Heterocyclic-heterocyclic Group IV transition metal catalysts for olefin polymerization

Abstract

The polymerization process of the present disclosure comprises polymerizing ethylene and one or more olefins under olefin polymerization conditions in the presence of a catalyst system to form an ethylene-based polymer. The catalyst system comprises a metal-ligand complex according to formula (I): (insert formula 1): [Case 1] JPEG2022512446000085.jpg164170

Description

Technical Field

[0001] Cross-reference to Related Applications This application claims the priority of U.S. Provisional Patent Application No. 62 / 783,515, filed on December 21, 2018, the entire disclosure of which is incorporated herein by reference.

[0002] Embodiments of the present disclosure generally relate to olefin polymerization catalyst systems and processes, and more specifically, the catalyst system includes a heterocyclic Group IV transition metal catalyst for olefin polymerization.

Background Art

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

[0004] Ethylene-based polymers and propylene-based polymers are manufactured for a wide variety of articles. Polyethylene and polypropylene polymerization processes can be modified in several ways to produce polyethylene resins that result in a wide variety of products with different physical properties, making various resins suitable for use in different applications. Ethylene monomers and optionally one or more comonomers are present in a liquid diluent (solvent, etc.) such as an alkane or isoalkane, e.g., isobutene. Hydrogen may also be added to the reactor. Catalytic systems for producing ethylene-based polymers typically include chromium-based catalytic systems, Ziegler-Natta catalytic systems, and / or molecular (either metallocene or non-metallocene) catalytic systems. The reactants in the diluent and catalytic system are circulated in the reactor at a high polymerization temperature, thereby producing ethylene-based homopolymers or copolymers. Periodically or continuously, a portion of the reaction mixture containing the polyethylene product dissolved in the diluent, along with unreacted ethylene and one or more optional comonomers, is removed from the reactor. The reaction mixture, once removed from the reactor, may be treated to remove polyethylene products from the diluent and unreacted reactants, which are typically recycled back into the reactor. Alternatively, the reaction mixture may be sent to a second reactor connected in series with the first reactor, where a second polyethylene fraction may be produced. Despite research efforts to develop suitable catalyst systems for olefin polymerization, such as polyethylene or polypropylene polymerization, there remains a need to increase the efficiency of catalyst systems capable of producing polymers with high molecular weight and narrow molecular weight distributions. [Overview of the project]

[0005] There is a continuing need to create catalytic systems or procatalysts with high selectivity for α-olefins during the copolymerization reaction of ethylene and α-olefins. Furthermore, these catalytic systems should possess high efficiency, high reactivity, and diverse capabilities to produce high-molecular-weight or low-molecular-weight polymers at high temperatures (above 140°C, or around 190°C, for example).

[0006] According to some embodiments, the polymerization process includes polymerizing ethylene and one or more olefins under olefin polymerization conditions and in the presence of a catalyst system to form an ethylene-based polymer. In one or more embodiments, the catalyst system includes a metal-ligand complex according to formula (I): [Chemical formula] .

[0007] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, and the metal has an oxidation state in the form of +2, +3, or +4. Each X is an unsaturated (C2-C 6a , 3a , 4a , 6a , 6a , 4a , 4a , 5a , 3a , 4a , 5a , 5a , 6a , 3a , 6a , 5a ) hydrocarbyl, an unsaturated (C2-C 50 ) heterohydrocarbyl, a (C1-C 50 ) hydrocarbyl, a (C6-C 50 ) aryl, a (C6-C 50 ) heteroaryl, a cyclopentadienyl, a substituted cyclopentadienyl, a (C4-C 12 ) diene, a halide, -N(R N )2, and -NCOR C and is a monodentate or bidentate ligand independently selected from. Subscript n is 2 and subscript m is 2, or subscript n is 3 and subscript m is 1.

[0008] In formula (I), each A is independently -C(R 3a )C(R 4a )C(R 5a )C(R 6a )-, -C(R 3a )C(R 4a )C(R 5a )N-, -C(R 3a )C(R 4a )NC(R 6a )-, -C(R 3a )NC(R 5a )C(R 6a )-, -NC(R 4a )NC(R 6a )-, or -NC(R 4a )C(R 5a )C(R 6a)- Selected from, and in the formula, R 3a and R 4a , or R 4a and R 5a , or R 5a and R 6a These may be covalently bonded to form an aromatic or non-aromatic ring. In some embodiments of formula (I), -C(R 3b )C(R 4b )G-, or -GC(R 4c )C(R 5c )-, in the formula, G is N(R 3c ), N(R 5b ), O, or S may be used, and optionally R 3b and R 4b , or R 4c and R 5c These may form covalent bonds to create an aromatic or non-aromatic ring. In formula (I), each z1 is independently N or C(R 1 ) is selected from, R 1 and R 11 The rings may form aromatic or non-aromatic rings without covalent bonding, and each z2 independently has N or C(R) 2 ) is selected from, R 1 and R 2 These may form covalent bonds to create an aromatic or non-aromatic ring.

[0009] In equation (I), each R 11 , R 1 , R 2 , R 3a , R 3b , R 3c , R 4a , R 4b , R 4c , R 5a , R 5c , and R 6a (C1-C 50 ) Hydrocarbyl, (C1-C 50 ) Heterohydrocarbyl, (C6-C 50 )Aaryl, (C4-C 50 ) Heteroaryl, -Si(R C )3, -Ge(R C )3, -P(RP )2, -N(R N )2, -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, -P(O)(R P )2, 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 ) Selected from the group consisting of 2NC(O)-, halogens, and -H, in the formula, each R N , R C , and R P (C1-C 20 ) Hydrocarbyl, (C1-C 20 ) Selected from the group consisting of heterohydrocarbyl and -H. z1 is CR 1で Yes, z2 is CR 2 And R 1 and R 2 However, if an aromatic or non-aromatic ring is formed without covalent bonding, then m is 1 and n is 3. [Modes for carrying out the invention]

[0010] Here, we will describe specific embodiments of the catalyst system. It should be understood that the catalyst system of this disclosure may be implemented in different forms and should not be construed as being limited to the specific embodiments described herein.

[0011] Common abbreviations are listed below.

[0012] Me: Methyl, Et: Ethyl, Ph: Phenyl, BN: Benzyl, t-Bu: Tert-butyl, AcOH: Acetic acid, SiO: Ethyl acetate, NH4OAc: Ammonium acetate, MMAO: Modified methylaluminoxane, GC: Gas chromatography, LC: Liquid chromatography, NMR: Nuclear magnetic resonance, MS: Mass spectrometry, mmol: Millimole, mL: Milliliter, M: Mole, min: Min, h: Hour, d: Day, DEZ: Diethylzinc, Mn : Number average molecular weight, M w : Weight average molecular weight, PDI: Polydispersity index.

[0013] The term "independently selected" means that the R groups such as R 1 , R 2 , R 3 , R 4 , and R 5 may be the same or different (for example, R 1 , R 2 , R 3 , R 4 , and R 5 may all be substituted alkyl, or R 1 and R 2 may be substituted alkyl, and R 3 may be aryl, etc.). The chemical names associated with the R groups are intended to convey the chemical structures recognized in the art as corresponding to the chemical structures of the chemical names. Thus, the chemical names are intended to supplement and exemplify the structural definitions known to those skilled in the art and are not intended to exclude.

[0014] The term "precursor catalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with the precursor catalyst to convert it into a catalytically active species. As used herein, the terms "promoter" and "activator" are interchangeable terms.

[0015] When used to describe a particular carbon atom-containing chemical group, the bracketed expression in the form of "(C x -C y )" means that the unsubstituted form of the chemical group has from x to y carbon atoms including x and y. For example, (C1-C 50 )alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, a particular chemical group is R SIt may be replaced by one or more substituents such as (C x -C y R defined using ")" S Substituting chemical groups are any group R S It can contain more than y carbon atoms depending on its identity. For example, "R S The exact single group R is phenyl (-C6H5) S Replaced by (C1-C 50 )alkyl can contain 7 to 56 carbon atoms. Therefore, generally, the parenthetical "(C x -C y A chemical group defined using ) is a substituent containing one or more carbon atoms R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group is, for both x and y, all carbon-containing substituents R S It is determined by adding up the total number of carbon atoms from each origin.

[0016] The term "substituted" refers to a substitution in which at least one hydrogen atom (-H) bonded to a carbon or heteroatom of the corresponding unsubstituted compound or functional group is substituted (e.g., R S This means that all hydrogen atoms (H) bonded to the carbon or heteroatom of the corresponding unsubstituted compound or functional group are replaced by substituents (e.g., R S This means that the atoms are replaced by a substituent. The term "polysubstituted" means that at least two, but fewer than all, hydrogen atoms bonded to the 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 covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0017] (C1-C 50 The term "(C1-C)" refers to a hydrocarbon radical having 1 to 50 carbon atoms. 50The term "hydrocarbylene" means a hydrocarbon diradical having 1 to 50 carbon atoms, where each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (having 3 or more carbon atoms, including monocyclic and polycyclic, condensed and non-condensed polycyclic, and bicyclic) or acyclic, and one or more R S It is either replaced by or not replaced by.

[0018] In this disclosure, (C1-C 50 ) Hydrocarbyl is either unsubstituted or substituted (C1-C 50 )alkyl, (C3-C 50 )Cycloalkyl, (C3-C 20 )Cycloalkyl-(C1-C 20 )Alkilen, (C6-C 40 )aryl, or (C6-C 20 )aryl-(C1-C 20 ) It may be an alkylene (such as benzyl(-CH2-C6H5)).

[0019] (C1-C 50 )alkyl" and "(C1-C 18 The term "alkyl" refers to an unsubstituted or one or more R S This refers to saturated linear or branched hydrocarbon radicals having 1 to 50 carbon atoms and saturated linear or branched hydrocarbon radicals having 1 to 18 carbon atoms, respectively, which are substituted by (C1-C). 50 Examples of alkyl groups include unsubstituted (C1-C 20 ) alkyl, unsubstituted (C1-C 10 )alkyl, unsubstituted (C1-C5)alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. Substituted (C1-C 40 Examples of alkyl groups include substitutions (C1-C 20 ) alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C45 It is alkyl. [C 45 The term "alkyl" means that there are up to 45 carbon atoms in a substituted radical, for example, one R is (C1-C5)alkyl. S (C 27 -C 40 ) is alkyl. Each (C1-C5) alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl. (C1-C 10 Examples of alkyl groups include all isomers of butyl, pentyl, hexyl, heptyl, nonyl, and decyl.

[0020] (C6C 50 The term "aryl" refers to an unsubstituted or (one or more R) having 6 to 40 carbon atoms. S This refers to a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical (C6-C6) that is substituted, and at least 6 to 14 of its carbon atoms are aromatic ring carbon atoms. A monocyclic aromatic hydrocarbon radical contains one aromatic ring, a bicyclic aromatic hydrocarbon radical has two rings, and a tricyclic aromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical exists, at least one of the rings of that radical is aromatic. One or more other rings of an aromatic hydrocarbon radical can independently be condensed or uncondensed aromatic or non-aromatic. Unsubstituted (C6-C6) 50 Examples of aryl groups include unsubstituted (C6-C 20 ) Aryl, unsubstituted (C6-C 18 Examples include aryl, 2-(C1-C5)alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. Substitutions (C6-C 40 Examples of aryl substitutions include (C1-C 20 )aryl, substitution (C6-C 18 )aryl, 2,4-bis([C 20Examples include (alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-one-1-yl.

[0021] “(C3-C 50 ) cycloalkyl” means a saturated cyclic hydrocarbon radical having 3 to 50 carbon atoms, which is unsubstituted or substituted by one or more R S . Other cycloalkyl groups (e.g., (C x -C y ) cycloalkyl) are defined in a similar manner as those having x to y carbon atoms, being either unsubstituted or substituted by one or more R S . Examples of unsubstituted (C3-C 40 ) cycloalkyl are unsubstituted (C3-C 20 ) cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3-C 40 ) cycloalkyl are substituted (C3-C 20 ) cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanone-2-yl, and 1-fluorocyclohexyl.

[0022] (C1-C 50 ) hydrocarbylene examples include unsubstituted or substituted (C6-C 50 ) arylene, (C3-C 50 ) cycloalkylene, and (C1-C 50 ) alkylene (e.g., (C1-C 20Examples include alkylenes. Diradicals may be located on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or three or more intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or α,ω-diradicals, while others include 1,2-diradicals. The α,ω-diradical is a diradical with the largest possible carbon skeleton spacing between radical carbons. (C2-C 20 Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CH2CH2-), propane-1,3-diyl (i.e., -CH2CH2CH2-), and 2-methylpropane-1,3-diyl (i.e., -CH2CH(CH3)CH2-). (C6-C 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0023] (C1-C 50 The term "alkylene" refers to an unsubstituted or one or more R S This refers to saturated linear or branched diradicals having 1 to 50 carbon atoms substituted by (i.e., the radical is not on a ring atom). Unsubstituted (C1-C 50 An example of alkylene is unsubstituted (C1-C 20 ) Alkylenes, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3), where "C*" represents a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Substituted (C1-C 50 An example of alkylene is substitution (C1-C 20 ) Alkylene, -CF2-, -C(O)-, and -(CH2) 14It is C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted n-1,20-eicosylene). As mentioned above, there are two R S They come together, (C1-C 18 )It can form an alkylene, so substitution (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.

[0024] (C3C 50 The term "cycloalkylene" refers to an unsubstituted or one or more R S This refers to a cyclic diradical having 3 to 50 carbon atoms substituted by (i.e., the radical is located on a ring atom).

[0025] 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)2, and Si(R). C )2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2-, or -Si(R C )- are listed, and each R C and each R P is non-substituted (C1-C 18 ) Hydrocarbyl or -H, each R N is non-substitutable (C1-C 18 ) is a hydrocarbyl. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by heteroatoms. 50 The term "heterohydrocarbyl" refers to a heterohydrocarbon radical having 1 to 50 carbon atoms, or "(C1-C 50 The term "heterohydrocarbylene" refers to a heterohydrocarbon diradical having 1 to 50 carbon atoms. (C1-C50 ) Heterohydrocarbyl or (C1-C 50 A heterohydrocarbylene heterohydrocarbon has one or more heteroatoms. The radical of a heterohydrocarbylene can be located on a carbon atom or on a heteroatom. The two groups of a heterohydrocarbylene can be located on a single carbon atom or on a single heteroatom. Furthermore, one of the two radicals of a diradical can be located on a carbon atom and the other radical can be located on a different carbon atom. One of the two radicals can be located on a carbon atom and the other can be located on a heteroatom. Or, one of the two radicals can be located on a heteroatom and the other radical can be located on a different heteroatom. Each (C1-C 50 )heterohydrocarbyl and (C1-C 50 ) Heterohydrocarbylenes are unsubstituted or (one or more R S They may be substituted, aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, fused polycyclic and non-fused polycyclic) or acyclic.

[0026] (C1-C 50 ) Heterohydrocarbyl may be unsubstituted or substituted. (C1-C 50 )A non-limiting example of heterohydrocarbil is (C1-C 50 ) Heteroalkyl, (C1-C 50 ) Hydrocarbyl-O-, (C1-C 50 ) Hydrocarbyl-S-, (C1-C 50 )hydrocarbyl-S(O)-,(C1-C 50 )hydrocarbyl-S(O)2-,(C1-C 50 ) Hydrocarbyl-Si(R C )2-, (C1-C 50 ) Hydrocarbyl-N(R N )-, (C1-C 50 ) Hydrocarbil-P(R P )-, (C2-C 50 ) Heterocycloalkyl, (C2-C 19) Heterocycloalkyl-(C1-C 20 )Alkilen, (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 )Alkilen, (C6-C 20 )aryl-(C1-C 19 )heteroalkylene, or (C1-C 19 )heteroaryl-(C1-C 20 Examples include heteroalkylenes.

[0027] (C4C 50 The term "heteroaryl" refers to a compound having a total of 4 to 50 carbon atoms and 1 to 10 heteroatoms, which is either unsubstituted or (one or more R) S This refers to monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radicals that are substituted by (C). 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. If a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. One or more other rings in a heteroaromatic radical can independently be condensed or uncondensed and aromatic or nonaromatic. Other heteroaryl groups (e.g., generally (C)) x -C y )heteroaryl, (C4-C 12 (e.g., heteroaryl compounds) have x to y carbon atoms (e.g., 4 to 12 carbon atoms) and are unsubstituted or have one or more R atoms. SIt is defined in a similar manner to those substituted by . Monocyclic heteroaromatic hydrocarbon radicals are five-membered or six-membered rings. A five-membered monocyclic heteroaromatic hydrocarbon radical 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 five-membered heteroaromatic hydrocarbon radicals include pyrrole-1-yl, pyrrole-2-yl, furan-3-yl, thiophen-2-yl, pyrazole-1-yl, isoxazole-2-yl, isothiazole-5-yl, imidazole-2-yl, oxazole-4-yl, thiazole-2-yl, 1,2,4-triazole-1-yl, 1,3,4-oxadiazole-2-yl, 1,3,4-thiadiazole-2-yl, tetrazole-1-yl, tetrazole-2-yl, and tetrazole-5-yl. Six-membered monocyclic heteroaromatic hydrocarbon radicals have 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 monocyclic heteroaromatic hydrocarbon radicals include pyridine-2-yl, pyrimidine-2-yl, and pyrazine-2-yl. Bicyclic heteroaromatic hydrocarbon radicals can be condensed 5,6- or 6,6-ring systems. Examples of condensed 5,6-ring bicyclic heteroaromatic hydrocarbon radicals include indole-1-yl and benzimidazole-1-yl. Examples of condensed 6,6-ring bicyclic heteroaromatic hydrocarbon radicals include quinoline-2-yl and isoquinoline-1-yl. Tricyclic heteroaromatic hydrocarbon radicals can be condensed 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. An example of a condensed 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indole-1-yl. An example of a condensed 5,6,6-ring system is 1H-benzo[f]indole-1-yl. An example of a condensed 6,5,6-ring system is 9H-carbazole-9-yl. An example of a condensed 6,5,6-ring system is 9H-carbazole-9-yl. An example of a condensed 6,6,6-ring system is acridine-9-yl.

[0028] (C1-C50 The term "(C1-C) heteroalkyl" refers to a saturated linear or branched radical containing 1 to 50 carbon atoms and one or more heteroatoms. 50 The term "heteroalkylene" refers to a saturated linear or branched diradical containing 1 to 50 carbon atoms and one or more heteroatoms. Examples of heteroatoms in 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, SR C Examples include S(O) and S(O)2, where each of the heteroalkyl and heteroalkylene groups is unsubstituted or has one or more R S It has been replaced by.

[0029] Unsubstituted (C2-C 40 Examples of heterocycloalkyl groups include unsubstituted (C2-C 20 ) Heterocycloalkyl, unsubstituted (C2-C 10 Examples include heterocycloalkyls, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidine-1-yl, tetrahydrothiophen-S,S-dioxide-2-yl, morpholine-4-yl, 1,4-dioxan-2-yl, hexahydroazepine-4-yl, 3-oxacyclooctyl, 5-thiocyclononyl, and 2-azacyclodecyl.

[0030] The terms "halogen atom" or "halogen" refer to radicals of fluorine (F), chlorine (Cl), bromine (Br), or iodine (I). The term "halogen" refers to fluoride (F) - ), chloride (Cl - ), bromide (Br - ), or iodide (I -This refers to the anionic form of a halogen atom.

[0031] The term "saturated" means the absence of 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 has one or more substituents R S If substituted by, one or more double and / or triple bonds may optionally have substituent R S It may be present in the group. The term "unsaturated" refers to a group containing one or more carbon-carbon double bonds or carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds, or carbon-silicon double bonds, with substituent R S This means that it does not contain any double bonds (if present) or any double bonds that may be present in an aromatic ring or heteroaromatic ring (if present).

[0032] Embodiments of this disclosure include methods for polymerizing ethylene and one or more olefins under olefin polymerization conditions and in the presence of a catalyst system to form ethylene-based polymers. In one or more embodiments, the catalyst system includes a metal-ligand complex according to formula (I): [ka] .

[0033] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, and the metal has a formal oxidation state of +2, +3, or +4: each X is unsaturated (C2-C 20 ) Hydrocarbyl, unsaturated (C2-C 50 ) Heterohydrocarbyl, (C1-C 50 ) Hydrocarbyl, (C6-C 50 )aryl, (C6-C 50 )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 ) Dienyl, halide, -N(R N )2, and -NCOR CIt is a single-seat or double-seat ligand selected independently from the others. Either the subscript n is 2 and the subscript m is 2, or the subscript n is 3 and the subscript m is 1.

[0034] In equation (I), each A is independent of -C(R 3a )C(R 4a )C(R 5a )C(R 6a )-,-C(R 3a )C(R 4a )C(R 5a )N-, -C(R 3a )C(R 4a )NC(R 6a )-,-C(R 3a )NC(R 5a )C(R 6a )-,-NC(R 4a )NC(R 6a )-, or -NC(R 4a )C(R 5a )C(R 6a )- Selected from, in the formula, R 3a and R 4a , or R 4a and R 5a , or R 5a and R 6a These may be covalently bonded to form an aromatic or non-aromatic ring. In some embodiments of formula (I), -C(R 3b )C(R 4b )G-, or -GC(R 4c )C(R 5c )-, in the formula, G is N(R 3c ), N(R 5b ), O, or S may be used, and optionally R 3b and R 4b , or R 4c and R 5c These may form an aromatic or non-aromatic ring by covalent bonding. In formula (I), each z1 is independently N or C(R 1 ) is selected from, R 1 and R 11 The rings may form aromatic or non-aromatic rings without covalent bonding, and each z2 independently consists of N or C(R). 2 ) is selected from, R1 and R 2 These may form covalent bonds to create an aromatic or non-aromatic ring.

[0035] In equation (I), each R 11 , R 1 , R 2 , R 3a , R 3b , R 3c , R 4a , R 4b , R 4c , R 5a , R 5c , and R 6a (C1-C 50 ) Hydrocarbyl, (C1-C 50 ) Heterohydrocarbyl, (C6-C 50 )Aaryl, (C4-C 50 ) Heteroaryl, -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)-, -P(O)(R P )2, 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 ) Selected from the group consisting of 2NC(O)-, halogens, and -H, in the formula, each R N , R C , and R P (C1-C 20 ) Hydrocarbyl, (C1-C 20 ) Selected from the group consisting of heterohydrocarbyl and -H. z1 is CR 1 There is a difference, and z2 is CR 2 And R 1 and R 2 However, if an aromatic or non-aromatic ring is formed without covalent bonding, then m is 1 and n is 3.

[0036] In some embodiments, the chemical groups of the metal-ligand complex of formula (I) (e.g., X, R) 11 , R 1 , R 2 , R 3a , R 3b , R 4a , R 4b , R 4c , R 5a , R 5c , and R 6a , Y, and z 1-2 ) any or all of these may be unsubstituted. In other embodiments, the chemical groups X, R of the metal-ligand complex of formula (I) 11 , R 1 , R 2 , R 3a , R 3b , R 4a , R 4b , R 4c , R 5a , R 5c , and R 6a , Y, and z 1-2 Any one or more of R S If not replaced by, or if any or all of them are replaced, then two or more R S If the R groups are bonded to the same chemical group in the metal-ligand complex of formula (I), then the individual R groups of the chemical group S These can bond to the same carbon atom or heteroatom, or to different carbon atoms or heteroatoms. In some embodiments, chemical groups X, R 11 , R 1 , R 2 , R 3a , R 3b , R 4a , R 4b , R 4c , R 5a , R 5c , and R 6a , Y, and z 1-2 All of them are R S They are either not oversubstituted, or one or all of them may be oversubstituted. S In chemical groups that are oversubstituted with R, each R SThey may all be identical, or they may be chosen independently.

[0037] In equation (I), if M is Ti, then each X is unsaturated (C2-C 20 ) Hydrocarbyl, unsaturated (C2-C 50 ) Heterohydrocarbyl, (C1-C 50 ) Hydrocarbyl, (C6-C 50 )aryl, (C6-C 50 )heteroaryl, (C4-C 12 ) Diene, halogen, -N(R N )2, and -NCOR C It is selected from the group consisting of the following.

[0038] The metal-ligand complex of formula (I) does not include formula (Ia): [ka] .

[0039] In some embodiments, each R 11 , carbazole, R S or two or more R S Carbazole-9-yl, phenyl, R substituted with S or two or more R S Phenyl, anthracenyl, R substituted with S or two or more R S Anthracene-9-yl, naphthyl, or R substituted with S or two or more R S Naphthyls may be selected from those substituted with R, where R S (C1-C 30 ) may be hydrocarbil. In one or more embodiments, R S is, (C 1- C 12 ) alkyl, (C 6- C 15 )aryl, or (C 3- C 12 ) may be selected from cycloalkyls. In various embodiments, R SThis may be selected from methyl, ethyl, propyl, 2-propyl, 2-methylpropyl, n-butyl, tert-butyl (also called 1,1-dimethylethyl), pentyl, hexyl, 1-cyclohexyl, heptyl, tert-octyl (also called 1,1,3,3-tetramethylbutyl), n-octyl, or nonyl.

[0040] In other embodiments, each R 11 This may be selected from carbazole-9-yl, 3,6-di-tert-butylcarbazole-9-yl, 2,7-di-tert-butylcarbazole-9-yl, anthracene-9-yl, 2,6-anthracene-9-yl, 2,7-anthracene-9-yl, 3,5-di-tert-butylphenyl, 1,1':3',1''-terphenyl-5'-yl, or 3,3'',5,5''-tetra-tert-butyl-1,1':3',1''-terphenyl-5'-yl.

[0041] In one or more embodiments, each Z 1は、 CR 1 And each R 1 , carbazole, R S or two or more R S Carbazole-9-yl, phenyl, R substituted with S or two or more R S Phenyl, anthracenyl, R substituted with S or two or more R S Anthracene-9-yl, naphthyl, or R substituted with S or two or more R S Naphthyls may be selected from those substituted with R, where R S (C1-C 30 ) may be hydrocarbil. In one or more embodiments, R S (C1-C 12 ) alkyl, (C 6- C 15 )aryl, or (C 3- C 12 ) may be selected from cycloalkyls. In various embodiments, R SThis may be selected from methyl, ethyl, propyl, 2-propyl, 2-methylpropyl, n-butyl, tert-butyl (also called 1,1-dimethylethyl), pentyl, hexyl, 1-cyclohexyl, heptyl, tert-octyl (also called 1,1,3,3-tetramethylbutyl), n-octyl, or nonyl.

[0042] In various embodiments, each Z2 is CR 2 And each R 2 , carbazole, R S or two or more R S Carbazole-9-yl, phenyl, R substituted with S or two or more R S Phenyl, anthracenyl, R substituted with S or two or more R S Anthracene-9-yl, naphthyl, or R substituted with S or two or more R S Naphthyls may be selected from those substituted with R, where R S (C1-C 30 ) may be hydrocarbil. In one or more embodiments, R S (C1-C 12 ) alkyl, (C 6- C 15 )aryl, or (C 3- C 12 ) may be selected from cycloalkyls. In various embodiments, R S This may be selected from methyl, ethyl, propyl, 2-propyl, 2-methylpropyl, n-butyl, tert-butyl (also called 1,1-dimethylethyl), pentyl, hexyl, 1-cyclohexyl, heptyl, tert-octyl (also called 1,1,3,3-tetramethylbutyl), n-octyl, or nonyl.

[0043] In some embodiments, each z1 is CR 1 and each z2 in N, in other embodiments, each z1 is N, and each z2 is CR 2 In one or more embodiments, each z1CR1 And each z2 is CR 2 That is the case.

[0044] In various embodiments of formula (I), A is -C(R 3a )C(R 4a )C(R 5a )C(R 6a )- and the metal-ligand catalyst has the structure according to formula (II): [ka] .

[0045] In equation (II), R 3a and R 4a , or R 4a and R 5a , or R 5a and R 6a These may be covalently bonded to form an aromatic or non-aromatic ring. Furthermore, each z1, z2, R 11 , R 3a , R 4a , R 5a , R 6a X, n, m, and M are defined as shown in equation (I).

[0046] In one or more embodiments of formula (I), each A is -GC(R 4c )C(R 5c )- and each G is N(R 3c ) and the metal-ligand catalyst has the structure of formula (III): [ka] .

[0047] In equation (III), R can be arbitrarily selected. 4c and R 5c These may be covalently bonded to form an aromatic or non-aromatic ring, with each of z1, z2, and R 11 , R 3c , R 4c , R 5c X, n, m, and M are defined as shown in equation (I).

[0048] In some embodiments of formula (I), each A is -C(R 3b )C(R 4b )G-, where G is N(R 5b ) and the metal-ligand catalyst has the structure of formula (IV): [ka] .

[0049] In equation (IV), R 3b and R 4b These may be covalently bonded to form an aromatic or non-aromatic ring, with each of z1, z2, and R 11 , R 3b , R 4b , R 3c X, n, m, and M are defined as shown in equation (I).

[0050] In some embodiments of equation (I), each A is -GC(R 4c )C(R 5c )-, where G is S, and the metal-ligand catalyst has the structure according to formula (V): [ka] .

[0051] In equation (V), R can be arbitrarily selected. 4c and R 5c These may be covalently bonded to form an aromatic or non-aromatic ring, with each of z1, z2, and R 11 , R 4c , R 5c X, n, m, and M are defined as shown in equation (I).

[0052] In each embodiment of formula (I), (II), (III), or (IV), the arrows in formulas (I), (II), (III), and (IV) represent donor bonds. The term "donation" (or coordination) refers to a bond between two atoms, where the bonding electrons are supplied by one of the two atoms. In each embodiment of formula (I), (II), (III), or (IV), the straight line from N to M represents an ionic bond.

[0053] In various embodiments of formulas (I), (II), (III), and (IV), m is 1 and n is 3.

[0054] In one or more embodiments of formulas (I), (II), (III), and (IV), z2 is N. In some embodiments, z2 is N and z1 is C(R 2 ) In other embodiments, z2 is N and z1 is CR 1 If R 1 and R 11 It forms an aromatic or non-aromatic ring without covalent bonding.

[0055] In some embodiments of formulas (I), (II), (III), and (IV), R 11 These are phenyl, (2,4,6-triisopropyl)phenyl, 3,5-di-tert-butylphenyl, naphthyl, or cyclopropyl.

[0056] In one or more embodiments, the polymerization process comprises one metal-ligand complex from formulas (I), (II), (III), and (IV), where R 11 is the radical of equation (VI). [ka]

[0057] In equation (VI), R 12 , R 13 , R 14 , R 15 , and R 16 (C1-C10 ) alkyl, (C6-C 10 ) Selected from aryl or -H.

[0058] In some embodiments of equation (VI), R 12 , R 13 , R 14 , R 15 , and R 16 This is selected from tert-butyl, 3,5-di-tert-butylphenyl, or -H.

[0059] In the metal-ligand complex of formula (I), M can be a transition metal such as titanium (Ti), zirconium (Zr), or hafnium (Hf), and the transition metal may have a formal oxidation state of +2, +3, or +4. (X) n Subscript n is an integer from 1, 2, or 3, which refers to the number of ligands X bonded to metal M.

[0060] The metal M in the metal-ligand complex of formula (I) may be derived from a metal precursor that is later subjected to a single-step or multi-step synthesis to prepare the metal-ligand complex. Suitable metal precursors may be monomers (one metal center) or dimers (two metal centers), or may have more than two metal centers, e.g., three, four, five, or six or more metal centers. Suitable hafnium and zirconium precursors include, for example, HfCl4, HfMe4, Hf(CH2Ph)4, Hf(CH2CMe3)4, Hf(CH2SiMe3)4, Hf(CH2Ph)3Cl, Hf(CH2CMe3)3Cl, Hf(CH2SiMe3)3Cl, Hf(CH2Ph)2Cl2, Hf(CH2CMe3)2Cl2, Hf(CH2SiMe3)2Cl2, Hf(NMe2)4, Hf(NEt2)4, and Hf(N(SiMe3)2)2Cl2; ZrCl4, ZrMe4, Zr(C Examples include, but are not limited to, H2Ph)4, Zr(CH2CMe3)4, Zr(CH2SiMe3)4, Zr(CH2Ph)3Cl, Zr(CH2CMe3)3Cl, Zr(CH2SiMe3)3Cl, Zr(CH2Ph)2Cl2, Zr(CH2CMe3)2Cl2, Zr(CH2SiMe3)2Cl2, Zr(NMe2)4, Zr(NEt2)4, Zr(NMe2)2Cl2, Zr(NEt2)2Cl2, Zr(N(SiMe3)2)2Cl2, TiBn4, TiCl4, and Ti(CH2Ph)4. Lewis base adducts of these examples are also suitable as metal precursors, and for example, ethers, amines, thioethers, and phosphines are suitable as Lewis bases. Specific examples include HfCl4(THF)2, HfCl4(SMe2)2, and Hf(CH2Ph)2Cl2(OEt2). Activated metal precursors include ionic or zwitterionic compounds, (M(CH2Ph)3 + )(B(C6F5)4 - ) or (M(CH2Ph)3 + )(PhCH2B(C6F5)3 - ) can be, and M is defined above as Hf or Zr.

[0061] In the metal-ligand complex of formula (I), each X is bonded to M via a covalent, coordinate, or ionic bond. When n is 1, X can be a monodentate or bidentate ligand, and when n is 2, each X is an independently selected monodentate ligand, which may be the same as or different from the other group X. In general, the metal-ligand complex of formula (I) is charge-neutral overall. In some embodiments, the monodentate ligand may be a monoanionic ligand. The monoanionic ligand has a net formal oxidation state of -1. Each monoanionic ligand is independently a hydride, (C1-C 40 ) Hydrocarbyl carbanion, (C1-C 40 ) Heterohydrocarbyl carbanion, halide, nitrate, HC(O)O - , HC(O)N(H) - , (C1-C 40 ) Hydrocarbyl C(O)O - , (C1-C 40 ) Hydrocarbyl C(O)N((C1-C 20 (Hydrocarbyl) - , (C1-C 40 ) Hydrocarbyl C(O)N(H) - , R K R L B - , R K R L N - , R K O - , R K S - , R K R L P - , or R M R K R L Si - This is possible, and in the formula, each R K , R L , and R M Independently, hydrogen, (C1-C 40 ) Hydrocarbyl, or (C1-C 40 ) Heterohydrocarbyl or R K and R L They come together, (C2-C 40 ) Hydrocarbylene or (C1-C20 ) Forms heterohydrocarbylene, R M This is as defined above.

[0062] In other embodiments, at least one monodentate ligand X may be a neutral ligand, independently of any other ligand X. In certain embodiments, the neutral ligand is R X NR K R L , R K Ure L , R K SR L , or R X PR K R L These are neutral Lewis base groups, and each R X Independently, hydrogen, (C1-C 10 ) Hydrocarbyl-Si[(C1-C 10 )hydrocarbyl]3 (i.e., -CH2Si(Me)3), (C1-C 40 ) Hydrocarbyl, [(C1-C 10 ) Hydrocarbyl]3Si-, or (C1-C 40 ) is a heterohydrocarbyl, and each R K and R L They are independent, as defined above.

[0063] Furthermore, each X is independent of any other ligand X, and is halogen, unsubstituted (C1-C 20 ) Hydrocarbyl, unsubstituted (C1-C 20 ) Hydrocarbyl C(O)O-, or R K R L It can be a monodentate ligand of N-, in the formula R K and R L Each of them is independent of the non-substitution (C1-C 20 ) is hydrocarbyl. In some embodiments, each monodentate ligand X is a chlorine atom, (C1-C 10 ) Hydrocarbyl (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C 10 ) Hydrocarbyl C(O)O-, or R K R L N-, and in the formula, RK and R L Each of them is independent of the non-substitution (C1-C 10 ) It is hydrocarbyl.

[0064] In some embodiments, X is benzyl, phenyl, or chloro. In further embodiments where n is 2 or 3, such that at least two groups X are present, any two groups X can combine to form a bidentate ligand. In exemplary embodiments including a bidentate ligand, the bidentate ligand may be a neutral bidentate ligand. In one embodiment, the neutral bidentate ligand is of formula (R D )2C=C(R D )-C(R D )=C(R D ) is a diene of 2, R D These 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 ) These are heterohydrocarbylenedicarbanions, phosphates, or sulfates.

[0065] 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, n is 2, and each X is the same. In some cases, at least two X are different from each other. In other embodiments, n is 2, and each X is one different from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, and chloro. In one embodiment, n is 2, and at least two X are independently monoanionic monodentate ligands. In certain embodiments, n is 2, and the two X groups combine to form a bidentate ligand. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

[0066] In certain embodiments of the catalytic system, the metal-ligand complex according to formula (I) may include, but is not limited to, a complex having any of the structures of pro-catalysts 1 to 29. [ka] [ka]

[0067] Procatalyst activation The catalyst systems of this disclosure include metal-ligand complexes according to formulas (I), (II), (III), and (IV). The metal-ligand complexes according to formulas (I), (II), (III), and (IV) may be in a catalytically active form, or they may be catalytically inactive, or they may be in a procatalytic form that is at least substantially less catalytically active than the catalytically active form. Procatalysts 1 to 29 are catalytically inactive forms of various metal-ligand complexes according to formula (I). Procatalytic systems comprising metal-ligand complexes of formulas (I), (II), (III), and (IV) in procatalytic form may be catalytically activated by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, the metal-ligand complexes of formulas (I), (II), (III), and (IV) may be catalytically activated by contacting the metal-ligand complex with an activated cocatalyst, or by combining the metal-ligand complex with an activated cocatalyst. Another example of a suitable activation technique is bulk electrolysis. Combinations of one or more of the activation cocatalysts and techniques described above are also considered. Subjecting the procatalytic forms of the metal-ligand complexes of formulas (I), (II), (III), and (IV) to any of such activation techniques yields catalytically activated forms of the metal-ligand complexes of formulas (I), (II), (III), and (IV). In some embodiments, the catalytically activated forms of the metal-ligand complexes of formulas (I), (II), (III), and (IV) may be the result of splitting at least one X from the procatalytic forms of the metal-ligand complexes of formulas (I), (II), (III), and (IV) by any of the aforementioned activation techniques.

[0068] Co-catalyst components Suitable activated cocatalysts for use herein include alkylaluminum, polymers or oligomeric aluminoxanes (also known as aluminoxanes), neutral Lewis acids, and nonpolymers, non-coordinating, ion-forming compounds (including the use of such compounds under oxidative conditions). A preferred activation technique is bulk electrolysis. Combinations of one or more of the aforementioned activated cocatalysts and techniques are also contemplated. The term "alkylaluminum" means monoalkylaluminum dihydride or monoalkylaluminum dihalide, dialkylaluminum hydride or dialkylaluminum halide, or trialkylaluminum. Examples of polymers or oligomeric aluminoxanes include methylaluminoxane, triisobutylaluminum-modified methylaluminoxane, and isobutylaluminoxane.

[0069] The Lewis acid activator (cocatalyst) is as described herein, comprising 1 to 3 (C1 to C 20 )Includes a group 13 metal compound containing a hydrocarbyl substituent.In one embodiment, the group 13 metal compound is tri((C1~C 20 )hydrocarbyl)-substituted aluminum, tri((C1~C 20 (hydrocarbyl)-boron compounds, tri((C1~C 10 )Alkyl) Aluminum, Tri((C6~C 18 These are aryl)boron compounds and their halogenated (including perhalated) derivatives. In further embodiments, the Group 13 metal compounds are tris(fluorosubstituted phenyl)borane and tris(pentafluorophenyl)borane. In some embodiments, the activation co-catalyst is tetrakis((C1~C 20 ) Hydrocarbyl borate or tri((C1~C 20 ) Hydrocarbyl) Ammonium tetrakis((C1~C 20 ()hydrocarbyl)borate (e.g., bis(octadecyl)methylammoniumtetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" means ((C1-C 20 ) Hydrocarbyl 4N+ , ((C1~C 20 ) Hydrocarbyl 3N(H) + , ((C1~C 20 )hydrocarbyl)2N(H)2 + , (C1~C 20 ) Hydrocarbyl N(H)3 + , or N(H)4 + This refers to nitrogen cations, and each (C1~C 20 If two or more hydrocarbyl molecules are present, they may be the same or different.

[0070] A combination of neutral Lewis acid activators (co-catalysts) is tri((C1~C4)alkyl)aluminum and halogenated tri((C6~C 18 Examples include mixtures containing aryl boron compounds, particularly combinations with tris(pentafluorophenyl)borane. Other embodiments include combinations of such neutral Lewis acid mixtures with polymers or oligomeric almoxanes, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymers or oligomeric almoxanes. The molar ratio of (metal-ligand complex):(tris(pentafluorophenylborane):(almoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluorophenylborane):(almoxane)] is 1:1:1 to 1:10:100, and in other embodiments, 1:1:1.5 to 1:5:30.

[0071] An activated catalyst composition can be formed by activating a catalyst system containing a metal-ligand complex of formula (I) and combining it with one or more cocatalysts, such as a strong Lewis acid, a cation-containing cocatalyst, or a combination thereof. Suitable activated cocatalysts include polymers or oligomeric aluminoxanes, particularly methyl aluminoxanes, as well as inert, compatible, non-coordinating, and ion-forming compounds. Exemplary suitable cocatalysts include tris(pentafluorophenyl)borane, modified methyl aluminoxane (MMAO), and bis(hydrogenated tulosealkyl)methyltetrakis(pentafluorophenyl)borate (1 -)amine (i.e., [HNMe(C 18 H 37 Examples include, but are not limited to, )2][B(C6F5)4]), and combinations thereof.

[0072] In some embodiments, one or more of the aforementioned activation co-catalysts are used in combination with each other. Particularly preferred combinations are tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or a mixture of ammonium borate with an oligomer or polymer-almoxane compound. The ratio of the total number of moles of one or more metal-ligand complexes of formula (I) to the total number of moles of one or more activation co-catalysts 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 10:1 or less, and in some other embodiments 1:1 or less. When an almoxane is used alone as an activation co-catalyst, the number of moles of almoxane used is preferably at least 100 times the number of moles of the metal-ligand complex of formula (I). When tris(pentafluorophenyl)borane is used alone as an activation 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 activation cocatalyst is generally used in a molar amount approximately equal to the total number of moles of one or more metal-ligand complexes of formula (I).

[0073] Chain shuttle agent The term “shutting agent” refers to a compound or mixture of compounds used in the compositions of this disclosure that, under polymerization conditions, can induce polymeryl exchange between at least two active catalytic sites of a catalyst contained in the composition. That is, the movement of polymer fragments occurs both to and from one or more of the active catalytic sites. In contrast to a shuttle agent, a “chain transfer agent” induces the cessation of polymer chain growth and corresponds to a single transfer of the growing polymer from the catalyst to the transfer agent. In some embodiments, the shuttle agent has an activity ratio RA-B / RB-A of 0.01–100, 0.1–10, 0.5–2.0, or 0.8–1.2. The activity ratio RA-B is the polymeryl transfer rate from the catalyst A active site to the catalyst B active site via the shuttle agent, and RB-A is the reverse polymeryl transfer rate, which is the exchange rate from catalyst B activity to catalyst A active site via the shuttle agent. The intermediate formed between the shuttle agent and the polymeryl chain is sufficiently stable so that chain cessation is relatively rare. In one or more embodiments, less than 90 percent, less than 75 percent, less than 50 percent, or less than 10 percent of the shuttle-polymer product is stopped before achieving three distinguishable polymer segments or blocks. The chain shuttle rate (defined by the time required to move the polymer chain from the catalytic site to the chain shuttle agent and then back to the catalytic site) is equal to or faster than the polymer stopping rate, and even up to 10 times, or even 100 times, faster than the polymer stopping rate. This allows polymer blocks to form on the same timescale as polymer propagation.

[0074] Polymer products having segments of different tacticity or regioerror, different block lengths, or different numbers of such segments or blocks in each copolymer can be prepared by selecting different combinations of catalysts and various shuttle agents. Catalysts can be selected from metal-ligand complexes of formula (I) having different polymerization capabilities, and various shuttle agents to pair with them, or mixtures of these catalysts and agents. For example, if the activity of the shuttle agent is low relative to the catalytic polymer chain propagation rate of one or more of the catalysts, multiblock copolymers and polymer blends with longer block lengths can be obtained. In contrast, if the shuttle is very fast relative to the propagation of polymer chains, copolymers with more random chain structures and shorter block lengths are obtained. Extremely fast shuttle agents can produce multiblock copolymers with substantially random copolymer properties. By appropriately selecting both the catalyst mixture and the shuttle agent, relatively pure block copolymers, copolymers containing relatively large polymer segments or blocks, and / or blends of the aforementioned with various homopolymers and / or copolymers can be obtained.

[0075] A suitable composition comprising catalyst A, catalyst B, and a chain shuttle agent can be obtained by the following multi-step procedure, which is specifically adapted for block differentiation based on tacticity or regioerror contents.

[0076] I. Polymerize one or more addition-polymerizable C3-30α-olefin monomers using a mixture containing a potential catalyst and a potential chain shuttle. This polymerization test is carried out using a batch or semi-batch reactor (i.e., without resupplying the catalyst or shuttle), preferably at a relatively constant monomer concentration, under solution polymerization conditions, and typically using a catalyst-to-chain shuttle molar ratio of 1:5 to 1:500. After forming a suitable amount of polymer, the reaction is stopped by adding a catalyst poison, and the polymer properties (tacticity and optionally regioerror contents) are measured.

[0077] II. The polymerization and polymer tests described above are repeated over several different reaction times to provide a range of polymers with yields and PDI values.

[0078] III. Catalyst / shutling agent pairs exhibiting significant polymer transfer both to and from the shuttle agent are characterized by polymer series with a minimum PDI of less than 2.0, more preferably less than 1.5, and most preferably less than 1.3. Furthermore, when chain shuttle is occurring, the Mn of the polymer increases linearly with increasing conversion. Catalyst-shutling agent pairs give polymer Mn as a function of conversion (or polymer yield) that fits a line with statistical precision (R²) greater than 0.95, preferably greater than 0.99.

[0079] Next, steps I–III were performed for one or more additional pairings of potential catalysts and / or assumed shuttling agents.

[0080] In one or more embodiments, a polymer composition comprising catalyst A, catalyst B, and one or more chain shuttles according to the present invention is then selected such that each of the two catalysts undergoes chain shuttle by one or more of the chain shuttles, wherein catalyst A has a higher ability to selectively form stereospecific polymers compared with catalyst B under the selected reaction conditions. At least one of the chain shuttles undergoes polymer transfer in both forward and reverse directions (as identified in the tests described above) in both catalyst A and catalyst B. In addition, it is preferable that the chain shuttle does not reduce the catalytic activity of any of the catalysts (measured in terms of the weight of polymer produced per unit time by the weight of catalyst) by more than 60 percent (compared to the activity in the absence of the shuttle), more preferably that the activity of such catalysts does not decrease by more than 20 percent, and most preferably that the catalytic activity of at least one of the catalysts increases compared to the catalytic activity in the absence of the shuttle.

[0081] Alternatively, catalyst-shutting agent pairs can be detected by performing a series of polymerizations under standard batch reaction conditions and measuring the properties of the resulting polymers. Suitable shuttling agents are characterized by a resulting reduction in Mn without significant PDI spreading or loss of activity (decrease in yield or rate).

[0082] The aforementioned tests are readily adaptable to high-speed throughput screening techniques using automated reactors and analytical probes, and to the formation of polymer blocks with different discriminative properties (syndiotactic, isotacticity, and optionally, regio-error contents). For example, a large number of potential shuttling agent candidates can be pre-identified or synthesized in situ by various combinations of organometallic compounds and various proton sources, and by compounds or reaction products added to polymerization reactions using olefin polymerization catalyst compositions. Several polymerizations are carried out by varying the molar ratio of the shuttling agent to the catalyst. As a minimum requirement, a suitable shuttling agent, as described above, produces a minimum PDI of less than 2.0 in variable yield experiments, while not significantly adversely affecting catalytic activity, and preferably improving catalytic activity.

[0083] Regardless of the method used to speculatively identify the shuttling agent, the term means a compound that can prepare the currently identified multiblock copolymers or that can be effectively used under the polymerization conditions disclosed herein. Very preferably, the average number of blocks or segments per mean chain (defined as the average number of blocks of different compositions divided by the Mn of the polymer) is greater than 3.0, more preferably greater than 3.5, even more preferably greater than 4.0, less than 25, preferably less than 15, more preferably less than 10.0, and most preferably less than 8.0, formed according to the present invention.

[0084] Suitable shuttle agents for use herein include metal compounds or complexes of groups 1, 2, 12, or 13 containing at least one C1-20 hydrocarbyl group, preferably hydrocarbyl-substituted aluminum, gallium, or zinc compounds containing 1 to 12 carbon atoms in each hydrocarbyl group, and reaction products thereof with a proton source. The hydrocarbyl group is an alkyl group, a linear or branched C2-8 alkyl group. In one or more embodiments of this disclosure, the shuttle agent may be added to the polymerization process. Suitable shuttle agents include trialkylaluminum and dialkylzinc compounds, particularly triethylaluminum, tri(i-propyl)aluminum, tri(i-butyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, triethylgallium, or diethylzinc. Additional suitable shuttling agents include reaction products or mixtures formed by combining the aforementioned organometallic compounds, preferably tri(C1-8)alkylaluminum or di(C1-8)alkylzinc compounds, particularly triethylaluminum, tri(i-propyl)aluminum, tri(i-butyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, or diethylzinc, with less than a stoichiometric amount (relative to the number of hydrocarbyl groups) of a secondary amine or hydroxyl compound, particularly bis(trimethylsilyl)amine, t-butyl(dimethyl)siloxane, 2-hydroxymethylpyridine, di(n-pentyl)amine, 2,6-di(t-butyl)phenol, ethyl(1-naphthyl)amine, bis(2,3,6,7-dibenzo-1-azacycloheptanamine), or 2,6-diphenylphenol. In some embodiments, the shuttling agent may be selected from amine or hydroxyl reagents such that one hydrocarbyl group remains per metal atom.The main reaction products of the aforementioned combinations for use as a shuttling agent in this disclosure are n-octylaluminum di(bis(trimethylsilyl)amide), i-propylaluminum bis(dimethyl(t-butyl)siloxide), and n-octylaluminum di(pyridinyl-2-methoxide), i-butylaluminum bis(dimethyl(t-butyl)siloxane), i-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide), i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminum bis(2,6-di-t-butylphenoxide), n-octylaluminum di(ethyl(1-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminum di(bis(trimethylsilyl)amide), and ethylaluminum These are bis(2,3,6,7-dibenzo-1-azacycloheptanamide), n-octylaluminum bis(2,3,6,7-dibenzo-1-azacycloheptanamide), n-octylaluminum bis(dimethyl(t-butyl)siloxide), ethylzinc(2,6-diphenylphenoxide), and ethylzinc(t-butoxide).

[0085] Those skilled in the art will understand that a shuttle agent suitable for a particular catalyst or combination of catalysts may not necessarily be good or even satisfactory when used with a different catalyst or combination of catalysts. Some potential shuttle agents may adversely affect the performance of one or more catalysts and may be excluded from use in the polymerization processes of this disclosure. Therefore, in order to achieve polymers having hard and soft segments, it is necessary to balance the activity of the chain shuttle agent with the catalytic activity of the catalyst.

[0086] However, generally speaking, shuttling agents possess the highest polymer migration speed and highest migration efficiency (reduced incidence of chain arrest). Such shuttling agents can still achieve a certain degree of shuttling even when used at low concentrations. In addition, such shuttling agents result in the generation of the shortest possible polymer block length. Due to the fact that the effective molecular weight of the polymer in the reactor decreases, chain shuttling agents with a single exchange site are used.

[0087] Polyolefins The catalyst systems described in the previous paragraph are used for the polymerization of olefins, mainly 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. Additional α-olefin comonomers typically have 20 or fewer carbon atoms. For example, an α-olefin comonomer may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene, ethylidene norbornene. For example, one or more α-olefin comonomers can be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively from the group consisting of 1-hexene and 1-octene.

[0088] In some embodiments, the ethylene-based polymer may contain at least 50 mole percent of ethylene-derived units. All individual values ​​and partial ranges from at least 60 mole percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer may contain at least 63 mole percent of ethylene-derived units, at least 86 mole percent of units, at least 90 mole percent of ethylene-derived units, or alternatively, 70 to 100 mole percent of ethylene-derived units, 70 to 89.5 mole percent of ethylene-derived units, or 69 to 85.5 mole percent of ethylene-derived units.

[0089] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50 mol%, in other embodiments it contains at least 1 mol% to 40 mol%, and in further embodiments the amount of additional α-olefin contains at least 10 mol% to 20 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0090] Ethylene-based polymers may be produced using any conventional polymerization process. Such conventional polymerization processes include, but are 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, etc., in parallel, in series, or any combination thereof.

[0091] In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a double reactor system, such as a double-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 co-catalysts. In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a double reactor system, such as a double-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 combination with optionally one or more other catalysts in a first reactor or a second reactor. In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a double reactor system, such as a double-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. In another embodiment, the ethylene-based polymer may be produced by solution polymerization in a single reactor system, for example, a single-loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system described in this disclosure and optionally one or more co-catalysts described in the previous paragraph.

[0092] In some embodiments, a polymerization process for producing ethylene-based polymers comprises polymerizing ethylene with at least one additional α-olefin in the presence of a catalyst system. In one or more embodiments, the catalyst system may comprise, in its catalytically active form, a metal-ligand complex according to formulas (I), (II), (III), and (IV), without a co-catalyst or additional catalyst. In further embodiments, the catalyst system may comprise, in combination with at least one co-catalyst, a metal-ligand complex according to formulas (I), (II), (III), and (IV), in its procatalytic form, its catalytically active form, or a combination of both forms. In further embodiments, the catalyst system may comprise, in combination with at least one co-catalyst and at least one additional catalyst, a metal-ligand complex according to formulas (I), (II), (III), and (IV), in its procatalytic form. In further embodiments, the catalyst system may include a first catalyst and at least one additional catalyst, and optionally at least one co-catalyst, the first catalyst being a metal-ligand complex according to formulas (I), (II), (III), and (IV) in its catalytically active form.

[0093] Ethylene polymers may further contain one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. Ethylene polymers may contain any amount of additives. Based on the weight of the ethylene polymer and one or more additives, the ethylene polymer may contain a total of about 0 to about 10 weight percent of such additives. Ethylene polymers may further contain fillers, which may include, but are not limited to, organic or inorganic fillers. Based on the total weight of the ethylene polymer and all additives or fillers, the ethylene polymer may contain about 0 to about 20 weight percent of fillers, such as calcium carbonate, talc, or Mg(OH)2. Ethylene polymers may be further compounded with one or more polymers to form blends.

[0094] In some embodiments, a polymerization process for producing an ethylene-based polymer may include polymerizing ethylene with 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). The polymer obtained from such a catalyst system incorporating a metal-ligand complex of formula (I) is then processed according to ASTM D792 (which is incorporated herein by reference in its entirety), for example, at 0.850 g / cm³. 3 ~0.950g / cm 3 , 0.880 g / cm³ 3 ~0.920g / cm 3 , 0.880 g / cm³ 3 ~0.910 g / cm³ 3 , or 0.880 g / cm³ 3 ~0.900g / cm 3 It may have a density of .

[0095] In another embodiment, the polymer obtained from a catalyst system containing the metal-ligand complex of formula (I) has a melt flow ratio of 5 to 15 (I 10 Melt index I2) may have / I2), where melt index I2 is measured according to ASTM D1238 (which is incorporated herein by reference in whole) at 190°C and a load of 2.16 kg, and melt index I 10 This is measured according to ASTM D1238 under a load of 10 kg at 190°C. In other embodiments, the melt flow ratio (I 10 The I2 ratio is 5-10, while the melt flow ratio is 5-9.

[0096] In some embodiments, the polymer obtained from a catalyst system containing the metal-ligand complex of formula (I) has a molecular weight distribution (MWD) of 1 to 10, where the MWD is M w / M n Defined as, M w This is the weight-average molecular weight, M n This is the number-average molecular weight. In other embodiments, the polymer obtained from the catalyst system has 1 to 6 MWDs. Another embodiment includes 1 to 3 MWDs, and yet another embodiment includes 1.5 to 2.5 MWDs.

[0097] The embodiments of the catalyst systems described herein result in unique polymer properties as a result of the high molecular weight of the formed polymer and the amount of comonomers incorporated into the polymer.

[0098] Batch reactor polymerization procedure Batch reactor polymerization is carried out in a 2 L Parr® batch reactor. The reactor is heated by an electrically heated 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. A dump valve is installed at the bottom of the reactor to empty the reactor contents into a stainless steel dump pot pre-filled with catalyst kill solution (typically 5 mL of Irgafos / Irganox / toluene mixture). Both the pot and the tank are purged with nitrogen and the dump pot is aerated to a 30 gal. blow tank. All solvents used for polymerization or catalyst replenishment are passed through a solvent purification column to remove any impurities that may affect polymerization. 1-Octene and IsoparE are passed through two columns: a first column containing A2 alumina and a second column containing Q5. Ethylene is passed through A204 alumina and 4

number

number

[0099] The reactor is initially filled with a shot tank that may contain IsoparE solvent and / or 1-octene, depending on the desired reactor load. The shot tank is filled to the load setpoint using a lab scale attached to the shot tank. After adding the liquid feed, the reactor is heated to the polymerization temperature setpoint. If using ethylene, ethylene is added to the reactor when the reaction temperature is reached to maintain the reaction pressure setpoint. The amount of ethylene added is monitored by a micromotion flow meter.

[0100] The catalyst and activator were mixed with appropriate amounts of purified toluene to obtain a solution of the desired molar concentration. The catalyst and activator were handled in an inert glove box, drawn into a syringe, and pressure-transferred to a catalyst shot tank. This was followed by three rinses with 5 mL each of toluene. The experimental timer was started immediately after catalyst addition. If ethylene was used, it was then added by Camile to maintain the reaction pressure setpoint in the reactor. These polymerizations were carried out for 10 minutes, then the stirrer was stopped and the bottom dump valve was opened to release the reactor contents into a dump pot. The contents of the dump pot were poured into a tray placed in a lab hood, where the solvent was allowed to evaporate overnight. The trays containing the remaining polymer were then transferred to a vacuum oven, where they were heated under vacuum to a maximum of 140°C to remove any remaining solvent. After the trays had cooled to ambient temperature, the polymers were weighed for yield / efficiency and subjected to polymer testing.

[0101] HT-GPC analysis using IR detection with embedded Octene High-temperature GPC analysis was performed using a Dow Robot-Assisted Delivery (RAD) system equipped with a PolymerChar infrared detector (IR5) and an Agilent PLgel Mixed A column. Decane (10 μL) was added to each sample for use as an internal flow marker. First, the samples were diluted in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm butylated hydroxyltoluene (BHT) to a concentration of 10 mg / mL and dissolved by stirring at 160°C for 120 minutes. Before injection, the samples were further diluted to a concentration of 2 mg / mL with BHT-stabilized TCB. The samples (250 μL) were eluted through one PL-gel 20 μm (50 × 7.5 mm) guard column, followed by two PL-gel 20 μm (300 × 7.5 mm) Mixed-A columns maintained at 160°C with BHT-stabilized TCB at a flow rate of 1.0 mL / min. The total run time was 24 minutes. To calibrate the molecular weight (MW), Agilent EasiCal polystyrene standards (PS-1 and PS-2) were dissolved by diluting them with 1.5 mL of BHT-stabilized TCB and stirring at 160°C for 15 minutes. The PS standards were then injected into the system without further dilution to create a cubic MW calibration curve with apparent units adjusted for homo-polyethylene (PE) using known Mark-Houwink coefficients for PS and PE. Octene incorporation was determined by using linear calibration developed by analyzing copolymers in known compositions.

[0102] One or more features of this disclosure are illustrated in terms of the following embodiments. [Examples]

[0103] starting materials Example 1 - Anthracenic isomer: Trans isomer: [ka] In a nitrogen-purged glove box, AlCl3 (1.81 g, 13.61 mmol) was added at room temperature to a round-bottom flask equipped with a reflux condenser containing a suspension of anthracene (50.00 g, 280.53 mmol) and t-BuCl (90.1 mL, 813.54 mmol) in CHCl3 (dried on molecular sieves) (200 mL). The mixture was heated at reflux temperature (approximately 50°C) for approximately 18 hours. After cooling to room temperature, the resulting turbid solution was filtered, collected, and dried under vacuum. The filtrate was 2,6-di-tert-butylanthracene (37.54 g, 46.1%). The filtrate contained a mixture of the two isomers, and CHCl3 was removed under reduced pressure. 2,7-di-tert-butylanthracene was obtained by extraction from the crude product with acetone (stirred in 50 mL of acetone and filtered three times). Acetone was removed under reduced pressure to obtain 2,7-di-tert-butylanthracene as pink crystals (12.54 g, 15.4%).

[0104] cis isomer: 1 H NMR(400 MHz,CDCl3)δ 8.40(d,J=1.0 Hz,1H),8.34(d,J=1.1 Hz,1H),7.98(d,J=0.8 Hz,1H),7.96-7.92(M,3H),7.60(d,J=2.0 Hz,1H),7.58(d,J=2.0 Hz,1H),1.52(s,18H).

[0105] trans isomer: 1 H NMR(400 MHz,CDCl3)δ 8.33(d,J=1.3 Hz,2H),7.94(d,J=8.9 Hz,2H),7.89(d,J=2.0 Hz,2H),7.56(dd,J=9.0,2.0 Hz,2H),1.48(s,18H). 13 C NMR(101 MHz,CDCl3)δ 147.28,131.62,130.51,127.70,125.33,124.65,122.28,34.87,30.98.

[0106] Example 2 - Anthracenyl bromide-trans isomer: [ka] In a 250 mL round-bottom flask pre-dried under nitrogen, 3.0 g of 2,6-di-tert-butylanthracene (0.0103 mol, 1.0 equivalent) was dissolved in 80 mL of anhydrous dichloromethane. 1,3-dibromo-5,5-dimethylhydantoin (1.477 g of 0.00516 mol, 0.50 equivalent) in 30 mL of acetonitrile was added dropwise over 29 minutes. The reactants were then stirred at room temperature for 2 hours. The reactants were light brown in color. The reactants were concentrated by adding approximately 50 mL of methanol and approximately 20 mL of dichloromethane until dissolved. The resulting solid was added to approximately 50 mL of methanol, the yellow solid was filtered off, and the mixture was washed with a minimal amount of methanol. The solid was added to approximately 50 mL of ethanol and heated under reflux until dissolved. After standing, a crystalline solid emerged from the solution. The suspension at room temperature was filtered, and the solid was rinsed with a minimal amount of ethanol. The filtrate was concentrated until approximately 30 mL of ethanol remained. The suspension was heated under reflux until all the solid was dissolved. Upon cooling to room temperature, a second harvest of crystalline solid was formed. The solid was filtered and rinsed with a minimal amount of ethanol. The material was dried in a vacuum oven and used without further purification. 2.08 g of the reactant was obtained (54% yield).

[0107] 1 H NMR(400 MHz,CDCl3)δ 8.43(dt,J=9.3,0.8 Hz,1H),8.39(dt,J=1.8,0.8 Hz,1H),8.34(s,1H),7.96-7.88(m,1H),7.87-7.82(m,1H),7.68(dd,J=9.3,2.0 Hz,1H),7.58(dd,J=8.9,1.9 Hz,1H),1.48(s,9H),1.45(s,9H).

[0108] Example 3 - Anthracenyl bromide cis isomer: [ka] In a 500 mL round-bottom flask pre-dried under nitrogen, 2,6-di-tert-butylanthracene (8.80 g, 0.0273 mol, 1.0 equivalent) was dissolved in 160 mL of anhydrous dichloromethane. (The starting material was estimated to be 90% pure. The theoretical amount was 7.92 g.) A solution of 1,3-dibromo-5,5-dimethylhydantoin (3.900 g, 0.0138 mol, 0.50 equivalent) in 60 mL of acetonitrile was added dropwise over 67 minutes. The reactants were stirred at room temperature for 4 hours. The reactants were concentrated and taken up in approximately 70 mL of hexane. The material was filtered, the solid was rinsed with hexane (xs), and the combined filtrate was concentrated. The material was purified mostly by chromatography using silica gel (100% hexane). The obtained material was taken up in boiling ethanol. The solution was concentrated until solids began to appear. The solution was cooled to room temperature. The solid was filtered and rinsed with a small amount of ethanol. The product was 3.86 g of an off-white crystalline solid, with a yield of 38%.

[0109] 1 H NMR(400 MHz,CDCl3)δ 8.42(s,2H),8.33(s,1H),7.92(d,J=8.9 Hz,2H),7.58(dd,J=8.9,1.8 Hz,2H),1.49(s,18H).

[0110] 13 C NMR(101 MHz,CDCl3)δ 149.64,130.56,128.29,125.84,124.86,122.29,121.94,35.43,30.95.

[0111] Example 4-2-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole [ka] Inside a nitrogen glove box, sodium hydride (1.094 g, 95%, 0.0433 mol, 4.00 equivalents) and 60 mL of dry THF were added to a 250 mL round-bottom flask. Then, pyrrole (3.01 mL, 0.0433 mol, 4.00 equivalents) was added dropwise. The mixture was vigorously stirred for 4 hours.

[0112] Zinc chloride (5.904 g, 0.0433 mol, 4.00 equivalents) was added gradually over several minutes. After stirring for 10 minutes, CyJohnPhos ligand (0.152 g, 4.332 × 10) was added. -4 (mol, 0.04 equivalents) and Pd2(dba)3, (Tris(dibenzylideneacetone)dipalladium(0), 0.198g, 2.166×10 -4 (mol, 0.02 equivalents) was added. The solution was stirred for a further 5 minutes, and 9-bromo-2,6-di-tert-butylanthracene (18-BT5449-1, 4.00 g, 0.108 mol, 1.00 equivalent) was added. A bellows condenser was attached, and the mixture was stirred at 80°C for 16 hours.

[0113] The solution was cooled and diluted with ethyl acetate. The reactants were slowly and carefully quenched with 50 mL of water. The suspension was filtered to remove the zinc salts. The product was extracted with a portion of ethyl acetate, the combined organic fraction was dried over magnesium sulfate and concentrated, and the residue was purified by chromatography on silica gel (0-5% ethyl acetate in hexane). 2.51-3.23 g of the product was isolated as a yellow-orange solid (65-84% yield).

[0114] 1 H NMR(400 MHz,CDCl3)δ 8.37(s,1H),8.28(s,1H),7.93(d,J=8.9 Hz,1H),7.89-7.81(m,3H),7.54(dd,J=8.9,1.9 Hz,1H),7.48(dd,J=9.3,1.9 Hz,1H),7.04(t,J=2.5 Hz,1H),6.51(q,J=2.8 Hz,1H),6.49-6.46(m,1H),1.43(s,9H),1.34(s,9H).

[0115] 13 C NMR(101 MHz,CDCl3)δ 147.67,147.12,131.37,131.20,130.40,130.14,127.91,127.79,127.58,126.47,126.3 3,125.10,124.55,122.46,120.70,117.77,111.07,108.92,35.04,34.77,30.92,30.88.

[0116] UP-LCMS(M+1)356.2

[0117] Example 5 - 2,6-di-tert-butylanthracenyl-2-pyrrole [ka] Inside a nitrogen glove box, 2-(2,6-di-tert-butylanthracene-9-yl)-1H-pyrrole (2.00 g, 0.00562 mol, 1.00 equivalent) and 50 mL of hexane were added to a 250 mL round-bottom flask. In a 20 mL vial, 0.056 g of [Ir(COD)OMe]2((1,5-cyclooctadiene)(methoxy)iridium(I) dimer was added, along with 8.438 × 10⁻¹⁴ ions. -5 0.015 mol and 10 mL of hexane were added. HBpin (4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 1.280 mL, 0.00844 mol, 1.5 equivalents) was added, followed by 4,4'-di-tert-butyl-2,2'-bipyridine (dtbbpy, 0.045 g, 1.688 × 10⁻¹⁵). -4 (mol, 0.03 equivalents) was added. The mixture was stirred for 6 minutes and added to the pyrrole-containing solution. The flask was connected to a tubular condenser and stirred overnight at 60°C.

[0118] The dark-colored solution was cooled. The reactants were diluted with 70 mL of ethyl acetate and slowly quenched by slowly adding approximately 10 mL of methanol. The reactants were stirred for 20 minutes. Volatile substances were removed by rotary evaporation. The residue was purified by chromatography on silica gel (20-60% dichloromethane in hexane). The product was isolated as a yellow-orange solid (1.44-180 g, 53-58%). The product contains approximately 15% of the 2-(2,6-di-tert-butylanthracene-9-yl)-1H-pyrrole starting material.

[0119] 1 H NMR(400 MHz,CDCl3)δ 8.88(s,1H),8.37(s,1H),7.93(d,J=8.9 Hz,1H),7.89-7.79(m,3H),7.54(dd,J=8.9,1.9 Hz,1H),7.48(dd,J=9.2,2.0 Hz,1H),7.10(dd,J=3.4,2.5 Hz,1H),6.55(dd,J=3.4,2.4 Hz,1H),1.43(s,9H),1.34(d,J=1.3 Hz,18H).

[0120] 13 C NMR(101 MHz,CDCl3)δ 147.70,147.11,132.83,131.15,131.08,130.10,130.08,127.89,127.31,126.67,126.25, 125.21,124.55,122.45,120.70,120.67,112.86,83.54,35.07,34.78,30.91,30.86,24.80.

[0121] UP-LCMS(M+1)482.3

[0122] Example 6 [ka] Inside a nitrogen glove box, a 100 mL RB flask was filled with 9-bromo-2,7-di-tert-butylanthracene (2.00 g, 0.005415 mol, 1.00 equivalent), 3,5-di-t-butylphenylboronic acid (1.902 g, 0.008122 mol, 1.50 equivalent), tripotassium phosphate (3.448 g, 0.01624 mol, 3.00 equivalent), and Pd(amphos)Cl , (Bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)-dichloropalladium(II), 0.114g, 4.090×10 -4 (0.10 equivalents of mol) was added. 40 mL of 1,4-dioxane and 8 mL of water were added. The reactants were heated to 50°C and stirred overnight.

[0123] After 18.5 hours, the reaction mixture was cooled and removed from the dry box. The mixture was diluted with 120 mL of ethyl acetate, and the organic matter was washed with water (50 mL x 3) and brine (50 mL x 1). The organic matter was dried over magnesium sulfate, filtered, and concentrated. The substance was purified by chromatography using silica gel (100% hexane) to obtain 2.516 g of a white crystalline solid in 97% yield.

[0124] 1 H NMR(400 MHz,CDCl3)δ 8.35(s,1H),7.95(d,J=8.9Hz,2H),7.69(s,2H),7.53(d,J=1.9Hz,1H),7.52-7.50(m,2H),7.30(d,J=1.8 Hz,2H),1.39(s,18H),1.29(s,18H).

[0125] 13 C NMR(101 MHz, CDCl3)δ150.19,146.98,137.85,137.56,130.16,129.82,127.92,125.95,124.94,124.08,121.39,120.38,35.03,34.98,31.62,30.91.

[0126] GCMS:(M+1)479.4

[0127] Example 7 [ka] In a 250 mL pre-dried RB flask under nitrogen, 2,7-di-tert-butyl-9-(3,5-di-tert-butylphenyl)anthracene (2.475 g, 0.005170 mol, 1.0 equivalent) was dissolved in 70 mL of anhydrous dichloromethane. 1,3-dibromo-5,5-dimethylhydantoin (0.754 g, 0.002636 mol, 0.51 equivalent) in 10 mL of acetonitrile was added dropwise over 20 minutes. The reactants were then stirred at room temperature for 3 hours. The reactants were concentrated and then taken up in approximately 50 mL of methanol containing dichloromethane until dissolved. The residue was purified by chromatography on silica gel (0-5% dichloromethane in hexane). The product was isolated as a pale yellow solid (2.742 g, 95%).

[0128] 1 H NMR(400 MHz,CDCl3)δ 8.50(d,J=9.8 Hz,2H),7.67-7.63(m,4H),7.53(t,J=1.9 Hz,1H),7.26(d,J=1.8 Hz,2H),1.38(s,18H),1.28(s,18H).

[0129] 13 C NMR(101 MHz,CDCl3)δ 150.39,147.28,138.50,137.27,131.07,128.56,127.38,125.89,125.77,121.94,121.34,120.67,34.98,34.87,31.58,30.79.

[0130] UP-LCMS(M+1)558.2

[0131] Example 8 [ka] Inside a nitrogen glove box, 95% sodium hydride (0.362 g, 0.0143 mol, 4.00 equivalents) and 40 mL of dry THF were placed in a 100 mL round-bottom flask. Pyrrole (1.00 mL, 0.0143 mol, 4.00 equivalents) was added dropwise. The mixture was vigorously stirred for 4 hours.

[0132] Zinc chloride (1.955 g, 0.0143 mol, 4.00 equivalents) was added gradually over several minutes. After stirring for 10 minutes, CyJohnPhos ligand (0.050 g, 1.434 × 10) was added. -4 (mol, 0.04 equivalents) and Pd2(dba)3, (Tris(dibenzylideneacetone)dipalladium(0), 0.066g, 7.173×10 -5 (mol, 0.02 equivalents) was added. The solution was stirred for an additional 5 minutes, and then 10-bromo-2,7-di-tert-butyl-9-(3,5-di-tert-butylphenyl)anthracene (2.00 g, 0.003586 mol, 1.00 equivalent) was added. A tubular condenser was attached, and the reactants were stirred at 80°C for 19 hours.

[0133] The solution was cooled and diluted with ethyl acetate. The reactants were slowly and carefully quenched with 20 mL of water. The suspension was filtered to remove the zinc salts. The product was extracted with a portion of ethyl acetate, and the combined organic fraction was dried over magnesium sulfate, concentrated, and the residue was purified by chromatography on silica gel (20-50% dichloromethane in hexane). 1.533 g of the product was isolated as a yellow-orange solid (65-84% yield).

[0134] 1 H NMR(400 MHz,CDCl3)δ 8.32(s,1H),7.88(d,J=9.2 Hz,2H),7.69(d,J=2.0 Hz,2H),7.53(t,J=1.9 Hz,1H),7.46(dd,J=9.2,2.0 Hz,2H),7.31(d,J=1.8 Hz,2H),7.10-7.03(m,1H),6.57-6.46(m,2H),1.40(s,18H),1.27(s,18H).

[0135] 13 C NMR(101 MHz,CDCl3)δ 150.32,146.85,138.87,137.69,129.94,129.86,127.96,127.25,126.36,125.8 6,124.46,121.59,120.49,117.79,111.16,108.87,35.00,34.89,31.61,30.83.

[0136] UP-LCMS(M+1)544.3

[0137] Example 9 [ka] Inside a nitrogen glove box, 2-(3,6-di-tert-butyl-10-(3,5-di-tert-butylphenyl)anthracene-9-yl)-1H-pyrrole (1.515 g, 0.00279 mol, 1.00 equivalent) and 50 mL of hexane were added to a 100 mL round-bottom flask. In a 20 mL vial, [Ir(COD)OMe]2(1,5-cyclooctadiene)(methoxy)iridium(I) dimer (0.028 g, 84.179 × 10⁻⁵ mol, 0.015 equivalent) and 10 mL of hexane were added. HBpin (4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 0.61 mL, 0.004179 mol, 1.5 equivalents) was added, followed by 4,4'-di-tert-butyl-2,2'-bipyridine (dtbbpy, 0.022 g, 8.257 × 10⁻⁵ mol, 0.03 equivalents). The mixture was stirred for 7 minutes and added to a pyrrole-containing flask. The flask was connected to a tubular condenser and stirred overnight at 60°C.

[0138] After 16 hours, the reactants were cooled and diluted with 70 mL of ethyl acetate. The reactants were quenched by slowly adding approximately 10 mL of methanol. The reactants were stirred for 20 minutes. Volatile substances were removed by rotary evaporation. The residue was purified by chromatography on silica gel (20-25% dichloromethane in hexane). The product was isolated as an orange solid (1.277 g, 68%).

[0139] 1 H NMR(400 MHz,CDCl3)δ 8.90(s,1H),7.84(d,J=9.2 Hz,2H),7.69(d,J=1.8 Hz,2H),7.53(t,J=1.8 Hz,1H),7.45(dd,J=9.2,2.0 Hz,2H),7.31(d,J=1.9 Hz,2H),7.12(dd,J=3.4,2.5 Hz,1H),6.55(dd,J=3.4,2.4 Hz,1H),1.40(s,18H),1.33(s,12H),1.27(d,J=1.5 Hz,18H).

[0140] 13 C NMR(101 MHz,CDCl3)δ 324.34,320.88,313.08,311.71,307.24,303.92,303.66,300.89,300.35,299.88, 298.55,295.59,294.62,294.53,287.00,209.00,208.90,205.62,204.83,198.84.

[0141] UP-LCMS(M+1)670.3

[0142] Example 10 [ka] Inside a nitrogen glove box, 95% sodium hydride (0.547 g, 0.0217 mol, 4.00 equivalents) and 40 mL of dry THF were placed in a 250 mL round-bottom flask. Pyrrole (1.50 mL, 0.0217 mol, 4.00 equivalents) was added dropwise. The mixture was vigorously stirred for 4 hours.

[0143] Zinc chloride (2.952 g, 0.0217 mol, 4.00 equivalents) was added gradually over several minutes. After stirring for 10 minutes, CyJohnPhos ligand (0.076 g, 2.17 × 10) was added. -4 (mol, 0.04 equivalents) and Pd2(dba)3, (Tris(dibenzylideneacetone)dipalladium(0), 0.099g, 1.08 × 10-4 (mol, 0.02 equivalents) was added. The solution was stirred for a further 5 minutes, and 9-bromo-2,7-di-tert-butylanthracene (2.00 g, 0.00542 mol, 1.00 equivalent) was added. A bellows condenser was attached, and the mixture was stirred at 80°C for 16 hours. The solution was cooled and diluted with 70 mL of ethyl acetate. The reactants were slowly and carefully quenched with 50 mL of water. The suspension was filtered to remove the zinc salt. The product was extracted with a portion of ethyl acetate, the combined organic fraction was dried over magnesium sulfate and concentrated, and the residue was purified by chromatography on silica gel (0-18% ethyl acetate in hexane) to yield 1.531 g of yellow solid (79% yield).

[0144] 1 H NMR(400 MHz,CDCl3)δ 8.34(s,1H),8.26(s,1H),7.92(d,J=8.9 Hz,2H),7.85-7.80(m,2H),7.52(dd,J=8.9,1.9 Hz,2H),7.04(td,J=2.7,1.5 Hz,1H),6.53-6.46(m,2H),1.34(s,18H).

[0145] 13 C NMR(101 MHz,CDCl3)δ 147.82,131.80,129.69,128.06,127.97,127.54,126.03,124.33,120.72,117.70,111.07,108.95,35.06,30.89.

[0146] UP-LCMS:(M+1)356.2

[0147] Example 11 [ka] Inside a nitrogen glove box, 2-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole (1.495 g, 0.00420 mol, 1.00 equivalent) and 40 mL of hexane were added to a 250 mL round-bottom flask. In a 20 mL vial, [Ir(COD)OMe]2((1,5-cyclooctadiene)(methoxy)iridium(I) dimer, 0.041 g, 6.307 × 10⁻¹⁴ -5 0.015 mol and 10 mL of hexane were added. HBpin (4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 0.915 mL, 0.00631 mol 1.5 equivalents) was added, followed by 4,4'-di-tert-butyl-2,2'-bipyridine (dtbbpy, 0.034 g, 1.261 × 10⁻¹⁵) -4 (mol, 0.03 equivalents) was added. The mixture was stirred for 6 minutes and added to a pyrrole-containing flask. The flask was connected to a serpentine condenser and stirred overnight at 60°C. After 19 hours, the solution was cooled. The reactants were diluted with 70 mL of ethyl acetate and slowly quenched by slowly adding approximately 10 mL of methanol. The reactants were stirred for 20 minutes. Volatile substances were removed by rotary evaporation. The residue was purified by chromatography on silica gel (0-90% dichloromethane in hexane). The product was isolated as a yellow-orange solid (1.063 g, 53%).

[0148] 1 H NMR(400 MHz,CDCl3)δ 8.89(s,1H),8.35(s,1H),7.93(d,J=8.9 Hz,2H),7.88-7.79(m,2H),7.53(dd,J=8.9,1.9 Hz,2H),7.11(dd,J=3.5,2.5 Hz,1H),6.58(dd,J=3.5,2.4 Hz,1H),1.35(d,J=2.2 Hz,30H).

[0149] 13C NMR(101 MHz,CDCl3)δ 147.89,132.86,131.37,129.70,128.00,127.47,126.20,124.33,120.73,120.70,120.68,112.87,83.52,35.09,30.86,24.79.

[0150] UP-LCMSL:(M+1)482.2

[0151] Example 12 [ka] Inside a nitrogen glove box, 0.160 g of 2-(2,6-di-tert-butylanthracene-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (anthracene-pyrrole-boronic acid ester) was added to a 45 mL vial with a septum cap. The anthracene-pyrrole-boronic acid ester contained 15% impurities, and therefore 0.136 g, 2.824 × 10⁻⁶ -4 It is assumed that the amount is 1.25 equivalents in moles. Also, the vial contains bromo or iodo heterocyclic (2.260 x 10⁻¹⁰) -4 (mol, 1.00 equivalent), 0.180 g of tripotassium phosphate (8.474 x 10) -4 mol, 3.00 equivalents), and 0.007 g of Pd(clotyl)(P-tBu3)Cl(1.695 × 10⁻⁶) -5 Add 0.06 equivalents (mol). Next, add 6 mL of 1,4-dioxane and 2 mL of water to the vial, heat the reaction mixture to 92°C, and stir overnight. After 16-18 hours, the reaction mixture was taken up in 15 mL of water and 15 mL of brine. Extract the organic matter with ethyl acetate (30 mL x 2). Dry the combined organic matter over magnesium sulfate, filter, and concentrate. Column purification was performed using 15-60% dichloromethane in hexane.

[0152] Example 13 - General synthesis for ligands [ka] Inside a nitrogen glove box, 0.160 g of 2-(2,7-di-tert-butylanthracene-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (anthracene-pyrrole-boronic acid ester) was placed in a 45 mL vial with a septum cap. The anthracene-pyrrole-boronic acid ester contained 15% impurities, and therefore 0.136 g, 2.824 × 10⁻⁴ -4 It is assumed that the amount is 1.25 equivalents in moles. Also, the vial contains bromo or iodo heterocyclic (2.260 x 10⁻¹⁰) -4 (mol, 1.00 equivalent), 0.180 g of tripotassium phosphate (8.474 x 10) -4 mol, 3.00 equivalents), and 0.007 g of Pd(clotyl)(P-tBu3)Cl(1.695 × 10⁻⁶) -5 Add 0.06 equivalents of mol. Next, add 6 mL of 1,4-dioxane and 2 mL of water to the vial, heat the reaction mixture to 92°C, and stir overnight. After 16-18 hours, the reaction mixture was taken up in 15 mL of water and 15 mL of brine. The organic matter was extracted with ethyl acetate (30 mL x 2). The combined organic matter was dried over magnesium sulfate, filtered, and concentrated.

[0153] Column purification using 15-60% dichloromethane in hexane. [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5] [Table 1-6] [Table 1-7] [Table 1-8] [Table 1-9] [Table 1-10] [Table 1-11] [Table 1-12] [Table 1-13] [Table 1-14] [Table 1-15]

[0154] General Procedures for Metal Complex Synthesis Inside a glove box, a ligand solution (0.5 mL, C6D6) was slowly added to solid M(Bn)4 (M=Zr or Hf) at room temperature. To ensure thorough mixing, the vial was swirled after each drop. After addition, the solution was transferred to an NMR tube. 1 H and 13 The sample was checked by 13C NMR. The sample was returned to the glove box to remove all volatile substances. The crude product was used for batch reactor testing without further purification.

[0155] Example 14 - Synthesis of Pro-Catalyst 1 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0156] 1 H NMR(400 MHz,C6D6)δ 8.42(d,J=1.9 Hz,1H),8.26(s,1H),8.19(d,J=9.2 Hz,1H),7.95-7.83(m,2H),7.52(ddd,J=16.6,9.1,2.0 Hz,2H),7.21-6.91(m,14H),6.89-6.62(m,7H),6.53(d,J=7.5 Hz,1H),6.42(d,J=7.6 Hz,6H),5.94(ddd,J=7.1,5.7,1.2 Hz,1H),1.88-1.69(m,6H),1.36(s,9H),1.36(s,9H).

[0157] 13 C NMR(101 MHz,C6D6)δ 154.08,147.84,147.76,147.10,144.18,143.21,140.60,139.08,138.55,137.51,13 2.14,131.66,131.53,131.39,130.66,129.91,128.96,128.60,128.48,128.43,128. 24,128.19,127.81,127.56,127.30,127.16,125.41,125.32,124.77,124.38,122.83,122.49,121.11,117.95,117.09,116.90,112.91,89.05,34.98,34.55,30.76,30.69.

[0158] Example 15 - Synthesis of Pro-Catalyst 2 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0159] 1H NMR(400 MHz,C6D6)δ 8.40(d,J=1.9 Hz,1H),8.27(s,1H),8.15(d,J=9.2 Hz,1H),7.95-7.84(m,2H),7.46(ddd,J=16.6,9.0,2.0 Hz,2H),7.19-6.83(m,19H),6.80-6.65(m,5H),6.43-6.32(m,3H),6.30-6.22(m,6H),5.98(ddd,J=7.1,5.7,1.3 Hz,1H),2.03-1.80(m,6H),1.34(s,9H),1.33(s,9H).

[0160] 13 C NMR(101 MHz,C6D6)δ 154.35,148.06,147.75,147.18,144.05,142.99,140.26,139.08,138.80,137.51, 131.94,131.92,131.56,131.46,130.69,130.59,129.19,128.96,128.36,128.26, 128.19, 128.04, 127.56, 126.85, 125.32, 125.26, 124.81, 124.15, 122.87, 122.52, 121.49, 117.52, 117.14, 116.49, 112.29, 78.59, 72.05, 34.93, 34.52, 30.75, 30.68.

[0161] Example 16 - Synthesis of Pro-Catalyst 16 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0162] 1H NMR(400 MHz,C6D6)δ 8.33-8.28(m,1H),8.21(s,1H),8.15(d,J=9.2 Hz,1H),7.95-7.85(m,2H),7.63(dd,J=9.2,2.0 Hz,1H),7.56-7.49(m,1H),7.19-6.83(m,18H),6.80(ddd,J=8.2,7.1,1.3 Hz,1H),6.74(tt,J=7.4,1.2 Hz,3H),6.59(d,J=3.5 Hz,1H),6.45-6.37(m,6H),1.97-1.84(m,6H),1.40(s,9H),1.39(s,9H).

[0163] 13 C NMR(101 MHz,C6D6)δ 168.29,149.08,148.17,147.18,146.59,143.28,137.51,134.67,132.07,131.90, 131.47,131.39,130.47,130.25,129.91,128.96,128.65,128.60,128.43,128.19,1 27.80, 127.56, 127.22, 126.77, 126.54, 125.74, 125.32, 124.80, 124.20, 123.06, 122.53, 121.40, 120.63, 120.57, 118.09, 117.59, 90.89, 35.04, 34.60, 30.79, 30.73.

[0164] Example 17 - Synthesis of Pro-Catalyst 4 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0165] 1H NMR(400 MHz,C6D6)δ 8.55-8.49(m,1H),8.34-8.22(m,2H),7.93-7.83(m,2H),7.42(ddd,J=30.8,9.1,1.9 Hz,2H),7.33(d,J=8.7 Hz,1H),7.15-6.72(m,21H),6.63(t,J=7.4 Hz,4H),6.32(dd,J=7.3,1.7 Hz,2H),6.19-6.10(m,6H),2.05-1.90(m,6H),1.26(s,9H),1.25(s,9H). 13 ¹³C NMR was not obtained.

[0166] Example 18 - Synthesis of Pro-Catalyst 20 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0167] 1 H NMR(400 MHz,C6D6)δ 8.45(dt,J=1.8,0.8Hz,1H),8.29(dt,J=9.3,0.8 Hz,1H),8.20(s,1H),7.90-7.84(m,2H),7.55(dd,J=9.2,2.0 Hz,1H),7.45(ddd,J=9.6,8.7,1.4 Hz,2H),7.14-6.85(m,16H),6.82(ddd,J=8.0,7.0,1.0 Hz, 1H), 6.71(d, J=3.4Hz, 1H), 6.66-6.59(m, 3H), 6.36-6.29(m, 6H), 1.97-1.79(m, 6H), 1.33(s, 9H), 1.31(s, 9H).13C data was not acquired.

[0168] Example 19 - Synthesis of Pro-Catalyst 17 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0169] 1H NMR(400 MHz,C6D6)δ 8.29-8.23(m,1H),8.20(s,1H),7.97(d,J=9.2 Hz,1H),7.89-7.81(m,2H),7.46(dd,J=9.1,1.9 Hz,2H),7.12-6.92(m,7H),6.87(t,J=7.6 Hz,7H),6.78(td,J=7.6,1.0 Hz,1H),6.74-6.68(m,3H),6.51(d,J=3.5 Hz,1H),6.26-6.19(m,5H),1.89(dd,J=69.3,10.9 Hz,6H),1.32(s,18H). 13 Data from C was not retrieved.

[0170] Example 20 - Synthesis of Procatalyst 8 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0171] 1 H NMR(400 MHz,C6D6)δ 8.53-8.45(m,1H),8.29(d,J=9.3 Hz,1H),8.25(s,1H),7.92-7.85(m,2H),7.44(dd,J=8.9,1.9 Hz,1H),7.33(dd,J=9.3,2.0 Hz,1H),6.83(t,J=7.6 Hz,6H),6.73(d,J=3.3 Hz,1H),6.70-6.59(m,4H),6.36-6.28(m,1H),6.15-6.07(m,6H),5.73(d,J=7.5 Hz,1H),1.86(s,3H),1.83-1.71(m,6H),1.26(s,9H),1.21(s,9H). 13 Data from C was not retrieved.

[0172] Example 21 - Synthesis of Procatalyst 7 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0173] 1 H NMR(400 MHz,C6D6)δ 8.47-8.39(m,1H),8.29-8.20(m,2H),8.18(s,1H),7.87-7.81(m,3H),7.53(dd,J=9.2,2.0 Hz,1H),7.48-7.44(m,1H),7.00-6.88(m,8H),6.80(d,J=3.3 Hz,1H),6.74-6.57(m,7H),6.38-6.31(m,6H),5.81-5.74(m,1H),1.76(s,3H),1.74-1.62(m,6H),1.31(s,18H). 13 Data from C was not retrieved.

[0174] Example 22 - Synthesis of Procatalyst [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0175] 1 H NMR(400 MHz,C6D6)δ 8.38(d,J=1.9 Hz,1H),8.26(s,1H),8.23(d,J=9.2 Hz,1H),7.97-7.88(m,2H),7.62(dd,J=9.2,2.0 Hz,1H),7.52(dd,J=8.9,1.9 Hz,1H),7.14-6.89(m,15H),6.76-6.68(m,5H),6.61(d,J=3.5 Hz,1H),2.73(s,3H),2.00-1.84(m,6H),1.41(s,9H),1.38(s,9H).

[0176] 131C NMR (101 MHz,C6D6)δ147.87,145.13,143.93,139.56,138.54,136.03,132.22,1 31.63,130.60,129.91,128.96,128.60,128.23,128.19,125.53,125.3 2,124.73,124.38,123.34,123.00,122.52,122.04,120.95,117.86,11 6.92,114.56,108.64,88.72,83.03,35.00,34.58,30.81,30.72,29.54.

[0177] Example 23 - Synthesis of Pro-Catalyst 23 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0178] A considerable amount of ZrBn4 remains. Significant resonance: 1 H NMR(400 MHz,C6D6)δ 8.38-8.31(m,1H),8.29(s,1H),8.15-8.09(m,1H),2.81(s,3H),2.00(dd,J=60.3,10.8Hz,6H),1.37(s,9H),1.35(s,9H).

[0179] Significant resonance. A considerable amount of ZrBn4 remains. 13 C NMR(101 MHz, C6D6)δ 139.08,130.59,124.14,72.05.

[0180] Example 24 - Synthesis of Pro-Catalyst 18 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0181] 1H NMR(400 MHz,C6D6)δ 8.24(d,J=2.6 Hz,3H),7.88(d,J=8.9 Hz,2H),7.49(dd,J=8.9,1.8Hz,2H),7.12(d,J=7.4 Hz,1H),7.04(d,J=16.5Hz,2H),6.98(t,J=7.4 Hz,7H),6.93(d,J=3.5Hz,1H),6.89-6.76(m,3H),6.73(t,J=7.5 Hz,3H),6.67(d,J=3.4 Hz,1H),6.42(d,J=7.6 Hz,6H),1.91(s,6H),1.37(s,18H).

[0182] 13 C NMR(101 MHz,C6D6)δ 168.40,149.22,148.34,147.04,143.60,134.94,132.68,132.12,130.62,128.69,128.51,128.20,12 7.25,127.01,125.33,124.64,124.18,122.52,121.34,120.58,118.04,117.47,91.03,35.01,30.71.

[0183] Example 25-Synthesis of プロcatalyst 19

change

[0184] 1 H NMR(400 MHz,C6D6)δ 8.29(s,1H),8.19(d,J=1.9 Hz,2H),7.89(d,J=8.9 Hz,2H),7.46(dd,J=8.9,1.9 Hz,2H),7.12(d,J=7.4 Hz,1H),7.06(s,1H),7.05-6.98(m,3H),6.90(t,J=7.6 Hz,6H),6.79(ddd,J=34.3,18.0,7.9 Hz,6H),6.62(d,J=3.4 Hz,1H),6.27(d,J=7.6 Hz,6H),1.96(s,6H),1.31(s,18H).

[0185] 13 C NMR(101 MHz,C6D6)δ 167.74,149.48,148.21,147.42,143.25,137.53,135.04,132.48,131.97,131.49,130.10,129.44,128.97,128.37,128.2 0,127.40,126.73,126.10,125.33,124.68,123.82,123.16,121.15,121.04,120.80,117.93,116.93,79.32,34.93,30.66.

[0186] Example 26 - Synthesis of Pro-Catalyst 5 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0187] 1 H NMR(400 MHz,C6D6)δ 8.41(d,J=9.2 Hz,2H),8.16(d,J=2.0 Hz,2H),7.73(t,J=1.8 Hz,1H),7.65(t,J=1.7 Hz,1H),7.61-7.51(m,3H),7.18-7.07(m,5H),7.00(t,J=7.7 Hz,8H),6.95-6.79(m,3H),6.79-6.71(m,4H),6.44-6.38(m,6H),6.00(ddd,J=7.0,5.7,1.2 Hz,1H),1.82(s,6H),1.40(s,9H),1.33(s,9H),1.23(s,18H).

[0188] 13¹¹C NMR (10¹ MHz, C6D6)δ 154.19, 150.84, 150.46, 147.84, 147.23, 144.25, 143.33, 140.74, 139.26, 139.11, 138.57, 131.08, 130.85, 130.73, 128.96, 128.42, 128.20, 127.85, 127.26, 126.91, 126.12, 125.33, 124.93, 122.43, 121.81, 120.62, 117.95, 117.10, 117.03, 112.88, 89.52, 34.75, 31.45, 31.37, 30.61.

[0189] Example 27 - Synthesis of Pro-Catalyst 4 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0190] 1 H NMR(400 MHz,C6D6)δ 8.28(s,1H),8.20(d,J=1.9Hz,2H),7.88(d,J=8.9 Hz,2H),7.45(dd,J=8.9,1.9 Hz,2H),7.13-6.95(m,6H),6.89(t,J=7.7 Hz,7H),6.75(t,J=7.4 Hz,3H),6.72-6.60(m,2H),6.26(d,J=7.6 Hz,6H),6.02-5.90(m,1H),1.89(s,6H),1.29(s,18H).

[0191] 13 C NMR(101 MHz,C6D6)δ 154.49,148.33,147.92,144.15,143.04,140.29,138.80,132.82,132.12,130.60,130.16,129.27,128.97,128.36,128.2 7,128.20,128.10,127.94,126.54,125.33,124.61,122.95,121.38,117.60,117.15,116.35,112.23,78.03,34.89,30.65.

[0192] Example 28 - Synthesis of Pro-Catalyst 3 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0193] 1 H NMR(400 MHz,C6D6)δ 8.32-8.21(m,3H),7.89(d,J=8.9 Hz,2H),7.46(dd,J=9.0,1.9 Hz,2H),7.20-6.89(m,14H),6.81(d,J=8.2 Hz,1H),6.75-6.69(m,4H),6.64(ddd,J=8.4,7.2,1.5Hz,1H),6.48-6.40(m,6H),5.92(ddd,J=7.1,5.7,1.3 Hz,1H),1.79(s,6H),1.32(s,18H).

[0194] 13 C NMR(101 MHz,C6D6)δ 154.26,148.00,147.97,144.60,143.15,140.55,139.07,132.95,131.66,130.18,129.92,128.97,128.61,128.5 2,128.47,128.20,126.83,125.33,124.59,122.61,121.03,118.04,117.17,116.89,112.83,88.75,34.94,30.66.

[0195] Example 29 - Synthesis of Pro-Catalyst 24 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0196] 1H NMR(400 MHz,C6D6)δ 8.32(d,J=1.9 Hz,1H),8.15(d,J=10.7 Hz,2H),7.87(d,J=9.0 Hz,2H),7.61(dd,J=9.1,2.0 Hz,1H),7.51(dd,J=8.9,1.9 Hz,1H),7.12(s,1H),7.03(d,J=7.8Hz,8H),6.80-6.72(m,4H),6.54(dd,J=10.3,5.4 Hz,2H),6.43(d,J=7.6 Hz,6H),5.49(s,1H),1.78(d,J=2.9 Hz,6H),1.69(s,3H),1.40(d,J=2.0 Hz,18H).

[0197] 13 ¹¹C NMR (10¹ MHz, C6D6)δ 168.24, 149.53, 148.02, 147.05, 144.13, 143.68, 137.52, 134.61, 132.25, 131.61, 131.42, 130.62, 130.49, 129.92, 128.97, 128.65, 128.61, 128.35, 128.20, 126.97, 125.50, 125.33, 124.70, 123.02, 122.43, 120.79, 116.93, 114.47, 109.81, 91.73, 35.02, 34.59, 30.80, 30.75, 15.95.

[0198] Example 30 - Synthesis of Pro-Catalyst 6 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0199] 1H NMR(400 MHz,C6D6)δ 8.41(d,J=9.2 Hz,2H),8.14(d,J=2.0 Hz,2H),7.74(q,J=1.6 Hz,1H),7.65(dq,J=11.9,1.4 Hz,2H),7.49(dt,J=9.3,1.4 Hz,2H),7.15-6.95(m,10H),6.94(t,J=7.6 Hz,7H),6.87-6.71(m,5H),6.38(d,J=7.6 Hz,1H),6.30(d,J=7.6 Hz,6H),6.09-5.95(m,1H),1.99(s,6H),1.40(s,9H),1.38(s,9H),1.19(s,18H).

[0200] 13 C NMR(101 MHz,C6D6)δ 154.44,150.76,150.60,148.17,147.31,144.32,142.97,140.33,139.10,138 .89,138.85,138.63,137.52,131.51,130.73,130.60,130.54,129.09,128.96, 128.37, 128.18, 126.68, 126.33, 125.33, 124.83, 124.15, 122.86, 121.53, 120.66, 117.50, 117.16, 116.77, 112.28, 79.40, 34.87, 34.85, 34.72, 31.43, 30.58.

[0201] Example 31 - Synthesis of Pro-Catalyst 12 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0202] 1H NMR(400 MHz,C6D6)δ 8.57(d,J=2.0 Hz,1H),8.30(s,1H),8.27(d,J=9.2 Hz,1H),7.51(ddd,J=8.2,6.0,2.0 Hz,2H),7.12(d,J=7.7 Hz,1H),7.09-6.98(m,3H),6.98-6.90(m,7H),6.80(d,J=3.3 Hz,1H),6.74-6.66(m,4H),6.56-6.49(m,2H),6.46-6.37(m,6H),2.05(s,3H),1.93-1.68(m,6H),1.54(s,3H),1.36(s,9H),1.33(s,9H).

[0203] 13 ¹¹C NMR (10¹ MHz, C6D6)δ 150.11,147.81,147.11,145.98,144.07,143.19,142.74,141.12,131.92,131.67,131.65,131.52,130.83,129.92,128.97,128.61,128.47,127.11,127.03,125.38,125.33,124.82,122.77,122.21,121.39,117.03,116.15,89.05,34.98,34.51,30.77,30.65,20.79,16.77.

[0204] Example 32 - Synthesis of Pro-Catalyst 10 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0205] 1H NMR(400 MHz,C6D6)δ 8.42(d,J=1.9 Hz,1H),8.27(s,1H),8.22(d,J=9.2 Hz,1H),7.95-7.84(m,2H),7.52(ddd,J=15.6,9.1,2.0 Hz,2H),7.14-6.89(m,12H),6.82(s,1H),6.74(dd,J=9.4,5.4 Hz,4H),6.46(d,J=7.6 Hz,6H),5.84(dd,J=5.9,1.7 Hz,1H),1.91-1.71(m,6H),1.58(s,3H),1.37(s,9H),1.36(s,9H).

[0206] 13 C NMR(101 MHz,C6D6)δ 154.02,151.30,147.79,147.46,147.09,143.97,143.38,140.52,137.5 2,132.23,131.69,131.57,130.68,129.92,128.97,128.48,128.41,128. 20, 127.24, 127.12, 125.38, 125.33, 124.77, 122.82, 122.43, 121.17, 119.51, 117.44, 116.82, 112.45, 88.86, 34.97, 34.55, 30.75, 30.70, 20.57.

[0207] Example 33 - Synthesis of Pro-Catalyst 22 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0208] 1H NMR(400 MHz,C6D6)δ 8.49(s,1H),8.32(d,J=9.2 Hz,1H),8.24(s,1H),7.92(dd,J=5.5,3.5Hz,2H),7.73(d,J=8.2 Hz,1H),7.62(dd,J=9.3,1.9 Hz,1H),7.53(dd,J=9.0,1.9 Hz,1H),7.18-6.96(m,8H),6.92(t,J=7.6 Hz,6H),6.76(d,J=3.1 Hz,1H),6.68(t,J=7.4 Hz,3H),6.49(d,J=8.6 Hz,1H),6.41(d,J=7.6 Hz,6H),2.76(s,3H),1.82(d,J=2.0 Hz,6H),1.39(d,J=1.6Hz,18H).

[0209] 13 C NMR(101 MHz, C6D6)δ 147.82,147.03,144.79,144.11,142.99,140.57,132.51,132.41,131.89,131.58,131.34,130.64,128.97,128.25,128.20,127. 15,125.33,124.76,122.90,122.32,121.54,121.20,117.63,115.59,112.03,108.75,90.83,35.01,34.58,34.03,30.79,30.74.

[0210] Example 34 - Synthesis of Pro-Catalyst 13 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0211] 1H NMR(400 MHz,C6D6)δ 8.47(s,1H),8.28(t,J=4.5 Hz,2H),7.92(d,J=8.8 Hz,2H),7.58-7.45(m,2H),7.14-6.95(m,13H),6.83-6.73(m,4H),6.55(d,J=7.6 Hz,6H),6.33(d,J=2.6 Hz,1H),5.36(dd,J=6.9,2.6 Hz,1H),2.03(s,6H),1.97-1.80(m,6H),1.36(s,9H),1.35(s,9H).

[0212] 13 ¹¹C NMR (10¹ MHz, C6D6)δ 155.40, 154.39, 148.04, 147.53, 146.98, 144.09, 142.77, 141.07, 137.53, 132.36, 132.20, 131.81, 131.62, 130.73, 128.97, 128.39, 128.29, 128.20, 128.02, 126.86, 125.33, 125.26, 124.70, 122.71, 122.13, 121.49, 116.39, 110.37, 102.47, 96.84, 88.07, 37.90, 34.96, 34.53, 30.77, 30.71.

[0213] Example 35 - Synthesis of Pro-Catalyst 14 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0214] 1H NMR(400 MHz,C6D6)δ 8.35(d,J=1.8 Hz,1H),8.25(s,1H),8.15(d,J=9.2 Hz,1H),7.96-7.83(m,2H),7.56(dd,J=9.2,2.0 Hz,1H),7.49(dd,J=9.0,1.9 Hz,1H),7.13-6.87(m,12H),6.72(dd,J=8.8,5.6 Hz,4H),6.65(d,J=3.4 Hz,1H),6.55-6.46(m,2H),6.39(d,J=7.6 Hz,6H),5.64(td,J=7.1,2.5 Hz,1H),1.84-1.65(m,6H),1.36(s,9H),1.35(s,9H).

[0215] 13 C NMR(101 MHz,C6D6)δ 157.46,157.35,151.36,151.26,147.98,147.17,144.86,143.02,139.79,138.56,13 2.12,131.59,131.52,131.05,130.63,129.92,128.97,128.61,128.53,128.50,128. 20,127.78,127.32,127.02,125.47,125.33,124.82,124.39,122.89,122.66,120.94,117.25,113.91,106.87,106.67,103.33,103.13,89.12,34.98,34.55,30.73,30.68.

[0216] Example 36 - Synthesis of Pro-Catalyst 25 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0217] 1H NMR(400 MHz,C6D6)δ 8.34(d,J=1.9 Hz,1H),8.18(t,J=4.4 Hz,2H),7.94-7.83(m,2H),7.61(dd,J=9.3,2.0 Hz,1H),7.51(dd,J=9.0,1.9 Hz,1H),7.14-6.95(m,10H),6.79-6.72(m,4H),6.58(d,J=3.3 Hz,1H),6.46(d,J=7.6 Hz,6H),1.80(d,J=2.5 Hz,6H),1.59(s,3H),1.51(s,3H),1.40(s,18H).

[0218] 13 ¹¹C NMR (10¹ MHz, C6D6)δ 164.92, 147.94, 147.02, 144.30, 143.40, 137.52, 134.66, 132.29, 131.63, 131.44, 130.78, 130.50, 128.96, 128.62, 128.28, 128.20, 127.12, 127.04, 125.47, 125.33, 124.69, 122.98, 122.35, 122.27, 120.88, 116.76, 113.86, 91.51, 35.02, 34.59, 30.80, 30.75, 13.96, 10.38.

[0219] Example 37 - Synthesis of Pro-Catalyst 28 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0220] 1H NMR(400 MHz,C6D6)δ 8.42(s,2H),8.26(s,1H),7.91(d,J=9.0 Hz,2H),7.68(d,J=8.2 Hz,1H),7.50(dd,J=9.1,1.8 Hz,2H),7.14-6.98(m,6H),6.90(t,J=7.6 Hz,6H),6.85-6.79(m,2H),6.65(t,J=7.4 Hz,3H),6.53(d,J=7.7 Hz,1H),6.45(d,J=8.5 Hz,1H),6.41(d,J=7.7 Hz,6H),2.75(s,3H),1.82(s,6H),1.38(s,18H).

[0221] 13 C NMR(101 MHz,C6D6)δ 147.91,144.72,144.32,143.21,140.86,133.12,132.60,131.69,130.23,129.92,129.27,128.96,128.60,128.26,128.20,126.8 5,126.76,125.33,124.56,124.39,122.37,122.28,121.42,121.19,117.55,115.54,111.92,108.69,90.94,35.00,33.96,30.76.

[0222] Example 38 - Synthesis of Pro-Catalyst 26 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0223] 1H NMR(400 MHz,C6D6)δ 8.30(s,2H),8.20(s,1H),7.87(d,J=8.9 Hz,2H),7.49(dd,J=8.9,1.9 Hz,2H),7.12(d,J=7.4Hz,1H),7.02(q,J=7.1,6.4 Hz,8H),6.81-6.70(m,4H),6.65(d,J=3.3 Hz,1H),6.42(d,J=7.6 Hz,6H),1.80(s,6H),1.60(s,3H),1.48(s,3H),1.38(s,18H).

[0224] 13 C NMR(101 MHz,C6D6)δ 164.84,148.06,144.63,144.33,143.75,134.92,132.82,131.13,130.12,128.97,128.68,128.32,128.20,1 27.00,126.78,125.33,124.52,122.54,122.33,120.88,116.74,113.76,91.81,35.01,30.74,13.77,10.37.

[0225] Example 39-Synthesis of プロcatalyst 11

change

[0226] 1 H NMR(400 MHz,C6D6)δ 8.29(m,3H),7.90(dd,J=8.9,1.9 Hz,2H),7.46(dd,J=9.1,2.2 Hz,2H),7.20-7.08(m,4H),7.08-6.90(m,10H),6.84-6.67(m,5H),6.47(d,J=7.6 Hz,6H),5.81(d,J=5.9 Hz,1H),1.82(d,J=2.1 Hz,6H),1.54(d,J=2.1 Hz,3H),1.32(d,J=2.1 Hz,18H).

[0227] 13C NMR(101 MHz,C6D6)δ 154.17,151.30,147.92,147.68,144.35,143.28,140.45,132.99,131.82,130.20,128.97,128.50,128.44,1 28.20,126.77,125.33,124.59,122.54,121.11,119.60,117.58,116.80,112.37,88.55,34.94,30.66,20.52.

[0228] Example 38 - Synthesis of Procatalyst 9 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0229] 1 H NMR(400 MHz,C6D6)δ 8.45(d,J=1.9 Hz,2H),8.26(s,1H),7.90(d,J=8.9 Hz,2H),7.48(dd,J=8.9,1.9 Hz,2H),7.12(d,J=7.4 Hz,1H),7.07-6.92(m,8H),6.90(d,J=3.3 Hz,1H),6.79(d,J=3.3 Hz,1H),6.72(dt,J=14.7,7.7 Hz,4H),6.63(t,J=7.8 Hz,1H),6.33(d,J=7.6 Hz,6H),5.80(d,J=7.5 Hz,1H),1.89(s,3H),1.74(s,6H),1.33(s,18H).

[0230] 13 C NMR(101 MHz,C6D6)δ 156.57,153.01,147.96,145.30,143.60,139.82,139.21,132.71,131.41,130.25,128.97,128.58,128.20,128.1 6,126.90,126.81,125.33,124.53,122.16,121.25,120.08,116.79,115.12,113.14,91.58,34.97,30.71,23.74.

[0231] Example 39 - Synthesis of Pro-Catalyst 15 [ka] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0232] 1 H NMR(400 MHz,C6D6)δ 8.34-8.24(m,3H),7.90(d,J=9.0 Hz,2H),7.47(dd,J=9.0,1.9 Hz,2H),7.14-7.03(m,4H),7.02-6.95(m,8H),6.78-6.69(m,4H),6.55-6.45(m,8H),5.72(dd,J=6.6,2.6 Hz,1H),2.90(s,3H),1.82(s,6H),1.33(s,18H).

[0233] 13 C NMR(101 MHz,C6D6)δ 167.89,156.54,149.78,147.92,144.31,143.38,140.38,133.01,131.85,130.20,129.92,128.97,128.61,128.50,128.44,128. 20,127.99,126.77,125.33,124.59,124.39,122.54,121.12,116.75,112.19,106.97,100.16,88.41,83.07,54.44,34.95,30.67.

[0234] Example 40 - Synthesis of Precursor and Pro-Catalyst 29 [ka] 3,5-di-tert-butylbenzaldehyde (360 mg, 4.00 mmol, 2.00 equivalent), 2-pyridinecarbonitride (208 mg, 2.00 mmol, 1.00 equivalent), and ammonium acetate (771 mg, 10.0 mmol, 5.00 equivalent) were placed in a capped vial and carefully heated at 170°C for 12 hours. After cooling to RT, the mixture was neutralized with a saturated aqueous solution of NaHCO3 and extracted with ethyl acetate (2 x 10 mL). The combined organic phase was washed with brine, dried over MgSO4, and the organic solvent was removed under vacuum. GC / MS analysis showed the formation of the desired product. The crude product was purified by flash chromatography (Biotage, CH2Cl2 / ethyl acetate) to obtain the desired product as a white solid (613 mg, 59%).

[0235] 1 H NMR(400 MHz,CDCl3)δ 10.52(brs,1H),8.53(ddd,J=4.9,1.7,0.9 Hz,1H),8.32(ddd,J=8.0,1.1,1.1 Hz,1H),7.78(ddd,J=9.3,7.6,1.8Hz,1H),7.42(d,J=1.9 Hz,2H),7.36(dd,J=1.8,1.8 Hz,1H),7.31(dd,J=1.9,1.9 Hz,1H),7.25-7.21(m,3H),1.25(s,36H).

[0236] 13 C NMR(101 MHz,CDCl3)δ 151.29,150.58,148.86,148.73,144.57,140.63,137.13,134.25,130.31,129.4 3,123.02,122.36,122.33,122.19,121.43,120.28,34.98,34.92,31.60,31.52.

[0237] GC / MS(M + )m / z521.39.

[0238] Example 40 - Synthesis of Pro-Catalyst 29 [Table 2]

[0239] The final procatalyst was synthesized using a general procedure for metal complex synthesis.

[0240] As described above, pro-catalysts 1-30 were reacted individually using polymerization conditions in a batch reactor system. The properties of the resulting polymers are reported in Tables 2 and 3. [Table 3-1] [Table 3-2]

[0241] In Table 2, when the reaction temperature for ethylene-octene semi-batch copolymerization is 120°C, the reaction consists of 46.3 g of ethylene, 302 g of 1-octene, 612 g of IsoparE, and 1.2 equivalents of [HNMe(C)] relative to the catalyst. 18 H 37 The reaction involves 43 g of ethylene, 301 g of 1-octene, 548 g of isoparE, and 1.2 equivalents of [HNMe(C)C)2] activator, 10 μmol of MMAO-3A, ​​and a reactor pressure of 290 psi. When the reaction temperature in ethylene-octene semibatch copolymerization is 150°C, the reaction involves 43 g of ethylene, 301 g of 1-octene, 548 g of isoparE, and 1.2 equivalents of [HNMe(C)C] relative to the catalyst. 18 H 37 The reactor contains 2][B(C6F5)4]activator, 10 μmol of MMAO-3A, ​​and a reactor pressure of 327 psi. [Table 4-1] [Table 4-2] [Table 4-3]

[0242] Table 3 shows that the reaction temperature was 120°C for the ethylene-octene copolymerization data under chain transfer conditions for a series of pyrrole-heterocyclic catalysts. The semi-batch reactor conditions were 11.3 g of ethylene, 57 g of 1-octene, 557 g of IsoparE, and 1.2 equivalents of [HNMe(C)] relative to the catalyst. 18 H 37 )2][B(C6F5)4]activator, 10 μmol of MMAO-3A, ​​and a reactor pressure of 138 psi are included. The present invention includes the following embodiments. Section 1. It is a polymerization process, The process involves polymerizing ethylene and one or more olefins under olefin polymerization conditions in the presence of a catalyst system to form an ethylene-based polymer, wherein the catalyst system comprises a metal-ligand complex according to formula (I). [ka] During the ceremony, M is a metal selected from titanium, zirconium, or hafnium, and the metal has a formal oxidation state of +2, +3, or +4. Each X is unsaturated (C2-C 20 ) hydrocarbons, unsaturated (C2-C 50 ) Heterohydrocarbons, (C1-C 50 ) Hydrocarbyl, (C6-C 50 )aryl, (C6-C 50 )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 ) Diene, halogen, -N(R N )2, and -NCOR C A monolocate or dilocate ligand that is selected independently of, m is 1 or 2, n is 2 or 3, m+n=4, Each A independently, -C(R 3a )C(R 4a )C(R 5a )C(R 6a )-,-C(R 3a )C(R 4a )C(R5a )N-, -C(R 3a )C(R 4a )NC(R 6a )-,-C(R 3a )NC(R 5a )C(R 6a )-,-NC(R 4a )C(R 5a )C(R 6a )-, or -NC(R 4a )NC(R 6a )-(In the formula, R can be any choice 3a and R 4a , or R 4a and R 5a , or R 5a and R 6a However, they may form an aromatic or non-aromatic ring by covalent bonding), or -C(R 3b )C(R 4b )G- or -GC(R 4c )C(R 5c )-(In the formula, G is N(R 3c ), N(R 5b ), O, or S, and optionally R 3b and R 4b , or R 4c and R 5c (However, they may be covalently bonded to form an aromatic or non-aromatic ring) Each z1 independently determines N or C(R 1 ) is selected from, R 1 and R 11 However, without covalent bonding, they form aromatic or non-aromatic rings. Each z2 independently determines N or C(R 2 ) is selected from, R 1 and R 2 However, they may form aromatic or non-aromatic rings by covalent bonding. Each R 11 , R 1 , R 2 , R 3a , R 3b , R 3c , R 4a , R 4b , R 4c , R 5a , R 5b , R5c , and R 6a However, independently, (C1-C 50 ) Hydrocarbyl, (C1-C 50 ) Heterohydrocarbyl, (C6-C 50 )Aaryl, (C4-C 50 ) Heteroaryl, -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)-, -P(O)(R P )2, 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 ) Selected from the group consisting of 2NC(O)-, halogens, and -H, in the formula, each R N , R C , and R P However, independently, (C1-C 20 ) Hydrocarbyl, (C1-C 20 ) Selected from the group consisting of heterohydrocarbyl and -H, However, z1 is CR 1 And z2 is CR 2 And R 1 and R 2 However, in polymerization processes where aromatic or non-aromatic rings are formed without covalent bonding, m is 1 and n is 3. Section 2. A is -C(R 3a )C(R 4a )C(R 5a )C(R 6a )- and in the formula, R 3a and R 4a , or R 4a and R 5a , or R 5a and R 6aHowever, they may covalently bond to form an aromatic ring or a non-aromatic ring, and the metal ligand catalyst has the structure according to formula (II). [ka] In the formula, each z1, z2, R 11 , R 3a , R 4a , R 5a , R 6a The polymerization process described in item 1, wherein X, n, m, and M are defined as in formula (I). Section 3. A is -GC(R 4c )C(R 5c )- and in the formula G is N(R 3c ) and optionally, R 4c and R 5c However, they may covalently bond to form an aromatic ring or a non-aromatic ring, and the metal ligand catalyst has a structure according to formula (III). [ka] In the formula, each z1, z2, R 11 , R 3c , R 4c , R 5c The polymerization process described in item 1, wherein X, n, m, and M are defined as in formula (I). Section 4. A is -C(R 3b )C(R 4b )G-, and in the formula G is N(R 5b ) and optionally, R 3b and R 4b However, they may covalently bond to form an aromatic ring or a non-aromatic ring, and the metal ligand catalyst has a structure according to formula (IV). [ka] In the formula, each z1, z2, R 11 , R 3b , R 4b , R 3c The polymerization process described in item 1, wherein X, n, m, and M are defined as in formula (I). Section 5. A is -GC(R 4c )C(R 5c )- and in the formula G is S, and arbitrarily R 4c and R 5c However, they may covalently bond to form an aromatic ring or a non-aromatic ring, and the metal ligand catalyst has a structure according to formula (V). [ka] In the formula, each z1, z2, R 11 , R 4c , R 5c The polymerization process described in item 1, wherein X, n, m, and M are defined as in formula (I). Section 6. A polymerization process according to any one of items 1 to 5, wherein m is 1. Section 7. A polymerization process according to any one of items 1 to 6, wherein z2 is N. Section 8. R 11 The polymerization process according to any one of claims 1 to 7, wherein the polymer is phenyl, (2,4,6-triisopropyl)phenyl, 3,5-di-tert-butylphenyl, naphthyl, or cyclopropyl. Section 9. A polymerization process according to any one of claims 1 to 8, wherein X is benzyl, phenyl, or chloro. Section 10. R 11 is the radical of equation (VI), [ka] In the formula, R 12 , R 13 , R 14 , R 15 , and R 16 However, (C1-C 10 ) alkyl, (C6-C 10 A polymerization process according to any one of items 1 to 7, selected from aryl or -H. Section 11. R 12 , R 13 , R 14 , R 15, and R 16 The polymerization process according to item 10, wherein the polymer is selected from tert-butyl, 3,5-di-tert-butylphenyl, or -H. Section 12. A polymerization process according to any one of items 1 to 11, wherein z2 is N. Section 13. z2 is N and z1 is CR 1 If R 1 and R 11 The polymerization process according to item 1, wherein the aromatic or non-aromatic ring is formed without covalent bonding. Section 14. The polymerization process according to item 1, wherein the metal-ligand complex is selected from the following: [ka] [ka]

Claims

1. It is a polymerization process, The process involves polymerizing ethylene and one or more olefins under olefin polymerization conditions in the presence of a catalyst system to form an ethylene-based polymer, wherein the catalyst system comprises a metal-ligand complex according to formula (I). 【Chemistry 1】 During the ceremony, M is a metal selected from titanium, zirconium, or hafnium, and the metal has a formal oxidation state of +2, +3, or +4. Each X is independently selected from (C6-C20)aryl-(C1-C20)alkylene, m is 1, n is 3, Each A is independently selected from: -C(R ３ａ )(R ４ａ )(R ５ａ )(R ６ａ )-, -C(R ３ａ )(R ４ａ )(R ５ａ )N-, -C(R ３ａ )(R ４ａ )NC(R ６ａ )-, -C(R ３ａ )NC(R ５ａ )(R ６ａ )-, -NC(R ４ａ )(R ５ａ )(R ６ａ )-, or -NC(R ４ａ )NC(R ６ａ )- (wherein, optionally, R ３ａ and R ４ａ , or R ４ａ and R ５ａ , or R ５ａ and R ６ａ may be covalently bonded to form an aromatic or non-aromatic ring), or, -C(R ３ｂ )(R ４ｂ )G- or -GC(R ４ｃ )(R ５ｃ )- (wherein G is N(R ３ｃ ), N(R ５ｂ ), O, or S, and optionally, R ３ｂ and R ４ｂ , or R ４ｃ and R ５ｃ may be covalently bonded to form an aromatic or non-aromatic ring), and is selected from: each z １ However, independently, N or C (R １ ) is selected from, R １ and R １１ However, they do not form aromatic or non-aromatic rings through covalent bonding. each z ２ However, independently, N or C (R ２ ) is selected from, R １ and R ２ However, they may form aromatic or non-aromatic rings by covalent bonding. Each R １ 、R ２ 、R ３ａ 、R ３ｂ 、R ３ｃ 、R ４ａ 、R ４ｂ 、R ４ｃ 、R ５ａ 、R ５ｂ 、R ５ｃ 、およびR ６ａ is independently selected from the group consisting of (C １ -C ５０ ), (C １ -C ５０ ), (C ６ -C ５０ ), (C ４ -C ５０ ), -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)-、-P(O)(R Ｐ ), ２ 、R Ｃ S(O) ２ -、(R Ｃ ), ２ C=N-、R Ｃ C(O)O-、R Ｃ OC(O)-、R Ｃ C(O)N(R)-、(R Ｃ ), ２ NC(O)-、halogen, and -H, wherein each R Ｎ 、R Ｃ 、およびR Ｐ is independently selected from the group consisting of (C １ -C [[ID=9 ２０ ), (C １ -C ２０ ), and -H. Each R １１ is anthracen-9-yl substituted with one or more R groups, and each R Ｓ is independently selected from the group consisting of (C １ -C １２ )alkyl, (C ６ -C １５ )aryl, and (C ３ -C １２ )cycloalkyl, polymerization process.

2. In formula (I), A is -C(R ３ａ ) C (R ４ａ ) C (R ５ａ ) C (R ６ａ ) - and arbitrarily, R ３ａ and R ４ａ , or R ４ａ and R ５ａ , or R ５ａ and R ６ａ However, they may covalently bond to form an aromatic or non-aromatic ring, and the catalyst system has a metal-ligand complex according to formula (II). 【Chemistry 2】 In the formula, each z １ , z ２ , R １１ , R ３ａ , R ４ａ , R ５ａ , R ６ａ The polymerization process according to claim 1, wherein X, n, m, and M are defined as in formula (I).

3. A in formula (I) is -GC(R ４ｃ ) C (R ５ｃ )- and G is N(R ３ｃ ) and optionally, R ４ｃ and R ５ｃ However, they may covalently bond to form an aromatic or non-aromatic ring, and the catalyst system has a metal-ligand complex according to formula (III). 【Transformation 3】 In the formula, each z １ , z ２ , R １１ , R ３ｃ , R ４ｃ , R ５ｃ The polymerization process according to claim 1, wherein X, n, m, and M are defined as in formula (I).

4. In formula (I), A is -C(R ３ｂ ) C (R ４ｂ ) G-, and G is N(R ５ｂ ) and optionally, R ３ｂ and R ４ｂ However, they may covalently bond to form an aromatic or non-aromatic ring, and the catalyst system has a metal-ligand complex according to formula (IV). 【Chemistry 4】 In the formula, each z １ , z ２ , R １１ , R ３ｂ , R ４ｂ The polymerization process according to claim 1, wherein R 5b, X, n, m, and M are defined as in formula (I).

5. A in formula (I) is -GC(R ４ｃ ) C (R ５ｃ ) - and G is S, and arbitrarily, R ４ｃ and R ５ｃ However, they may covalently bond to form an aromatic or non-aromatic ring, and the catalyst system has a metal-ligand complex according to formula (V). 【Transformation 5】 In the formula, each z １ , z ２ , R １１ , R ４ｃ , R ５ｃ The polymerization process according to claim 1, wherein X, n, m, and M are defined as in formula (I).

6. z ２ The polymerization process according to any one of claims 1 to 5, wherein is N.

7. The polymerization process according to any one of claims 1 to 6, wherein X is benzyl.

8. R １１ is the radical of equation (VI), 【Transformation 6】 In the formula, R １２ , R １３ , R １４ , R １５ , and R １６ However, (C １ -C １０ ) alkyl, (C ６ -C １０ A polymerization process according to any one of claims 1 to 6, wherein R12, R13, R14, R15, and R16 are not all -H, selected from aryl or -H.

9. R １２ , R １３ , R １４ , R １５ , and R １６ The polymerization process according to claim 8, wherein R12, R13, R14, R15, and R16 are not all -H, selected from tert-butyl, 3,5-di-tert-butylphenyl, or -H.

10. The polymerization process according to claim 1, wherein the metal-ligand complex is selected from the following. 【Chemistry 7-1】 【Chemistry 7-2】

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