Heterocycle-heterocycle-based group iv transition metal catalysts for olefin polymerization

Abstract

To provide an olefin polymerization process capable of producing a polymer with high molecular weight and a narrow molecular weight distribution.SOLUTION: A polymerization process includes polymerizing ethylene and one or more olefins in the presence of a catalyst system under olefin polymerization conditions to form an ethylene-based polymer. The catalyst system comprises a metal-ligand complex according to a formula (I).SELECTED DRAWING: None

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. Provisional Patent Application No. 62 / 78, filed December 21, 2018. No. 3,515, the entire disclosure of which is incorporated herein by reference.

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

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

[0004] Ethylene- and propylene-based polymers are manufactured for a wide variety of articles. The ethylene and polypropylene polymerization process produces a variety of resins suitable for use in different applications. This produces a wide variety of resulting polyethylene resins with different physical properties. In order to produce a copolymer, several aspects can be varied. The above comonomers may be used in a liquid diluent such as an alkane or an isoalkane, e.g., isobutene. Hydrogen can also be added to the reactor. Catalyst systems for the synthesis of chromium-based catalyst systems, Ziegler-Natta catalyst systems, and and / or a molecular (either metallocene or non-metallocene) catalyst system. The reactants in the catalyst system are circulated in the reactor at high polymerization temperatures, thereby Periodically or continuously, the product is dissolved in a diluent to produce a homopolymer or copolymer of the tertiary amine group. A portion of the reaction mixture containing the reacted polyethylene product is separated by removing unreacted ethylene and one or more optional The reaction mixture as it is removed from the reactor is preferably 0.1 to 1.0% by weight, and more ...2 to 1.0% by weight. The polyethylene product may be treated to remove it from the diluent and unreacted reactants. Instead, the diluent and unreacted reactants are typically recycled back into the reactor. The mixture may be sent to a second reactor connected in series to the first reactor, where the second polymer is Polyethylene fractions can be produced. Despite research efforts to develop suitable catalyst systems for olefin polymerization, There remains a need to improve the efficiency of catalytic systems capable of producing polymers having fabrics. There is. Summary of the Invention

[0005] High selectivity to α-olefins during copolymerization of ethylene and α-olefins There is a continuing need to create catalytic systems or procatalysts that have high efficiency. High molecular weight at high temperature (higher than 140℃ or about 190℃) The polymer should have the versatile ability to produce high or low molecular weight polymers.

[0006] According to some embodiments, the polymerization process comprises carrying out a polymerization reaction under olefin polymerization conditions in the presence of a catalyst system. and polymerizing ethylene and one or more olefins in the presence of a tert-butyl ether to form an ethylene-based polymer. In one or more embodiments, the catalyst system comprises a metal-ligand complex according to formula (I): Including: [ka] .

[0007] In formula (I), M is a metal selected from titanium, zirconium, or hafnium. In the group of aryl groups, the metal has a formal oxidation state of +2, +3, or +4, and each X is an 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, halogen Nitride, -N(R N )2, and -NCOR C Monodentate or bidentate configurations selected independently from Subscript n is 2 and subscript m is 2, or subscript n is 3 and The 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(R6a )-, and is selected from the formula Medium, Optional, R 3a and R 4a , or R 4a and R 5a , or R 5a and R 6 a may be covalently linked to form an aromatic or non-aromatic ring. In an embodiment, -C(R 3b )C(R 4b )G-, or -GC(R 4c )C(R 5 c )-, where G is N(R 3c ), N(R 5b ), O, or S, optionally To, R 3b and R 4b , or R 4c and R 5c is covalently bonded to an aromatic ring or In formula (I), each z1 is independently N or C(R 1 ) Selected from R 1 and R 11 forms an aromatic or non-aromatic ring without a covalent bond. each z2 may independently be N or C(R 2 ) and R 1 and R 2 Share They may be linked to form an aromatic or non-aromatic ring.

[0009] In formula (I), each R 11 , R 1 , R 2 , R 3a , R 3b , R 3c , R 4a , R 4 b , R 4c , R 5a , R 5c , and R6a are independent, (C1-C 50 ) Hydrocarbohydrates le, (C1-C 50 )heterohydrocarbyl, (C6-C 50 )Aryl, (C4-C5 0) 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 O.C. O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogens, and -H wherein each R N , R C , and R P are independent, (C1-C 20 ) H Dorocarbyl, (C1-C 20 ) heterohydrocarbyl, and -H z1 is CR 1で Yes, z2 is CR 2 and R 1 and R 2 But covalently bonded When the rings form an aromatic or non-aromatic ring without any other rings, m is 1 and n is 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Specific embodiments of the catalyst system will now be described. The catalyst system of the present disclosure can be implemented in different forms. and should not be construed as being limited to the specific embodiments described in this disclosure. Please understand that this is not the case.

[0011] Common abbreviations are listed below.

[0012] Me: methyl, Et: ethyl, Ph: phenyl, BN: benzyl, t-Bu: tert t-Butyl, AcOH: acetic acid, EtOAc: ethyl acetate, NHOAc: ammonium acetate MMAO: modified methylaluminoxane, GC: gas chromatography, LC: liquid chromatography Chromatography, NMR: Nuclear Magnetic Resonance, MS: Mass Spectroscopy, mmol: millimole, mL : milliliters, M: moles, min: minutes, h: hours, d: days, DEZ: diethylzinc, M n :Number average molecular weight, M w : Weight average molecular weight, PDI: Polydispersity index.

[0013] The term "independently selected" means 1 , R 2 , R 3 , R 4 , and R 5 etc. The R groups may be the same or different (e.g., R 1 , R 2 , R 3 , R 4 ,oh YobiR 5 may all be substituted alkyl, or R 1 and R 2 is a substituted alkyl R 3 may be aryl, etc. The chemical names associated with the R group are understood by those skilled in the art to correspond to the chemical structure of the chemical name. Chemical names are intended to convey chemical structures as recognized in the art. It is intended to supplement and illustrate structural definitions known to those of skill in the art, not to preclude them. Not illustrated.

[0014] The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a compound that converts a procatalyst to a catalytically active species. As used herein, "cocatalyst" and "cocatalyst" refer to compounds that react chemically with the catalyst. The terms "activator" and "activator" are interchangeable terms.

[0015] When used to describe certain carbon atom-containing chemical groups, "(C x -C y ) " means that the unsubstituted form of the chemical group has x carbon atoms, inclusive of x and y. It means that the cation has y carbon atoms. For example, (C1-C 50 ) Al In its unsubstituted form, alkyl is an alkyl group having 1 to 50 carbon atoms. In the embodiments and general structures of the present invention, certain chemical groups are S One or more substituents such as may be replaced by the parenthesized "(C x -C y )" S Place The substituent is any group R S may contain more than y carbon atoms according to the identity of For example, "R S Exactly one group R is phenyl (-C6H5) S Replaced by (C1-C 50 )Alkyl" can contain 7 to 56 carbon atoms. Thus, In general, parenthesized "(C x -C y ) is a chemical group defined using one or more carbon atoms. child-containing substituent R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group , both x and y are any carbon atom-containing substituent R S Add the total number of carbon atoms from It is determined by.

[0016] The term "substituted" refers to a carbon atom or hetero atom of a corresponding unsubstituted compound or functional group. At least one hydrogen atom (-H) attached to an atom is replaced by a substituent (e.g., R S ) by The term "oversubstituted" means that the corresponding unsubstituted compound or functional group All hydrogen atoms (H) attached to carbon atoms or heteroatoms of the group are replaced by substituents (e.g., R S The term "polysubstituted" means replaced by the corresponding unsubstituted at least two, but not all, of the aryl groups bonded to carbon or heteroatoms of the compound or functional group; "-H" means that fewer than all hydrogen atoms are replaced by a substituent. The term "hydrogen" means a hydrogen or hydrogen radical that is covalently bonded to another atom. " and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0017] "(C1-C 50 The term "hydrocarbyl" refers to a group having 1 to 50 carbon atoms. It means a hydrocarbon radical, "(C1-C 50 The term "hydrocarbylene" refers to a compound having 1 to 1 means a hydrocarbon diradical having 50 carbon atoms, where each hydrocarbon radical and and each hydrocarbon diradical may be aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched. Branched, cyclic (having 3 or more carbons, monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and one or more R S Is it replaced by , or has not been replaced.

[0018] In the present disclosure, (C1-C 50 ) Hydrocarbyl is unsubstituted or substituted (C1-C 50 )Alkyl, (C3-C 50 )cycloalkyl, (C3-C 20 )Cycloalkyl- (C1-C 20 ) alkylene, (C6-C 40 ) aryl, or (C6-C 20 ) Ant Rule-(C1-C 20 ) alkylene (such as benzyl (-CH2-C6H5)) .

[0019] "(C1-C 50 ) alkyl" and "(C1-C 18 The term "alkyl" means Unsubstituted or one or more R S are replaced by 1 to 50, respectively. Saturated linear or branched hydrocarbon radicals having carbon atoms and having 1 to 18 carbon atoms means a saturated straight-chain or branched hydrocarbon radical that is unsubstituted (C1-C 50 ) Alkyl Examples of unsubstituted (C1-C 20 ) Alkyl, unsubstituted (C1-C 10 ) Alkyl, unsubstituted ( C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2 -Butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl , 1-heptyl, 1-nonyl, and 1-decyl. 40 ) Alkyl Examples of substitutions (C1-C 20 ) Alkyl, Substituted (C1-C 10 ) Alkyl, trifluoro Methyl, and [C 45 ] alkyl.45 The term "alkyl" refers to a substituted This means that there are up to 45 carbon atoms in the radical containing the group, e.g., , one R being (C1-C5) alkyl S is replaced by (C 27 -C 40 ) Each (C1-C5) alkyl is methyl, trifluoromethyl, ethyl, It may be 1-propyl, 1-methylethyl, or 1,1-dimethylethyl. C 10 Examples of alkyl include butyl, pentyl, hexyl, heptyl, nonyl, and Examples include all isomers of octyl, ... and decyl.

[0020] "(C6-C 50 The term "aryl" refers to unsubstituted aryl groups having 6 to 40 carbon atoms. or (one or more R S Monocyclic, bicyclic, or tricyclic aromatic carbonyl groups substituted with A hydrogen radical, at least 6 to 14 of which are aromatic ring carbon atoms. Monocyclic aromatic hydrocarbon radicals contain one aromatic ring, whereas bicyclic aromatic hydrocarbon radicals Aromatic hydrocarbon radicals have two rings and tricyclic aromatic hydrocarbon radicals have three rings. When a tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical One of the rings in the aromatic radical is aromatic. The other ring or rings in the aromatic radical may be independently fused or non-fused. It can be fused aromatic or non-aromatic. Unsubstituted (C6-C 50 ) Examples of aryl are , unsubstituted (C6-C 20 )Aryl, unsubstituted (C6-C 18 )Aryl, 2-(C1-C 5) Alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indane indenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydroindenyl Substituted (C6-C 40 ) Aryl Examples of substitutions (C1-C 20 )Aryl, Substituted (C6-C 18 ) Aryl, 2,4 -Bis([C 20 ]alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl Examples of fluorenyl include fluoren-9-on-1-yl.

[0021] "(C3-C 50 The term "cycloalkyl" means unsubstituted or one or more R S A saturated cyclic hydrocarbon radical having 3 to 50 carbon atoms, substituted by Other cycloalkyl groups, such as (C x -C y )Cycloalkyl) is x~ It has y carbon atoms and is unsubstituted or has one or more R S has been replaced by Unsubstituted (C3-C 40 ) Cycloal Examples of kills are non-substitutions (C3-C 20 )Cycloalkyl, unsubstituted (C3-C 10 ) Cycloa alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C3-C 20 )Cycloalkyl, substituted (C3-C 10 ) Cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl. do.

[0022] (C1-C 50 Examples of hydrocarbylenes include unsubstituted or substituted (C6-C 50 )Arylene, (C3-C 50 ) cycloalkylene, and (C1-C 50 ) Alkylene (For example, (C1-C 20 ) alkylene). Diradicals are those that have two alkoxy groups on the same carbon atom. (e.g. -CH2-) or on adjacent carbon atoms (i.e. 1,2-diradicals). or separated by 1, 2, or 3 or more intervening carbon atoms. (e.g. 1,3-diradical, 1,4-diradical, etc.) Examples include 1,2-, 1,3-, 1,4-, or α,ω-diradicals, and others Examples of diradicals include 1,2-diradicals. α,ω-diradicals have a maximum of 1,2-diradicals between the radical carbons. It is a diradical with a carbon skeleton spacing of 1.5 mm. (C2-C 20 ) Alkylene α,ω-diyl Some examples of dialkyls are ethane-1,2-diyl (i.e. -CH2CH2-) , propane-1,3-diyl (i.e. -CH2CH2CH2-), 2-methylpropane -1,3-diyl (i.e., -CH2CH(CH3)CH2-). C 50 Some examples of arylene α,ω-diradicals are phenyl-1,4-di naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0023] "(C1-C 50 The term "alkylene" refers to an unsubstituted or substituted alkylene with one or more R S By Saturated linear or branched diradicals having 1 to 50 carbon atoms substituted with (i.e., the radical is not on a ring atom). 50 ) Examples of alkylene is unsubstituted (C1-C 20 ) alkylene, unsubstituted -CH2CH2-, -(CH2) 3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, - (CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3) wherein "C*" is a hydrogen atom forming a secondary or tertiary alkyl radical. Substitution (C1-C 50 Examples of alkylenes are substituted (C 1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH 3) 2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosyl As mentioned above, the two R S Together, (C1-C 18 ) Alkylene Since it is possible to form a substitution (C1-C 50 Examples of alkylene 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 is also included.

[0024] "(C3-C 50 The term "cycloalkylene" refers to an unsubstituted or substituted cycloalkylene with one or more R S Cyclic diradicals having 3 to 50 carbon atoms substituted by The aryl group is a ring atom.

[0025] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing the above heteroatoms include O, S, S(O), S(O)2, Si(R C )2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2-, or -S i(R C )-, and each R C and each R P is unsubstituted (C1-C 18 ) Hydrocarbohydrates R is -H or -H. N is unsubstituted (C1-C 18 ) hydrocarbyl. The term "hydrocarbon" refers to a hydrocarbon in which one or more carbon atoms have been replaced by a heteroatom. "(C1-C 50 ) Heterohydrocarbyl means a heterohydrocarbon radical having 1 to 50 carbon atoms, and "(C1-C 50 The term "heterohydrocarbylene" refers to a heterohydrocarbylene having 1 to 50 carbon atoms. It means an atomic diradical. (C1-C 50 )heterohydrocarbyl or (C1-C 50 The heterohydrocarbon of the heterohydrocarbylene has one or more heteroatoms. The hydrocarbyl radical can be present on a carbon atom or a heteroatom. The two groups of a heterohydrocarbylene are located on a single carbon atom or a single heteroatom. Furthermore, one of the two radicals of the diradical can be present on a carbon atom. One radical can be present on a different carbon atom, and the other radical can be present on a different carbon atom. One of the radicals can be on a carbon atom and the other on a heteroatom. Alternatively, one of the two radicals may be present on a heteroatom. and the other radical can be on a different heteroatom. 0) Heterohydrocarbyl and (C1-C 50 Heterohydrocarbylene is unsubstituted or or (one or more R S ) substituted, aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or may be acyclic.

[0026] (C1-C 50 ) Heterohydrocarbyl may be unsubstituted or substituted. (C1 -C 50 Non-limiting examples of heterohydrocarbyls include (C-C 50 ) Heteroar Kill, (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 ) H Dorocarbyl-N(R N )-, (C1-C 50 ) hydrocarbyl-P(R P )-, (C2 -C 50 )heterocycloalkyl, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 )Cycloalkyl-(C1-C 19) Heteroalkyl N, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) heteroalkylene, (C 1-C 50 )heteroaryl, (C1-C 19 )Heteroaryl-(C1-C 20 ) Al Kiren, (C6-C 20 )Aryl-(C1-C 19 ) heteroalkylene, or (C1 -C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene.

[0027] "(C4-C 50 The term "heteroaryl" refers to any group having a total of 4 to 50 carbon atoms and and 1 to 10 heteroatoms, unsubstituted or (one or more R S (by means a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical having a ring structure Heteroaromatic hydrocarbon radicals contain one heteroaromatic ring and are bicyclic heteroaromatic hydrocarbons. A hydrogen radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. When bicyclic or tricyclic heteroaromatic hydrocarbon radicals are present, the radicals have At least one of the rings in the heteroaromatic radical is heteroaromatic. The ring or rings may be independently fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups, such as, for example, generally (C x -C y ) heteroaryl, ( C4-C 12 ) Heteroaryl, etc.) is a group consisting of x to y carbon atoms (e.g., 4 to 12 carbon atoms). etc.) and is unsubstituted or has one or more R S Replaced by A monocyclic heteroaromatic hydrocarbon radical is defined in the same manner as A five-membered monocyclic heteroaromatic hydrocarbon radical has 5 minus h carbon atoms. where h is the number of heteroatoms and can be 1, 2, or 3, and each heteroatom is selected from the group consisting of O , S, N, or P. Examples of five-membered heteroaromatic hydrocarbon radicals include pyridine, ... 1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrrol- ...2-yl, pyrrol-3-yl, pyrrol-2-yl, pyrrol-3-yl, furan-3-yl, thiophen-2-yl, pyrrol-3-yl, pyrrol-2-yl, pyrrol-3-yl, furan- isoxazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazolium 2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazolyl 1,3,4-oxadiazol-1-yl, 1,3,4-thiadiazol-2-yl, tetrazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazo A six-membered monocyclic heteroaromatic hydrocarbon radical is a 6-minus It has h carbon atoms, where h is the number of heteroatoms, which may be 1 or 2; The alkyl group may be N or P. Examples of six-membered heteroaromatic hydrocarbon radicals include pyridine, ... Bicyclic rings include pyridine-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. The heteroaromatic hydrocarbon radical may be a fused 5,6- or 6,6-ring system. Examples of 5,6-ring bicyclic heteroaromatic hydrocarbon radicals include indol-1-yl and benzimidazol-1-yl. Examples of aromatic hydrocarbon radicals are quinolin-2-yl and isoquinolin-1-yl. Tricyclic heteroaromatic hydrocarbon radicals include fused 5,6,5- and 5,6,6 Examples of fused 5,6,5-ring systems include An example of such a condensation reaction is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is 9H-carbazol-9-yl. It is clidin-9-yl.

[0028] "(C1-C 50 The term "heteroalkyl" refers to an alkyl group having 1 to 50 carbon atoms and 1 "(C1-C2)" means a saturated linear or branched radical containing one or more heteroatoms. 50 The term "heteroalkylene" refers to an alkyl group having 1 to 50 carbon atoms and 1 or 2 or more heteroalkyl groups. Heteroalkyl means a saturated straight or branched chain diradical containing the above heteroatoms. Or the heteroatom of the heteroalkylene is Si(R C )3, Ge(R C )3, Si (R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C , S, S.R. C , S(O), and S(O)2; heteroalkyl groups may be mentioned. Each of the alkyl and heteroalkylene groups may be unsubstituted or may have one or more R S Replaced by There are.

[0029] Unsubstituted (C2-C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 )Heterocycloalkyl, unsubstituted (C2-C 10 ) Heterocycloalkyl, Aziridine- 1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl tetrahydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4-Dioxan-2-yl, Hexahydroazepin-4-yl, 3-Oxa-cyclo octyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0030] The term "halogen atom" or "halogen" refers to a fluorine atom (F), a chlorine atom ( "Halogen" refers to the radical of an iodine atom (I), a bromine atom (Br), or an iodine atom (I). The term "fluoride" refers to fluoride (F - ), chloride (Cl - ), bromide (Br - ),or Iodide (I - ) means the anionic form of a halogen atom.

[0031] The term "saturated" refers to carbon-carbon double bonds, carbon-carbon triple bonds, and (hetero)- (b) In the atom-containing group, carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds are lacking. It means that saturated chemical groups are one or more substituents R S If replaced by one or more The double and / or triple bonds may optionally be substituted with a substituent R S It may be present in The term "unsaturated" refers to a group consisting of one or more carbon-carbon double bonds or carbon-carbon triple bonds, or (in a heteroatom-containing group) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds or containing a carbon-silicon double bond, and the substituent R S (if present), or aromatic ring or does not include any double bonds that may be present in the heteroaromatic ring (if present). do.

[0032] Embodiments of the present disclosure comprise the step of reacting ethylene and one or more olefins in the presence of a catalyst system under olefin polymerization conditions. The present invention includes a process for polymerizing the above olefins to form an ethylene-based polymer. In the above embodiment, the catalyst system comprises a metal-ligand complex according to formula (I): [ka] .

[0033] In formula (I), M is a metal selected from titanium, zirconium, or hafnium. The metal has a formal oxidation state of +2, +3, or +4; each X is an 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, halogen Nitride, -N(R N )2, and -NCOR C Monodentate or bidentate configurations selected independently from Subscript n is 2 and subscript m is 2, or subscript n is 3 and The subscript m is 1.

[0034] 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 )-, and is selected from the formula Medium, Optional, R 3a and R 4a , or R 4a and R 5a , or R 5a and R 6 a may be covalently linked to form an aromatic or non-aromatic ring. In an embodiment, -C(R 3b )C(R 4b )G-, or -GC(R 4c )C(R 5 c )-, where G is N(R 3c ), N(R 5b ), O, or S, optionally To, R 3b and R 4b , or R 4c and R 5c is covalently bonded to an aromatic ring or In formula (I), each z1 is independently N or C(R 1 ) Selected from R 1 and R 11 forms an aromatic or non-aromatic ring without a covalent bond. each z2 may independently be N or C(R 2 ) and R 1 and R 2 Share They may be linked to form an aromatic or non-aromatic ring.

[0035] In formula (I), each R 11 , R 1 , R 2 , R 3a , R 3b , R 3c , R 4a , R 4 b , R 4c , R 5a , R 5c , and R 6a are independent, (C1-C 50 ) Hydrocarbohydrates le, (C1-C 50 )heterohydrocarbyl, (C6-C 50 )Aryl, (C4-C5 0) 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 O.C. O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogens, and -H wherein each R N , R C , and R P are independent, (C1-C 20 ) H Dorocarbyl, (C1-C 20 ) heterohydrocarbyl, and -H z1 is CR 1 and z2 is CR 2 and R 1 and R 2 But covalently bonded When the rings form an aromatic or non-aromatic ring without any other rings, m is 1 and n is 3.

[0036] In some embodiments, the chemical group 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 BiR 6a , y, and z 1-2 Any or all of the groups may be unsubstituted. In another embodiment, 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 None of the following has one or more R S or among them Any or all of R may be substituted. S is represented by formula (I) When attached to the same chemical group in a metal-ligand complex, the individual R S The same carbon The carbon atom or heteroatom may be bonded to the ring or ring structure, or to different carbon atoms or heteroatoms. In some embodiments, the 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 None of these are R S Over R may be unsubstituted or any or all of them may be over-substituted. S In chemical groups that are over-substituted with S are all the same, but are selected independently. This is also fine.

[0037] In formula (I), when M is Ti, each X is an unsaturated (C2-C 20 ) Hydroca aryl, unsaturated (C2-C 50 )heterohydrocarbyl, (C1-C 50 ) Hydrocarbohydrates Ru, (C6-C 50 )Aryl, (C6-C 50 )heteroaryl, (C4-C 12 )J En, halogen, -N(R N )2, and -NCOR C is selected from the group consisting of:

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

[0039] In some embodiments, each R 11 is carbazole, R S Or two or more R S carbazol-9-yl, phenyl, R S Or two or more R S Place Substituted phenyl, anthracenyl, R S Or two or more R S Anthra replaced with Sen-9-yl, naphthyl, or RS or two or more R S From naphthyl substituted with may be selected, where R S is (C1-C 30 ) hydrocarbyl. In the above embodiment, R S is (C 1- C 12 ) alkyl, (C 6- C 15 ) Aryl , or (C 3- C 12 ) cycloalkyl. , R S is methyl, ethyl, propyl, 2-propyl, 2-methylpropyl, n-butyl , tert-butyl (also called 1,1-dimethylethyl), pentyl, hexyl, 1 -Cyclohexyl, heptyl, tert-octyl (1,1,3,3-tetramethylbutyric acid The alkyl group may be selected from the group consisting of n-octyl, n-butyl, and n-nonyl.

[0040] In other embodiments, each R 11 Carbazol-9-yl, 3,6-di-tert-butyl t-Butylcarbazol-9-yl, 2,7-di-tert-butylcarbazol-9- Anthracenyl, Anthracen-9-yl, 2,6-Anthracen-9-yl, 2,7-Anthracenyl 3,5-di-tert-butylphenyl, 1,1':3',1''-tert-butylphenyl Phenyl-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 is carbazole, RS Or two or more R S carbazol-9-yl, phenyl, R S if Usually two or more R S Phenyl, anthracenyl, R S Or two or more R S anthracen-9-yl, naphthyl, or R S or two or more R S in substituted naphthyl, where R S is (C1-C 30 ) Hydrocal In one or more embodiments, R S is (C1-C 12 ) alkyl, ( C 6- C 15 ) aryl, or (C 3- C 12 ) cycloalkyl. In various embodiments, R S is methyl, ethyl, propyl, 2-propyl, 2-methyl n-propyl, n-butyl, tert-butyl (also called 1,1-dimethylethyl), Pentyl, hexyl, 1-cyclohexyl, heptyl, tert-octyl (1,1,3 ,3-tetramethylbutyl), n-octyl, or nonyl. good.

[0042] In various embodiments, each Z2 is CR 2 And each R 2 is carbazole, R S Or two or more R S carbazol-9-yl, phenyl, R S or Two or more R's S Phenyl, anthracenyl, R S Or two or more RS in Substituted anthracen-9-yl, naphthyl, or R S or two or more R S Replace with naphthyl, wherein R S is (C1-C 30 ) Hydrocarbyl In one or more embodiments, R S is (C1-C 12 ) alkyl, (C6 - C 15 ) aryl, or (C 3- C 12 ) cycloalkyl. In certain embodiments, R S are methyl, ethyl, propyl, 2-propyl, and 2-methylpropyl. propyl, n-butyl, tert-butyl (also called 1,1-dimethylethyl), pentabutyl 1-cyclohexyl, hexyl, heptyl, tert-octyl (1,1,3,3 -tetramethylbutyl), n-octyl, or nonyl .

[0043] In some embodiments, each z1 is CR 1 and each z2 in N, In an embodiment, each z1 is N and each z2 is CR 2 In one or more embodiments, In each case, z1CR 1 and each z2 is CR 2 It is.

[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 a structure according to formula (II): [ka] .

[0045] In formula (II), R 3a and R 4a , or R 4a and R 5a , or R 5 a and R 6a may be covalently linked to form an aromatic or non-aromatic ring. z1, z2, R 11 , R 3a , R 4a , R 5a , R 6a , X, n, m, and M are expressed by the formula ( It is defined as follows:

[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 a structure according to formula (III) Has: [ka] .

[0047] In formula (III), optionally, R 4c and R 5c is covalently bonded to an aromatic ring or may form a non-aromatic ring, and each of z1, z2, R 11 , R 3c , R 4c , R 5c , X, n , m, and M are defined as in formula (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 according to formula (IV) Having: [ka] .

[0049] In formula (IV), optionally, R 3b and R 4b is covalently bonded to an aromatic ring or Each of z1, z2, and R may form a non-aromatic ring. 11 , R 3b , R 4b , R 3c ,X,n, m, and M are defined as in formula (I).

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

[0051] In formula (V), optionally, R 4c and R 5c is covalently bonded to an aromatic or non-aromatic ring. Each of z1, z2, and R may form an aromatic ring. 11 , R 4c , R 5c , X, n, m, and M is defined as in formula (I).

[0052] In each embodiment of formula (I), (II), (III), or (IV), formula (I) The arrows at (II), (III), and (IV) represent dative bonds. The term coordination refers to a bond between two atoms, where the bonding electrons are located on one of the In each embodiment of formula (I), (II), (III), or (IV), In this diagram, the line from N to M represents an ionic bond.

[0053] In various embodiments of formula (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 another embodiment, z2 is N and z1 is CR 1 If R 1 and R 11 forms an aromatic or non-aromatic ring without a covalent bond.

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

[0056] In one or more embodiments, the polymerization process comprises reacting a cyclic alkyl group represented by formula (I), (II), (III), and (IV), wherein R 11 is the formula (V I) is a radical. [ka]

[0057] In formula (VI), R 12 , R 13 , R 14 , R 15 , and R 16 is (C1- C 10 )Alkyl, (C6-C 10 ) aryl, or -H.

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

[0059] In the metal-ligand complex of formula (I), M is titanium (Ti), zirconium (Zr), or or hafnium (Hf), where the transition metal is a +2, +3, or +4 (X) n Subscript of n is the number of ligands X bound to the metal M and is an integer from 1, 2, or 3.

[0060] The metal M in the metal-ligand complex of formula (I) may be selected from the group consisting of aryl, ... It may be derived from a metal precursor which is subsequently subjected to a one-step synthesis or a multi-step synthesis. can be monomeric (one metal center) or dimeric (two metal centers), or More than two metal centers, e.g., three, four, five, or six or more metal centers Specific examples of suitable hafnium and zirconium precursors include, for example: HfCl4, HfMe4, Hf(CH2Ph)4, Hf(CH2CMe3)4, Hf(C H2SiMe3)4, Hf(CH2Ph)3Cl, Hf(CH2CMe3)3Cl, Hf (CH2SiMe3)3Cl, Hf(CH2Ph)2Cl2, Hf(CH2CMe3)2 Cl2, Hf(CH2SiMe3)2Cl2, Hf(NMe2)4, Hf(NEt2)4 , and Hf(N(SiMe3)2)2Cl2; ZrCl4, ZrMe4, Zr(CH2 Ph)4, Zr(CH2CMe3)4, Zr(CH2SiMe3)4, Zr(CH2Ph )3Cl, Zr(CH2CMe3)3Cl, Zr(CH2SiMe3)3Cl, Zr(C H2Ph)2Cl2, Zr(CH2CMe3)2Cl2, Zr(CH2SiMe3)2C l2, Zr(NMe2)4, Zr(NEt2)4, Zr(NMe2)2Cl2, Zr(N Et2)2Cl2, Zr(N(SiMe3)2)2Cl2, TiBn4, TiCl4, and Examples of these include, but are not limited to, Lewis Base adducts are also suitable as metal precursors, e.g., ethers, amines, thioethers, and phosphines are suitable as Lewis bases. Specific examples include HfCl4 (THF )2, HfCl4(SMe2)2, and Hf(CH2Ph)2Cl2(OEt2). The activated metal precursors are ionic or zwitterionic compounds, (M(CH2Ph) 3 + )(B(C6F5)4 - ) or (M(CH2Ph)3 + )(PhCH2B(C6F 5)3 - ), etc., where M is defined above to be Hf or Zr.

[0061] In the metal-ligand complex according to formula (I), each X is a covalent bond, a coordinate bond, or an isotopic composition. When n is 1, X is a monodentate or bidentate ligand. and when n is 2, each X is an independently selected monodentate ligand and is independent of other groups X. Generally, the metal-ligand complex according to formula (I) is In some embodiments, the monodentate ligand is a monoanionic ligand. It is possible. The monoanionic ligands have a net formal oxidation state of -1. Each monoanion The functional ligands are independently hydride, (C1-C 40 ) hydrocarbyl carbanion, (C1 -C 40 ) Heterohydrocarbyl carbanions, halides, nitrates, HC(O) O - , HC(O)N(H) - , (C1-C 40 ) Hydrocarbyl C(O)O - , (C1- C 40 ) HydrocarbylC(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 S - where each R K , R L , and BiR M are independently hydrogen, (C1-C 40 ) hydrocarbyl, or (C1-C 40 ) Heterohydrocarbyl or R K and R L Together, (C2-C 40 ) hydrocarbylene or (C1-C 20 ) forms a heterohydrocarbylene, R M teeth , as defined above.

[0062] In other embodiments, at least one monodentate ligand X is independent of any other ligand X. In certain embodiments, the neutral ligand is R X NR K R L , R K OR L , R K S.R. L , or R X PR K R L are neutral Lewis base groups such as R X are independently hydrogen, (C1-C 10 )hydrocarbyl-Si[(C1-C 10 )Hido locarbyl]3 (i.e., -CH2Si(Me)3), (C1-C 40 ) Hydrocarbohydrates ru, [(C1-C 10 )hydrocarbyl]3Si-, or (C1-C 40 ) Heterohydrin Each R K and R L are independently as defined above.

[0063] Further, each X may be, independently of any other X, a halogen, an unsubstituted (C 20 ) Hydrocarbyl, unsubstituted (C1-C 20 ) hydrocarbylC(O)O-, or R K R L N-, where R K and R L each independently is unsubstituted (C1-C 20) hydrocarbyl. In some embodiments, each monodentate ligand X is Chlorine atom, (C1-C 10 ) hydrocarbyl (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C 10 ) hydrocarbylC(O)O-, or R K R L N- where R K and R L each independently is unsubstituted (C 10 ) Hydrocarbohydrates It is.

[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 Any two groups X together can form a bidentate ligand. In an exemplary embodiment, the bidentate ligand may be a neutral bidentate ligand. The neutral bidentate ligand has the formula (R D )2C=C(R D )-C(R D )=C(R D )2 diene Yes, R D are each independently H, unsubstituted (C1-C6) alkyl, phenyl, or is naphthyl. In some embodiments, the bidentate ligand is a monoanionic-mono(l 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 may independently be a carbonate, an oxalate (i.e., - O2C C(O)O - ), (C2-C 40 ) hydrocarbylene dicarbanion, (C1-C 40) It is a heterohydrocarbylene dicarbanion, a phosphate, or a sulfate.

[0065] In further embodiments, X is methyl, ethyl, 1-propyl, 2-propyl, 1- Butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, or 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. Each X is methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethyl The different aryl groups are ethylpropyl, trimethylsilylmethyl, phenyl, benzyl, and chloro. In one embodiment, n is 2 and at least two Xs are independently selected from the group consisting of In certain embodiments, n is 2 and the two X groups are monodentate. Together, they form a bidentate ligand. In a further embodiment, the bidentate ligand is a 2,2-di methyl-2-silapropane-1,3-diyl or 1,3-butadiene.

[0066] In certain embodiments of the catalyst system, the metal-ligand complex according to formula (I) is The present invention may include, but is not limited to, complexes having any of the structures of: [ka] [ka]

[0067] Procatalyst activation The catalyst system of the present disclosure comprises a metal- Metal-coordinated ligand complexes according to formulae (I), (II), (III), and (IV) The child complex may be in a catalytically active form, or may be catalytically inactive or It may be a form of the procatalyst that is at least substantially less catalytically active than the catalytically active form. Procatalysts 1-29 are catalytically inactive forms of various metal-ligand complexes according to formula (I) The procatalytic forms of the metal-coordinated cations of formulae (I), (II), (III), and (IV) are Procatalyst systems containing proteolytic complexes are useful in the art for activating metal-based catalysts in olefin polymerization reactions. The catalyst may be made catalytically active by any technique known in the art. For example, the catalyst of formula (I), (II) The metal-ligand complexes of formula (III), (IV), and (IV) act as activating cocatalysts. or by combining the metal-ligand complex with an activating cocatalyst. It can be made catalytically active. Another example of a suitable activation technique is bulk electrolysis. Combinations of one or more of the foregoing activating cocatalysts and techniques are also contemplated. Metal-ligand complexes according to formulae (I), (II), (III), and (IV) in procatalytic form Subjecting the body to any of these activation techniques results in the production of the compounds of formula (I), (II), (III) and Catalytically activated forms of the metal-ligand complexes (III) and (IV) are obtained. In one embodiment, the metal-compounds according to formulae (I), (II), (III), and (IV) The catalytically activated form of the ligand complex can be prepared by any of the activation techniques described above to form a compound of formula (I ), (II), (III), and (IV) from the procatalytic forms of metal-ligand complexes It may be the result of splitting at least one X.

[0068] Cocatalyst Component Suitable activating cocatalysts for use herein include aluminum alkyls, poly Monomeric or oligomeric alumoxanes (also known as aluminoxanes), neutral Lewis acids and non-polymeric, non-coordinating, ion-forming compounds (including those that are not intended to be used under oxidizing conditions). The preferred activation technique is bulk electrolysis. Combinations of one or more of the above and techniques are also contemplated. The term monoalkylaluminum dihydride or monoalkylaluminum Dihalides, dialkylaluminum hydrides or dialkylaluminum halides or trialkylaluminum. Polymeric or oligomeric alumoxane Examples of the compound include methylalumoxane, triisobutylaluminum modified methylalumoxane, and isobutylalumoxane.

[0069] The Lewis acid activator (cocatalyst) may be any of the Lewis acid activators described herein, which may be any of the Lewis acid activators having one to three (C1-C 20 In one embodiment, the Group 13 metal compounds contain hydrocarbyl substituents. Group 13 metal compounds are tri((C1-C 20 ) Hydrocarbyl) -substituted aluminum, tri Ri((C1~C 20 )hydrocarbyl)-boron compounds, tri((C1-C 10 ) Alki Aluminum, Tri(C6-C 18 )aryl)boron compounds and their derivatives In a further embodiment, the group 13 metal derivatives are halogenated (including perhalogenated) derivatives. The compounds are tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane, In some embodiments, the activating cocatalyst is a tetrakis((C20 ) Hydrocarbyl borate or tri((C1-C 20 ) Hydrocarbyl) Ammonium Tetra Torakis ((C1~C 20 )hydrocarbyl)borates (e.g., bis(octadecyl) methylammonium tetrakis(pentafluorophenyl)borate). When used in the present specification, the term "ammonium" means ((C1-C 20 ) Hydrocarbyl )4N + , ((C1~C 20 )hydrocarbyl)3N(H) + , ((C1~C 20 )Hido LOCALBIL)2N(H)2 + , (C1~C 20 ) HydrocarbylN(H)3 + , or N (H)4 + Each of the nitrogen cations (C1 to C 20 ) Hydrocarbyl is two or more When present, they may be the same or different.

[0070] As a combination of neutral Lewis acid activators (cocatalysts), tri((C1-C4) alkyl Aluminum and trihalides (C6-C 18 )Aryl)boron compounds, especially and mixtures containing tris(pentafluorophenyl)borane. Other embodiments include the use of such a neutral Lewis acid mixture with a polymeric or oligomeric alumoxane. In combination with sulphonates and single neutral Lewis acids, especially tris(pentafluorophenyl ) a combination of borane with a polymeric or oligomeric alumoxane. (Metal-coordinating (diphenylborane):(tris(pentafluorophenylborane):(alumoxane) [e.g., (Group 4 metal-ligand complexes): (Tris(pentafluorophenylborane): (Aluminum In another embodiment, the molar ratio of 1:1:1 to 1:10:100 is used. :1:1.5~1:5:30.

[0071] A catalyst system comprising a metal-ligand complex of formula (I) may be activated by the addition of one or more cocatalysts, e.g. , a strong Lewis acid, a cation-containing cocatalyst, or a combination thereof. Suitable activating cocatalysts include polymers, or oligomeric aluminoxanes, especially methylaluminoxane, as well as inert, compatible , non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include tris( pentafluorophenyl)borane, modified methylaluminoxane (MMAO), bis(hydrogen (1) methyl tetrakis(pentafluorophenyl)borate - ) Ami (i.e., [HNMe(C 18 H 37 )2][B(C6F5)4]), and These include, but are not limited to, combinations of:

[0072] In some embodiments, one or more of the aforementioned activating cocatalysts are combined with one another. A particularly preferred combination is tri((C1-C4) hydrocarbyl ) aluminum, tri((C1-C4) hydrocarbyl) borane, or ammonium borate The alumoxane compound of formula (I) is a mixture of alumoxane and an oligomeric or polymeric alumoxane compound. The ratio of the total number of moles of the one or more metal-ligand complexes to the total number of moles of the one or more activating cocatalysts is 1 In some embodiments, the ratio is at least 1:10,000 to 100:1. :5000, in some other embodiments at least 1:1000, and 10: 1 or less, and in some other embodiments, 1:1 or less. When used alone as an activating cocatalyst, the number of moles of alumoxane used is determined by the formula (I): It is preferred that the molar amount of the metal-ligand complex is at least 100 times that of the metal-ligand complex. When (pentafluorophenyl)borane is used alone as an activating cocatalyst, some In another embodiment, the molar ratio of the one or more metal-ligand complexes of formula (I) to the total number of moles of the one or more metal-ligand complexes of formula (I) is 1: The mole ratio of tris(pentafluorophenyl)borane to be used is 0.5:1 to 10:1, 1: The remaining activating cocatalyst is generally one of the formula (I) It is used in a molar amount approximately equal to the total molar amount of the metal-ligand complex or complexes.

[0073] Chain Shuttling Agent The term "shuttle agent" refers to at least one shuttling agent that, under polymerization conditions, inhibits the release of at least one of the catalysts contained in the composition. The compositions of the present disclosure are capable of inducing polymeric exchange between two active catalytic sites. This refers to a compound or mixture of compounds used to Shuttling occurs both to and from one or more of the catalytic sites. In contrast, "chain transfer agents" cause the termination of growing polymer chains and transfer them away from the catalyst. In some embodiments, the chattering agent is a single transfer of the growing polymer to the agent. The blocking agent has an activity of 0.01-100, 0.1-10, 0.5-2.0, or 0.8-1.2. The activity ratio RA-B / RB-A is the ratio of the catalytic activity of A via the shuttling agent. is the rate of polymeryl transfer from the catalytic B active site to the catalytic B active site, and RB-A is the rate of reverse polymeryl transfer. is the rate of transfer from catalyst B to catalyst A via a shuttling agent. The intermediate formed between the shuttling agent and the polymeryl chain is the chain-terminating In one or more embodiments, the three Before achieving distinct polymer segments or blocks, the shuttle-polymerization step is Less than 90 percent, 75 percent, 50 percent, or 10 percent of the composition The rate of chain shuttling (the rate at which polymer chains are pulled away from the catalytic site) is The time required to transfer the amine to the shuttle agent and then back to the catalytic site is determined. (defined as the rate of polymer termination) is equal to or faster than the rate of polymer termination and can even exceed the rate of polymer termination. This is 10 or even 100 times faster than the termination rate of the mer. The polymer blocks are then formed on the same time scale as seeding.

[0074] Segments of different tacticity or regioerror, different block lengths, or Polymers having different numbers of such segments or blocks in each copolymer can be produced. The composition is prepared by selecting different combinations of catalysts and various shuttling agents. The catalysts can be prepared by mixing metal-ligand complexes of formula (I) having different polymerization capabilities, and and mixtures of various shuttling agents paired with these catalysts or combinations of agents For example, the activity of the shuttling agent can be selected from the group consisting of one or more of the catalysts. When the catalyst is low relative to the polymer chain propagation rate, the longer block length multiblock copolymers In contrast, shuttling can be used to obtain polymers and polymer blends. -When the propagation of the chain is very fast, more random chain structures and shorter block lengths are preferred. The extremely fast shuttling agent produces a copolymer having a substantially random copolymer structure. It is possible to produce multi-block copolymers with polymeric properties. By appropriately selecting both the copolymer and the shuttling agent, relatively pure block copolymers can be obtained. , copolymers containing relatively large polymer segments or blocks, and / or or blends of the foregoing with various homopolymers and / or copolymers. It is possible.

[0075] A preferred composition comprising Catalyst A, Catalyst B, and a chain shuttling agent is tactically The following multi-step procedure was specifically adapted for block differentiation based on error content or region-error content: It can be obtained by

[0076] I. Using a mixture containing a potential catalyst and a potential chain shuttling agent, The above addition-polymerizable C3-30 α-olefin monomers are polymerized. Using a batch or semi-batch reactor (i.e., without refeeding catalyst or shuttling agent) ), preferably operated under solution polymerization conditions at a relatively constant monomer concentration, typically at 1 The molar ratio of catalyst to chain shuttling agent is 1:5 to 1:500. After the polymer is formed, the reaction is stopped by adding a catalyst poison, and the polymer properties (tacticity) are The error (and optionally the regioerror content) is measured.

[0077] II. The above polymerization and polymer testing were repeated for several different reaction times. The method provides a series of polymers having a range of yields and PDI values.

[0078] III. Catalysts / Catalysts that Show Significant Polymer Transfer Both to and from the Shuttling Agent The shuttling agent pair should have a minimum PDI of less than 2.0, more preferably less than 1.5; and Most preferably, the polymer is characterized by a chain shuttling ratio of less than 1.3. When this occurs, the Mn of the polymer increases linearly with increasing conversion. Pairing with a chattering agent should have a statistical significance greater than 0.95, preferably greater than 0.99. Fit the line with a reasonable accuracy (R2) to the polymer Mn as a function of conversion (or polymer yield). This gives the following:

[0079] Steps I-III are then combined with potential catalysts and / or potential shuttling One or more additional pairings of agents were performed.

[0080] In one or more embodiments, catalyst A, catalyst B, and one or more catalysts according to the present invention are then The polymer composition containing the chain shuttling agent is subjected to a chain shuttling reaction in which each of the two catalysts is a chain shuttling agent. to undergo chain shuttling by one or more of the catalysts, is capable of selectively forming stereospecific polymers compared to catalyst B under selected reaction conditions. At least one of the chain shuttling agents is highly effective against both Catalyst A and Catalyst B. The polymer undergoes polymer transport in both the forward and reverse directions (as determined in the previous tests). In addition, the chain shuttling agent reduces the catalytic activity (the amount of catalyst per unit time) of any catalyst. (measured as weight of polymer produced per weight of solvent) (in the absence of shuttling agent) Preferably, the activity is not reduced by more than 60 percent (compared to the activity at or the activity of such catalyst is not reduced by more than 20 percent, and most preferably The catalytic activity of at least one of the catalysts is compared to the catalytic activity in the absence of the shuttling agent. increases compared to

[0081] Alternatively, a series of polymerizations were carried out under standard batch reaction conditions and the resulting polymer properties were analyzed. By measuring, it is also possible to detect pairs of catalysts and shuttling agents. Shuttling agents do not cause significant broadening of the PDI or loss of activity (reduced yield or rate). and is characterized by the resulting reduction in Mn.

[0082] The aforementioned studies were carried out using automated reactors and analytical probes for rapid throughput screening. screening techniques and the different distinguishing characteristics (syndiotactic, isotactic, and In particular, it is easily adapted to the formation of polymer blocks having regioerror content. , combinations of various organometallic compounds with various proton sources, and olefin polymerization catalysts Depending on the compound or reaction product added to the polymerization reaction using the composition, a large number of potential Candidate shuttling agents can be identified in advance or synthesized in situ. Several polymerizations are carried out with varying molar ratios of the catalyst to the catalyst. While the glycerol produced a minimum PDI of less than 2.0 in variable yield experiments, as described above, As mentioned above, those which do not significantly adversely affect the catalytic activity and preferably improve the catalytic activity. It is.

[0083] Regardless of the method for presumptively identifying the shuttling agent, the term is used to refer to the currently identified The multi-block copolymers described herein can be prepared by the methods disclosed herein. It is intended to refer to compounds which are effectively used under the polymerization conditions described above. The average number of blocks or segments per average chain (the average number of blocks of different compositions) The Mn of the polymer is preferably greater than 3.0. is greater than 3.5, even more preferably greater than 4.0 and less than 25, preferably is less than 15, more preferably less than 10.0, and most preferably less than 8.0 according to the present invention. It is formed.

[0084] Shuttling agents suitable for use herein include at least one C1-20 hi Group 1, 2, 12, or 13 metal compounds or complexes containing hydrocarbyl groups, preferably or hydrocarbyl-substituted aluminum containing 1 to 12 carbons in each hydrocarbyl group. and their reaction products 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 the disclosure, a shuttling agent may be added to the polymerization process. Shuttling agents include trialkylaluminum and dialkylzinc compounds, especially Triethylaluminum, tri(i-propyl)aluminum, tri(i-butyl)aluminum aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, Additional suitable shuttling agents include triethylgallium, diethylzinc, and diethylzinc. The organometallic compounds mentioned above are preferably tri(C1-8)alkylaluminum compounds. Di(C1-8)alkylzinc compounds, especially triethylaluminum, tri(i-pro (pyl)aluminum, tri(i-butyl)aluminum, tri(n-hexyl)aluminum ammonium, tri(n-octyl)aluminum, or diethylzinc in less than stoichiometric amounts ( (relative to the number of dihydrocarbyl groups) secondary amines or hydroxyl compounds, especially bis(trimethylsilyl) Methylsilyl)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 the reaction product formed by combining with 2,6-diphenylphenol In some embodiments, the shuttling agent is a metal atom or mixture. Select from amine or hydroxyl reagents so that one hydrocarbyl group remains per molecule. The main reaction products of the aforementioned combinations for use in the present disclosure as shuttling agents are The compound is n-octylaluminum di(bis(trimethylsilyl)amide), i-propyl Trialuminum bis(dimethyl(t-butyl)siloxide), and n-octyl aluminum aluminum di(pyridinyl-2-methoxide), i-butylaluminum bis(dimethyl (t-butyl)siloxane), i-butylaluminum bis(di(trimethylsilyl) )amide), n-octylaluminum di(pyridine-2-methoxide), i-butyl Aluminum bis(di(n-pentyl)amide), n-octylaluminum bis( 2,6-di-t-butylphenoxide), n-octylaluminum di(ethyl(1- naphthylamide), ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminum bis (2,3,6,7-dibenzo-1-azacycloheptanamide), n-octylaluminium Bis(2,3,6,7-dibenzo-1-azacycloheptanamide), n-octyl Trialuminum bis(dimethyl(t-butyl)siloxide), ethylzinc(2,6-difluoro The compounds are ethylzinc(t-butoxide), ethylphenylphenoxide, and ethylzinc(t-butoxide).

[0085] A suitable shuttling agent for a given catalyst or combination of catalysts may be a shuttling agent for a different catalyst or combination of catalysts. may not necessarily be good or even satisfactory for use in combination with Those skilled in the art will appreciate that some potential shuttling agents include one or more may adversely affect the performance of the above catalysts and are excluded from use in the polymerization processes of the present disclosure. Thus, a polymer having hard and soft segments can be achieved. To achieve this, it is necessary to balance the activity of the chain shuttling agent with the catalytic activity of the catalyst. There is.

[0086] In general, however, the shuttling agent is selected to provide the highest polymer transfer rate and the highest transfer rate. Such shuttling agents possess high efficiency (reduced incidence of chain termination). Even when using a suction pump, some degree of shuttling can still be achieved. The stringing agent results in the production of the shortest possible polymer block length. Due to the fact that the effective molecular weight of the polymer in A shuttling agent is used.

[0087] Polyolefin The catalyst system described in the previous paragraph is useful for the polymerization of olefins, primarily ethylene and propylene. In some embodiments, a single olefin or Only α-olefins are present, forming homopolymers. However, additional α-olefins The additional α-olefin comonomer may be incorporated into the polymerization procedure. , 20 or less carbon atoms. For example, the α-olefin comonomer has 3 to 10 Exemplary α-olefin comonomers include: The following are examples of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene: 1-pentene, 1-nonene, 1-decene, and 4-methyl-1-pentene, ethylidene norborna For example, one or more α-olefin como The monomers are selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene. or alternatively may be selected from the group consisting of 1-hexene and 1-octene. .

[0088] In some embodiments, the ethylene-based polymer comprises at least one unit derived from ethylene. 50 mole percent. At least 60 mole percent of all the individual components. Each value and subrange is included herein and is disclosed herein as a separate embodiment. For example, the ethylene-based polymer may contain at least 63 mole percent units derived from ethylene. , at least 86 mole percent of units derived from ethylene, at least 90 mole percent of units derived from ethylene or alternatively, 70 to 100 mole percent of units derived from ethylene, 70 to 89.5 mole percent of units derived from ethylene, or 69 to 85 mole percent of units derived from ethylene It may contain .5 mole percent.

[0089] In some embodiments of the ethylene-based polymer, the amount of the additional α-olefin is %. In other embodiments, the mol % is at least 1 mole percent (mol %) to 40 mole %. In a further embodiment, the amount of additional α-olefin is at least 10 In some embodiments, the additional α-olefin comprises 1-octyl olefin. It's a ten.

[0090] Any conventional polymerization process may be used to produce the ethylene-based polymer. Conventional polymerization processes include one or more conventional reactors, e.g., loop reactors, isothermal reactors, Reactors such as fluidized bed gas phase reactors, stirred tank reactors, batch reactors, etc., can be used in parallel, in series, or in any combination thereof. A solution polymerization process, a gas phase polymerization process, a slurry phase polymerization process, using any combination of processes, and any combination thereof.

[0091] In one embodiment, the ethylene-based polymer is produced in a dual reactor system, e.g., a dual loop reactor system. wherein ethylene, and optionally The one or more α-olefins may be produced by the catalytic system described herein and, optionally, one or more In another embodiment, the ethylene-based polymer is polymerized in a dual reactor system. can be produced by solution polymerization, for example in a dual loop reactor system, where The ethylene, and optionally one or more α-olefins, may be any of the olefins described in this disclosure and herein. The polymer is polymerized in the presence of the catalyst system described herein and, optionally, one or more other catalysts. The catalyst system described above, optionally in combination with one or more other catalysts, is then reacted in the first reactor or the second reactor. In one embodiment, the ethylene-based polymer can be used in a dual reaction reactor. The copolymer can be produced by solution polymerization in a reactor system, such as a dual loop reactor system, wherein ethylene, and optionally one or more α-olefins, are reacted with a catalyst as described herein. In another embodiment, the ethylene-based polymer is polymerized in both reactors in the presence of the system. can be produced by solution polymerization in a single reactor system, e.g., a single loop reactor system. wherein ethylene and, optionally, one or more α-olefins are as described within this disclosure. and optionally one or more cocatalysts as described in the previous paragraph. are combined.

[0092] In some embodiments, the polymerization process for producing an ethylene-based polymer comprises The process comprises polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst. In one or more embodiments, the catalyst system exhibits its catalytic activity without a cocatalyst or additional catalyst. metal-ligands according to formulae (I), (II), (III), and (IV) in a form which is reactive to In a further embodiment, the catalyst system may be combined with at least one cocatalyst. in its procatalyst form, its catalytically active form, or a combination of both forms, It may include metal-ligand complexes according to formulas (I), (II), (III), and (IV). In a further embodiment, the catalyst system comprises at least one cocatalyst and at least one additional in combination with a catalyst of formula (I), (II), (III), and In a further embodiment, the catalyst system may comprise a first metal-ligand complex according to (IV). The catalyst and at least one additional catalyst, and optionally at least one cocatalyst. The first catalyst, in its catalytically active form, can be represented by the formula (I), (II), (II I), and (IV).

[0093] The ethylene-based polymer may further include one or more additives. Additives include antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, etc. These include, but are not limited to, antioxidants, processing aids, UV stabilizers, and combinations thereof. Not limited. The ethylene-based polymer may contain any amount of additives. based on the weight of the ethylene-based polymer and one or more additives, The ethylene-based polymer may further comprise a filler, in total, from about 0 to about 10 weight percent. The filler may include organic or inorganic fillers. The ethylene-based polymer includes, but is not limited to, an ethylene-based polymer and any additives or is based on the total weight of the filler, e.g., calcium carbonate, talc, or Mg(OH)2 The ethylene-based polymer may contain from about 0 to about 20 weight percent of a filler such as one or more It can be further compounded with the above polymers to form a blend.

[0094] In some embodiments, the polymerization process for producing an ethylene-based polymer comprises The process comprises polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst. and the catalyst system incorporates at least one metal-ligand complex of formula (I): The polymers obtained from such catalyst systems incorporating the metal-ligand complexes of formula (I) are For example, according to STM D792 (which is incorporated herein by reference in its entirety), , 0.850g / cm 3 ~0.950g / cm 3 , 0.880g / cm 3 ~0.920g / cm 3 , 0.880g / cm 3 ~0.910g / cm 3 , or 0.880 g / cm 3 ~0.900g / cm 3 The density of the sintered body may be 0.01 to 0.01.

[0095] In another embodiment, the polymer obtained from a catalyst system comprising a metal-ligand complex of formula (I) is the melt flow ratio (I 10 / I2), where the melt inclusion Glass I2 was tested at 190° C. and a load of 2.16 kg (the entire contents of which are incorporated herein by reference). (Incorporated into the ) Measured in accordance with ASTM D1238, Melt Index I 10 teeth The thermal expansion coefficient is measured according to ASTM D1238 at 190°C and a load of 10 kg. In the embodiment, the melt flow ratio (I 10 / I2) is 5~10, otherwise, the melt flow The ratio is 5 to 9.

[0096] In some embodiments, the poly(ethylene glycol) derivative obtained from a catalyst system comprising a metal-ligand complex of formula (I) The polymer has a molecular weight distribution (MWD) of 1 to 10, w / M n Defined as R, M w is the weight average molecular weight, M n is the number average molecular weight. In another embodiment, The polymers obtained from the catalyst system have an MWD of 1 to 6. Another embodiment has an MWD of 1 to 3. WD and other embodiments include MWD of 1.5 to 2.5.

[0097] The embodiments of the catalyst system described in this disclosure provide high molecular weight and high molecular weight polymers formed. The amount of comonomer incorporated into a mer results in unique polymer properties.

[0098] Batch Reactor Polymerization Procedure Batch reactor polymerizations are carried out in a 2 L Parr™ batch reactor. heated by an electric heating mantle and cooled by an internal serpentine cooling coil containing cooling water Both the reactor and the heating / cooling system were manufactured using the Camile™ TG process controller. The reactor is controlled and monitored by a computer. At the bottom of the reactor, a catalyst deactivator solution (catalyst deactivator solution) is placed. lyst kill solution) (typically 5 mL of Irgafos / Irg The inside of the reactor was filled with a stainless steel dump pot pre-filled with a toluene / anox mixture. Empty the container and install the dump valve. Purge both the pot and the tank with nitrogen. Vent the dump pot to a 30 gal. blow tank for polymerization or catalyst refilling. All solvents used were passed through a solvent purification column to remove any impurities that may affect the polymerization. The 1-octene and Isopar E were mixed with a first column containing A2 alumina. The ethylene is passed through two columns, the first containing A204 ethylene and the second containing Q5. Mina and 4

number

number

[0099] The reactor was cooled with IsoparE solvent and / or 1-octyl ether depending on the desired reactor loading. The shot tank, which may contain ten, is filled first. Fill to the load set point using a lab scale attached to the chuck. After this, the reactor is heated to the polymerization temperature set point. When ethylene is used, Ethylene is added to the reactor at regular intervals to maintain the reaction pressure set point. Monitored by a Chromomotion flow meter.

[0100] The catalyst and activator were mixed with an appropriate amount of purified toluene to obtain a solution of the desired molar concentration. Catalysts and activators were handled in an inert glove box and drawn into syringes and then catalyzed. The mixture was pressure transferred to a medium shot tank, followed by three rinses of 5 mL each of toluene. Immediately after adding the catalyst, start the experiment timer. If ethylene is used, then Camile Ethylene was added via the reactor to maintain the reaction pressure set point in the reactor. The reaction was continued for 10 minutes, then the agitator was stopped and the bottom dump valve was opened to dump the reactor contents into the dump pot. The contents of the dump pot were poured into a tray placed inside the lab hood, where The solvent is allowed to evaporate overnight. The tray containing the remaining polymer is then transferred to a vacuum oven. There they are heated under vacuum up to 140° C. to remove any remaining solvent. After the ray has cooled to ambient temperature, the polymer is weighed for yield / efficiency and polymer testing is performed. Provided.

[0101] HT-GPC analysis with IR detection of octene incorporation PolymerChar infrared detector (IR5) and Agilent PLgel Dow Robot Assisted Delive with Mixed A Column High-temperature GPC analysis was performed using the ry(RAD) system. Decane (10 μL) was added to each sample for use in the analysis. 1,2,4-Trimethylolpropane stabilized with 300 ppm butylated hydroxytoluene (BHT) Dilute in chlorobenzene (TCB) to a concentration of 10 mg / mL and heat at 160°C for 120 min. Prior to injection, the samples were dissolved in BHT-stabilized TCB. The sample (250 μL) was diluted further to a concentration of 2 mg / mL. l 20 μm (50 × 7.5 mm) guard column, followed by BHT at a flow rate of 1.0 mL / min. Two PL-gels (20 μm, 300 × 7.5 mm) were kept at 160 °C in TCB stabilized with 1,2-dichloroethane. The elution was performed through a Mixed-A column (mm). The total run time was 24 min. To calibrate the MW, Agilent EasiCal polystyrene standards (PS-1 and PS-2) were diluted with 1.5 mL of TCB stabilized with BHT and incubated at 160°C for 15 min. The PS standard was injected into the system without further dilution to obtain the P Using the known Mark-Houwink coefficients for S and PE, A third order MW calibration curve was constructed with apparent units adjusted to ethylene (PE). The incorporation of methacrylate was determined by linear calibration developed by analyzing copolymers with known compositions. Determined by positive use.

[0102] One or more features of the present disclosure will be illustrated with reference to the following examples. EXAMPLES

[0103] starting materials Example 1 - Anthracene Cis Isomer:Trans Isomer: [ka] In a nitrogen-purged glove box, AlCl3 (1.81 g, 13.61 mmol) was l) in CHCl3 (dried over molecular sieves) (200 mL) (50.00 g, 280.53 mmol) and t-BuCl (90.1 mL, 813.54 The mixture was added to a round-bottom flask equipped with a reflux condenser containing a suspension of 100 mmol of 1,2-dichlorophenyl ether at room temperature. The mixture was heated at reflux temperature (about 50° C.) for about 18 hours. After cooling to room temperature, the obtained The cloudy solution was filtered, collected and dried under vacuum. butylanthracene (37.54 g, 46.1%). The filtrate was a mixture of the two isomers. The crude product was extracted with acetone, and the CHCl3 was removed under reduced pressure. 2,7-di-tert-butylanthracene was obtained by stirring in 50 mL of acetone. The acetone was removed under reduced pressure to give 2,7-di-tert-butyl acetone. Anthracene was obtained 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 predried under nitrogen, 2,6-di-tert-butyl Dissolve 3.0 g (0.0103 mol, 1.0 equiv.) in 80 mL of anhydrous dichloromethane. Dissolve 1,3-dibromo-5,5-dimethyl-2,4-dimethyl-2,5-dimethyl-1,3-dibromo-2,5 ... Chilhydantoin (1.477 g, 0.00516 mol, 0.50 equiv.) was added over 29 min. The reaction mass was then stirred at room temperature for 2 hours. The reaction mass was light brown in color. The reaction material was concentrated and dissolved in approximately 50 mL of methanol and dichloromethane ( The resulting solid was taken up in methanol (approximately 50 mL) and concentrated. The yellow solid was filtered off and washed with a minimum amount of methanol. The solid was then added to approximately 50 mL of ethanol. The mixture was taken up in a flask and heated to reflux until dissolved. Upon standing, a crystalline solid came out of solution. The room temperature suspension was filtered and the solids were rinsed with a minimal amount of ethanol. The filtrate was concentrated until the alcohol remained. The suspension was heated to reflux until all solids were dissolved. Upon cooling to room temperature, a second crop of crystalline solid formed. The solid was filtered and concentrated to a minimum. The material was dried in a vacuum oven and used without further purification. The reactant was obtained in an amount of 2.08 g (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 predried under nitrogen, 2,6-di-tert-butyl Dissolve ruanthracene (8.80 g, 0.0273 mol, 1.0 equiv.) in 160 mL of anhydrous distilled water. The starting material was assumed to be 90% pure. The theoretical amount was 1.25 ml. , 7.92 g of material. 1,3-Dibromo-5,5 -A solution of dimethylhydantoin (3.900 g, 0.0138 mol, 0.50 equiv.) The reaction mass was stirred at room temperature for 4 hours. The reaction mass was concentrated to about The material was filtered and the solids were rinsed with hexane (xs). The combined filtrates were concentrated. Most of the filtrate was purified by chromatography on silica gel (100% The material was purified by hexane. The resulting material was taken up in boiling ethanol. The solution was concentrated until solids began to appear. The solution was cooled to room temperature. The solids were filtered. The product was 3.86 g of an off-white crystalline solid. The yield was 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 ,1.8Hz,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-butylanthracen-9-yl)-1H- Pyrrole [ka] Inside a nitrogen glovebox, add sodium hydride (1. 0.094g, 95%, 0.0433mol, 4.00eq) and 60mL of dry THF Then, pyrrole (3.01 mL, 0.0433 mol, 4.00 equiv.) was added dropwise. The mixture was stirred vigorously for 4 hours.

[0112] Zinc chloride (5.904 g, 0.0433 mol, 4.00 equiv.) was added in small portions over several minutes. After stirring for 10 minutes, CyJohnPhos ligand (0.152 g, 4.3 32×10 -4 mol, 0.04 equiv.) and Pd2(dba)3, (Tris(diphenyl Lithium tetraacetone)dipalladium(0), 0.198 g, 2.166 x 10 -4 mol, 0 The solution was stirred for an additional 5 minutes and 9-bromo-2,6-di-tert-butyl ether was added. t-Butylanthracene (18-BT5449-1, 4.00g, 0.108mol, 1 A condenser was attached and the mixture was stirred at 80 °C for 16 h. Ta.

[0113] The solution was cooled and diluted with ethyl acetate. The reaction mixture was washed slowly and carefully with 50 mL of water. The suspension was filtered to remove zinc salts. The product was washed with a portion of ethyl acetate. The extracted and combined organic fractions were dried over magnesium sulfate, concentrated, and the residue was purified by silica gel column chromatography. The product was purified by chromatography on a 100% column (0-5% ethyl acetate in hexane). 51-3.23 g of 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,3 H),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, 127.7 9,127.58,126.47,126.33,125.10,124.55,122 .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, add 2-(2,6-di-tetramethylphenyl)tetrahydrofuran to a 250 mL round-bottom flask. rt-Butylanthracen-9-yl)-1H-pyrrole (2.00 g, 0.00562 mol, 1.00 equiv.) and 50 mL of hexane. [Ir(COD)OMe]2((1,5-cyclooctadiene)(methoxy)iridium (I) Dimer, 0.056g, 8.438×10 -5 mol, 0.015 equivalents) and 1 0 mL of hexane was added. HBpin (4,4,5,5-tetramethyl-1,3,2 -dioxaborolane, 1.280 mL, 0.00844 mol, 1.5 equiv.), followed by 4 , 4'-di-tert-butyl-2,2'-bipyridine (dtbbpy, 0.045 g, 1.688×10 -4 The mixture was stirred for 6 min and pyrrolidinium was added. The flask was connected to a serpentine condenser and stirred at 60° C. overnight.

[0118] The dark solution was cooled. The reaction mass was diluted with 70 mL of ethyl acetate and approximately 10 mL of methanol. The reaction was slowly quenched by slow addition of ethanol. The reaction was allowed to stand for 20 min. The volatiles were removed by rotary evaporation. Chromatography on silica gel The residue was purified by dichloromethane (20-60% in hexanes). The product was isolated as a yellow solid (1.44-180 g, 53-58%). -(2,6-di-tert-butylanthracen-9-yl)-1H-pyrrole starting material Contains:

[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,3 H),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=3.4,2.4Hz,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, 127.8 9,127.31,126.67,126.25,125.21,124.55,122 .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, add 9-bromo-2,7-dichlorobenzene to a 100 mL RB flask. -tert-Butylanthracene (2.00 g, 0.005415 mol, 1.00 equiv. ), 3,5-di-t-butylphenylboronic acid (1.902 g, 0.008122 mol , 1.50 equiv.), potassium phosphate tribasic (3.448 g, 0.01624 mol, 3.00 equivalents) and Pd(amphos)Cl , (Bis(di-tert-butyl(4-dimethyl -aminophenyl)phosphine)-dichloropalladium(II), 0.114g, 4.0 90×10 -4 mol, 0.10 equivalents) was added. 40 mL of 1,4-dioxane and and 8 mL of water were added. The reaction mass was heated to 50° C. and stirred overnight.

[0123] After 18.5 hours, the reaction was cooled and removed from the drybox. Dilute with 50 mL of ethyl acetate and wash the organics with water (50 mL × 3) and brine (50 mL × 1 The organics were dried over magnesium sulfate, filtered and concentrated. The material was purified by filtration using silica gel. Purification by chromatography on gel (100% hexane) gave 2.516 g of white A colored crystalline solid was obtained, 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] 13C NMR(101 MHz,CDCl3)δ150.19,146.98,1 37.85, 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 RB flask predried under nitrogen, 2,7-di-tert-butyl 1,2-di-tert-butylphenyl)anthracene (2.475 g, 0. 005170 mol, 1.0 eq) was dissolved in 70 mL of anhydrous dichloromethane. 1,3-Dibromo-5,5-dimethylhydantoin (0.75 mL) in acetonitrile 4g, 0.002636mol, 0.51eq) was added dropwise over 20 minutes. The reaction mass was stirred at room temperature for 3 hours. The reaction mass was concentrated and diluted with dichloromethane until dissolved. The mixture was taken up in approximately 50 mL of methanol containing 10% CO and concentrated. The residue was purified by hexanes (0-5% dichloromethane). The compound was isolated as is (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, 125.8 9,125.77,121.94,121.34,120.67,34.98,34.8 7, 31.58, 30.79.

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

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

[0132] Zinc chloride (1.955 g, 0.0143 mol, 4.00 equiv.) was added in small portions over several minutes. After stirring for 10 minutes, CyJohnPhos ligand (0.050 g, 1.4 34×10 -4 mol, 0.04 equiv.) and Pd2(dba)3, (Tris(diphenyl Lithium tetraacetone)dipalladium(0), 0.066g, 7.173 x 10 -5 mol, 0 The solution was stirred for an additional 5 minutes and then 10-bromo-2,7-dichlorobenzene (.02 equiv.) was added. -tert-butyl-9-(3,5-di-tert-butylphenyl)anthracene(2 0.00g, 0.003586mol, 1.00eq) was added. The reaction mass was stirred at 80° C. for 19 hours.

[0133] The solution was cooled and diluted with ethyl acetate. The reaction mixture was washed slowly and carefully with 20 mL of water. The suspension was filtered to remove zinc salts. The product was washed with a portion of ethyl acetate. The extracted and combined organic fractions were dried over magnesium sulfate, concentrated, and the residue was purified by silica gel column chromatography. The mixture was purified by chromatography on a column (20-50% dichloromethane in hexane). 1.533 g of 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),6.5 7-6.46(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, 127.2 5,126.36,125.86,124.46,121.59,120.49,117 .79, 111.16, 108.87, 35.00, 34.89, 31.61, 30.8 3.

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

[0137] Example 9 [ka] Inside a nitrogen glove box, add 2-(3,6-di-tetramethylphenyl)tetrahydrofuran to a 100 mL round-bottom flask. rt-Butyl-10-(3,5-di-tert-butylphenyl)anthracene-9-yl (1.515 g, 0.00279 mol, 1.00 equiv.)-1H-pyrrole (1.515 g, 0.00279 mol, 1.00 equiv.) and 5 10 mL of hexane was added to a 20 mL vial. ,5-Cyclooctadiene)(methoxy)iridium(I) dimer, 0.028g, 84 0.179×10-5 mol, 0.015 equiv.) and 10 mL of hexane. Bpin (4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 0.61 m L, 0.004179 mol 1.5 eq.), followed by 4,4'-di-tert-butyl- 2,2'-bipyridine (dtbbpy, 0.022 g, 8.257 × 10-5 mol, 0 The mixture was stirred for 7 minutes and then added to the flask containing pyrrole. The Lasco was connected to a coil condenser and stirred at 60° C. overnight.

[0138] After 16 hours, the reaction mass was cooled and diluted with 70 mL of ethyl acetate. The reaction was quenched by slow addition of methanol. The mixture was stirred for 1 min. The volatiles were removed by rotary evaporation. Chromatography on silica gel The residue was purified by elution with 20-25% dichloromethane in hexane. Isolated as an orange solid (1.277g, 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=3.4,2.5H z,1H),6.55(dd,J=3.4,2.4 Hz,1H),1.40(s,18 H),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, 300.8 9,300.35,299.88,298.55,295.59,294.62,294 .53,287.00,209.00,208.90,205.62,204.83,1 98.84.

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

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

[0143] Zinc chloride (2.952 g, 0.0217 mol, 4.00 equiv.) was added in small portions over several minutes. After stirring for 10 minutes, CyJohnPhos ligand (0.076 g, 2.1 7×10 -4 mol, 0.04 equiv.) and Pd2(dba)3, (tris(dibenzoyl) Deneacetone)dipalladium(0), 0.099 g, 1.08 x 10 -4 mol, 0.0 2 eq.) was added. The solution was stirred for an additional 5 min and 9-bromo-2,7-di-tert- Butylanthracene (2.00 g, 0.00542 mol, 1.00 equiv) was added. A coiled condenser was attached and the mixture was stirred at 80° C. for 16 hours. The solution was cooled and diluted with 70 ml of The reaction was then diluted with 50 mL of ethyl acetate. The reaction was then slowly and carefully quenched with 50 mL of water. The suspension was filtered to remove zinc salts. The product was extracted with a portion of ethyl acetate and combined. The combined organic fractions were dried over magnesium sulfate, concentrated, and the residue was chromatographed on silica gel. The product was purified by chromatography (0-18% ethyl acetate in hexane) to give 1.531 g of yellow ethyl acetate. A colored solid was obtained (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,2 H),7.52(dd,J=8.9,1.9 Hz,2H),7.04(td,J=2. 7,1.5Hz,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, 124.3 3,120.72,117.70,111.07,108.95,35.06,30.8 9.

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

[0147] Example 11 [ka] Inside a nitrogen glove box, add 2-(2,7-di-tetramethylphenyl)tetrahydrofuran to a 250 mL round-bottom flask. rt-Butylanthracen-9-yl)-1H-pyrrole (1.495 g, 0.0042 0 mol, 1.00 equiv.) and 40 mL of hexane were added to a 20 mL vial. [Ir(COD)OMe]2((1,5-cyclooctadiene)(methoxy)iridium Zn(I) dimer, 0.041 g, 6.307 x 10 -5 mol, 0.015 equivalents) and 10 mL of hexane was added. HBpin (4,4,5,5-tetramethyl-1,3, 2-Dioxaborolane, 0.915 mL, 0.00631 mol (1.5 equiv.), followed by 4,4'-Di-tert-butyl-2,2'-bipyridine (dtbbpy, 0.034 g , 1.261×10 -4 The mixture was stirred for 6 min and then cooled to 37°C. The flask was then connected to a coil condenser and stirred at 60° C. overnight. After 19 hours, the solution was cooled. The reaction mixture was diluted with 70 mL of ethyl acetate and approximately 10 The reaction was slowly quenched by the slow addition of 1 mL of methanol. The mixture was stirred for 20 min. The volatiles were removed by rotary evaporation. Chromatography on silica gel The residue was purified by chromatography (0 to 90% dichloromethane in hexanes). The material 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,2 H),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] 13 C NMR(101 MHz,CDCl3)δ 147.89,132.86, 131.37, 129.70, 128.00, 127.47, 126.20, 124.3 3,120.73,120.70,120.68,112.87,83.52,35.0 9, 30.86, 24.79.

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

[0151] Example 12 [ka] Inside a nitrogen glove box, add 0.1 mL of ethanol to a 45 mL vial with a septum cap. 60 g of 2-(2,6-di-tert-butylanthracen-9-yl)-5-(4,4 ,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (Anthracene-pyrrole-boronic acid ester) was added. Anthracene-pyrrole- The boronic ester had 15% impurity, therefore 0.136 g, 2.824 x 100 10 -4 mol, 1.25 equivalents are assumed. Also, the vial contains bromo or iodo complexes. Ring(2.260x10 -4 mol, 1.00 equivalent), 0.180 g of potassium phosphate tribasic ( 8.474x10 -4mol, 3.00 equiv.), and 0.007 g of Pd(crotyl) (P-tBu3)Cl(1.695×10 -5 mol, 0.06 equivalents) is added. The reaction mixture was added to a vial containing 6 mL of 1,4-dioxane and 2 mL of water at 92°C. The mixture was heated to 5° C. and stirred overnight. After 16–18 h, the reaction mixture was diluted with 15 mL of water and 15 ml of The organics were extracted with ethyl acetate (30 mL x 2). The combined organics were dried over magnesium sulfate, filtered, and concentrated. Column purification using 0% dichloromethane.

[0152] Example 13 - General synthesis for ligands [ka] Inside a nitrogen glove box, add 0.1 mL of ethanol to a 45 mL vial with a septum cap. 60 g of 2-(2,7-di-tert-butylanthracen-9-yl)-5-(4,4 ,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (Anthracene-pyrrole-boronic acid ester) was added. Anthracene-pyrrole- The boronic ester had 15% impurity, therefore 0.136 g, 2.824 x 100 10 -4 mol, 1.25 equivalents are assumed. Also, the vial contains bromo or iodo complexes. Ring(2.260x10 -4 mol, 1.00 equivalent), 0.180 g of potassium phosphate tribasic ( 8.474x10 -4 mol, 3.00 equiv.), and 0.007 g of Pd(crotyl) (P-tBu3)Cl(1.695×10 -5 mol, 0.06 equivalents) is added. The reaction mixture was then mixed in a vial with 6 mL of 1,4-dioxane and 2 mL of water at 92°C. The reaction mixture was heated to 5° C. and stirred overnight. After 16–18 h, the reaction mixture was diluted with 15 mL of water and 15 ml of The organics were extracted with ethyl acetate (30 mL x 2). The combined organics were 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 procedure for the synthesis of metal complexes Inside the glove box, a solution of the ligand (0.5 mL, C6D6) was added to the solid M(Bn) 4 (M = Zr or Hf) was added slowly at room temperature. Each drop was stirred to ensure mixing. After addition, the vial was swirled. After addition, the solution was transferred to an NMR tube and 1 H and 13 C The sample was returned to the glove box and all volatiles were removed. The crude product was used without further purification for batch reactor studies.

[0155] Example 14 - Synthesis of Procatalyst 1 [ka] The final procatalyst was synthesized using the 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=16.6,9.1,2.0Hz,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 154.08,147.84,1 47.76, 147.10, 144.18, 143.21, 140.60, 139.08 ,138.55,137.51,132.14,131.66,131.53,131. 39,130.66,129.91,128.96,128.60,128.48,12 8.43,128.24,128.19,127.81,127.56,127.30, 127.16, 125.41, 125.32, 124.77, 124.38, 122.8 3,122.49,121.11,117.95,117.09,116.90,112 .91, 89.05, 34.98, 34.55, 30.76, 30.69.

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

[0159] 1 H 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=16.6,9.0,2.0Hz,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 154.35,148.06,1 47.75, 147.18, 144.05, 142.99, 140.26, 139.08 ,138.80,137.51,131.94,131.92,131.56,131. 46,130.69,130.59,129.19,128.96,128.36,12 8.26,128.19,128.04,127.56,126.85,125.32, 125.26, 124.81, 124.15, 122.87, 122.52, 121.4 9,117.52,117.14,116.49,112.29,78.59,72.0 5, 34.93, 34.52, 30.75, 30.68.

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

[0162] 1 H NMR(400 MHz,C6D6)δ 8.33-8.28(m,1H), 8.21(s,1H),8.15(d,J=9.2Hz,1H),7.95-7.85 (m,2H),7.63(dd,J=9.2,2.0 Hz,1H),7.56-7.4 9(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=3.5Hz,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 168.29,149.08,1 48.17, 147.18, 146.59, 143.28, 137.51, 134.67 ,132.07,131.90,131.47,131.39,130.47,130. 25,129.91,128.96,128.65,128.60,128.43,12 8.19,127.80,127.56,127.22,126.77,126.54, 125.74, 125.32, 124.80, 124.20, 123.06, 122.5 3,121.40,120.63,120.57,118.09,117.59,90. 89, 35.04, 34.60, 30.79, 30.73.

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

[0165] 1 H 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,1 H),7.15-6.72(m,21H),6.63(t,J=7.4 Hz,4H), 6.32(dd,J=7.3,1.7Hz,2H),6.19-6.10(m,6H) ,2.05-1.90(m,6H),1.26(s,9H),1.25(s,9H). 1 3 C NMR was not obtained.

[0166] Example 18 - Synthesis of Procatalyst 20 [ka] The final procatalyst was synthesized using the 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=9.3,0.8Hz,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=8.0,7.0,1.0Hz,1H ),6.71(d,J=3.4Hz,1H),6.66-6.59(m,3H),6.3 6-6.29(m,6H),1.97-1.79(m,6H),1.33(s,9H), 1.31(s,9H).13C data not obtained.

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

[0169] 1 H NMR(400 MHz,C6D6)δ 8.29-8.23(m,1H), 8.20(s,1H),7.97(d,J=9.2Hz,1H),7.89-7.81 (m,2H),7.46(dd,J=9.1,1.9 Hz,2H),7.12-6.9 2(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 No data were obtained for C.

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

[0171] 1 H NMR(400 MHz,C6D6)δ 8.53-8.45(m,1H), 8.29(d,J=9.3Hz,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),6.7 3(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=7.5Hz ,1H),1.86(s,3H),1.83-1.71(m,6H),1.26(s,9 H), 1.21(s,9H). 13 No data were obtained for C.

[0172] Example 21 - Synthesis of Procatalyst 7 [ka] The final procatalyst was synthesized using the 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,3 H),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=3.3Hz,1H), 6.74-6.57(m,7H),6.38-6.31(m,6H),5.81-5.7 4(m,1H),1.76(s,3H),1.74-1.62(m,6H),1.31( s,18H). 13 No data were obtained for C.

[0174] Example 22 - Synthesis of Procatalyst [ka] The final procatalyst was synthesized using the 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=9.2,2.0Hz,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=3.5Hz,1H),2.73(s ,3H),2.00-1.84(m,6H),1.41(s,9H),1.38(s,9 H).

[0176] 13 C NMR(101 MHz,C6D6)δ147.87,145.13,14 3.93,139.56,138.54,136.03,132.22,131.63, 130.60,129.91,128.96,128.60,128.23,128.1 9,125.53,125.32,124.73,124.38,123.34,123 .00,122.52,122.04,120.95,117.86,116.92,1 14.56,108.64,88.72,83.03,35.00,34.58,30. 81, 30.72, 29.54.

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

[0178] Significant amounts of ZrBn4 remain. Notable resonances: 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=60.3,10.8 Hz,6H),1.37(s,9H),1.35(s,9H).

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

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

[0181] 1 H 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=3.5 Hz,1H),6.89-6.76(m,3H),6.73(t,J=7.5 Hz,3 H),6.67(d,J=3.4 Hz,1H),6.42(d,J=7.6 Hz,6 H), 1.91(s,6H), 1.37(s,18H).

[0182] 13 C NMR(101 MHz,C6D6)δ 168.40,149.22,1 48.34,147.04,143.60,134.94,132.68,132.12 ,130.62,128.69,128.51,128.20,127.25,127. 01,125.33,124.64,124.18,122.52,121.34,12 0.58,118.04,117.47,91.03,35.01,30.71.

[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 167.74,149.48,1 48.21, 147.42, 143.25, 137.53, 135.04, 132.48 ,131.97,131.49,130.10,129.44,128.97,128. 37, 128.20, 127.40, 126.73, 126.10, 125.33, 12 4.68,123.82,123.16,121.15,121.04,120.80, 117.93, 116.93, 79.32, 34.93, 30.66.

[0186] Example 26 - Synthesis of Procatalyst 5 [ka] The final procatalyst was synthesized using the 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=1.7Hz,1H),7.61-7.51(m,3H), 7.18-7.07(m,5H),7.00(t,J=7.7Hz,8H),6.95 -6.79(m,3H),6.79-6.71(m,4H),6.44-6.38(m, 6H),6.00(ddd,J=7.0,5.7,1.2Hz,1H),1.82(s ,6H),1.40(s,9H),1.33(s,9H),1.23(s,18H).

[0188] 13 C NMR(101 MHz,C6D6)δ 154.19,150.84,1 50.46,147.84,147.23,144.25,143.33,140.74 ,139.26,139.11,138.57,131.08,130.85,130. 73,128.96,128.42,128.20,127.85,127.26,12 6.91,126.12,125.33,124.93,122.43,121.81, 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 Procatalyst 4 [ka] The final procatalyst was synthesized using the 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=8.9Hz,2H),7.45(d d,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=7.6Hz,6H),6.02-5.90 (m,1H),1.89(s,6H),1.29(s,18H).

[0191] 13 C NMR(101 MHz,C6D6)δ 154.49,148.33,1 47.92, 144.15, 143.04, 140.29, 138.80, 132.82 ,132.12,130.60,130.16,129.27,128.97,128. 36, 128.27, 128.20, 128.10, 127.94, 126.54, 12 5.33,124.61,122.95,121.38,117.60,117.15, 116.35, 112.23, 78.03, 34.89, 30.65.

[0192] Example 28 - Synthesis of Procatalyst 3 [ka] The final procatalyst was synthesized using the 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=8.4,7.2,1.5 Hz,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 154.26,148.00,1 47.97, 144.60, 143.15, 140.55, 139.07, 132.95 ,131.66,130.18,129.92,128.97,128.61,128. 52,128.47,128.20,126.83,125.33,124.59,12 2.61, 121.03, 118.04, 117.17, 116.89, 112.83, 88.75, 34.94, 30.66.

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

[0196] 1 H 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= 8.9,1.9Hz,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. 0Hz,18H).

[0197] 13 C NMR(101 MHz,C6D6)δ 168.24,149.53,1 48.02, 147.05, 144.13, 143.68, 137.52, 134.61 ,132.25,131.61,131.42,130.62,130.49,129. 92,128.97,128.65,128.61,128.35,128.20,12 6.97,125.50,125.33,124.70,123.02,122.43, 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 Procatalyst 6 [ka] The final procatalyst was synthesized using the general procedure for metal complex synthesis.

[0199] 1 H 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),1.1 9(s,18H).

[0200] 13 C NMR(101 MHz,C6D6)δ 154.44,150.76,1 50.60,148.17,147.31,144.32,142.97,140.33 ,139.10,138.89,138.85,138.63,137.52,131. 51,130.73,130.60,130.54,129.09,128.96,12 8.37,128.18,126.68,126.33,125.33,124.83, 124.15, 122.86, 121.53, 120.66, 117.50, 117.1 6,116.77,112.28,79.40,34.87,34.85,34.72, 31.43,30.58.

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

[0202] 1 H 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),6.8 0(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 C NMR(101 MHz,C6D6)δ 150.11,147.81,1 47.11, 145.98, 144.07, 143.19, 142.74, 141.12 ,131.92,131.67,131.65,131.52,130.83,129. 92,128.97,128.61,128.47,127.11,127.03,12 5.38,125.33,124.82,122.77,122.21,121.39, 117.03, 116.15, 89.05, 34.98, 34.51, 30.77, 30 .65,20.79,16.77.

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

[0205] 1 H 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=15.6,9.1,2.0Hz,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=5.9,1.7Hz,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 154.02,151.30,1 47.79, 147.46, 147.09, 143.97, 143.38, 140.52 ,137.52,132.23,131.69,131.57,130.68,129. 92,128.97,128.48,128.41,128.20,127.24,12 7.12,125.38,125.33,124.77,122.82,122.43, 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 Procatalyst 22 [ka] The final procatalyst was synthesized using the general procedure for metal complex synthesis.

[0208] 1 H 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=8.2Hz,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=7.6Hz,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=1.6H z,18H).

[0209] 13 C NMR(101 MHz, C6D6)δ 147.82,147.03, 144.79, 144.11, 142.99, 140.57, 132.51, 132.4 1,131.89,131.58,131.34,130.64,128.97,128 .25,128.20,127.15,125.33,124.76,122.90,1 22.32, 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 Procatalyst 13 [ka] The final procatalyst was synthesized using the general procedure for metal complex synthesis.

[0211] 1 H 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 C NMR(101 MHz,C6D6)δ 155.40,154.39,1 48.04, 147.53, 146.98, 144.09, 142.77, 141.07 ,137.53,132.36,132.20,131.81,131.62,130. 73,128.97,128.39,128.29,128.20,128.02,12 6.86,125.33,125.26,124.70,122.71,122.13, 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 Procatalyst 14 [ka] The final procatalyst was synthesized using the general procedure for metal complex synthesis.

[0214] 1 H 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=9.2,2.0Hz,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,1 H),6.55-6.46(m,2H),6.39(d,J=7.6 Hz,6H),5 .64(td,J=7.1,2.5Hz,1H),1.84-1.65(m,6H), 1.36(s,9H),1.35(s,9H).

[0215] 13 C NMR(101 MHz,C6D6)δ 157.46,157.35,1 51.36, 151.26, 147.98, 147.17, 144.86, 143.02 ,139.79,138.56,132.12,131.59,131.52,131. 05,130.63,129.92,128.97,128.61,128.53,12 8.50,128.20,127.78,127.32,127.02,125.47, 125.33, 124.82, 124.39, 122.89, 122.66, 120.9 4,117.25,113.91,106.87,106.67,103.33,103 .13,89.12,34.98,34.55,30.73,30.68.

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

[0217] 1 H NMR(400 MHz,C6D6)δ 8.34(d,J=1.9 Hz, 1H),8.18(t,J=4.4Hz,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,4 H),6.58(d,J=3.3 Hz,1H),6.46(d,J=7.6 Hz,6 H),1.80(d,J=2.5 Hz,6H),1.59(s,3H),1.51(s ,3H),1.40(s,18H).

[0218] 13 C NMR(101 MHz,C6D6)δ 164.92,147.94,1 47.02, 144.30, 143.40, 137.52, 134.66, 132.29 ,131.63,131.44,130.78,130.50,128.96,128. 62,128.28,128.20,127.12,127.04,125.47,12 5.33,124.69,122.98,122.35,122.27,120.88, 116.76, 113.86, 91.51, 35.02, 34.59, 30.80, 30 .75,13.96,10.38.

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

[0220] 1 H 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=8.2H z,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,2 H),6.65(t,J=7.4 Hz,3H),6.53(d,J=7.7 Hz,1 H),6.45(d,J=8.5 Hz,1H),6.41(d,J=7.7 Hz,6 H),2.75(s,3H),1.82(s,6H),1.38(s,18H).

[0221] 13 C NMR(101 MHz,C6D6)δ 147.91,144.72,1 44.32, 143.21, 140.86, 133.12, 132.60, 131.69 ,130.23,129.92,129.27,128.96,128.60,128. 26,128.20,126.85,126.76,125.33,124.56,12 4.39, 122.37, 122.28, 121.42, 121.19, 117.55, 115.54, 111.92, 108.69, 90.94, 35.00, 33.96, 3 0.76.

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

[0223] 1 H 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 164.84,148.06,1 44.63,144.33,143.75,134.92,132.82,131.13 ,130.12,128.97,128.68,128.32,128.20,127. 00,126.78,125.33,124.52,122.54,122.33,12 0.88,116.74,113.76,91.81,35.01,30.74,13. 77,10.37.

[0225] Example 39 - Synthesis of Procatalyst 11 [ka] The final procatalyst was synthesized using the general procedure for metal complex synthesis.

[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] 13 C NMR(101 MHz,C6D6)δ 154.17,151.30,1 47.92,147.68,144.35,143.28,140.45,132.99 ,131.82,130.20,128.97,128.50,128.44,128. 20,126.77,125.33,124.59,122.54,121.11,11 9.60,117.58,116.80,112.37,88.55,34.94,30 .66,20.52.

[0228] Example 38-Synthesis of プロcatalyst 9

change

[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=3.3Hz,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 156.57,153.01,1 47.96, 145.30, 143.60, 139.82, 139.21, 132.71 ,131.41,130.25,128.97,128.58,128.20,128. 16,126.90,126.81,125.33,124.53,122.16,12 1.25,120.08,116.79,115.12,113.14,91.58,3 4.97, 30.71, 23.74.

[0231] Example 39 - Synthesis of Procatalyst 15 [ka] The final procatalyst was synthesized using the 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),6.7 8-6.69(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 167.89,156.54,1 49.78,147.92,144.31,143.38,140.38,133.01 ,131.85,130.20,129.92,128.97,128.61,128. 50,128.44,128.20,127.99,126.77,125.33,12 4.59, 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 procatalyst 29 [ka] 3,5-Di-tert-butyl in glacial AcOH (6 mL) Benzaldehyde (360 mg, 4.00 mmol, 2.00 equiv.), 2-pyridinecarbamate bonitrile (208 mg, 2.00 mmol, 1.00 equiv.), and ammonium acetate (771 mg, 10.0 mmol, 5.00 equiv.) was placed in a capped vial. The mixture was then carefully heated at 170 °C for 12 h. After cooling to RT, the mixture was It was neutralized with saturated aqueous solution and extracted with EtOAc (2x10 mL). The solution was washed with water, dried over MgSO4, and the organic solvent was removed under vacuum. GC / MS analysis indicated the formation of the desired product. The crude product was purified by flash chromatography (Biot The desired product was purified by filtration (HCl / EtOAc) to give a white solid (61 3 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=1.9Hz,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, 134.2 5,130.31,129.43,123.02,122.36,122.33,122 .19, 121.43, 120.28, 34.98, 34.92, 31.60, 31.5 2.

[0237] GC / MS(M + ) m / z 521.39.

[0238] Example 40 - Synthesis of Procatalyst 29 [Table 2]

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

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

[0241] In Table 2, the reaction temperature in ethylene-octene semi-batch copolymerization is 120°C. At one time, 46.3 g of ethylene, 302 g of 1-octene, and 612 g of IsoparE 1.2 equivalents of [HNMe(C 18 H 37 )2][B(C6F5)4] activity agent, 10 μmol of MMAO-3A, ​​and a reactor pressure of 290 psi. -octene semi-batch copolymerization, 43 g of ethylene at 150°C. , 301 g of 1-octene, 548 g of IsoparE, and 1.2 equivalents of [H NMe(C 18 H 37 )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] In Table 3, the reaction temperatures are shown under chain transfer conditions for a series of pyrrole-heterocycle catalysts. The temperature was 120° C. for the ethylene-octene copolymerization data. The semi-batch reactor conditions were: 11.3g ethylene, 57g 1-octene, 557g IsoparE, catalyst 1.2 equivalents of [HNMe(C 18 H 37 )2][B(C6F5)4]activator, 10μ mol of MMAO-3A, ​​reactor pressure of 138 psi.

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 (III), formula (IV), or formula (V). 【Transformation 3】 【Chemistry 4】 【Transformation 5】 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 unsaturated (C ２ -C ２０ ) hydrocarbons, unsaturated (C ２ -C ５０ ) heterohydrocarbons, (C １ -C ５０ ) hydrocarbyls, (C ６ -C ５０ ) aryls, (C ６ -C ５０ ) heteroaryls, cyclopentadienyls, substituted cyclopentadienyls, (C ４ -C １２ ) dienes, halogens, -N(R Ｎ ) ２ , and -NOCOR Ｃ ; m is 1 or 2, n is 2 or 3, m + n = 4, 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 of R1, R2, R3b, R3c, R4b, R4c, R5b, and R5c is independent of (C １ -C ５０ ) Hydrocarbyl, (C １ -C ５０ ) Heterohydrocarbyl, (C ６ -C ５０ ) Aryl, (C ４ -C ５０ ) heteroaryl, -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 Selected from the group consisting of NC(O)-, halogens, and -H, in the formula, each R Ｎ , R Ｃ , and R Ｐ However, independently, (C １ -C ２０ ) Hydrocarbyl, (C １ -C ２０ ) Selected from the group consisting of heterohydrocarbyl and -H, Optionally, R3b and R4b, or R4c and R5c, may be covalently bonded to form an aromatic or non-aromatic ring. Each R11 is phenyl, phenyl substituted with one or more Rs, naphthyl, naphthyl substituted with one or more Rs, anthracenyl, or anthracene-9-yl substituted with one or more Rs, and each R is independently selected from the group consisting of (C1-C12) alkyl, (C6-C15) aryl, and (C3-C12) cycloalkyl. However, z １ CR １ and z ２ CR ２ And R １ and R ２ However, if covalent bonding does not form aromatic or non-aromatic rings, then m is 1 and n is 3 in the polymerization process.

2. The polymerization process according to claim 1, wherein m is 1.

3. The polymerization process according to claim 1 or 2, wherein z1 is N.

4. R １１ The polymerization process according to any one of claims 1 to 3, wherein the polymer is phenyl, (2,4,6-triisopropyl)phenyl, 3,5-di-tert-butylphenyl, naphthyl, or cyclopropyl.

5. The polymerization process according to any one of claims 1 to 4, wherein X is benzyl, phenyl, or chloro.

6. 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 3, wherein the polymerization process is selected from aryl or -H.

7. R １２ , R １３ , R １４ , R １５ , and R １６ The polymerization process according to claim 6, wherein the selected molecule is tert-butyl, 3,5-di-tert-butylphenyl, or -H.

8. z ２ The polymerization process according to any one of claims 1 to 7, wherein is N.

9. z ２ is N, and z １ is CR １ in the case where it is, R １ and R １１ The polymerization process according to claim 1, which do not form an aromatic ring or a non-aromatic ring by covalent bonding.

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

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