is added to the reactor at the reaction temperature to maintain the reaction pressure set point. The amount of ethylene added is monitored by a micromotion flow meter. In some experiments, standard conditions at 120°C are 88g ethylene and 568g 1-octene in 1155g IsoparE, and standard conditions at 150°C are 81g ethylene and 570g 1-octene in 1043g IsoparE.

[0082] The procatalyst and activator are mixed with an appropriate amount of purified toluene to obtain a molar solution. The procatalyst and activator are handled in an inert glove box, drawn into a syringe, and pressure transferred into the catalyst shot tank. The syringe is rinsed three times with 5 mL of toluene. Immediately after the catalyst is added, a run timer is started. If ethylene is used, it is added by Camille to maintain the reaction pressure set point in the reactor. The polymerization reaction is run for 10 minutes, then the agitator is stopped and the bottom dump valve is opened to transfer the reactor contents to a dump pot. The dump pot contents are poured into a tray and placed in a lab hood where the solvent is allowed to evaporate overnight. The tray with the remaining polymer is transferred to a vacuum oven and heated to 140°C under vacuum to remove any remaining solvent. After the tray is cooled to ambient temperature, the polymer yield is measured to measure efficiency and subjected to polymer testing. EXAMPLES

[0083] Examples 1-33 are synthetic procedures for ligand intermediates, ligands, and isolated procatalysts. Ligand structures 1-8 are shown in FIG. 1. Procatalysts 1-16 were synthesized from ligands 1-8. One or more features of the present disclosure are illustrated in view of the following examples.

[0084] Example 1: Synthesis of Procatalyst 1 [ka]

[0085] To a clear, colorless solution of Zr(CH2SiMe3)4 (12.3 mg, 0.0279 mmol, 1.10 equiv) in C6D6 (0.50 mL) in a nitrogen-filled glovebox at 23 °C was added a solution of aminopyridine (12.0 mg, 0.0254 mmol, 1.00 equiv) in C6D6 (1.2 mL) dropwise. The canary yellow solution was stirred vigorously (500 rpm) for 2 h, after which an aliquot was removed and NMR showed complete conversion of the starting ligand to the monoligated complex. The resulting solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and this suspension / concentration process was repeated three more times to remove residual C6D6, filter insoluble impurities, and the canary yellow foam was suspended in pentane (3 mL), stirred vigorously (500 rpm) for 1 min, filtered through a 0.45 μm PTFE submicron filter, rinsed with pentane (3×3 mL), and the filtrate was concentrated to give the zirconium complex as a canary yellow amorphous foam (20.9 mg, 0.0253 mmol, 100%). NMR showed the product.

[0086] 1 H NMR (500MHz, benzene-d6) δ 8.24(s,1H),7.84(dd,J=8.9,0.7Hz,2H),7.80(dd,J=1.9,0.9Hz,2H),7.40(ddd ,J=7.9,3.4,1.5Hz,4H),7.28(t,J=7.7Hz,2H),7.14-7.09(m,1H),6.90(ddd,J=8 .6,7.2,0.6Hz,1H),6.28(dd,J=7.2,0.9Hz,1H),5.85(dd,J=8.6,0.9Hz,1H),4. 77(s,2H),1.33(s,18H),1.24(s,2H),0.62(s,4H),-0.03(s,18H),-0.04(s,9H). 13C NMR (126MHz, benzene-d6) δ 170.84, 155.30, 148.25, 141.82, 140.01, 132.32, 130.33, 129.90, 128.49, 128.41, 126.98, 126.67, 126.49, 124.55, 119.76, 113.96, 103.76, 72.22, 51.93, 34.90, 30.54, 2.42, -0.39.

[0087] Example 2: Synthesis of Procatalyst 2 [ka]

[0088] To a clear, colorless solution of Hf(CH2SiMe3)4 (9.2 mg, 0.0175 mmol, 1.10 equiv) in C6D6 (0.50 mL) in a nitrogen-filled glovebox at 23 °C, a solution of aminopyridine (7.5 mg, 0.0159 mmol, 1.00 equiv) in C6D6 (1.2 mL) was added dropwise. The canary yellow solution was stirred vigorously (500 rpm) for 2 h, after which an aliquot was removed and NMR showed complete conversion of the starting ligand to the monoligated complex. The resulting solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and this suspension / concentration process was repeated three more times to remove residual C6D6, filter insoluble impurities, and the canary yellow foam was suspended in pentane (3 mL), stirred vigorously (500 rpm) for 1 min, filtered through a 0.45 μm PTFE submicron filter, rinsed with pentane (3×3 mL), and the filtrate was concentrated to give the hafnium complex as a canary yellow amorphous foam (14.5 mg, 0.0159 mmol, 100%). NMR showed the product.

[0089] 1H NMR(400MHz,ベンゼン-d6)δ 8.23(s,1H),7.82(dt,J=8.9,0.6Hz,2H),7.76(dt,J=1.7,0.8Hz,2H),7. 41(td,J=4.5,1.9Hz,2H),7.39-7.35(m,2H),7.28-7.23(m,2H),6.88(dd, J=8.6,7.2Hz,2H),6.30(dd,J=7.2,0.9Hz,1H),5.79(dd,J=8.6,0.9Hz,1 H),4.83(s,2H),1.32(s,18H),0.05(s,6H),-0.04(s,18H),-0.06(s,9H). 13 C NMR(101MHz,ベンゼン-d6)δ 158.57,157.42,148.26,147.01,139.87,136.86,130.41,130.14,128.25,128.20,126.70,126 .40,125.82,124.14,121.04,119.75,116.07,105.02,78.34,45.54,34.74,30.58,2.75,-0.40.

[0090] Example 3: Synthesis of プロcatalyst 3

change

[0091] To a clear, colorless solution of Zr(CH2SiMe3)4 (14.0 mg, 0.0316 mmol, 1.15 equiv) in C6D6 (0.56 mL) was added dropwise a solution of aminopyridine (11.0 mg, 0.0275 mmol, 1.00 equiv) in C6D6 (0.44 mL) in a nitrogen-filled glovebox at 23 °C. The canary yellow solution was stirred vigorously (500 rpm) for 2 h, after which an aliquot was removed and NMR showed complete conversion of the starting ligand to the monoligated complex. The resulting solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and this suspension / concentration process was repeated three more times to remove residual C6D6, filter insoluble impurities, and the canary yellow foam was suspended in pentane (3 mL), stirred vigorously (500 rpm) for 1 min, filtered through a 0.45 μm PTFE submicron filter, rinsed with pentane (3×3 mL), and the filtrate was concentrated to give the zirconium complex as a pale yellow amorphous foam (19.3 mg, 0.0257 mmol, 93%). NMR showed the product.

[0092] 1 H NMR(500MHz,benzene-d6)δ 6.79-6.77(m,2H),6.75-6.72(m,2H),6.06(d,J=1.3Hz,1H),5.61(d,J=1.2Hz,1H),3.22(s,2H) ),2.15(s,6H),2.14(s,3H),2.13(s,3H),2.09(s,6H),0.94(s,6H),0.93(s,9H),0.21(s,27H). 13 C NMR (126 MHz, benzene-d6) δ 170.76, 156.31, 155.77, 137.78, 137.36, 136.94, 135.82, 135.14, 134.27, 128.49, 128.18, 112.80, 103.42, 70.99, 60.01, 34.52, 28.40, 20.69, 20.27, 19.96, 2.81.

[0093] Example 4: Synthesis of Procatalyst 4 [ka]

[0094] To a clear, colorless solution of Hf(CH2SiMe3)4 (24.3 mg, 0.0459 mmol, 1.15 equiv) in C6D6 (1.0 mL) was added dropwise a solution of aminopyridine (16.0 mg, 0.0399 mmol, 1.00 equiv) in C6D6 (0.64 mL) in a nitrogen-filled glovebox at 23 °C. The pale golden solution was stirred vigorously (500 rpm) for 2 h, after which an aliquot was removed and NMR showed complete conversion of the starting ligand to the monoligated complex. The resulting solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and this suspension / concentration process was repeated three more times to remove residual C6D6, filter insoluble impurities, and the canary yellow foam was suspended in pentane (3 mL), stirred vigorously (500 rpm) for 1 min, filtered through a 0.45 μm PTFE submicron filter, rinsed with pentane (3×3 mL), and the filtrate was concentrated to give the hafnium complex as a pale yellow amorphous foam (31.3 mg, 0.0372 mmol, 93%). NMR showed the product.

[0095] 1 H NMR(500MHz,benzene-d6)δ 6.79-6.76(m,2H),6.76-6.73(m,2H),6.04(d,J=1.2Hz,1H),5.62(dd,J=1.1,0.6Hz,1H),3.33(s, 2H),2.16(s,6H),2.14(s,3H),2.13(s,3H),2.08(s,6H),0.92(s,9H),0.37(s,6H),0.22(s,27H). 13 C NMR (126 MHz, benzene-d6) δ 169.56, 156.26, 155.98, 137.87, 137.31, 137.00, 135.60, 135.11, 134.27, 128.46, 128.19, 113.05, 103.92, 77.13, 59.44, 34.53, 28.41, 20.69, 20.32, 19.99, 3.20.

[0096] Example 5: Synthesis of Procatalyst 5 [ka]

[0097] To a clear, colorless solution of Zr(CH2SiMe3)4 (15.2 mg, 0.0345 mmol, 1.15 equiv) in C6D6 (1.0 mL) was added dropwise a solution of aminopyridine (11.0 mg, 0.0300 mmol, 1.00 equiv) in C6D6 (0.44 mL) in a nitrogen-filled glovebox at 23 °C. The pale golden solution was stirred vigorously (500 rpm) for 2 h, after which an aliquot was removed and NMR showed complete conversion of the starting ligand to the monoligated complex. The resulting solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and this suspension / concentration process was repeated three more times to remove residual C6D6, filter insoluble impurities, and the canary yellow foam was suspended in pentane (3 mL), stirred vigorously (500 rpm) for 1 min, filtered through a 0.45 μm PTFE submicron filter, rinsed with pentane (3×3 mL), and the filtrate was concentrated to give the zirconium complex as a pale yellow amorphous foam (18.9 mg, 0.0263 mmol, 88%). NMR showed the product.

[0098] 1 H NMR(500MHz,benzene-d6)δ 7.10(s,2H),6.90(ddd,J=8.8,7.2,0.7Hz,1H),6.09(dt,J=7.2,0.8Hz,1H),5.99(dd,J=8.7,0.8Hz,1H),3.24(s,2H),2.98(q, J=6.8Hz,1H),2.83(dt,J=14.6,7.2Hz,2H),1.33(d,J=6.8Hz,6H),1.24(dt,J=7.1,1.0Hz,6H),1.05(d,J=6.7Hz,6H),0.95(br s,15H),0.21(s,27H). 13C NMR (126 MHz, benzene-d6) δ 171.63, 155.93, 149.51, 146.07, 140.49, 134.18, 120.96, 112.87, 102.90, 72.18, 60.46, 34.47, 34.38, 30.43, 28.70, 27.03, 26.03, 23.93, 22.76, 2.80.

[0099] Example 6: Synthesis of Procatalyst 6 [ka]

[0100] To a clear, colorless solution of Hf(CH2SiMe3)4 (26.0 mg, 0.0491 mmol, 1.20 equiv) in C6D6 (1.0 mL) was added dropwise a solution of aminopyridine (15.0 mg, 0.0409 mmol, 1.00 equiv) in C6D6 (0.60 mL) in a nitrogen-filled glovebox at 23 °C. The pale golden solution was stirred vigorously (500 rpm) for 2 h, after which an aliquot was removed and NMR showed complete conversion of the starting ligand to the monoligated complex. The resulting solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and this suspension / concentration process was repeated three more times to remove residual C6D6, filter insoluble impurities, and the canary yellow foam was suspended in pentane (3 mL), stirred vigorously (500 rpm) for 1 min, filtered through a 0.45 μm PTFE submicron filter, rinsed with pentane (3×3 mL), and the filtrate was concentrated to give the hafnium complex as a pale yellow amorphous foam (31.3 mg, 0.0388 mmol, 95%). NMR showed the product.

[0101] 1H NMR(500MHz,benzene-d6)δ 7.11(br s,2H),6.90(dd,J=8.8,7.2Hz,1H),6.14(dd,J=7.2,0.8Hz,1H),5.97(dd,J=8.8,0.9Hz,1H),3.34(s,2H),2.87-2.73(m,3 H),1.34(d,J=6.8Hz,6H),1.24(d,J=6.9Hz,6H),1.04(d,J=6.7Hz,6H),0.93(d,J=2.4Hz,9H),0.36(s,6H),0.21(s,27H). 13 C NMR (126 MHz, benzene-d6) δ 170.30, 155.78, 149.61, 146.10, 140.59, 134.00, 120.98, 113.10, 103.38, 78.31, 59.91, 34.48, 34.41, 30.45, 28.71, 26.14, 23.92, 22.66, 3.15.

[0102] Example 7: Synthesis of Procatalyst 7 [ka]

[0103] In a nitrogen-filled glove box at 23 °C, a solution of aminopyridine (20.0 mg, 0.0670 mmol, 1.00 equiv) in C6D6 (0.80 mL) was added dropwise to a clear, colorless solution of Zr(CH2SiMe3)4 (38.3 mg, 0.0871 mmol, 1.30 equiv) in anhydrous, deoxygenated C6D6 (1.0 mL). The pale golden solution was stirred vigorously (1000 rpm) for 1 h, concentrated, suspended in anhydrous, deoxygenated pentane (3 mL), concentrated, and the suspension / concentration process was repeated two more times to remove residual C6D6 and Me4Si, and the resulting mixture was suspended in pentane (3 mL), filtered through a 0.20 μm PTFE filter, rinsed with pentane (3 × 3 mL), and the filtrate was concentrated to give the zirconium complex (42.5 mg, 0.0654 mmol, 98%). NMR showed the product.

[0104] 1H NMR(500MHz,benzene-d6)δ 6.94(ddd,J=8.6,7.2,0.6Hz,1H),6.72(s,2H),5.86-5.82(m,1H),5.80(dd,J=8. 6,0.9Hz,1H),3.09(s,2H),2.11(s,3H),2.09(s,6H),0.89(s,6H),0.20(s,27H). 13 C NMR (126 MHz, benzene-d6) δ 169.89, 156.39, 141.68, 137.80, 135.79, 135.07, 128.46, 110.59, 102.08, 70.85, 40.53, 20.66, 20.15, 2.79.

[0105] Example 8: Synthesis of Procatalyst 8 [ka]

[0106] To a clear, colorless solution of Hf(CH2SiMe3)4 (32.0 mg, 0.0603 mmol, 1.20 equiv) in C6D6 (1.0 mL) was added dropwise a solution of aminopyridine (15.0 mg, 0.0503 mmol, 1.00 equiv) in C6D6 (0.60 mL) in a nitrogen-filled glovebox at 23 °C. The pale golden solution was stirred vigorously (500 rpm) for 2 h, after which an aliquot was removed and NMR showed complete conversion of the starting ligand to the monoligated complex. The resulting solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and this suspension / concentration process was repeated three more times to remove residual C6D6, filter insoluble impurities, and the canary yellow foam was suspended in pentane (3 mL), stirred vigorously (500 rpm) for 1 min, filtered through a 0.45 μm PTFE submicron filter, rinsed with pentane (3×3 mL), and the filtrate was concentrated to give the hafnium complex as a pale yellow amorphous foam (35.4 mg, 0.0479 mmol, 95%). NMR showed the product.

[0107] 1H NMR(500MHz,benzene-d6)δ 6.94(dd,J=8.6,7.2Hz,1H),6.74-6.70(m,2H),5.88(dd,J=7.2,0.9Hz,1H),5.77(dd,J=8.6,0.9Hz ,1H),3.15(s,2H),2.10(s,3H),2.09(s,3H),2.09(s,3H),0.31(s,6H),0.20(s,27H),0.08(s,9H). 13 C NMR (126 MHz, benzene-d6) δ 168.72, 156.30, 141.88, 137.89, 135.58, 135.05, 128.45, 128.19, 110.75, 102.41, 77.07, 39.91, 20.65, 20.20, 20.14, 3.16, -1.32.

[0108] Example 9: Synthesis of Procatalyst 9 [ka]

[0109] To a clear, colorless solution of Zr(CHSiMe) (33.8 mg, 0.0707 mmol, 1.20 equiv) in anhydrous, deoxygenated C6D6 (1.0 mL) was added dropwise a solution of aminopyridine (15.0 mg, 0.0590 mmol, 1.00 equiv) in C6D6 (0.60 mL) in a nitrogen-filled glove box at 23 °C. The solution of canary gold was stirred vigorously (1000 rpm) for 2 h, an aliquot was removed, NMR showed complete conversion of the starting ligand, the solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and the suspension / concentration process was repeated two more times to remove residual C6D6 and Me4Si, the resulting mixture was filtered through a 0.20 μm PTFE filter, suspended in pentane (3 mL), rinsed with pentane (3×3 mL), and the filtrate was concentrated to give the zirconium complex as a canary yellow foam (35.7 mg, 0.0589 mmol, 99%). NMR showed pure product.

[0110] 1H NMR(500MHz,benzene-d6)δ 6.96-6.92(m,1H),6.71(d,J=1.4Hz,2H),5.92(dt,J=7.2,0.8Hz,1H),5.82-5.78(m,1H),3.36( hept,J=6.5Hz,1H),2.14(s,3H),2.08(s,6H),1.24(d,J=6.4Hz,6H),0.89(s,6H),0.17(s,27H). 13 C NMR (126 MHz, benzene-d6) δ 170.16, 157.14, 141.61, 137.71, 136.21, 135.18, 128.27, 111.86, 102.44, 69.17, 47.59, 23.23, 20.70, 20.19, 2.76.

[0111] Example 10: Synthesis of procatalyst 11 [ka]

[0112] To a clear, colorless solution of Zr(CHSiMe) (18.2 mg, 0.0413 mmol, 1.30 equiv) in anhydrous, deoxygenated C6D6 (1.0 mL) was added dropwise a solution of aminopyridine (15.0 mg, 0.0317 mmol, 1.00 equiv) in C6D6 (0.60 mL) in a nitrogen-filled glove box at 23 °C. The solution of canary gold was stirred vigorously (1000 rpm) for 1 h, an aliquot was removed, NMR showed complete conversion of the starting ligand, the solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and the suspension / concentration process was repeated two more times to remove residual C6D6 and Me4Si, the resulting mixture was filtered through a 0.20 μm PTFE filter, suspended in pentane (3 mL), rinsed with pentane (3×3 mL), and the filtrate was concentrated to give the zirconium complex as a canary yellow foam (25.7 mg, 0.0311 mmol, 98%). NMR showed product.

[0113] 1H NMR(500MHz,ベンゼン-d6)δ 8.23(s,1H),7.87-7.76(m,4H),7.42(ddd,J=9.4,7.3,1.9Hz,4H),7.26(t,J=7.7Hz,2H),7.13-7.08(m,1H),6.93(dd,J=8.7,7.3Hz,1H), 6.27(dd,J=7.2,0.9Hz,1H),5.89(dd,J=8.7,0.9Hz,1H),4.85-4.62(m,2H),1.33(s,9H),1.32(s,9H),0.70-0.58(m,6H),-0.02(s,27H). 13 C NMR(126MHz,ベンゼン-d6)δ 170.82,154.99,147.95,147.17,141.78,140.03,131.96,131.31,130.34,129.96,128.70,128.54,128.36,126.76 ,126.66,125.82,125.78,124.76,122.84,119.93,113.93,103.72,72.19,52.32,34.87,34.50,30.59,30.51,2.49.

[0114] Example 11: Synthesis of プロcatalyst 12

change

[0115] To a clear, colorless solution of Hf(CHSiMe) (18.1 mg, 0.0344 mmol, 1.30 equiv) in anhydrous, deoxygenated C6D6 (1.0 mL) was added dropwise a solution of aminopyridine (12.5 mg, 0.0265 mmol, 1.00 equiv) in C6D6 (0.50 mL) in a nitrogen-filled glove box at 23 °C. The solution of canary gold was stirred vigorously (1000 rpm) for 1 h, an aliquot was removed, NMR showed complete conversion of the starting ligand, the solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and the suspension / concentration process was repeated two more times to remove residual C6D6 and Me4Si, the resulting mixture was filtered through a 0.20 μm PTFE filter, suspended in pentane (3 mL), rinsed with pentane (3×3 mL), and the filtrate was concentrated to give the hafnium complex as a canary yellow foam (22.5 mg, 0.0247 mmol, 93%). NMR showed product.

[0116] 1 H NMR(500MHz,benzene-d6)δ 8.24(s,1H),7.87-7.78(m,3H),7.74(dt,J=1.8,0.8Hz,1H),7.45-7.39(m,3H),7.28-7.23( m,2H),7.14-7.10(m,1H),7.09(d,J=7.4Hz,1H),6.92(ddd,J=8.6,7.2,0.5Hz,1H),6.31(dd, J=7.2,0.9Hz,1H),5.86(dd,J=8.6,0.8Hz,1H),4.91(d,J=16.2Hz,1H),4.75(d,J=16.2Hz,1 H),1.33(s,9H),1.32(s,9H),0.13(d,J=12.0Hz,3H),0.03(d,J=12.2Hz,3H),-0.02(s,27H). 13C NMR (126MHz, benzene-d6) δ 169.43, 154.88, 147.96, 147.18, 141.92, 139.91, 131.71, 131.32, 130.35, 129.97, 128.60, 128.54, 128.37, 126.76, 126.52, 125.83, 124.78, 122.85, 119.99, 114.23, 104.17, 78.24, 51.99, 34.87, 34.51, 30.59, 30.50, 2.84.

[0117] Example 12: Synthesis of procatalyst 13 [ka]

[0118] To a clear, colorless solution of Zr(CHSiMe) (14.6 mg, 0.0333 mmol, 1.30 equiv) in anhydrous, deoxygenated C6D6 (1.0 mL) in a nitrogen-filled glove box at 23 °C was added dropwise a solution of aminopyridine (12.0 mg, 0.0256 mmol, 1.00 equiv) in C6D6 (0.48 mL). The canary gold solution was stirred vigorously (1000 rpm) for 20 min, an aliquot was removed, NMR showed complete conversion of the starting ligand, the solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and the suspension / concentration process was repeated two more times to remove residual C6D6 and Me4Si, the resulting mixture was filtered through a 0.20 μm PTFE filter, suspended in pentane (3 mL), rinsed with pentane (3×3 mL), and the filtrate was concentrated to give the zirconium complex as a canary yellow foam (20.2 mg, 0.0246 mmol, 96%). NMR showed pure product.

[0119] 1H NMR(500MHz,benzene-d6)δ 8.22(s,1H),7.89-7.78(m,4H),7.46-7.39(m,2H),7.10-7.03(m,1H),6.23(dd,J=7.2,0.9Hz,1H),5.98(dd,J=8.7,0.9Hz,1 H),3.25(d,J=15.1Hz,1H),3.08(d,J=15.1Hz,1H),1.32(s,9H),1.31(s,9H),0.66-0.57(m,6H),0.17(s,6H),0.04(s,27H). 13 C NMR (126MHz, benzene-d6) δ 169.94, 154.84, 147.80, 147.11, 141.51, 132.15, 131.30, 130.37, 129.93, 128.57, 128.35, 125.96, 125.74, 124.75, 122.88, 120.10, 112.61, 102.78, 71.85, 40.60, 34.85, 34.50, 30.60, 30.55, 2.65, -1.32.

[0120] Example 13: Synthesis of procatalyst 14 [ka]

[0121] To a clear, colorless solution of Hf(CHSiMe) (27.8 mg, 0.0527 mmol, 1.30 equiv) in anhydrous, deoxygenated C6D6 (1.0 mL) in a nitrogen-filled glove box at 23 °C was added dropwise a solution of aminopyridine (19.0 mg, 0.0405 mmol, 1.00 equiv) in C6D6 (0.76 mL). The canary gold solution was stirred vigorously (1000 rpm) for 30 min, an aliquot was removed, NMR showed complete conversion of the starting ligand, the solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and the suspension / concentration process was repeated two more times to remove residual C6D6 and Me4Si, the resulting mixture was filtered through a 0.20 μm PTFE filter, suspended in pentane (3 mL), rinsed with pentane (3×3 mL), and the filtrate was concentrated to give the zirconium complex as a canary yellow foam (36.2 mg, 0.0399 mmol, 98%). NMR showed product.

[0122] 1 H NMR (400MHz, benzene-d6) δ 8.21(s,1H),7.88-7.79(m,3H),7.76(dt,J=1.9,0.8Hz,1H),7.43(ddd,J=16.8,9 .1,1.8Hz,2H),7.06(dd,J=8.7,7.2Hz,1H),6.25(dd,J=7.2,0.8Hz,1H),5.93(dd ,J=8.7,0.9Hz,1H),3.30(d,J=15.2Hz,1H),3.12(d,J=15.2Hz,1H),1.30(s,9H), 1.30(s,9H),0.16(s,2H),0.14(s,9H),0.04(s,2H),0.01(s,2H),-0.00(s,27H). 13 C NMR (101MHz, benzene-d6) δ 168.75, 154.76, 147.77, 147.10, 141.64, 131.93, 131.28, 130.36, 129.93, 128.47, 128.35, 126.05, 125.71, 124.77, 122.87, 120.14, 112.84, 103.06, 77.83, 39.91, 34.84, 34.50, 30.58, 30.53, 3.00, -1.36.

[0123] Example 14: Synthesis of procatalyst 15 [ka]

[0124] To a solution of Zr(CHSiMe) (20.9 mg, 0.0474 mmol, 1.30 equiv) in anhydrous, deoxygenated C6D6 (1.0 mL) was added a solution of aminopyridine (16.0 mg, 0.0365 mmol, 1.00 equiv) in C6D6 (0.64 mL) dropwise at 23 °C in a nitrogen-filled glove box. The pale golden solution was stirred vigorously (1000 rpm) for 20 min, an aliquot was removed, NMR showed complete consumption of the starting ligand, the canary yellow solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and the suspension / concentration process was repeated two more times to remove residual C6D6 and Me4Si, the resulting mixture was filtered through a 0.20 μm PTFE filter, suspended in pentane (3 mL), rinsed with pentane (3×3 mL), and the filtrate was concentrated to give the zirconium complex (28.6 mg, 0.0362 mmol, 99%). NMR showed product.

[0125] 1 H NMR(500MHz,benzene-d6)δ 8.22(s,1H),7.87-7.77(m,4H),7.41(td,J=9.5,2.0Hz,2H),7.08(ddd,J=8.8,7.2,0.6Hz,1H),6.28(dt,J=7.1,0.8Hz,1H),6.01(d,J=8.7Hz, 1H),3.29(d,J=7.2Hz,2H),1.99(hept,J=6.8Hz,1H),1.32(s,9H),1.30(s,9H),1.01(dd,J=6.6,5.4Hz,6H),0.66-0.55(m,6H),0.00(s,27H). 13C NMR (126MHz, benzene-d6) δ 170.65, 155.02, 147.88, 147.12, 141.58, 132.10, 131.30, 130.35, 129.88, 128.71, 128.35, 125.90, 125.74, 124.74, 122.85, 120.03, 113.24, 102.77, 71.75, 56.64, 34.83, 34.50, 30.61, 30.52, 29.24, 20.74, 20.67, 2.58.

[0126] Example 15: Synthesis of procatalyst 16 [ka]

[0127] In a nitrogen-filled glove box at 23 °C, a solution of Hf(CH2SiMe3)4 (20.3 mg, 0.0385 mmol, 1.30 equiv.) in anhydrous, deoxygenated C6D6 (1.0 mL) was added dropwise with a solution of aminopyridine (13.0 mg, 0.0296 mmol, 1.00 equiv.) in C6D6 (0.52 mL). The pale golden solution was stirred vigorously (1000 rpm) for 30 min, concentrated, suspended in anhydrous, deoxygenated pentane (3 mL), concentrated, and the suspension / concentration process was repeated two more times to remove residual C6D6 and Me4Si, and the resulting mixture was suspended in pentane (3 mL), filtered through a 0.20 μm PTFE filter, rinsed with pentane (3 × 3 mL), and the filtrate was concentrated to give the hafnium complex (25.4 mg, 0.0289 mmol, 98%). NMR showed the product.

[0128] 1H NMR(400MHz,benzene-d6)δ 8.21(s,1H),7.85-7.74(m,4H),7.44-7.38(m,2H),7.10-7.03(m,1H),6. 31(dt,J=7.2,0.9Hz,1H),5.97(dt,J=8.7,0.9Hz,1H),3.36(d,J=7.2Hz, 2H),1.94(hept,J=6.7Hz,2H),1.31(s,9H),1.29(s,9H),0.97(ddd,J=6. 7,5.8,0.9Hz,6H),0.44(s,2H),0.16(s,2H),0.15(s,2H),0.01(s,27H). 13 C NMR (101MHz, benzene-d6) δ 169.37, 154.90, 147.86, 147.12, 141.69, 131.85, 131.28, 130.35, 129.87, 128.61, 128.36, 125.98, 125.71, 124.76, 122.85, 120.06, 113.48, 103.12, 77.83, 56.16, 34.82, 34.49, 30.60, 30.51, 29.11, 20.66, 20.58, 2.93.

[0129] Example 16: Synthesis of intermediates to ligands 1 and 6-8 [ka]

[0130] In a nitrogen-filled glove box, to a suspension of anthracene (50.0 g, 280.53 mmol, 1.00 equiv.) and t-BuCl (90.1 mL, 813.54 mmol, 2.90 equiv.) in anhydrous CHCl3 (200 mL) at 23 °C was added solid AlCl3 (1.81 g, 13.61 mmol, 0.05 equiv.). The mixture was placed in a glass coil condenser and heated to 50 °C. After stirring (500 rpm) for 18 h, the resulting cloudy solution was removed from the mantle and allowed to cool to ambient temperature, and solid 2,6-di-t-butylanthracene crystallized from solution, filtered with suction, washed with CHCl3 (3 × 10 mL), collected, and dried in vacuum to give the product as a pale yellow crystalline solid (37.54 g, 129.25 mmol, 46%). The resulting filtrate was concentrated, suspended in acetone (50 mL), stirred (500 rpm) for 5 min, suction filtered, rinsed with acetone (3×20 mL), this process was repeated two more times, and the resulting filtrate was concentrated to give 2,7-di-t-butylanthracene as a pink solid (12.54 g, 43.174 mmol, 15%). NMR showed both products.

[0131] Characterization of 2,7-di-t-butylanthracene: 1 H NMR(400MHz,CDCl3)δ 8.40(d,J=1.0Hz,1H),8.34(d,J=1.1Hz,1H),7.98(d,J=0.8Hz,1H),7.96 -7.92(m,3H),7.60(d,J=2.0Hz,1H),7.58(d,J=2.0Hz,1H),1.52(s,18H).

[0132] Characterization of 2,6-di-t-butylanthracene: 1 H NMR(400MHz,CDCl3)δ 8.33(d,J=1.3Hz,2H),7.94(d,J=8.9Hz,2H),7.89(d,J=2.0Hz,2H),7.56(dd,J=9.0,2.0Hz,2H),1.48(s,18H). 13C NMR(101MHz,CDCl3)δ 147.28,131.62,130.51,127.70,125.33,124.65,122.28,34.87,30.98.

[0133] Example 17: Synthesis of ligands 6-8 from intermediates [ka]

[0134] To a solution of di-t-butylanthracene (3.000 g, 10.329 mmol, 1.00 equiv) in anhydrous CHCl (80 mL) under nitrogen at 23° C. was added a solution of 1,3-dibromo-5,5-dimethylhydantoin (1.477 g, 5.168 mmol, 0.50 equiv) in MeCN (30 mL) dropwise over 30 min. After stirring (500 rpm) for 2 h at 23° C., the light brown mixture was concentrated, suspended in methanol (50 mL), stirred for 10 min, and the resulting insoluble yellow mixture was suction filtered and the yellow solid was washed with methanol (3×10 mL), collected, and recrystallized from ethanol to give bromoanthracene as a pale yellow solid (2.080 g, 5.632 mmol, 54%). NMR showed the product.

[0135] 1 H NMR(400MHz,CDCl3)δ 8.43(dt,J=9.3,0.8Hz,1H),8.39(dt,J=1.8,0.8Hz,1H),8.34(s,1H),7.96-7.88(m,1H),7.87- 7.82(m,1H),7.68(dd,J=9.3,2.0Hz,1H),7.58(dd,J=8.9,1.9Hz,1H),1.48(s,9H),1.45(s,9H).

[0136] Example 18: Synthesis of Ligand 1 from Intermediates [ka]

[0137] To a pale yellow slight suspension of di-t-butylanthracene (1.035 g, 3.563 mmol, 1.00 equiv) in CHCl / MeCN (50 mL, 1:1) at 23° C. was added solid dibromo-dimethylhydantoin (0.510 g, 1.782 mmol, 0.50 equiv) all at once. At this point the dark bright yellow suspension was stirred (500 rpm) for 90 min, after which the mixture was concentrated, suspended in MeOH (30 mL), placed in a heated mantle at 70° C. and stirred vigorously (1000 rpm) for 30 min, then the bright yellow mixture was slowly and gradually cooled to 23° C., suction filtered, and the resulting solid was washed with MeOH (4×10 mL) and dried under reduced pressure to give bromo-di-t-butylanthracene (0.623 g, 1.687 mmol, 47%) as an off-white powder. NMR showed pure product.

[0138] 1 H NMR (400MHz, chloroform-d) δ 8.40(dt,J=1.6,0.7Hz,2H),8.31(s,1H),7.90(dt,J=8.9,0.6Hz,2H),7.56(dd,J=8.8,1.8Hz,2H),1.47(s,18H). 13 C NMR (101 MHz, chloroform-d) δ 149.61, 130.53, 130.51, 128.26, 125.81, 124.83, 122.25, 121.90, 35.41, 30.93.

[0139] Example 19: Synthesis of ligands 6-8 from intermediates [ka]

[0140] In a nitrogen-filled glove box at -35 °C (pre-cooled for 16 h), solid anthracenyl bromide (1.000 g, 2.708 mmol, 1.00 equiv) was added to a pre-cooled solution of t-BuLi (5.0 mL, 8.124 mmol, 3.00 equiv, 1.7 M in pentane) in anhydrous, deoxygenated pentane (25 mL). A pre-cooled solution of pentane / Et2O (10 mL, 1:1) was then added dropwise rapidly with vigorous stirring (1000 rpm). The golden mixture was placed in a freezer (-35 °C) for 4 h, after which neat i-PrOBPin (1.10 mL, 5.416 mmol, 2.00 equiv) was added to the golden brown mixture via syringe. The pale yellow heterogeneous mixture was stirred at 23° C. for 3 h, i-PrOH (3 mL) was added, the mixture was removed from the glove box, water (20 mL) and Et2O (30 mL) were added, the biphasic mixture was stirred for 2 min, poured into a separatory funnel, separated, the organic phase was washed with water (2×25 mL), the remaining organic phase was extracted with Et2O (2×25 mL), combined, dried over solid Na2SO4, decanted, concentrated, the resulting pale yellow mixture was suspended in hexanes (20 mL), suction filtered through silica gel, rinsed with hexanes (4×25 mL), then with CHCl2 (4×25 mL), and the resulting filtrate solution was concentrated to give the anthracenyl boropinacolate ester (1.104 g, 2.653 mmol, 98%) as a pale yellow foam. NMR indicated product. This material was used in the next reaction without further purification.

[0141] 1 H NMR (400 MHz, chloroform-d) δ 8.42-8.38 (m, 3H), 7.93 (dd, J = 8.9, 2.2 Hz, 1H), 7.87 (d, J = 2.2 Hz, 1H), 7.64-7.57 (m, 1H), 7.53 (dt, J = 9.0, 1.7 Hz, 1H), 1.59 (s, 12H), 1.47 (s, 9H), 1.46 (s, 9H). 13C NMR (101 MHz, chloroform-d) δ 147.36, 146.64, 135.83, 134.76, 131.02, 129.91, 128.67, 128.29, 127.88, 125.31, 124.32, 122.88, 122.75, 84.15, 35.29, 34.77, 31.02, 30.95, 25.28.

[0142] Example 20: Synthesis of intermediates for ligand 1 [ka]

[0143] A solution of bromoanthracene (1.000 g, 2.707 mmol, 1.00 equiv) in anhydrous, deoxygenated THF (5 mL) was placed in a -78 °C cooling bath for 1 h, then a solution of n-BuLi (1.80 mL, 2.98 mmol, 1.10 equiv, titrated at 1.6 M in hexanes) was added dropwise, then the solution was placed in an ice-water bath and stirred (500 rpm) for 5 h, i-ProBPin (0.7 mL, 3.52 mmol, 1.30 equiv) was added anhydrous, and the mixture was allowed to cool for 16 h. The mixture was allowed to warm gradually to 23 °C over a period of time, water (2 mL) was added, diluted with CHCl (10 mL), the mixture was poured into a separatory funnel, fractionated, the organic layer was washed with water (3 x 50 mL), the residual organics were extracted from the aqueous layer using CHCl (3 x 25 mL), combined, concentrated onto Celite, and purified by silica gel chromatography with hexane-10% EtOAC in hexane to give the boropinacolate ester as a white solid (0.94 g, 2.257 mmol, 83%). NMR showed the product.

[0144] 1 H NMR(400MHz,chloroform-d)δ 8.33(ddt,J=12.8,1.8,0.7Hz,3H),7.91(dt,J=8.9,0.6Hz,2H),7.52(dd,J=8.9,1.9Hz,2H),1.60(s,12H),1.46(s,18H). 13C NMR (101 MHz, chloroform-d) δ 147.46, 136.17, 129.47, 128.31, 128.06, 124.09, 122.64, 84.08, 31.04, 25.38.

[0145] Example 21: Synthesis of intermediates to ligands 6-8 [ka]

[0146] To a mixture of boropinacolate ester (2.800 g, 6.724 mmol, 1.00 equiv), K3PO4 (4.34 g, 20.446 mmol, 3.04 equiv), Pd(PPh3)4 (0.390 g, 0.3375 mmol, 0.05 equiv) and dibromopyridine (2.420 g, 10.216 mmol, 1.52 equiv) was added deoxygenated toluene (100 mL) and water (15 mL) under nitrogen, the mixture was placed in a heating mantle at 100 °C and stirred (500 rpm) for 72 min. The mixture was removed from the mantle and cooled to 23 °C, water (25 mL) and EtOAc (25 mL) were added, the biphasic mixture was poured into a separatory funnel, partitioned, the organic layer was washed with water (1 x 25 mL), the residual organics were extracted from the aqueous layer (1 x 25 mL), combined, dried over solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexane-2% EtOAc in hexane to give the anthracenyl bromopyridine (2.500 g, 5.600 mmol, 83%). NMR showed the product.

[0147] 1 H NMR (400 MHz, chloroform-d) δ 8.44 (s, 1H), 7.95 (dq, J = 8.9, 0.6 Hz, 1H), 7.92-7.87 (m, 1H), 7.75 (ddd, J = 8.0, 7.4, 0.7 Hz, 1H), 7.63 (dt, J = 8.0, 0.8 Hz, 1H), 7.58-7.51 (m, 2H), 7.51-7.46 (m, 3H), 1.43 (s, 9h), 1.31 (s, 9H). 13C NMR (101 MHz, chloroform-d) δ 159.75, 148.00, 147.07, 142.09, 138.35, 132.37, 131.13, 130.09, 129.57, 128.66, 128.06, 127.34, 126.59, 125.86, 125.67, 125.22, 124.60, 122.62, 119.62, 35.08, 34.80, 30.90, 30.76.

[0148] Example 22: Synthesis of intermediates to ligand 1 [ka]

[0149] In a nitrogen filled glove box at 23 °C, to a solution of anthracene (3.000 g, 8.122 mmol, 1.00 equiv) in anhydrous deoxygenated THF (30 mL) was added magnesium turnings (0.79 g, 32.504 mmol, 4.00 equiv), followed by 1,2-dibromoethane (20 μL), the mixture was then placed in a heating mantle at 50 °C and stirred for 16 h, after which the solution was added to a solution of 2,6-dibromopyridine (2.890 g, 12.200 mmol, 1.50 equiv), PCy3 (5.0 mg, 0.01783 mmol, 0.002 equiv) and nickel(II) bromide ethylene glycol dimethyl ether complex (3.0 mg, 0.00972 mmol, 0.001 equiv) in anhydrous deoxygenated THF (50 mL). The solution was placed in a 60° C. heated mantle and stirred (500 rpm) for 24 h, removed from the mantle, cooled slowly to ambient temperature, removed from the glovebox, water (50 mL) and EtOAc (50 mL) were added, the mixture was poured into a separatory funnel, fractionated, the organic layer was washed with water (2×25 mL), the organic layer was dried over solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexane-2% EtOAc in hexane to give the bromopyridine (3.510 g, 7.862 mmol, 97%). NMR showed the product.

[0150] 1H NMR (400 MHz, chloroform-d) δ 8.41 (s, 1H), 8.00-7.88 (m, 2H), 7.81-7.70 (m, 1H), 7.64 (dt, J = 7.9, 0.8 Hz, 1H), 7.60-7.42 (m, 5H), 1.48-1.12 (s, 18H). 13 C NMR (101 MHz, chloroform-d) δ 159.86, 148.18, 142.02, 138.31, 132.52, 130.03, 129.65, 128.14, 126.98, 126.50, 125.94, 124.37, 119.63, 35.11, 30.78.

[0151] Example 23: Synthesis of Ligand 1 [ka]

[0152] To a mixture of bromopyridine (0.100 g, 0.22 mmol, 1.00 equiv), NaOt-Bu (64.9 mg, 0.67 mmol, 3.00 equiv), Pd2dba3 (10.3 mg, 0.01 mmol, 0.05 equiv) and rac-BINAP (13.9 mg, 0.02 mmol, 0.10 equiv) in anhydrous, deoxygenated toluene (25 mL) at 23 °C in a nitrogen filled glove box, benzylamine (0.73 mL, 6.72 mmol, 1.50 equiv) was added and the mixture was placed in a heated mantle at 100 °C and stirred (500 rpm) for 3 h, resulting in a brown solid. The mixture was removed from the mantle, allowed to cool to ambient temperature, removed from the glovebox, water (20 mL) and EtOAc (20 mL) were added, the biphasic mixture was poured into a separatory funnel, partitioned, the organic layer was washed with water (2×10 mL), the residual organics were extracted using EtOAc (2×10 mL), combined, dried over solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexanes-15% EtOAc in hexanes to give the aminopyridine as a pale yellow amorphous foam (11.6 mg, 0.023 mmol, 11%). NMR showed the product.

[0153] 1H NMR(400MHz,クロロホルム-d)δ 8.37(d,J=1.0Hz,1H),7.94(dt,J=8.9,0.7Hz,2H),7.70(dq,J=1.7,0.8Hz,2H),7.66-7.59(m,1H),7.52(dd,J=8.9,1.9Hz,2H),7. 39-7.25(m,5H),6.84(dt,J=7.1,0.7Hz,1H),6.46(dt,J=8.4,0.8Hz,1H),5.36-5.21(m,1H),4.51(d,J=6.1Hz,2H),1.35(s,18H). 13 C NMR(101MHz,クロロホルム-d)δ 158.74,157.03,147.34,139.26,137.61,135.16,129.99,129.83,128.58,127.9 4,127.12,127.09,125.87,124.18,120.52,116.46,104.28,46.36,35.06,30.88.

[0154] Example 24: Synthesis of Coordinator 6

change

[0155] To a mixture of bromopyridine (2.000 g, 4.48 mmol, 1.00 equiv), NaOt-Bu (1.298 g, 13.44 mmol, 3.00 equiv), Pd2dba3 (0.205 g, 0.22 mmol, 0.05 equiv), and rac-BINAP (0.279 g, 0.45 mmol, 0.10 equiv) in anhydrous, deoxygenated toluene (25 mL) at 23 °C in a nitrogen-filled glove box, benzylamine (0.73 mL, 6.72 mmol, 1.50 equiv) was added and the mixture was placed in a heated mantle at 100 °C and stirred (500 rpm) for 3 h. The colored mixture was removed from the mantle and allowed to cool to ambient temperature, removed from the glovebox, water (20 mL) and EtOAc (20 mL) were added, the biphasic mixture was poured into a separatory funnel, partitioned, the organic layer was washed with water (2×10 mL), the residual organics were extracted using EtOAc (2×10 mL), combined, dried over solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexanes-15% EtOAc in hexanes to give the aminopyridine as a pale yellow amorphous foam (1.70 g, 3.597 mmol, 80%).

[0156] 1 H NMR(500MHz,chloroform-d)δ 8.22(s,1H),8.06(dd,J=2.0,1.0Hz,1H),7.98(dd,J=9.2,0.9Hz,1H),7.88(d,J =8.9Hz,1H),7.85(d,J=2.0Hz,1H),7.44(dd,J =8.9,1.9Hz,1H),7.30(dd,J=9.2,2.0Hz,1H),7.18(dd,J=8.4,7.2Hz,1H),7.12(d,J=3.1Hz,2H),7.06-7.04 m,3H),6.74(dd,J=7.2,0.8Hz,1H),6.01(dd,J=8.4,0.8Hz,1H),4.66(s,1H),4.26-3.85(m,2H),1.31(s,9H),1.25(s,9H). 13C NMR (101 MHz, chloroform-d) δ 158.65, 157.18, 146.86, 146.53, 139.85, 136.91, 136.11, 131.57, 130.51, 129.92, 129.10, 128.22, 128.14, 127.35, 126.89, 126.63, 124.71, 124.33, 122.49, 121.01, 115.91, 105.09, 45.57, 34.75, 34.43, 30.63, 30.61.

[0157] Example 25: Synthesis of Ligand 7 [ka]

[0158] To a mixture of bromopyridine (2.840 g, 6.36 mmol, 1.00 equiv), NaOt-Bu (1.834 g, 19.08 mmol, 3.00 equiv), Pd2dba3 (0.291 g, 0.32 mmol, 0.05 equiv), and rac-BINAP (0.396 g, 0.64 mmol, 0.10 equiv) in anhydrous, deoxygenated toluene (75 mL) at 23 °C in a nitrogen-filled glove box, add the amine (1.27 mL, 9.54 mmol, 1.50 equiv), place the mixture in a heated mantle at 100 °C and stir (500 rpm) for 3 h to give a brown solid. The mixture was removed from the mantle and allowed to cool to ambient temperature, removed from the glovebox, water (20 mL) and EtOAc (20 mL) were added, the biphasic mixture was poured into a separatory funnel, partitioned, the organic layer was washed with water (2×10 mL), the residual organics were extracted using EtOAc (2×10 mL), combined, dried over solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexanes-15% EtOAc in hexanes to give the aminopyridine as a pale yellow amorphous foam (2.50 g, 5.333 mmol, 86%).

[0159] 1H NMR(400MHz, CDCl3)δ 8.38(s,1H),7.97-7.90(m,1H),7.87(t,J=1.6Hz,1H),7.74-7.62(m,3H),7.51(dt,J=8.9,1.6Hz,1H),7.45(dt,J=9.3,1.7Hz,1H), 6.80(dd,J=7.2,0.8Hz,1H),6.61(d,J=8.3Hz,1H),4.65(s,1H),2.87-2.49(m,2H),1.42(s,9H),1.32(s,9H),0.14(d,J=1.4Hz,9H). 13 C NMR(101MHz,CDCl3)δ 160.81,156.78,147.14,146.77,137.69,135.02,131.31,130.30,129.49,128.64,127.84,126.16, 126.05,124.93,124.38,122.38,120.50,115.83,102.98,35.01,34.76,32.57,30.93,30.83,-2.61.

[0160] Example 26: Synthesis of Coordinator 8

change

[0161] To a mixture of bromopyridine (2.840 g, 6.36 mmol, 1.00 equiv), NaOt-Bu (1.834 g, 19.08 mmol, 3.00 equiv), Pd2dba3 (0.291 g, 0.32 mmol, 0.05 equiv), and rac-BINAP (0.396 g, 0.64 mmol, 0.10 equiv) in anhydrous, deoxygenated toluene (40 mL) at 23 °C in a nitrogen-filled glove box, add the amine (0.95 mL, 9.54 mmol, 1.50 equiv), place the mixture in a heated mantle at 100 °C and stir (500 rpm) for 3 h to give a brown solid. The mixture was removed from the mantle, allowed to cool to ambient temperature, removed from the glovebox, water (20 mL) and EtOAc (20 mL) were added, the biphasic mixture was poured into a separatory funnel, partitioned, the organic layer was washed with water (2×10 mL), the residual organics were extracted using EtOAc (2×10 mL), combined, dried over solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexanes-15% EtOAc in hexanes to give the aminopyridine as a pale yellow amorphous foam (2.50 g, 5.699 mmol, 90%).

[0162] 1 H NMR(400MHz,CDCl3)δ 8.39(t,J=1.0Hz,1H),7.94(dt,J=8.9,0.6Hz,1H),7.88(dd,J=2.0,0.6Hz,1H),7.72(dq,J=9.2,0. 6Hz,1H),7.68-7.60(m,2H),7.52(dd,J=8.9,1.9Hz,1H),7.46(dd,J=9.2,2.0Hz,1H),6.79(dt,J=7 .1,0.6Hz,1H),6.50(dd,J=8.4,0.8Hz,1H),4.83(t,J=5.9Hz,1H),3.13(dd,J=6.7,5.9Hz,2H),1.9 4(dh,J=13.3,6.7Hz,1H),1.43(d,J=4.2Hz,9H),1.32(d,J=0.5Hz,9H),1.01(dd,J=6.7,0.8Hz,6H). 13C NMR(101MHz,CDCl3)δ 159.18,156.90,147.13,146.78,137.58,135.06,131.31,130.29,129.50,128.62,127.85,126.16,126.05 ,124.92,124.38,122.39,120.51,115.81,103.54,50.37,35.01,34.77,30.94,30.83,28.41,20.41,0.01.

[0163] Example 27: Synthesis of intermediate to ligand 2 [ka]

[0164] To a solution of 2,4-dibromopyridine (25.0 g, 105.5 mmol, 1.00 equiv.), NiCl2(PCy3)2 (1.45 g, 2.11 mmol, 0.02 equiv.) in anhydrous, deoxygenated THF (500 mL) at 25 °C in a nitrogen-filled glove box was added mesitylmagnesium bromide (237.5 mL, 237.5 mmol, 2.25 equiv., 1 M in THF) dropwise via an addition funnel. After stirring for 1 h after the addition was complete, the solution was removed from the glove box, water (100 mL) was added, the THF was removed by rotary evaporation, the mixture was diluted with 1N HCl (200 mL) and CHCl (200 mL), poured into a separatory funnel, fractionated, the organic layer was washed with water (1×50 mL), the organic layer was extracted from the aqueous layer using CHCl (2×25 mL), combined, dried over solid NaSO, decanted, concentrated, suspended in CHCl (25 mL), the dark red solution was suction filtered through a plug of silica gel, rinsed with CHCl (4×50 mL), and the filtrate solution was concentrated to give dimesitylpyridine (26.5 g, 84.00 mmol, 80%). NMR showed product.

[0165] 1H NMR(400MHz, CDCl3)δ 8.79(dd,J=5.0,0.9Hz,1H),7.08(dd,J=5.0,1.7Hz,1H),7.06(dd,J=1.6,0.9Hz,1H),7. 02-6.98(m,2H),6.98-6.94(m,2H),2.37(s,3H),2.36(s,3H),2.12(s,6H),2.09(s,6H). 13 C NMR(101MHz,CDCl3)δ 160.31,149.83,149.72,137.80,137.42,137.31,136.44,135.55,134.99,128.38,128.31,125.68,122.61,21.13,21.07,20.59,20.18.

[0166] Example 28: Synthesis of intermediates of ligand 2

change

[0167] Under nitrogen, a solution of dimethylaminoethanol (17.636 g, 19.9 mL, 142.65 mmol, 3.00 equiv) in anhydrous, deoxygenated hexane (250 mL) was placed in an ice-water bath. After stirring (500 rpm) for 30 min, n-BuLi (115.0 mL, 285.30 mmol, 6.00 equiv, 2.49 M titration in hexane) was added dropwise rapidly over 20 min. The clear, colorless solution changed to a pale yellow solution, and after stirring for 1 h, pyridine (15.000 g, 47.550 mmol, 1.00 equiv) was added dropwise rapidly over 30 min as a solution in Et2O (150 mL). After stirring for 2 h, the golden solution was placed in a -78 °C cooling bath and after 1 h, a solution of CBr4 (55.192 g, 166.43 mmol, 3.50 equiv) in Et2O (100 mL) was added dropwise rapidly over 20 min. After stirring for 1 h, the now brown solution was removed from the cold bath and allowed to warm gradually to 23 °C. After stirring at 23 °C for 2 h, the now heterogeneous mixture was neutralized with water (100 mL), stirred vigorously (1000 rpm) for 2 min, poured into a separatory funnel, partitioned, the organic layer washed with water (3 × 50 mL), the residual organics extracted from the aqueous layer using EtO (2 × 50 mL), combined, dried over solid NaSO, decanted, concentrated onto Celite, vacuum filtered through a silica gel pad by washing first with hexanes (4 × 100 mL) to elute / remove residual CBr, then eluting the product with CHCl (4 × 100 mL), which was concentrated onto Celite, vacuum filtered through this silica gel pad one more time, the CHCl filtrate concentrated onto Celite, and purified by silica gel chromatography using an ISCO with hexanes-30% CHCl in hexane to give the bromide as a golden amorphous oil (17.364 g, 44.031 mmol, 93%). NMR showed the product.

[0168] 1 H NMR (400 MHz, chloroform-d) δ 7.32 (d, J = 1.3 Hz, 1H), 7.02 (d, J = 1.3 Hz, 1H), 7.00-6.97 (m, 2H), 6.97-6.95 (m, 2H), 2.37 (s, 3H), 2.35 (s, 3H), 2.14 (s, 6H), 2.10 (s, 6H).13 C NMR (101 MHz, chloroform-d) δ 161.15, 152.60, 142.09, 137.94, 137.88, 136.37, 135.57, 134.99, 134.88, 128.50, 128.42, 126.61, 125.09, 21.14, 21.09, 20.60, 20.26.

[0169] Example 29: Synthesis of Ligand 2 [ka]

[0170] To a heterogeneous mixture of bromide (17.364 g, 44.031 mmol, 1.00 equiv), neopentylamine (6.525 g, 74.853 mmol, 1.70 equiv) and NaOt-Bu (9.394 g, 97.749 mmol, 2.22 equiv) in PhMe (85 mL) at 23 °C in a nitrogen filled glove box was added Pd2dba3 (0.403 g, 0.4403 mmol, 0.01 equiv) followed by BINAP (0.274 g, 0.4403 mmol, 0.01 equiv). The now golden yellow heterogeneous mixture was placed in a heating mantle at 110 °C. After stirring (500 rpm) for 12 hours, the dark golden brown mixture was removed from the mantle, cooled slowly to 23° C., removed from the glovebox, diluted with EtOAc (50 mL) and water (50 mL), suction filtered through a pad of Celite, rinsed with EtOAc (3×30 mL), poured into a separatory funnel, fractionated, the organic layer washed with water (2×50 mL), the residual organics extracted from the aqueous layer using EtOAc (2×25 mL), combined, dried over solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexane-80% CHCl2 in hexane to give the 2-aminopyridine as a viscous canary yellow oil (14.805 g, 36.986 mmol, 84%). The 2-aminopyridine ligand was azeotropically dried using PhMe (3×10 mL) prior to use. NMR showed the product.

[0171] 1H NMR(500MHz,chloroform-d)δ 6.98-6.96(m,2H),6.96-6.90(m,2H),6.34(d,J=1.2Hz,1H),6.19(d,J=1.2Hz,1H),4.82(t,J=6. 2Hz,1H),3.06(d,J=6.2Hz,2H),2.36(s,3H),2.33(s,3H),2.17(s,6H),2.15(s,6H),1.02(s,9H). 13 C NMR (126 MHz, chloroform-d) δ 158.61, 137.74, 135.50, 135.15, 129.05, 128.21, 128.11, 114.60, 103.50, 54.36, 32.25, 27.58, 27.55, 21.10, 21.05, 20.44, 20.12.

[0172] Example 30: Synthesis of intermediates to ligand 3 [ka]

[0173] To a solution of 2,4,6-triisopropylbenzene (3.52 g, 12.41 mmol, 1.00 equiv) in anhydrous, deoxygenated THF (10 mL) at 23 °C in a nitrogen filled glove box, magnesium turnings (1.19 g, 49.64 mmol, 4.00 equiv) were added followed by 1,2-dibromoethane (20 μL), the mixture was placed in a heating mantle at 50 °C and stirred for 16 h, after which the mixture was gravity filtered directly into a solution of 2,6-dibromopyridine (2.94 g, 12.41 mmol, 1.50 equiv), NiCl2(PCy3)2 (0.086 g, 0.12 mmol, 0.10 equiv) in anhydrous, deoxygenated THF (30 mL). The solution was stirred (500 rpm) at 23 °C for 15 h, concentrated, diluted with CHCl (50 mL), removed from the glove box, water (50 mL) was added, the mixture was poured into a separatory funnel, partitioned, and the organic layer was washed with water (2 × 25 mL) and the organics with CHCl (2 × 25 mL). を使用して水層から抽出し、混合し、固体Na2Dry over SO4, decant, concentrate onto Celite, and chromatograph on silica gel with hexane to give the bromopyridine (3.57 g, 9.907 mmol, 80%). NMR showed the product.

[0174] 1 H NMR(400MHz,CDCl3)δ 7.48-7.36(m,3H),6.90(s,2H),2.86(hept,J=6.9Hz,3H),1.24(d,J=6.9Hz,18H).

[0175] Example 31: Synthesis of Ligand 3 [ka]

[0176] To a mixture of bromopyridine (0.500 g, 1.39 mmol, 1.00 equiv), NaOt-Bu (0.296 g, 3.08 mmol, 3.00 equiv), Pd2dba3 (13.0 mg, 0.0142 mmol, 0.01 equiv), and rac-BINAP (17.0 mg, 0.0284 mmol, 0.02 equiv) in anhydrous, deoxygenated toluene (10 mL) at 23 °C in a nitrogen-filled glove box, add the amine (0.24 mL, 2.08 mmol, 1.50 equiv), place the mixture in a heated mantle at 100 °C, stir (500 rpm) for 3 h, and brown. The colored mixture was removed from the mantle and allowed to cool to ambient temperature, removed from the glovebox, water (20 mL) and EtOAc (20 mL) were added, the biphasic mixture was poured into a separatory funnel, partitioned, the organic layer was washed with water (2×10 mL), the residual organics were extracted using EtOAc (2×10 mL), combined, dried over solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexanes-15% EtOAc in hexanes to give the aminopyridine as a pale yellow amorphous foam (0.332 g, 0.9056 mmol, 65%).

[0177] 1H NMR(400MHz,CDCl3)δ 7.48(t,J=7.8Hz,1H),7.13(s,2H),6.60(d,J=7.2Hz,1H),6.39(d,J=8.4Hz,1H),4.75(t,J=5.8Hz,1H),3.12(d,J=6.0Hz,2H),2.99( hept,J=6.8Hz,1H),2.77(hept,J=6.5Hz,2H),1.35(dd,J=6.9,1.3Hz,6H),1.25(d,J=6.8Hz,6H),1.19(d,J=6.8Hz,6H),1.04(s,9H). 13 C NMR(101MHz,CDCl3)δ 158.97,158.50,148.19,146.10,137.13,137.00,120.66,113.94,102.99,54.13,34.50,32.10,30.24,27.60,24.66,24.23,24.09.

[0178] Example 32: Synthesis of intermediates to ligands 4 and 5 [ka]

[0179] To a solution of 2,6-dibromopyridine (25.0 g, 211.07 mmol, 1.00 equiv.), NiCl2(PCy3)2 (1.457 g, 2.11 mmol, 0.01 equiv.) in anhydrous, deoxygenated THF (500 mL) at 25 °C in a nitrogen-filled glove box was added mesitylmagnesium bromide (211 mL, 211.07 mmol, 1.00 equiv., 1 M in THF) dropwise via an addition funnel. After stirring for 3 h after the addition was complete, the solution was removed from the glove box, water (100 mL) was added, the THF was removed by rotary evaporation, the mixture was diluted with 1N HCl (150 mL) and EtOAc (300 mL), poured into a separatory funnel, fractionated, the organic layer was washed with water (1×50 mL), extracted from the aqueous layer with EtOAc (2×25 ml), combined, the organics were dried over solid Na2SO4, decanted, concentrated through Celite, and purified by silica gel chromatography with hexane-10% EtOAc in hexane to give mesitylpyridine (25.3 g, 91.608 mmol, 87%). NMR showed product.

[0180] 1 H NMR(400MHz,CDCl3)δ 7.58(td,J=7.8,1.5Hz,1H),7.47-7.38(m,1H),7.16(dq,J=7.5,1.0Hz,1H),6.95-6.82(m,2H),2.29(s,3H),2.02(s,6H). 13 C NMR(101MHz,CDCl3)δ 161.13,141.71,138.46,137.89,135.60,128.33,127.02,125.92,123.69,21.07,20.15.

[0181] Example 33: Synthesis of Ligand 5 [ka]

[0182] To a mixture of bromopyridine (0.370 g, 1.34 mmol, 1.00 equiv), NaOt-Bu (0.286 g, 2.97 mmol, 2.22 equiv), Pd2dba3 (61.0 mg, 0.0666 mmol, 0.05 equiv) and rac-BINAP (42.0 mg, 0.0675 mmol, 0.01 equiv) in anhydrous, deoxygenated toluene (8 mL) at 23 °C in a nitrogen-filled glove box, add amine (0.19 mL, 2.28 mmol, 1.70 equiv), place the mixture in a heated mantle at 100 °C and stir (500 rpm) for 15 h to give a brown solid. The mixture was removed from the mantle and allowed to cool to ambient temperature, removed from the glovebox, water (20 mL) and EtOAc (20 mL) were added, the biphasic mixture was poured into a separatory funnel, partitioned, the organic layer was washed with water (2×10 mL), the residual organics were extracted using EtOAc (2×10 mL), combined, dried over solid Na2SO4, decanted, concentrated onto Celite, and purified by silica gel chromatography with hexanes-20% EtOAc in hexanes to give the aminopyridine as a pale yellow amorphous foam (0.220 g, 0.8649 mmol, 65%).

[0183] 1 H NMR(400MHz,CDCl3)δ 7.46(dd,J=8.4,7.3Hz,1H),6.88(s,2H),6.45(dd,J=7.3,0.6Hz,1H),6.30(d,J=8.3 Hz,1H),4.52(s,1H),3.81(p,J=6.2Hz,1H),2.28(s,3H),2.06(s,6H),1.22(d,J=6.4 Hz,6H). 13 C NMR(101MHz,CDCl3)δ 158.54,158.15,138.40,137.58,136.83,135.60,128.17,113.32,103.91,43.25,23.04,21.09,20.13.

[0184] Example 34: Synthesis of Zr(CH2SiMe3)4 precursor [ka]

[0185] In a nitrogen-filled glove box at 23 °C, a heterogeneous mixture of canary yellow ZrCl4 (1.523 g, 6.536 mmol, 1.00 equiv) in anhydrous, deoxygenated PhMe (50 mL) was stirred vigorously (1000 rpm) for 15 min to disperse the powder, after which a solution of trimethylsilylmethylmagnesium chloride (26.1 mL, 26.143 mmol, 4.00 equiv, 1.0 M in Et2O, not titrated) was added dropwise over 10 min. After stirring (1000 rpm) for 2 h, the now thick white heterogeneous mixture was filtered through a 0.45 μm submicron PTFE filter, concentrated, hexane (5 mL) was added, the mixture was concentrated and this was repeated three more times to remove PhMe, EtO and to triturate residual magnesium salts, the resulting off-white solid mixture was suspended in hexane (10 mL), stirred vigorously (1000 rpm) for 2 min, filtered through a 0.45 μm submicron PTFE filter, concentrated and the resulting clear light brown viscous heterogeneous oil was suspended in hexane (5 mL) and stirred vigorously for 1 min. The resulting opaque golden oil was suspended in pentane (5 mL), stirred vigorously (1000 rpm) for 1 min, filtered through a 0.45 μm submicron PTFE filter, rinsed with pentane (3×5 mL), concentrated, and the pentane filtration process was repeated once more to give tetrakis-trimethylsilylmethylzirconium complex (2.816 g, 6.399 mmol, 98%, ca. 98% pure) as a clear golden free-flowing oil. NMR showed the product.

[0186] 1 H NMR (500 MHz, benzene-d6) δ 1.08 (s, 8H), 0.17 (s, 36H). 13 C NMR (126 MHz, benzene-d6) δ 75.48, 2.37.

[0187] Example 35: Synthesis of Hf(CH2SiMe3)4 precursor [ka]

[0188] In a nitrogen-filled glove box at 23 °C, a canary yellow heterogeneous mixture of HfCl4 (2.322 g, 7.250 mmol, 1.00 equiv) in anhydrous, deoxygenated PhMe (50 mL) was stirred vigorously (700 rpm) for 15 min to disperse the powder, after which a solution of trimethylsilylmethylmagnesium chloride (29.0 mL, 28.999 mmol, 4.00 equiv, 1.0 M in Et2O, not titrated) was added slowly dropwise over 10 min, transforming the canary yellow mixture into a thick, viscous, white heterogeneous mixture. After stirring (700 rpm) for 2 hours, the now slightly pale yellow heterogeneous mixture was filtered through a 0.45 μm submicron PTFE filter, concentrated, hexane (5 mL) was added, the mixture was concentrated, and this was repeated three more times to remove PhMe, Et2O, and to triturate residual magnesium salts, and the resulting off-white solid mixture was suspended in hexane (10 mL), vigorously stirred (1000 rpm) for 2 minutes, filtered through a 0.45 μm submicron PTFE filter, concentrated, and the resulting clear light brown viscous heterogeneous oil was suspended in pentane (5 mL), vigorously stirred (1000 rpm) for 1 minute, filtered through dual 0.45 μm submicron PTFE filters, rinsed with pentane (3×5 mL), and concentrated to give tetrakis-trimethylsilylmethylhafnium complex as a clear golden yellow free-flowing oil (3.640 g, 6.902 mmol, 95%). NMR showed the product.

[0189] 1 H NMR (400 MHz, benzene-d6) δ 0.43 (s, 8H), 0.15 (s, 36H). 13 C NMR (101 MHz, benzene-d6) δ 86.07, 2.61.

[0190] Example 36 - Polymerization Process The catalytic activity (in terms of quench time and polymer yield) as well as the properties of the resulting polymers were evaluated for procatalysts 1 to 16. The polymerization reactions were carried out in parallel polymerization reactors (PPR) and / or semi-batch reactors.

[0191] PPR polymerization experiments were performed using [HNMe(C 18 H 37 )2][B(C6F5)4] was used as the activator in an amount of 1.5 molar equivalents relative to the procatalyst and was carried out at both 120 and 150 °C, with MMAO-3 (500 nmol at 120 °C or 750 nmol at 150 °C) as the scavenger. [Table 1]

[0192] Standard PPR reactor conditions were varied with temperature. At 120°C, the ethylene pressure was 150 psi, 500 nmol MMAO-3A, ​​and 1.5 equivalents of activator. When the reaction was run at 150°C, the ethylene pressure was 213 psi, the amount of MMAO-3A was 750 nmol, and 1.5 equivalents of activator. At both temperatures, the octene to ethylene ratio ([C8]:[C2]) was 2.24. The run time was 30 minutes or up to 50 psi conversion at 120°C or 75 psi conversion at 150°C, after which the reaction was quenched with 10% CO.

[0193] The results summarized in Table 1 show that the procatalysts can produce polymers at temperatures up to 150 °C with low to high quench times (43 s to 1278 s), with faster quench times (i.e., 43 s) indicating higher catalytic activity. Procatalysts 5, 7, 9, 11, 12, 13, and 15 show the highest catalytic activity based on their low quench times (<100 s) in PPR experiments at 120 °C, and procatalysts 5, 7, 8, 11, and 13 show the highest catalytic activity at 150 °C. Overall, higher catalytic activity was observed for catalyst structures with 2,4,6-trimethylphenyl or mesityl, 2,4,6-triisopropylphenyl, or 2,7-di-t-butylanthracene substituents at the 2-position of the pyridine and 2-aminotrimethylsilylmethyl and 2-aminoneopentyl substituents at the 6-position.

[0194] Polymerization reactions in semi-batch reactors were carried out in a 4 L semi-batch reactor, first without diethylzinc (DEZ) at 120 °C and 150 °C, and then with three different DEZ loadings (0, 95 and 380 μmol) at 150 °C. The activator used was 1.2 molar equivalents of [HNMe(C 18 H 37 )2][B(C6F5)4] and the scavenger used was MMAO-3 (19.0 μmol). [Table 2] Standard semi-batch reactor conditions were: 88 g ethylene and 568 g 1-octene in 1155 g IsoparE at 120° C. and 281 psi pressure; 81 g ethylene and 570 g 1-octene in 1043 g IsoparE at 150° C. and 317 psi pressure. Mol% octene or C8 / olefin is defined as (moles 1-octene / (total moles 1-octene and ethylene))×100. Scavenger=MMAO-3 (19.0 μmol). Activator=[HNMe(C 18 H 37 )][B(C6F5)4] (1.2 equiv.). Reactor run time = 10 min. ND = not determined.

[0195] Under these reactor conditions in the semi-batch tests, at 120°C, most of the procatalysts produce high Mw (>300,000 g / mol) polymers, with procatalysts 3, 4, 7, 8, 9, 13, 14 and 16 showing ultra-high molecular weight tolerance (>600,000 g / mol). Procatalysts 4, 8, 13 and 14 can produce the highest molecular weight polymers (>1,000,000 g / mol) at 120°C, and procatalysts 8, 13 and 14 can produce this molecular weight even at 150°C.

[0196] The procatalysts produced polymers with a wide range of PDIs in the PPR and semibatch reactors. Procatalysts 4, 6, 8, 9, 11, 13, 14, and 16 produced polymers with reasonably narrow PDIs (5 or less) under these reactor conditions.

[0197] Under the aforementioned conditions, very low (<1 mol%) to low (<5 mol%) comonomer incorporation was observed for catalyst systems containing procatalysts 7, 8, 13, 14, and 16. These catalyst systems produced polymers with the lowest comonomer incorporation under these reactor conditions. [Table 3]

[0198] The high chain transfer constants Ca of procatalysts 11 and 15 at 150 °C indicate that these catalysts have high sensitivity to chain transfer agents and undergo rapid chain transfer with these agents, whereas moderate sensitivity to CSA (Ca ≥ 0.5) is observed for procatalysts 8, 9 and 14. When the amount of Et2Zn(DEZ) is increased, a decrease in the PDI of procatalysts 8, 9 or 14 or its relatively persistent narrowing is observed, providing evidence that these particular procatalysts undergo irreversible chain transfer with CSA rather than reversible chain transfer. The present invention may include the following aspects. [1] A process for polymerizing olefins, comprising the steps of: (a) reacting ethylene with any one or more (C 3 -C 12 ) contacting an α-olefin with a catalyst system comprising a metal-ligand complex having a structure according to formula (I):

change

change

[10] Each X is benzyl, (C 1 -C 12 ) alkyl, -CH 2 SiR R 3 or -(CH 2 ) n (SiR C ) 3 where n is an integer from 1 to 10, and each R R But (C 1 -C 12 ) alkyl, and each R C is independent, (C 1 -C 30 ) hydrocarbyl, (C 1 -C 30 ) heterohydrocarbyl or -H.

[11] The polymerization process according to any one of [1] to

[10] , wherein the contacting occurs in a reactor at a reactor temperature of 120° C. or more.

[12] The polymerization process according to any one of [1] to

[11] , wherein the contacting occurs in a solution polymerization reactor at a reactor pressure of 10 psi to 2000 psi.

[13] The polymerization process according to any one of [1] to

[12] , wherein the contacting occurs in a reactor containing therein the catalyst system and a chain transfer agent or chain shuttle agent.

[14] The polymerization process according to

[13] , wherein the chain transfer agent or chain shuttle agent is diethylzinc.

Claims

1. A process for polymerizing olefins, comprising the steps of: (a) reacting ethylene with any one or more (C ３ -C １２ ) contacting an α-olefin with a catalyst system comprising a metal-ligand complex having a structure according to formula (I): 【Chemistry 1】 During the ceremony, M is titanium, zirconium or hafnium; Each X is benzyl, (C1-C １２ ) alkyl, halogen atom, or -CH ２ SIR Ｒ ３ and each R Ｒ But (C １ -C １２ ) alkyl; R １ is selected from the group consisting of 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 １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, —Si(R Ｔ ) ３ , -Ge(R Ｔ ) ３ , -P(R Ｔ ) ２ , -N(R Ｔ ) ２ , -N=CHR Ｔ , -OR Ｔ , -SR Ｔ , -NO ２ , -CN, -CF ３ , R Ｔ S(O)-, R Ｔ S (O) ２ -, (R Ｔ ) ２ C=N-, R Ｔ C(O)O-, R Ｔ OC(O)-, R Ｔ C(O)N(R Ｔ ) -, (R Ｔ ) ２ NC(O)—, halogen or —H; R Ｔ But (C １ -C ３０ ) hydrocarbyl or —H; R ２ , R ３ and R ４ 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 C(O)O-, R Ｃ OC(O)-, (R Ｃ ) ２ NC(O)- or halogen; Ｃ , each R Ｎ , and each R Ｐ However, (C １ -C ３０ ) hydrocarbyl, (C １ -C ３０ ) heterohydrocarbyl or —H; R ５ is benzyl, (C １ -C ２０ ) alkyl, or -CH ２ SIR Ｒ ３ and R Ｒ But (C １ -C １２ ) alkyl, the process.

2. R １ is a radical having the formula (II), R ３１ , R ３３ and R ３５ is independent, (C １ -C １２ ) alkyl or (C ６ -C ２０ ) aryl.

3. R １ is a radical having the formula (II), R ３２ and R ３４ is independent, (C １ -C １２ ) alkyl or (C ６ -C ２０ ) aryl.

4. R １ is a radical having the formula (IV) and R ５２ and R ５８ is independent, (C １ -C １２ ) alkyl or (C ６ -C ２０ ) aryl.

5. R １ is a radical having the formula (IV) and R ５３ and R ５８ is independent, (C １ -C １２ ) alkyl or (C ６ -C ２０ ) aryl.

6. R １ is a radical having the formula (IV) and R ５３ and R ５７ is independent, (C １ -C １２ ) alkyl or (C ６ -C ２０ ) aryl.

7. R １ is a radical having the formula (IV) and R ５３ , R ５５ and R ５７ is independent, (C １ -C １２ ) alkyl or (C ６ -C ２０ ) aryl.

8. The polymerization process of any one of claims 1 to 7, wherein the contacting occurs in a reactor at a reactor temperature of 120°C or greater.

9. The polymerization process of any one of claims 1 to 8, wherein the contacting occurs in a solution polymerization reactor at a reactor pressure of from 10 psi to 2000 psi.

10. 10. The polymerization process of any one of claims 1 to 9, wherein the contacting occurs in a reactor containing therein the catalyst system and a chain transfer or shuttle agent.

11. 11. The polymerization process of claim 10, wherein the chain transfer or shuttle agent is diethyl zinc.

12. The structure according to formula (I) is as follows: 【Chemistry 3】 【Chemistry 4】 2. The polymerization process of claim 1, wherein the polymerization is selected from the group consisting of:

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