Aryl-heterocyclic-pyrrole catalyst for olefin polymerization

Abstract

It is a metal-ligand complex according to formula (I). [Formula 1] JPEG2026511469000018.jpg61170

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims the benefits of U.S. Provisional Application No. 63 / 493,440, filed on 31 March 2023, the contents of which are incorporated herein by reference in their entirety.

[0002] (Field of invention) Embodiments of this disclosure, as a whole, relate to processes for polymerizing olefin monomers in the presence of aryl-heterocyclic-pyrrole catalysts, and to the synthesis and study of aryl-heterocyclic-pyrrole catalysts. [Background technology]

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

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

[0005] There is a continuing need to create catalyst systems or metal-ligand complexes with high selectivity for ethylene during the copolymerization reaction of ethylene and α-olefins. Furthermore, these metal-ligand complexes should possess high catalytic efficiency and versatile capabilities to produce high molecular weight polymers at high reactor temperatures (such as above 120°C, above 150°C, or approximately 190°C).

[0006] Embodiments of the present disclosure include metal-ligand complexes according to formula (I).

[0007]

Chemical formula

[0008] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, and the metal has an oxidation state in the form of +2, +3, or +4. Each X is a monodentate ligand or a bidentate ligand independently selected from (C1-C 50 ) hydrocarbyl, halogen, -(CH2) w Si(R X )3, -N(R N )2, and -NCOR C , where w is 1 to 10 and R X is (C1-C 20 ) alkyl. When X is monodentate, the subscript n of (X) n is 2, and when X is bidentate, the subscript n of (X) n is 1 or 2.

[0009] In formula (I), z1 is independently selected from N or C(R 1 ), and R 1 and R 11 do not covalently bond to form an aromatic or non-aromatic ring. z2 is independently selected from N or C(R 2 ), and R 1 and R 2 may covalently bond to form an aromatic or non-aromatic ring. z3 is independently selected from O, S, N, R N , or C(R 3 ), and R 3 and R 4 may covalently bond to form an aromatic or non-aromatic ring. z4 is independently selected from O, S, N, NR N , or C(R 4 ), and R 4 and R 3 may covalently bond to form an aromatic or non-aromatic ring.

[0010] In equation (I), R 1 , R 2 , R 3 , R 4 , R 11 , R 12 , R 13 , R 14 , and R 15 (C1~C 50 ) Hydrocarbyl, (C1~C 50 ) Heterohydrocarbyl, (C6~C 50 ) Aryl, (C4~C 50 ) Heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, -P(O)(R P )2, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C ) Independently selected from the group consisting of 2NC(O)-, halogens, and -H, where R 12 and R 13 They are optionally joined to form a ring, R 13 and R 14 They are optionally joined to form a ring, and R 14 and R 15 They are optionally joined to form a ring.

[0011] In equation (I), each R N , R C , and R P (C1~C 20 ) Hydrocarbyl, (C1~C 20 ) Selected from the group consisting of heterohydrocarbyl and -H.

[0012] In one or more embodiments, the metal-ligand complex of formula (I) is such that z3 is CR 3And z4 is CR 4 And R 3 and R 4 The combination of these elements forms an aromatic ring, and the metal-ligand structure has the structure shown in formula (II).

[0013] [ka]

[0014] In equation (I), z1, z2, z5, R 11 , R 12 , R 13 , R 14 , R 15 X, n, and M are defined as in equation (I), and R z1 , R z2 , R z3 , and R z4 is hydrogen, (C1~C 20 ) alkyl, (C6~C 50 )aryl, (C1~C 10 ) Heterohydrocarbyl, -NR N , -OR C , -SR C Independently selected from the group consisting of halogen, CF3-NO2, or -CN, where R C (C1~C 20 ) alkyl, (C6~C 20 ) is aryl. In some embodiments, z5 is N in equation (II).

[0015] In some embodiments, the metal-ligand complex of formula (I) is R 11 This includes the fact that it is a radical of formula (III).

[0016] [ka]

[0017] In equation (III), R 21 , R 22 , R 23 , R 24 , and R 25is independently selected from (C1-C 10 )alkyl, (C6-C 10 )aryl, or -H.

[0018] In one or more embodiments, R 13 and R 14 are covalently bonded to form an aromatic ring, and the metal-ligand has a structure according to formula (IV).

[0019]

Chemical formula

[0020] In formula (IV), R 11 , R 12 , R 15 , z1, z2, z3, z4, z5, M, X, and n are as defined in formula (I). In formula (IV), R 13a , R 13b , R 14a , and R 14b are independently selected from the group consisting of hydrogen, chloro, fluoro, benzyl, (C1-C 10 )alkyl, cyclic (C1-C 10 )heteroalkyl, -OR C , -NR N 2, wherein R C and R N are (C1-C 12 )alkyl.

Modes for Carrying Out the Invention

[0021] Here, specific embodiments of the catalyst system will be described. It should be understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments described in the present disclosure.

[0022] Common abbreviations are listed below.

[0023] R, Z, M, X, and n: as defined above, Me: methyl, Et: ethyl, Ph: phenyl, Bn: benzyl, i-Pr: isopropyl, t-Bu: tert-butyl, t-Oct: tert-octyl(2,4,4-trimethylpentan-2-yl), Tf: trifluoromethanesulfonate, CV: column volume (when used in column chromatography), SiO: ethyl acetate, TEA: triethylaluminum, MAO: methylaluminoxane, MMAO: modified methylaluminoxane, LiCH2TMS: (trimethylsilyl)methyllithium, TMS: trimethylsilyl, Pd(AmPhos)Cl2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II), Pd(AmPhos): chloro(clotyl)(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II), Pd(dppf )Cl2:[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride, ScCl3:scandium(III) chloride, PhMe:toluene, THF:tetrahydrofuran, CH2Cl2:dichloromethane, DMF:N,N-dimethylformamide, siRNA:ethyl acetate, Et2O:diethyl ether, MeOH:methanol, NH4Cl:ammonium chloride, MgSO4:magnesium sulfate, Na2SO4:sodium sulfate, NaOH:sodium hydroxide, brine:saturated sodium chloride aqueous solution, SiO2:silica, CDCl3:chloroform-D, GC:gas chromatography, LC:liquid chromatography, NMR:nuclear magnetic resonance, MS:mass spectrometry, mmol:millimole, mL:milliliter, M:molar concentration, min or mins:minute, h or hrs:hour, d:day, TLC:thin-layer chromatography, rpm:revolutions per minute, rt:room temperature.

[0024] The term "independently selected" is used in R 1 , R 2 , R 3 , R 4 , and R 5 The R groups, such as R, may be the same or different (for example, R 1 , R 2 , R3 , R 4 , and R 5 All of them may be substituted alkyls, or R 1 and R 2 R may be a substituted alkyl group, 3 The term R is used herein to indicate that a group may be an aryl group, etc. The chemical name associated with the R group is intended to convey the chemical structure recognized in the art as corresponding to the chemical structure of the chemical name. Therefore, the chemical name is intended to supplement and illustrate, and not to exclude, structural definitions well known to those skilled in the art.

[0025] When used to describe a chemical group containing a specific carbon atom, use "(C x ~C y The parenthetical expression in the form of ")" means that the unsubstituted form of the chemical group has x carbon atoms to y carbon atoms, including x and y. For example, (C1~C 50 ) Alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups are R S It may be replaced by one or more substituents such as (C x ~C y R defined using ")" S Substituting chemical groups are any group R S It may contain more than y carbon atoms depending on its identity. For example, "R S Strictly speaking, one group R is phenyl (-C6H5). S Replaced by (C1~C 50 )alkyl can contain 7 to 56 carbon atoms. Therefore, generally, the parenthetical "(C x ~C y A substituent R, defined using ")", contains one or more carbon atoms in the chemical group. S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group is such that both x and y contain all carbon atoms of substituent R. S It is determined by adding up the total number of carbon atoms from each origin.

[0026] The term "substitution" means that at least one hydrogen atom (-H) bonded to a carbon or heteroatom or functional group of the corresponding unsubstituted compound is a substituent (e.g., R S This means that all hydrogen atoms (H) bonded to the carbon or heteroatom of the corresponding unsubstituted compound or functional group are replaced by substituents (e.g., R S This means that the atoms are replaced by a substituent. The term "polysubstituted" means that at least two, but fewer than all, hydrogen atoms bonded to the carbon or heteroatom of the corresponding unsubstituted compound or functional group are replaced by a substituent. The term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0027] (C1~C 50 The term "hydrocarbyl" refers to a hydrocarbon radical consisting of 1 to 50 carbon atoms. 50 The term "hydrocarbylene" means a hydrocarbon diradical having 1 to 50 carbon atoms, and each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (having 3 or more carbon atoms, including monocyclic and polycyclic, condensed and non-condensed polycyclic, and bicyclic) or acyclic, and contains 1 or more R S It is either replaced by or not replaced by.

[0028] In this disclosure, (C1~C 50 Hydrocarbyl is either unsubstituted or substituted (C1-C 50 ) alkyl, (C3~C 50 )Cycloalkyl, (C3~C 20 )Cycloalkyl-(C1~C 20 ) Alkilen, (C6~C 40 )aryl, or (C6~C 20 )Aaryl-(C1~C 20 ) It may be an alkylene (such as benzyl (-CH2~C6H5)).

[0029] (C1~C 50 )alkyl" and "(C1~C 18 The term "alkyl" refers to an unsubstituted or one or more R S This refers to saturated linear or branched hydrocarbon radicals of 1 to 50 carbon atoms and saturated linear or branched hydrocarbon radicals of 1 to 18 carbon atoms, respectively, which are substituted by (C1-C). 50 Examples of alkyl groups include unsubstituted (C1~C 20 ) alkyl, unsubstituted (C1~C 10 ) Alkyl, unsubstituted (C1~C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. Substituted (C1~C 40 Examples of alkyl groups include substitutions (C1~C 20 ) alkyl, substituted (C1~C 10 ) alkyl, trifluoromethyl, and [C 45 It is alkyl. [C 45 The term "alkyl" means that there are up to 45 carbon atoms in the radical, including substituents, for example, one R is (C1-C5) alkyl. S (C 27 ~C 40 Each (C1-C5) alkyl group may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0030] (C~C 50 The term "aryl" refers to an unsubstituted or (one or more R) having 6 to 40 carbon atoms. SThis refers to a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical (C6~C) that is substituted, and at least 6 to 14 of its carbon atoms are aromatic ring carbon atoms. A monocyclic aromatic hydrocarbon radical contains one aromatic ring, a bicyclic aromatic hydrocarbon radical has two rings, and a tricyclic aromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical exists, at least one of the rings of the radical is aromatic. One or more other rings of the aromatic radical may independently be condensed or uncondensed, and aromatic or non-aromatic. Unsubstituted (C6~C 50 Examples of aryl compounds include unsubstituted (C6~C) 20 ) Aryl, unsubstituted (C6~C 18 Examples include aryl, 2-(C1~C5) alkylphenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. Substitutions (C6~C 40 Examples of aryl substitutions include C1~C 20 ) Aryl, substitution (C6~C 18 )aryl, 2,4-bis([C 20 Examples include alkyl)phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0031] (C3~C 50 The term "cycloalkyl" refers to unsubstituted or one or more R S This refers to saturated cyclic hydrocarbon radicals of 3 to 50 carbon atoms that are substituted with (C). Other cycloalkyl groups (e.g., (C) x ~C y A cycloalkyl group has x to y carbon atoms and is either unsubstituted or has one or more R atoms. S It is defined in a similar format as either being replaced by (C3~C). 40 Examples of cycloalkyl groups include unsubstituted (C3~C) 20 ) Cycloalkyl, unsubstituted (C3~C 10These are cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substitutions (C3~C 40 Examples of cycloalkyl groups include substitutions (C3~C 20 )Cycloalkyl, substituted (C3~C 10 These are cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0032] (C1~C 50 Examples of hydrocarbylenes include unsubstituted or substituted (C6~C 50 ) Alliren, (C3~C 50 )Cycloalkylene, and (C1~C 50 ) Alkylene (for example (C1~C 20 Examples include alkylenes. Diradicals may be located on the same carbon atom (e.g., -CH2-) or on an adjacent carbon atom (e.g., a 1,2-diradical), or may be separated by one, two, or three or more interposing carbon atoms (e.g., a 1,3-diradical, a 1,4-diradical, etc.). Some examples of diradicals include 1,2-, 1,3-, 1,4-, or α,ω-diradicals, while others include the 1,2-diradical. The α,ω-diradical is a diradical that has the largest carbon skeleton spacing between radical carbons. (C2~C 20 Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CH2CH2-), propane-1,3-diyl (i.e., -CH2CH2CH2-), and 2-methylpropane-1,3-diyl (i.e., -CH2CH(CH3)CH2-). (C6~C 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0033] (C1~C 50 The term "alkylene" refers to an unsubstituted or one or more R SThis refers to a saturated linear or branched diradical of 1 to 50 carbon atoms that is substituted by (i.e., the radical is not present on the ring atom). Unsubstituted (C1~C 50 Examples of alkylenes include unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, and -CH2C. * HCH3 and -(CH2)4C * (H)CH3 unsubstituted (C1~C 20 ) is an alkylene, and in the formula, "C * " represents a carbon atom from which a hydrogen atom is removed in order to form a secondary or tertiary alkyl radical. Substitution (C1~C 50 ) An example of alkylene is substitution (C1~C 20 ) Alkylene, -CF2-, -C(O)-, and -(CH2) 14 It is C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted n-1,20-eicosylene). As mentioned above, there are two R S They come together (C1~C 18 )Alkylenes can be formed, so substitution (C1~C 50 Examples of alkylenes include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0034] (C3~C 50 The term "cycloalkylene" refers to an unsubstituted or one or more R S This refers to a cyclic diradical having 3 to 50 carbon atoms substituted by (i.e., the radical is located on a ring atom).

[0035] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include O, S, S(O), S(O)2, and Si(R). C )2, P(R P ), N(R N ), -N=C(RC )2, -Ge(R C )2-,-Si(R C Examples include )-, boron (B), aluminum (Al), gallium (Ga), or indium (In), and each R C and each R P is non-substitutable (C1~C 18 ) Hydrocarbyl or -H, each R N is non-substitution (C1~C 18 ) is a hydrocarbyl. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by heteroatoms. (C1~C 50 The term "heterohydrocarbyl" means a heterohydrocarbon radical having 1 to 50 carbon atoms. 50 The term "heterohydrocarbylene" refers to a heterohydrocarbon diradical having 1 to 50 carbon atoms. (C1~C 50 ) Heterohydrocarbyl or (C1~C 50 A heterohydrocarbylene heterohydrocarbon has one or more heteroatoms. The radical of heterohydrocarbylene may be located on a carbon atom or on a heteroatom. The two radicals of heterohydrocarbylene may be located on a single carbon atom or on a single heteroatom. In addition, one of the two radicals of a diradical may be located on a carbon atom and the other radical may be located on a different carbon atom, one of the two radicals may be located on a carbon atom and the other on a heteroatom, or one of the two radicals may be located on a heteroatom and the other radical may be located on a different heteroatom. Each (C1~C 50 )heterohydrocarbyl and (C1~C 50 ) Heterohydrocarbylene may be unsubstituted, (one or more R S They may be substituted by, and may be aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0036] (C1~C 50) Heterohydrocarbyl may be unsubstituted or substituted. (C1~C 50 ) Non-limiting examples of heterohydrocarbils include (C1~C 50 ) Heteroalkyl, (C1~C 50 ) Hydrocarbyl-O-, (C1~C 50 ) Hydrocarbyl-S-, (C1~C 50 ) Hydrocarbyl-S(O)-, (C1~C 50 )hydrocarbyl-S(O)2-, (C1~C 50 ) Hydrocarbyl-Si(R C )2-, (C1~C 50 ) Hydrocarbyl-N(R N )-, (C1~C 50 ) Hydrocarbil-P(R P )-, (C2~C 50 ) Heterocycloalkyl, (C2~C 19 ) Heterocycloalkyl-(C1~C 20 ) Alkilen, (C3~C 20 )Cycloalkyl-(C1~C 19 ) Heteroalkylene, (C2~C 19 ) Heterocycloalkyl-(C1~C 20 ) Heteroalkylene, (C1~C 50 ) Heteroaryl, (C1~C 19 ) Heteroaryl-(C1~C 20 ) Alkilen, (C6~C 20 )Aaryl-(C1~C 19 ) Heteroalkylene, or (C1~C 19 ) Heteroaryl-(C1~C 20 Examples include heteroalkylenes.

[0037] (C1~C 50 The term "heteroaryl" refers to a compound consisting of a total of 1 to 50 carbon atoms and 1 to 10 heteroatoms, which are either unsubstituted or (one or more R) atoms. SThis refers to monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radicals substituted by (C). A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring, a bicyclic heteroaromatic hydrocarbon radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. If a bicyclic or tricyclic heteroaromatic hydrocarbon radical exists, at least one of the rings in the radical is heteroaromatic. One or more other rings in the heteroaromatic radical may independently be condensed or uncondensed, and aromatic or nonaromatic. Other heteroaryl groups (e.g., generally (C)) x ~C y ) Heteroaryls, for example (C1~C 12 Similarly, heteroaryl compounds have x to y carbon atoms (for example, 1 to 12 carbon atoms) and are either unsubstituted or have one or two or more R atoms. SIt is defined as being substituted by a monocyclic heteroaromatic hydrocarbon radical. A monocyclic heteroaromatic hydrocarbon radical is a five-membered or six-membered ring. A five-membered monocyclic heteroaromatic hydrocarbon radical has 5 minus h carbon atoms, where h is the number of heteroatoms, which may be 1, 2, 3, or 4, and each heteroatom may be O, S, N, or P. Examples of five-membered heteroaromatic hydrocarbon radicals include pyrrole-1-yl, pyrrole-2-yl, furan-3-yl, thiophene-2-yl, pyrazole-1-yl, isoxazole-2-yl, isothiazol-5-yl, imidazole-2-yl, oxazole-4-yl, thiazol-2-yl, 1,2,4-triazole-1-yl, 1,3,4-oxadiazole-2-yl, 1,3,4-thiadiazole-2-yl, tetrazole-1-yl, tetrazole-2-yl, and tetrazole-5-yl. A six-membered monocyclic heteroaromatic hydrocarbon radical has 6 minus h carbon atoms, where h is the number of heteroatoms, which may be 1 or 2, and the heteroatoms may be N or P. Examples of six-membered monocyclic heteroaromatic hydrocarbon radicals include pyridine-2-yl, pyrimidine-2-yl, and pyrazine-2-yl. Bicyclic heteroaromatic hydrocarbon radicals may be condensed 5,6- or 6,6-ring systems. Examples of condensed 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indole-1-yl and benzimidazole-1-yl. Examples of condensed 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinoline-2-yl and isoquinoline-1-yl. Tricyclic heteroaromatic hydrocarbon radicals may be condensed 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. An example of a condensed 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indole-1-yl. An example of a condensed 5,6,6-ring system is 1H-benzo[f]indole-1-yl. An example of a condensed 6,5,6-ring system is 9H-carbazole-9-yl. An example of a condensed 6,5,6-ring system is 9H-carbazole-9-yl. An example of a condensed 6,6,6-ring system is acridine-9-yl.

[0038] (C1~C 50The term "(C1~C) heteroalkyl" refers to a saturated linear or branched radical containing 1 to 50 carbon atoms and one or more heteroatoms. 50 The term "heteroalkylene" refers to a saturated linear or branched diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of heteroalkyl or heteroalkylene include Si(R) C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C S, SR C It may also contain S(O) and S(O)2, and each of the heteroalkyl and heteroalkylene groups may be unsubstituted or have one or more R S It has been replaced by.

[0039] Unsubstituted (C2~C 40 Examples of heterocycloalkyl groups include unsubstituted (C2~C 20 ) Heterocycloalkyl, unsubstituted (C2~C 10 Examples include heterocycloalkyls, aziridine-l-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidine-l-yl, tetrahydrothiophen-S,S-dioxide-2-yl, morpholine-4-yl, 1,4-dioxan-2-yl, hexahydroazepine-4-yl, 3-oxacyclooctyl, 5-thiocyclononyl, and 2-azacyclodecyl.

[0040] The terms "halogen atom" or "halogen" refer to the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I). The term "halide" refers to the anionic form of a halogen atom, fluoride (F - ), chloride (Cl - ), bromide (Br - ), or yogurt (I - ) means.

[0041] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. A saturated chemical group has one or more substituents R S If substituted by, one or more double and / or triple bonds are optionally substituted by substituent R S It may be present in the group. The term "unsaturated" refers to a group containing one or more carbon-carbon double bonds or carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds, or carbon-silicon double bonds, and substituent R S This means that it does not contain any double bonds (if present) or any double bonds that may be present in an aromatic ring or heteroaromatic ring (if present).

[0042] Embodiments of this disclosure include one or more catalyst systems. The catalyst system includes one or more metal-ligand complexes according to formula (I).

[0043] [ka]

[0044] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, and the metal has a formal oxidation state of +2, +3, or +4. Each X is (C1~C 50 ) Hydrocarbyl, halogen, -(CH2) w Si(R X )3, -N(R N )2, and -NCOR C A mono-coordinating ligand or a di-coordinating ligand selected independently from, where w is 1 to 10, and R X (C1~C 20 ) is alkyl. If X is monodentate, (X) n If the subscript n is 2 and X is bilocate, then (X) n The subscript n is either 1 or 2.

[0045] In equation (I), z1 is independently N or C(R 1 ) is selected from, R 1 and R 11 Without covalent bonding, it forms an aromatic or non-aromatic ring, and z2 is independently N or C(R 2 ) is selected from, R 1 and R 2 These may form an aromatic or non-aromatic ring by covalent bonding. z3 can independently be O, S, N, R N , or C(R 3 ) is selected from, R 3 and R 4 The atoms may be covalently bonded to form an aromatic or non-aromatic ring, and z4 can independently be O, S, N, or NR. N , or C(R 4 ) is selected from, R 4 and R 3 These may form aromatic or non-aromatic rings through covalent bonding.

[0046] In equation (I), R 1 , R 2 , R 3 , R 4 , R 11 , R 12 , R 13 , R 14 , and R 15 (C1~C 50 ) Hydrocarbyl, (C1~C 50 ) Heterohydrocarbyl, (C6~C 50 ) Aryl, (C4~C 50 ) Heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, -P(O)(R P )2, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (RC ) Independently selected from the group consisting of 2NC(O)-, halogens, and -H, where R 12 and R 13 They are optionally joined to form a ring, R 13 and R 14 They are optionally joined to form a ring, and R 14 and R 15 They are optionally joined to form a ring.

[0047] In equation (I), each R N , R C , and R P (C1~C 20 ) Hydrocarbyl, (C1~C 20 ) Selected from the group consisting of heterohydrocarbyl and -H.

[0048] In one or more embodiments, z3 is CR 3 If so, z4 is CR 4 And R 3 and R 4 These elements combine to form an aromatic ring, and the metal-ligand structure has the configuration of formula (II).

[0049] [ka]

[0050] In equation (II), z1, z2, z5, R 11 , R 12 , R 13 , R 14 , R 15 X, n, and M are defined as in equation (I), and R z1 , R z2 , R z3 , and R z4 is hydrogen, (C1~C 20 ) alkyl, (C6~C 50 )aryl, (C1~C 10 ) Heterohydrocarbyl, -NR N , -OR C , -SR CIndependently selected from the group consisting of halogen, CF3-NO2, or -CN, where R C (C1~C 20 ) alkyl, (C6~C 20 ) is aryl. In some embodiments, z5 is N in equation (II).

[0051] In one or more embodiments, z5 is N in formula (I). In some embodiments, z1 is N, and in other embodiments, z2 is N. In some embodiments, in formula (I) or formula (II), only one of z1 and z2 is N.

[0052] In various embodiments, in formula (I) or formula (II), z2 is N and z1 is CR. 1 If R 1 and R 11 It forms an aromatic or non-aromatic ring without covalent bonding.

[0053] In one or more embodiments, in formula (I) or formula (II), X is benzyl, (C1-C 20 )Alkyl, -CH2Si[(C1~C 30 )alkyl]3,-N[(C1~C 20 ) Alkyl]3 or halogen.

[0054] In one or more embodiments, in formula (I) or formula (II), X is benzyl, methyl, -CH2Si[(C1~C 20 )alkyl]3,-N[(C1~C 10 )alkyl]3 or chloro.

[0055] In some embodiments, in formula (I) or formula (II), R 11 These are 2,4,6-triisopropylphenyl, mesityl, substituted and unsubstituted anthracenyl, 3,5-ditertbutylphenyl, and naphthyl.

[0056] In some embodiments of the metal-ligand catalyst according to formula (I) or formula (II), R 11These are 3,5-di-tert-butylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, 3,5-diisopropylphenyl, carbazolyl, carbazol-9-yl, 1,2,3,4-tetrahydrocarbazolyl, 1,2,3,4,5,6,7,8-octahydrocarbazolyl, 3,6-bis-(3,5-di-tert-butylphenyl)carbazol-9-yl, 3,6-bis-(2,4,6-tri Methylphenyl)carbazole-9-yl, 3,6-bis-(2,4,6-triisopropylphenyl)carbazole-9-yl, 2,7-di(tertiary butyl)-carbazole-9-yl, 2,7-di(tertiary octyl)-carbazole-9-yl, 2,7-diphenylcarbazole-9-yl, 2,7-bis(2,4,6-trimethylphenyl)carbazole-9-ylanthracenyl, 1,2,3,4-tetrahydroanthracenyl 1,2,3,4,5,6,7,8-Octahydroanthracenyl, phenantrenyl, 1,2,3,4,5,6,7,8-Octahydrophenantrenyl, 1,2,3,4-Tetrahydronaphthyl, 2,6-Dimethylphenyl, 2,6-Diisopropylphenyl, 3,5-Diphenylphenyl, 1-Naphthyl, 2-Methyl-1-Naphthyl, 2-Naphthyl, 1,2,3,4-Tetrahydronaphtha-5-yl, 1,2,3,4-Tetrahydro Selected from dronaphthal-6-yl, anthracene-9-yl, 1,2,3,4-tetrahydroanthracene-9-yl, 1,2,3,4,5,6,7,8-octahydroanthracene-9-yl, 1,2,3,4,5,6,7,8-octahydrophenanthrene-9-yl, indolyl, indolinyl, quinolinyl, 1,2,3,4-tetrahydroquinolinyl, isoquinolinyl, or 1,2,3,4-tetrahydroisoquinolinyl.

[0057] In various embodiments, in formula (I) or formula (II), R 11 is the radical of equation (III).

[0058] [ka]

[0059] In equation (III), R 21 , R 22 , R 23 , R 24 , and R 25 (C1~C 10 ) alkyl, (C6~C 10 ) Selected from aryl or -H.

[0060] In various embodiments, in equation (III), R 21 , R 22 , R 23 , R 24 , and R 25 is independently selected from tert-butyl, 3,5-di-tert-butylphenyl, or -H.

[0061] In embodiments of this disclosure, R 13 and R 14 The two molecules are covalently bonded to form an aromatic ring, and the metal-ligand has the structure shown in formula (IV).

[0062] [ka]

[0063] In one or more embodiments, in formulas (I), (II), and (IV), R 12 , R 13 (R 13a and R 13b (including), R 14 (R 14a and R 14b (including), and R 15 These are hydrogen, chloro, fluoro, benzyl, (C1~C 10 ) alkyl, cyclic (C1~C 10 ) Heteroalkyl, -OR C , -NRN 2 Independently selected from the group consisting of, in the formula, R C and R N (C1~C 12 It is alkyl.

[0064] In one or more embodiments, R13 and R 15 is chloro, fluoro, or (C1~C 10 It is alkyl.

[0065] In some embodiments, R 13 and R 14 is -ORC, where R C It is an (C1-C8) alkyl group.

[0066] In various embodiments, R 14 (C1~C 10 ) alkyl, cyclic (C1~C 10 ) Heteroalkyl, -OR C , -NR N Selected from a group consisting of 2, in the formula, R C and R N These are (C1-C8) alkyl groups.

[0067] In some embodiments, the chemical groups of the metal-ligand complex of formula (I) (e.g., X and R) are used. 1-59 ) any or all of these may be unsubstituted. In other embodiments, the chemical groups X and R of the metal-ligand complex of formula (I) 1~59 Any one or more of the following R S Even if they are not replaced by one or all of them, one or more R S It may also be replaced by two or more R's. S If the R groups are bonded to the same chemical group in the metal-ligand complex of formula (I), then the individual R groups of the chemical group S These can bond to the same carbon atom or heteroatom, or to different carbon atoms or heteroatoms. In some embodiments, chemical groups X and R 1~59 All of the above are R S Even if they are not oversubstituted, one or all of them are R S In some cases, it may be oversubstituted. S In chemical groups that are oversubstituted with R, each R S These may all be the same, or they may be selected independently. In one or more embodiments, R S (C1~C 20) Hydrocarbyl, (C1~C 20 ) Alkyl, (C1~C 20 ) Heterohydrocarbyl, or (C1~C 20 ) Selected from heteroalkyl groups.

[0068] In the metal-ligand complex of formula (I), X is bonded to M through covalent or ionic bonds. In some embodiments, X may be a monoanionic ligand having a net formal oxidation state of -1. Each monoanionic ligand is independently a hydride, (C1-C 40 ) Hydrocarbyl carbanion, (C1~C 40 ) Heterohydrocarbyl carbanions, halides, nitrates, carbonates, phosphates, sulfates, HC(O)O - , HC(O)N(H) - , (C1~C 40 ) Hydrocarbyl C(O)O - , (C1~C 40 ) Hydrocarbyl C(O)N((C1~C 20 (Hydrocarbyl) - , (C1~C 40 ) Hydrocarbyl C(O)N(H) - , R K R L B - , R K R L N - , R K O - , R K S - , R K R L P - , or R M R K R L Si - This is possible, but in the formula, each R K , R L , and R M Independently, hydrogen, (C1~C 40 ) Hydrocarbyl, or (C1~C 40 ) Heterohydrocarbyl or R K and R L They come together, (C2~C 40) Hydrocarbylene or (C1~C 20 ) Forms heterohydrocarbylene, R M This is as defined above.

[0069] In some embodiments, X is a halogen, unsubstituted (C1~C 20 ) Hydrocarbyl, unsubstituted (C1~C 20 ) Hydrocarbyl C(O)O-, or R K R L N-, and in the formula, R K and R L Each of these is independent of the non-substitutable (C1~C 20 ) is hydrocarbyl. In some embodiments, each monodentate ligand X is a chlorine atom, (C1~C 10 ) Hydrocarbyl (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C 10 ) Hydrocarbyl C(O)O-, or R K R L N-, and in the formula, R K and R L Each of these is independent of the non-substitutable (C1~C 10 ) It is hydrocarbyl.

[0070] In further embodiments, X is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, or chloro. X is a different from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, and chloro. In one embodiment, n is 2, and at least two X are independently monoanionic monodentate ligands. In a particular embodiment, n is 2, and the two X groups together form a bidentate ligand. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

[0071] In one or more embodiments, each X is independently -(CH2)SiR X 3, and in the formula, each RX is independently, (C1 - C 30 )alkyl or (C1 - C 30 )heteroalkyl, and at least one R X is (C1 - C 30 )alkyl. In some embodiments, when one of the R X is (C1 - C 30 )heteroalkyl, the heteroatom is a silicon or oxygen atom. In some embodiments, R X is methyl, ethyl, propyl, 2 - propyl, butyl, 1,1 - dimethylethyl (or, tert - butyl), pentyl, hexyl, heptyl, n - octyl, tert - octyl, or nonyl.

[0072] In one or more embodiments, X is -(CH2)Si(CH3)3, -(CH2)Si(CH3)2(CH2CH3); -(CH2)Si(CH3)(CH2CH3)2, -(CH2)Si(CH2CH3)3, -(CH2)Si(CH3)2(n - butyl), -(CH2)Si(CH3)2(n - hexyl), -(CH2)Si(CH3)(n - Oct)R X , -(CH2)Si(n - Oct)R X 2, -(CH2)Si(CH3)2(2 - ethylhexyl), -(CH2)Si(CH3)2(dodecyl), -CH2Si(CH3)2CH2Si(CH3)3 (referred to herein as -CH2Si(CH3)2CH2TMS). Optionally, in some embodiments, the metal - ligand complex according to formula (I) has exactly two R X covalently bonded or exactly three R X covalently bonded.

[0073] In some embodiments, X is -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (ORC ) Q wherein, in the above formula, the subscript Q is 0, 1, 2, or 3, and each R C is independently a substituted or unsubstituted (C1-C 30 ) hydrocarbyl, or a substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl.

[0074] In an exemplary embodiment, the catalyst system may include a metal-ligand complex according to formula (I) having the structure of any one of metal-ligands 1 to 10.

[0075]

Chemical formula

[0076] Additive component In some embodiments, the catalyst system does not include an additive. An additive is a chemical agent present during the polymerization reaction and does not suppress the chain transfer reaction of olefins. In one or more embodiments, the catalyst system further includes an additive. In some embodiments, the additive functions as a cocatalyst. In other embodiments, the additive functions as a scavenger or sweep agent. A cocatalyst is a reagent that catalyzes a reaction in cooperation with a catalyst or improves the catalytic activity of the catalyst.

[0077] A scavenger is not an activator in nature because it blocks impurities in the reactor before adding the precatalyst. When the loading amount of aluminoxane is low, it does not act as a cocatalyst but rather functions as a scavenger.

[0078] Suitable additives may include, but are not limited to, alkylaluminum, polymeric or oligomeric almoxanes (also known as aluminoxanes), neutral Lewis acids, and nonpolymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidative conditions). Combinations of one or more of the aforementioned additives and techniques are also contemplated. The term "alkylaluminum" means monoalkylaluminum dihydride or monoalkylaluminum dihalide, dialkylaluminum hydride or dialkylaluminum halide, or trialkylaluminum. Examples of polymeric or oligomeric almoxanes include methylaluminoxane, triisobutylaluminum-modified methylaluminoxane, and isobutylaluminoxane.

[0079] In some embodiments, the additive is as described herein (C1-C 20 )A Lewis acid group 13 metal compound containing a hydrocarbyl substituent. In some embodiments, the additive is tri((C1~C 20 )hydrocarbyl)-substituted aluminum or tri((C1~C 20 The additive contains a tri(hydrocarbyl)-boron compound. In other embodiments, the additive is tri((C1~C)-substituted aluminum, tri((C1~C 20 (hydrocarbyl)-boron compounds, tri((C1~C 10 )Alkyl) Aluminum, Tri((C6~C 18 These are aryl boron compounds and halogenated (including perhalated) derivatives thereof.

[0080] In one or more embodiments, the polymerization process further comprises a borate-based additive. In some embodiments, the borate-based additive is selected from tris(fluorosubstituted phenyl)borane and tris(pentafluorophenyl)borane. In some embodiments, the co-catalyst is tri((C1~C 20 ) Hydrocarbyl ammonium tetra((C1~C 20(C1-C) )hydrocarbyl) borate (e.g., bis(octadecyl)methylammoniumtetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" means ((C1-C) 20 ) Hydrocarbyl 4N + , ((C1~C 20 ) Hydrocarbyl 3N(H) + , ((C1~C 20 )hydrocarbyl)2N(H)2 + , (C1~C 20 ) Hydrocarbyl N(H)3 + , or N(H)4 + This refers to nitrogen cations, and each (C1~C 20 ) If two or more hydrocarbyl molecules are present, they may be the same or different.

[0081] In one or more embodiments, the additives may be selected from polymers or oligomeric aluminoxanes, particularly methyl aluminoxanes, and inert, compatible, non-coordinating, and ion-forming compounds. Exemplary preferred additives include, but are not limited to, modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)ammonium, triethylaluminum, butylated hydroxytoluenediethylaluminum, bis-(butylated hydroxytoluene)ethylaluminum, tris-(butylated hydroxytoluene)aluminum, and combinations thereof.

[0082] In some embodiments, one or more co-catalysts can be used in combination with each other. Specific examples of co-catalyst combinations include tri((C1-C8)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, and tri((C6-C 18The mixture is an aryl)borane or ammonium borate and an oligomer or polymer-almoxane compound. The ratio of the total number of moles of one or more metal-ligand complexes of formula (I) to the total number of moles of one or more co-catalysts is 1:10,000 to 100:1. In some embodiments, this ratio is at least 1:5000, in some other embodiments it is at least 1:1000 and 10:1 or less, and in some other embodiments it is 1:1 or less. When an almoxane alone is used as a co-catalyst, preferably the ratio of Al in the almoxane to the metal of the metal-ligand complex of formula (I) (Al / M) is at least 20. When tris(pentafluorophenyl)borane alone is used as a co-catalyst, in some other embodiments the number of moles of tris(pentafluorophenyl)borane used relative to the total number of moles of one or more metal-ligand complexes of formula (I) is 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1.

[0083] Polymerization process Embodiments of the present disclosure include a polymerization process. The polymerization process includes 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 includes a metal-ligand complex according to formula (I), formula (II), or formula (IV).

[0084] One or more embodiments of the present disclosure are processes for polymerizing polymers, wherein in a reactor, in the presence of a catalyst system, ethylene and one or more (C3-C3) are optionally polymerized. 12 The process includes contacting α-olefins. The catalyst system may include a procatalyst of a metal-ligand complex of formula (I) and an activator. The polymerization process may include, but is not limited to, solution polymerization, gas-phase polymerization, slurry-phase polymerization, and combinations thereof, using one or more reactors, such as loop reactors, isothermal reactors, fluidized bed gas-phase reactors, continuous stirred tank reactors, and batch reactors, in parallel, in series, and / or any combination thereof.

[0085] The polymerization process of the present disclosure can produce ethylene-based polymers, such as homopolymers and / or interpolymers (including copolymers) of ethylene, and optionally, one or more comonomers, such as α-olefins, may be produced via a solution-phase polymerization process using, for example, one or more loop reactors, isothermal reactors, and combinations thereof.

[0086] In some embodiments, the solution-phase polymerization process is carried out in one or more well-agitated reactors, such as one or more loop reactors or one or more spherical isothermal reactors, at a temperature in the range of 120–300°C, e.g., 150–190°C, and at a pressure in the range of 300–1500 psi, e.g., 400–750 psi. The residence time in the solution-phase polymerization process is typically in the range of 2–30 minutes, e.g., 10–20 minutes. Ethylene, one or more solvents, one or more catalyst systems, such as a catalyst system containing a metal-ligand complex of formula (I), optionally one or more co-catalysts, and optionally one or more comonomers are continuously supplied to one or more reactors. Exemplary solvents include, but are not limited to, isoparaffins. For example, such solvents are commercially available from ExxonMobil Chemical Co., (Houston, Texas) under the name ISOPAR E. The resulting mixture of the ethylene polymer and solvent is then removed from the reactor to isolate the ethylene polymer. The solvent is typically recovered via a solvent recovery unit, namely a heat exchanger and a gas-liquid separator drum, and then recycled back into the polymerization system.

[0087] Co-catalyst components A catalyst system comprising the metal-ligand complex of formula (I) may be catalytically activated by any technique known in the art for activating metal catalysts in olefin polymerization reactions. For example, a procatalyst of the metal-ligand complex of formula (I) may be catalytically activated by contacting the complex with an activating co-catalyst or by combining the complex with an activating co-catalyst. In addition, the metal-ligand complex of formula (I) includes both a neutral procatalyst form and a catalytic form that can be positively charged by the loss of a monoanionic ligand such as benzyl or phenyl. Suitable activating co-catalysts for use herein may include, but are not limited to, alkylaluminum, polymer or oligomeric alumoxanes (also known as aluminoxanes), neutral Lewis acids, and nonpolymer, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the aforementioned activating co-catalysts and techniques are also conceived. The term "alkylaluminum" refers to monoalkylaluminum dihydride or monoalkylaluminum dihalide, dialkylaluminum hydride or dialkylaluminum halide, or trialkylaluminum. Examples of polymers or oligomers of almoxane include methylalmoxane, triisobutylaluminum-modified methylalmoxane, and isobutylalmoxane.

[0088] In some embodiments, suitable co-catalysts for use include polymers or oligomeric aluminoxanes, particularly methyl aluminoxanes, and inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable co-catalysts include, but are not limited to, modified methyl aluminoxane (MMAO), bis(hydride-tulose alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine (RIBS-2), triethyl aluminum (TEA), and combinations thereof.

[0089] Lewis acid activation co-catalysts are as described herein (C1-C 20 )Includes a group 13 metal compound containing a hydrocarbyl substituent.In some embodiments, the group 13 metal compound is tri((C1~C 20 )hydrocarbyl)-substituted aluminum or tri((C1~C 20 The (hydrocarbyl)-boron compound is a tri(hydrocarbyl)-substituted aluminum, tri((C1~C 20 (hydrocarbyl)-boron compounds, tri((C1~C 10 )Alkyl) Aluminum, Tri((C6~C 18 The aryl)boron compounds and their halogenated (including perhalated) derivatives. In further embodiments, the Group 13 metal compounds are tris(fluorosubstituted phenyl)borane and tris(pentafluorophenyl)borane. In some embodiments, the activation co-catalyst is tris((C1~C 20 ) Hydrocarbyl borate (e.g., trityltetrafluoroborate) or tri((C1~C 20 ) Hydrocarbyl ammonium tetra((C1~C 20 ()hydrocarbyl)borane (e.g., bis(octadecyl)methylammoniumtetrakis(pentafluorophenyl)borane). As used herein, the term "ammonium" means ((C1-C 20 ) Hydrocarbyl 4N + , ((C1~C 20 ) Hydrocarbyl 3N(H) + , ((C1~C 20 )hydrocarbyl)2N(H)2 + , (C1~C 20 ) Hydrocarbyl N(H)3 + , or N(H)4 + This refers to nitrogen cations, and each (C1~C 20 ) If two or more hydrocarbyl molecules are present, they may be the same or different.

[0090] A combination of neutral Lewis acid activation cocatalysts is tri((C1~C4)alkyl)aluminum and halogenated tri((C6~C 18 Examples include mixtures containing aryl)boron compounds, particularly combinations with tris(pentafluorophenyl)borane. Other embodiments include combinations of such neutral Lewis acid mixtures with polymers or oligomers of almoxane, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymers or oligomers of almoxane. The molar ratio of (metal-ligand complex):(tris(pentafluorophenylborane):(almoxane) [e.g., Group 4 metal-ligand complex):(tris(pentafluorophenylborane):(almoxane)] is 1:1:1 to 1:10:30, and in other embodiments, 1:1:1.5 to 1:5:10.

[0091] An activated catalyst composition can be formed by activating a catalyst system containing a metal-ligand complex of formula (I) and combining it with one or more co-catalysts, such as cation-forming co-catalysts, strong Lewis acids, or combinations thereof. Suitable activating co-catalysts include polymers or oligomers of aluminoxanes, particularly methylaluminoxanes, and inert, miscible, non-coordinating, and ion-forming compounds. Exemplary suitable co-catalysts include, but are not limited to, modified methyl aluminoxane (MMAO), bis(hydride-tulose alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amines, and combinations thereof.

[0092] In some embodiments, two or more of the foregoing activating cocatalysts may be used in combination with each other. Specific examples of the combination of cocatalysts are mixtures of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate with an oligomeric or polymeric aluminoxane compound. The ratio of the total number of moles of one or more metal-ligand complexes of formula (I) to the total number of moles of one or more of the activating cocatalysts is from 1:10,000 to 100:1. In some embodiments, this ratio is at least 1:5000, in some other embodiments, at least 1:1000 and not more than 10:1, and in some other embodiments, not more than 1:1. When using aluminoxane alone as an activating cocatalyst, the number of moles of aluminoxane used is preferably at least 100 times the number of moles of the metal-ligand complex of formula (I). When using tris(pentafluorophenyl)borane alone as an activating cocatalyst, in some other embodiments, the number of moles of tris(pentafluorophenyl)borane used relative to the total number of moles of one or more metal-ligand complexes of formula (I) is 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1. The remaining activating cocatalysts are generally used in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of formula (I).

[0093] Polyolefin The catalyst systems described in the previous paragraph are used for the polymerization of olefins, mainly ethylene and propylene. In some embodiments, only one type of olefin or α-olefin is used in the polymerization scheme, so a monopolymer is produced. However, additional α-olefins may be incorporated into the polymerization procedure. Additional α-olefin copolymer monomers typically have 20 or fewer carbon atoms. For example, α-olefin copolymer monomers may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-olefin copolymer monomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, one or more α-olefin copolymer monomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-hexene and 1-octene.

[0094] Ethylene-based polymers, such as monopolymers and / or interpolymers (including copolymers) of ethylene, and optionally one or more copolymerizable monomers such as α-olefins, may contain at least 50% by weight of monomer units derived from ethylene. All individual values ​​and subranges encompassed by "at least 50% by weight" are disclosed herein as separate embodiments, for example, ethylene-based polymers, monopolymers of ethylene, and / or interpolymers (including copolymers) of ethylene and optionally one or more copolymerizable monomers such as α-olefins may contain at least 60% by weight of monomer units derived from ethylene, at least 70% by weight of monomer units derived from ethylene, at least 80% by weight of monomer units derived from ethylene, or 50 to 100% by weight of monomer units derived from ethylene, or 80 to 100% by weight of units derived from ethylene.

[0095] In some embodiments, the ethylene-based polymer may contain at least 90 mole percent units derived from ethylene. All individual values ​​and sub-ranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer may contain at least 93 mole percent units, at least 96 mole percent units, at least 97 mole percent units derived from ethylene, or alternatively, 90 to 100 mole percent units derived from ethylene, 90 to 99.5 mole percent units derived from ethylene, or 97 to 99.5 mole percent units derived from ethylene.

[0096] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50%, in other embodiments it contains at least 0.5 mol% to 25 mol%, and in further embodiments the amount of additional α-olefin is at least 5 mol% to 10 mol%. In some embodiments the additional α-olefin is 1-octene.

[0097] Ethylene-based polymers may be produced using any conventional polymerization process. Such conventional polymerization processes include, but are not limited to, solution polymerization processes, gas-phase polymerization processes, slurry-phase polymerization processes, and combinations thereof, using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized-bed gas-phase reactors, stirred-tank reactors, batch reactors, etc., in parallel, in series, or in any combination thereof.

[0098] In one embodiment, the ethylene polymer may be produced by solution polymerization in a double reactor system, for example, a double-loop reactor system, and ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system described herein and optionally one or more co-catalysts. In another embodiment, the ethylene polymer may be produced by solution polymerization in a double reactor system, for example, a double-loop reactor system, and ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system described herein and optionally one or more other catalysts. The catalyst systems described herein may be used in combination with optionally one or more other catalysts in a first reactor or a second reactor. In one embodiment, the ethylene polymer may be produced by solution polymerization in a double reactor system, for example, a double-loop reactor system, and ethylene and optionally one or more α-olefins are polymerized in both reactors in the presence of a catalyst system described herein.

[0099] In another embodiment, the ethylene-based polymer may be produced by solution polymerization in a single reactor system, for example, a single-loop reactor system, and ethylene and optionally one or more α-olefins are polymerized as described in the previous paragraph in the presence of the catalyst system described in this disclosure and optionally one or more co-catalysts.

[0100] The ethylene polymer may further contain one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene polymer may contain any amount of additives. The ethylene polymer may be compromised by about 0 to about 10 percent in the total weight of such additives, based on the weight of the ethylene polymer and one or more additives. The ethylene polymer may further contain fillers, which include, but are not limited to, organic or inorganic fillers. The ethylene polymer may contain about 0 to about 20% by weight of fillers, such as calcium carbonate, talc, or Mg(OH)2, based on the total weight of the ethylene polymer and all additives or fillers. The ethylene polymer may be further compounded with one or more polymers to form a blend.

[0101] In some embodiments, the polymerization process for producing an ethylene-based polymer may include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, the catalyst system incorporating at least one metal-ligand complex of formula (I). The polymer obtained from such a catalyst system incorporating the metal-ligand complex of formula (I) is, for example, 0.850 g / cm³ according to ASTM D792 (which is incorporated herein by reference in its entirety). 3 ~0.950g / cm 3 , 0.880 g / cm³ 3 ~0.920g / cm 3 , 0.880 g / cm³ 3 ~0.910 g / cm³ 3 , or 0.880 g / cm³ 3 ~0.900g / cm 3 It may have a density.

[0102] In another embodiment, the polymer obtained from a catalyst system containing the metal-ligand complex of formula (I) has a melt flow ratio of 5 to 15 (I 10The melt index I2 is measured at 190°C and a 2.16 kg load according to ASTM D1238 (which is incorporated herein by reference in its entirety). 10 This is measured at 190°C and a 10kg load according to ASTM D1238. In other embodiments, the melt flow ratio (I 10 In other embodiments, the melt flow ratio is 5 to 9, and in other embodiments, the melt flow ratio is 5 to 9.

[0103] In some embodiments, the polymer obtained from the catalyst system containing the metal-ligand complex of formula (I) has a molecular-weight distribution (MWD) of 1 to 25, where MWD is defined as Mw / Mn, and Mw is the weight-average molecular weight and Mn is the number-average molecular weight. In other embodiments, the polymer obtained from the catalyst system has an MWD of 1 to 6. Another embodiment has an MWD of 1 to 3, and other embodiments have an MWD of 1.5 to 2.5.

[0104] The embodiments of the catalyst systems described herein result in unique polymer properties as a result of the high molecular weight of the formed polymer and the amount of copolymerization monomers incorporated into the polymer.

[0105] All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passing them through activated alumina and, in some cases, the Q-5 reactant. Solvents used in experiments conducted in nitrogen-filled glove boxes were further dried by storage on activated 4Å molecular sieves. Moisture-sensitive glassware used for reactions was dried overnight in an oven before use. NMR spectra were recorded using a Varian 400-MR spectrometer and a VNMRS-500 spectrometer. LC-MS analysis was performed using a Waters e2695 separation module combined with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separation is performed using an XBridge C18 3.5 μm 2.1 × 50 mm column with a 5:95 to 100:0 gradient of acetonitrile and water (containing 0.1% formic acid as an ionizing agent). HRMS analysis is performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8 μm 2.1 × 50 mm column, combined with an Agilent 6230 TOF mass spectrometer with electrospray ionization. 1 The 1H NMR data is reported as follows: chemical shift (multiplicity (br=broadline, s=monabyl, d=doubleline, t=triplet, q=quadlet, p=quintlet, sex=hexabyl, sept=hendlet, and m=multipleline), integral value, and assignment). 1 Chemical shifts in 1H NMR data are reported in ppm from internal tetramethylsilane (TMS, δ scale) to low magnetic field, using residual protons in the deuterated solvent as reference. 13 The 13C NMR data is 1 The chemical shift is determined using H decoupling, and is reported in ppm from tetramethylsilane (TMS, δ scale) to low magnetic field, using residual carbon in the deuterated solvent as the reference.

[0106] HT-GPC analysis using IR detection with embedded Octene High-temperature GPC analysis was performed using a Dow Robot-Assisted Delivery (RAD) system equipped with a PolymerChar infrared detector (IR5) and an Agilent PLgel Mixed A column. Decane (10 μL) was added to each sample for use as an internal flow marker. First, the samples were diluted to a concentration of 10 mg / mL in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm butylated hydroxytoluene (BHT) and dissolved by stirring at 160°C for 120 minutes. Before injection, the samples were further diluted to a concentration of 2 mg / mL with BHT-stabilized TCB. The samples (250 μL) were eluted at a flow rate of 1.0 mL / min through one PL-gel 20 μm (50 × 7.5 mm) guard column, followed by two PL-gel 20 μm (300 × 7.5 mm) Mixed-A columns, maintained at 160°C with BHT-stabilized TCB. The total run time was 24 minutes. To calibrate the molecular weight, Agilent EasiCal polystyrene standards (PS-1 and PS-2) were dissolved by diluting them in 1.5 mL of TCB stabilized with BHT and stirring at 160°C for 15 minutes. The PS standards were injected into the system without further dilution to create a cubic MW calibration curve with apparent units adjusted for homo-polyethylene (PE) using the well-known Mark-Houwink coefficients for PS and PE. Octene incorporation was determined by using a linear calibration developed by analyzing copolymers of known compositions.

[0107] Batch reactor polymerization procedure Batch reactor polymerization was carried out in a 2-L Parr® batch reactor. The reactor was heated by an electrically heated mantle and cooled by an internal helical cooling coil containing cooling water. Both the reactor and the heating / cooling system were controlled and monitored by a Camile® TG process computer. The bottom of the reactor was fitted with a dump valve, thereby emptying the contents of the reactor into a stainless steel dump pot pre-filled with a catalyst deactivation solution (typically 5 mL of Irgafos / Irganox / toluene mixture). The dump pot was vented into a 30-gallon blowdown tank, and both the pot and the tank were purged with nitrogen. All solvents used for polymerization or catalyst replenishment were passed through a solvent purification column to remove any impurities that could affect polymerization. 1-Octene and Isopar E were passed through two columns: a first column containing activated A2 alumina and a second column containing activated Q5 reactant. Ethylene was passed through two columns: a first column containing A204 alumina and a 4Å molecular sieve, and a second column containing the Q5 reactant. The N2 used for transfer was passed through a single column containing A204 alumina, a 4Å molar sieve, and Q5.

[0108] The reactor is initially loaded with shot tanks containing Isopar E solvent and / or 1-octene, according to the desired reactor load. The shot tanks are filled to the load setpoint using a lab scale equipped with the shot tanks. After the addition of the liquid feed, the reactor is heated to the polymerization temperature setpoint. If using ethylene, ethylene is added to the reactor when the reaction temperature is reached to maintain the reaction pressure setpoint. The amount of ethylene added is monitored by a micro-motion flow meter.

[0109] The catalyst and activator were mixed with an appropriate amount of purified toluene to obtain a solution of the desired molar concentration. The catalyst and activator were processed in an inert glove box, drawn into a syringe, and pressure-transferred to a catalyst shot tank. This was followed by three rinses with 5 mL each of toluene. Immediately after catalyst addition, the run timer was started. If ethylene was used, ethylene was then added by Camile to maintain the reaction pressure setpoint in the reactor. These polymerizations were carried out for 10 minutes, then the stirrer was stopped and the bottom dump valve was opened to transfer the reactor contents to a dump pot. The contents of the dump pot were poured into a tray placed in a laboratory hood, where the solvent was evaporated overnight. The trays containing the remaining polymer were then transferred to a vacuum oven, where they were heated to 140°C under vacuum to remove any remaining solvent. After the trays cooled to ambient temperature, the polymers were weighed for yield / efficiency and subjected to polymer testing. [Examples]

[0110] Examples 1-20 describe the synthesis procedures for ligand intermediates, ligands, and isolated procatalysts. Metal-ligand complexes 1 to 10 (MLC-1 to MLC-10) of the present invention were synthesized from various ligands disclosed herein. One or more features of this disclosure are illustrated by the following examples.

[0111] Example 1: For the synthesis of MLC-2 3-Bromo-1-(3,5-dimethylphenyl)-1H-indazole: For the synthesis of MLC-2 3-bromo-1H-indazole (600 mg, 3.05 mmol, 100 mol%), 1-iodo-3,5-dimethylbenzene (1060 mg, 4.57 mmol, 150 mol%), trans-cyclohexane-1,2-diamine (139 mg, 1.22 mmol, 40 mol%), CuI (116 mg, 0.61 mmol, 20 mol%), and K2CO3 (631 mg, 4.57 mmol, 150 mol%) were weighed in vials. Toluene (3 mL) was added, and the mixture was stirred overnight at 110°C. The reaction product was diluted with hexane (3 mL), filtered, and the solvent was removed under reduced pressure. The residue was subjected to column chromatography on silica (Hex → Hex / Â 3:7) to obtain the product (599.2 mg) in 65% yield.

[0112] 1 H NMR (400MHz, CDCl3)δ 7.74-7.67(m, 2H), 7.47(ddd, J=8.4, 6.9, 1.2Hz, 1H), 7.33-7.27(m, 3H), 7.02(s, 1H), 2.41(s, 6H). 13 C NMR (101MHz, CDCl3)δ 139.98, 139.55, 139.52, 128.94, 128.32, 125.00, 123.57, 122.27, 120.79, 120.62, 110.98, 21.51.

[0113] 3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1-(3,5-dimethylphenyl)-1H-indazole: For the synthesis of MLC-2 3-Bromo-1-(3,5-dimethylphenyl)-1H-indazole (99 mg, 0.33 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracene-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (234 mg, 0.41 mmol, 125 mol%, purity 85%), Pd(PPh3)4 (38 mg, 0.03 mmol, 10 mol%), and K3PO4 (210 mg, 0.99 mmol, 300 mol%) were weighed in vials. Dioxane (5 mL) and H2O (2 mL) were added, and the mixture was heated to 90°C. o The mixture was stirred in 1C for 16 hours. The reaction product was diluted with H2O (6 mL), extracted with GaN (2 × 8 mL), and washed with brine (5 mL). The combined organic layer was dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was subjected to column chromatography on silica (Hex → Hex / DCM 7:3) to obtain the product (82.7 mg) as a yellow solid in 44% yield.

[0114] 1 H NMR (400MHz, CDCl3)δ 9.50(s, 1H), 8.40(s, 1H), 8.24(dt, J=8.1, 1.0Hz, 1H), 8.08(dt, J=1.8, 0.8Hz , 2H), 7.98(d, J=8.9Hz, 2H), 7.82-7.77(m, 1H), 7.57(dd, J=8.9, 1.9Hz, 2H), 7 .50(ddd, J=8.4, 7.0, 1.1Hz, 1H), 7.39-7.32(m, 3H), 7.20(dd, J=3.5, 2.6Hz, 1 H), 6.98-6.95(m, 1H), 6.68(dd, J=3.5, 2.7Hz, 1H), 2.40(s, 6H), 1.38(s, 18H). 13 C NMR (101MHz, CDCl3)δ 148.11, 140.22, 140.13, 139.63, 139.33, 131.75, 129.92, 128.97, 128.20, 127.54, 127.35, 126.43, 12 5.44, 124.55, 122.28, 121.81, 121.73, 120.98, 120.47, 112.88, 110.93, 108.76, 35.31, 31.08, 21.54.

[0115] Example 2: For the synthesis of MLC-3 3-Bromo-1-(3,5-dimethoxyphenyl)-1H-indazole: For the synthesis of MLC-3 3-bromo-1H-indazole (600 mg, 3.05 mmol, 100 mol%), 1-iodo-3,5-dimethoxybenzene (1206 mg, 4.57 mmol, 150 mol%), trans-cyclohexane-1,2-diamine (139 mg, 1.22 mmol, 40 mol%), CuI (116 mg, 0.61 mmol, 20 mol%), and K2CO3 (631 mg, 4.57 mmol, 150 mol%) were weighed in vials. Toluene (3 mL) was added, and the mixture was stirred overnight at 110°C. The reaction product was diluted with hexane (3 mL), filtered, and the solvent was removed under reduced pressure. The residue was subjected to column chromatography on silica (Hex→Hex / DCM 4:6) to obtain the product (462.1 mg) in 46% yield.

[0116] 1 H NMR (400MHz, CDCl3)δ 7.77(dt, J=8.7, 1.0Hz, 1H), 7.70-7.66(m, 1H), 7.48(ddd, J=8.4, 7.0, 1.2Hz, 1H), 7.29 (ddd, J=8.0, 6.9, 0.8Hz, 1H), 6.87(d, J=2.2Hz, 2H), 6.47(t, J=2.3Hz, 1H), 3.86(s, 6H). 13 C NMR (101MHz, CDCl3)δ 161.52, 141.25, 139.94, 128.55, 125.20, 124.03, 122.49, 120.86, 111.11, 101.16, 99.34, 55.80.

[0117] For the synthesis of 3-(5-(2,6-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1-(3,5-dimethoxyphenyl)-1H-indazole:MLC-3 3-Bromo-1-(3,5-dimethoxyphenyl)-1H-indazole (100 mg, 0.30 mmol, 100 mol%), 2-(2,6-di-tert-butylanthracene-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (181 mg, 0.38 mmol, 125 mol%), Pd(PPh3)4 (35 mg, 0.03 mmol, 10 mol%), and K3PO4 (191 mg, 0.90 mmol, 300 mol%) were weighed into vials. Dioxane (5 mL) and H2O (2 mL) were added, and the mixture was heated to 90°C. o The mixture was stirred in 1C for 16 hours. The reaction product was diluted with H2O (6 mL), extracted with ethyl acetate (2 × 8 mL), and washed with brine (5 mL). The combined organic layer was dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was subjected to column chromatography on silica (Hex / DCM 6:4) to obtain the product (139.3 mg) as a yellow solid in 76% yield.

[0118] 1 H NMR (400MHz, CDCl3)δ 9.68(s, 1H), 8.37(s, 1H), 8.16(dt, J=8.1, 1.0Hz, 1H), 8.02-7.93(m, 3H), 7.87(d, J=2.0H z, 1H), 7.77(d, J=8.5Hz, 1H), 7.56(dd, J=8.9, 1.9Hz, 1H), 7.48(ddd, J=8.4, 5.3, 1.6Hz, 2 H), 7.34(ddd, J=7.9, 6.9, 0.9Hz, 1H), 7.16(dd, J=3.5, 2.6Hz, 1H), 6.86(d, J=2.3Hz, 2H), 6.62(dd, J=3.5, 2.7Hz, 1H), 6.35(t, J=2.3Hz, 1H), 3.77(s, 6H), 1.44(s, 9H), 1.35(s, 9H). 13¹³C NMR (10¹ MHz, CDCl3) δ 161.38, 147.87, 147.28, 141.73, 140.09, 139.91, 131.41, 131.30, 13 0.47, 130.27, 129.24, 128.10, 127.58, 127.26, 126.90, 126.48, 125. 39, 125.22, 124.71, 122.61, 122.48, 121.95, 121.85, 120.91, 112.88 , 111.10, 109.04, 100.69, 98.68, 55.66, 35.24, 34.94, 31.10, 31.04. HRMS(ESI)[M+H] + =608.326

[0119] Example 3: For the synthesis of LC-7 3-Bromo-1-(4-(tert-butyl)phenyl)-1H-pyrazole 3-bromo-1H-pyrazole (500 mg, 3.40 mmol, 100 mol%), 1-(tert-butyl)-4-iodobenzene (1327 mg, 5.10 mmol, 150 mol%), trans-cyclohexane-1,2-diamine (163 μL, 1.36 mmol, 40 mol%), CuI (130 mg, 0.68 mmol, 20 mol%), and K2CO3 (705 mg, 5.10 mmol, 150 mol%) were weighed in vials. Toluene (3.4 mL) was added, and the mixture was stirred overnight at 110°C. The reaction product was diluted with hexane (3 mL), filtered, and the solvent was removed under reduced pressure. The residue was subjected to column chromatography on silica (Hex→Hex / DCM 1:1) to obtain the product (193.6 mg) in 20% yield.

[0120] 1 H NMR (400MHz, CDCl3) δ 7.77(d, J=2.5Hz, 1H), 7.58-7.54(m, 2H), 7.48-7.43(m, 2H), 6.46(d, J=2.4Hz, 1H), 1.34(s, 9H).

[0121] 13C NMR (101MHz, CDCl3)δ 150.35, 137.38, 128.74, 127.93, 126.48, 118.94, 110.42, 34.75, 31.46.

[0122] 1-(4-(tert-butyl)phenyl)-3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1H-pyrazole: For the synthesis of MLC-7 3-Bromo-1-(4-tert-butylphenyl)-1H-pyrazole (83 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracene-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4 (34 mg, 0.03 mmol, 10 mol%), and K3PO4 (189 mg, 0.89 mmol, 300 mol%) were weighed in vials. 1,4-Dioxane (5 mL) and H2O (2 mL) were added, and the mixture was heated to 90°C. o The mixture was stirred in 1C for 16 hours. The reaction product was diluted with H2O (6 mL), extracted with GaN (2 × 8 mL), and washed with brine (5 mL). The combined organic layer was dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was subjected to column chromatography on silica (Hex / DCM 9:1) to obtain the product (85.8 mg) as a yellow solid in 52% yield.

[0123] 1 H NMR (400MHz, CDCl3)δ 9.24(s, 1H), 8.38(s, 1H), 8.02(dd, J=1.9, 0.9Hz, 2H), 7.96(d, J=8.9Hz, 2H), 7.91(d, J=2.5Hz, 1H), 7.61-7.58(m, 2H), 7.56(dd, J=8.9, 1 .9Hz, 2H), 7.45-7.40(m, 2H), 6.82(dd, J=3.5, 2.5Hz, 1H), 6.71(d, J=2.5Hz, 1H), 6.55(dd, J=3.5, 2.7Hz, 1H), 1.36(s, 18H), 1.33(s, 9H).

[0124] 13 C NMR (101MHz, CDCl3)δ 149.34, 148.08, 146.81, 137.85, 131.83, 129.93, 128.55, 128.16, 127.95, 127.81, 126.38, 1 26.32, 126.12, 124.53, 121.04, 118.61, 112.61, 107.67, 103.91, 35.30, 34.66, 31.48, 31.09.

[0125] Example 4: For the synthesis of MLC-4 3-Bromo-1-(4-methoxyphenyl)-1H-pyrazole 3-bromo-1H-pyrazole (500 mg, 3.40 mmol, 100 mol%), 1-iodo-4-methoxybenzene (1194 mg, 5.10 mmol, 150 mol%), trans-cyclohexane-1,2-diamine (163 μL, 1.36 mmol, 40 mol%), CuI (130 mg, 0.68 mmol, 20 mol%), and K2CO3 (705 mg, 5.10 mmol, 150 mol%) were weighed in vials. Toluene (3.4 mL) was added, and the mixture was stirred overnight at 110°C. The reaction product was diluted with hexane (3 mL), filtered, and the solvent was removed under reduced pressure. The residue was subjected to column chromatography on silica (Hex / DCM 1:1 → DCM) to obtain the product (136.8 mg) in 16% yield.

[0126] 1 H NMR (400MHz, CDCl3) δ 7.70(d, J=2.4Hz, 1H), 7.57-7.51(m, 2H), 6.99-6.93(m, 2H), 6.44(d, J=2.4Hz, 1H), 3.84(s, 3H).

[0127] 13 C NMR (101MHz, CDCl3) δ 158.76, 133.52, 128.89, 127.61, 120.98, 114.69, 110.23, 55.73.

[0128] For the synthesis of 3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1-(4-methoxyphenyl)-1H-pyrazole:MLC-4 3-Bromo-1-(4-methoxyphenyl)-1H-pyrazole (75 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracene-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4 (34 mg, 0.03 mmol, 10 mol%), and K3PO4 (189 mg, 0.89 mmol, 300 mol%) were weighed in vials. 1,4-Dioxane (5 mL) and H2O (2 mL) were added, and the mixture was heated to 90°C. o The mixture was stirred in 1C for 16 hours. The reaction product was diluted with H2O (6 mL), extracted with Âti (2 × 8 mL), and washed with brine (5 mL). The combined organic layer was dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was subjected to column chromatography on silica (Hex / DCM 8:2 → Hex / DCM 4:6) to obtain the product (103.0 mg) as a yellow solid in 65% yield.

[0129] 1 H NMR (400MHz, CDCl3)δ 9.21(s, 1H), 8.38(s, 1H), 8.03-8.00(m, 2H), 7.96(d, J=8.7Hz, 2H), 7.84(d, J=2.5Hz, 1H), 7.61-7.52(m, 4H), 6.97-6. 89(m, 2H), 6.81(dd, J=3.5, 2.6Hz, 1H), 6.69(d, J=2.5Hz, 1H), 6.54(dd, J=3.5, 2.7Hz, 1H), 3.82(s, 3H), 1.36(s, 18H).

[0130] 13C NMR (101MHz, CDCl3)δ 158.11, 148.05, 146.72, 134.08, 131.84, 129.93, 128.43, 128.16, 127.99, 127.84, 126.3 0, 126.19, 124.52, 121.05, 120.49, 114.65, 112.56, 107.49, 103.70, 55.71, 35.29, 31.09.

[0131] Example 5: For the synthesis of LC-5 3-Bromo-1-(3,4-dimethoxyphenyl)-1H-pyrazole (EXP-21-CL5419-R3, DCI18651) 3-bromo-1H-pyrazole (500 mg, 3.40 mmol, 100 mol%), 4-iodo-1,2-dimethoxybenzene (1347 mg, 5.10 mmol, 150 mol%), trans-cyclohexane-1,2-diamine (163 μL, 1.36 mmol, 40 mol%), CuI (130 mg, 0.68 mmol, 20 mol%), and K2CO3 (705 mg, 5.10 mmol, 150 mol%) were weighed in vials. Toluene (3.4 mL) was added, and the mixture was stirred overnight at 110°C. The reaction product was diluted with hexane (3 mL), filtered, and the solvent was removed under reduced pressure. The residue was subjected to column chromatography on silica (Hex / DCM 1:1 → DCM) to obtain the product (210.0 mg) in 22% yield.

[0132] 1 H NMR (400MHz, CDCl3)δ 7.72(d, J=2.4Hz, 1H), 7.27(d, J=2.5Hz, 1H), 7.06(dd, J=8.6, 2.5Hz, 1H), 6.89(d, J=8.6Hz, 1H), 6.45(d, J=2.4Hz, 1H), 3.95(s, 3H), 3.91(s, 3H). 13 C NMR (101MHz, CDCl3)δ 149.83, 148.33, 133.76, 129.03, 127.65, 111.31, 110.93, 110.33, 104.41, 56.35, 56.33.

[0133] For the synthesis of 3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1-(3,4-dimethoxyphenyl)-1H-pyrazole:MLC-5 3-Bromo-1-(3,4-dimethoxyphenyl)-1H-pyrazole (84 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracene-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4 (34 mg, 0.03 mmol, 10 mol%), and K3PO4 (189 mg, 0.89 mmol, 300 mol%) were weighed in vials. 1,4-Dioxane (5 mL) and H2O (2 mL) were added, and the mixture was heated to 90°C. o The mixture was stirred in 1C for 16 hours. The reaction product was diluted with H2O (6 mL), extracted with toluene (2 × 8 mL), and washed with brine (5 mL). The combined organic layer was dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was subjected to column chromatography on silica (Hex / toluene 8:2 → Hex / toluene 1:1 → DCM) to obtain the product (92.3 mg) as a green solid in 55% yield.

[0134] 1 H NMR (400MHz, CDCl3)δ 9.25(s, 1H), 8.38(s, 1H), 8.03-8.01(m, 2H), 7.98-7.94(m, 2H), 7.85(d, J=2. 5Hz, 1H), 7.55(dd, J=8.9, 1.9Hz, 2H), 7.33(d, J=2.5Hz, 1H), 7.09(dd, J=8.7, 2.5Hz, 1H), 6.87(d, J=8.7Hz, 1H), 6.82(dd, J=3.5, 2.6Hz, 1H), 6.69(d, J=2.5 Hz, 1H), 6.55(dd, J=3.5, 2.7Hz, 1H), 3.90(s, 3H), 3.89(s, 3H), 1.36(s, 18H).

[0135] 13C NMR (101MHz, CDCl3)δ 149.78, 148.06, 147.61, 146.76, 134.31, 131.83, 129.93, 128.46, 128.18, 128.12, 127.85, 126.33, 1 26.10, 124.53, 121.04, 112.59, 111.45, 110.32, 107.63, 103.97, 103.85, 56.34, 56.23, 35.29, 31.08.

[0136] Example 6: For the synthesis of MLC-6 1-(benzo[d][1,3]dioxol-5-yl)-3-bromo-1H-pyrazole 3-bromo-1H-pyrazole (500 mg, 3.40 mmol, 100 mol%), 5-iodobenzo[d][1,3]dioxol (1266 mg, 5.10 mmol, 150 mol%), trans-cyclohexane-1,2-diamine (163 μL, 1.36 mmol, 40 mol%), CuI (130 mg, 0.68 mmol, 20 mol%), and K2CO3 (705 mg, 5.10 mmol, 150 mol%) were weighed in vials. Toluene (3.4 mL) was added, and the mixture was stirred overnight at 110 °C. The reaction product was diluted with hexane (3 mL), filtered, and the solvent was removed under reduced pressure. The residue was subjected to column chromatography on silica (Hex / DCM 1:1 → DCM) to obtain the product (154.8 mg) in 17% yield.

[0137] 1 H NMR (400MHz, CDCl3)δ 7.67(d, J=2.4Hz, 1H), 7.17(d, J=2.2Hz, 1H), 7.05(dd, J=8.4, 2.2Hz, 1H), 6.84(d, J=8.4Hz, 1H), 6.44(d, J=2.4Hz, 1H), 6.03(s, 2H).

[0138] 13 C NMR (101MHz, CDCl3)δ 148.62, 146.84, 134.68, 129.05, 127.75, 112.71, 110.39, 108.43, 101.98, 101.98.

[0139] For the synthesis of 1-(benzo[d][1,3]dioxol-5-yl)-3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1H-pyrazole:MLC-6 1-(benzo[d][1,3]dioxol-5-yl)-3-bromo-1H-pyrazole (79 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracene-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4 (34 mg, 0.03 mmol, 10 mol%), and K3PO4 (189 mg, 0.89 mmol, 300 mol%) were weighed in vials. 1,4-dioxane (5 mL) and H2O (2 mL) were added, and the mixture was heated to 90°C. o The mixture was stirred in 1C for 16 hours. The reaction product was diluted with H2O (6 mL), extracted with siRNA (2 × 8 mL), and washed with brine (5 mL). The combined organic layer was dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was subjected to column chromatography on silica (Hex / DCM 8:2 → Hex / DCM 4:6) to obtain the product (114.0 mg) as a yellow solid in 70% yield.

[0140] 1 H NMR (400MHz, CDCl3)δ 9.21(s, 1H), 8.38(s, 1H), 8.01(dt, J=1.8, 0.8Hz, 2H), 7.96(dt, J=8.9, 0.6Hz, 2H), 7.81(d, J=2.5Hz, 1H), 7.55(dd, J=8.9, 1.9Hz, 2H), 7.20(d , J=2.2Hz, 1H), 7.09(dd, J=8.4, 2.2Hz, 1H), 6.84-6.79(m, 2H), 6.68(d, J=2.5Hz, 1H), 6.54(dd, J=3.5, 2.7Hz, 1H), 5.99(s, 2H), 1.36(s, 16H).

[0141] 13C NMR (101MHz, CDCl3)δ 148.54, 148.08, 146.75, 146.11, 135.25, 131.84, 129.92, 128.59, 128.20, 128.16, 127.76, 126.33 , 126.00, 124.52, 121.02, 112.59, 112.12, 108.43, 107.67, 103.86, 101.78, 101.56, 35.29, 31.08.

[0142] Example 7: For the synthesis of MLC-8 3-Bromo-1-(3,5-dimethylphenyl)-1H-pyrazole (EXP-21-CL5446-R1, DCI19068) 3-bromo-1H-pyrazole (500 mg, 3.40 mmol, 100 mol%), 1-iodo-3,5-dimethylbenzene (1184 mg, 5.10 mmol, 150 mol%), trans-cyclohexane-1,2-diamine (163 μL, 1.36 mmol, 40 mol%), CuI (130 mg, 0.68 mmol, 20 mol%), and K2CO3 (705 mg, 5.10 mmol, 150 mol%) were weighed in vials. Toluene (3.4 mL) was added, and the mixture was stirred overnight at 110°C. The reaction product was diluted with hexane (3 mL), filtered, and the solvent was removed under reduced pressure. The residue was subjected to column chromatography on silica (Hex→Hex / DCM 4:6) to obtain the product (208 mg) in 24% yield.

[0143] 1 H NMR (400MHz, CDCl3) δ 7.77(d, J=2.5Hz, 1H), 7.26(s, 2H), 6.94(s, 1H), 6.45(d, J=2.5Hz, 1H), 2.36(s, 6H).

[0144] 13 C NMR (101MHz, CDCl3) δ 139.62, 139.53, 128.82, 128.78, 127.94, 116.99, 110.38, 21.46.

[0145] 3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1-(3,5-dimethylphenyl)-1H-pyrazole for the synthesis of MLC-8 3-Bromo-1-(3,5-dimethylphenyl)-1H-pyrazole (76 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracene-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4 (34 mg, 0.03 mmol, 10 mol%), and K3PO4 (189 mg, 0.89 mmol, 300 mol%) were weighed in vials. 1,4-Dioxane (5 mL) and H2O (2 mL) were added, and the mixture was heated to 90°C. o The mixture was stirred in 1C for 16 hours. The reaction product was diluted with H2O (6 mL), extracted with GaN (2 × 8 mL), and washed with brine (5 mL). The combined organic layer was dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was subjected to column chromatography on silica (Hex → Hex / DCM 4:6) to obtain the product (93.3 mg) as a yellow solid in 59% yield.

[0146] 1 H NMR (500MHz, CDCl3)δ 9.26(s, 1H), 8.38(s, 1H), 8.05-8.03(m, 2H), 7.96(d, J=8.9Hz, 2H), 7.91(d, J=2.5Hz, 1H), 7.56(dd, J=8.9, 1.9Hz, 2H), 7.31(dt, J=1.5, 0.7Hz , 2H), 6.88(tt, J=1.6, 0.8Hz, 1H), 6.82(dd, J=3.4, 2.6Hz, 1H), 6.70(d, J=2.5Hz, 1H), 6.55(dd, J=3.5, 2.7Hz, 1H), 2.34(s, 6H), 1.37(s, 18H).

[0147] 13C NMR (126MHz, CDCl3)δ 148.05, 146.80, 140.13, 139.35, 131.79, 129.94, 128.55, 128.18, 128.00, 127.86, 127.8 0, 126.30, 126.13, 124.52, 121.07, 116.68, 112.58, 107.65, 103.91, 35.30, 31.09, 21.51.

[0148] Example 8: For the synthesis of MLC-9 3-Bromo-1-(3,5-dimethoxyphenyl)-1H-pyrazole 3-bromo-1H-pyrazole (500 mg, 3.40 mmol, 100 mol%), 1-iodo-3,5-dimethoxybenzene (1347 mg, 5.10 mmol, 150 mol%), trans-cyclohexane-1,2-diamine (163 μL, 1.36 mmol, 40 mol%), CuI (130 mg, 0.68 mmol, 20 mol%), and K2CO3 (705 mg, 5.10 mmol, 150 mol%) were weighed in vials. Toluene (3.4 mL) was added, and the mixture was stirred overnight at 110°C. The reaction product was diluted with hexane (3 mL), filtered, and the solvent was removed under reduced pressure. The residue was subjected to column chromatography on silica (Hex→Hex / DCM 4:6) to obtain the product (308 mg) in 32% yield.

[0149] 1 H NMR (400MHz, CDCl3) δ 7.77 (d, J=2.5Hz, 1H), 6.81 (d, J=2.2Hz, 2H), 6.46 (d, J=2.5Hz, 1H), 6.39 (t, J=2.2Hz, 1H), 3.84 (s, 6H).

[0150] 13 C NMR (101MHz, CDCl3) δ 161.58, 141.32, 129.00, 128.22, 110.69, 99.15, 97.69, 55.80.

[0151] 3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1-(3,5-dimethoxyphenyl)-1H-pyrazole for the synthesis of MLC-9 3-Bromo-1-(3,5-dimethoxyphenyl)-1H-pyrazole (86 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracene-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4 (34 mg, 0.03 mmol, 10 mol%), and K3PO4 (189 mg, 0.89 mmol, 300 mol%) were weighed in vials. 1,4-Dioxane (5 mL) and H2O (2 mL) were added, and the mixture was heated to 90°C. o The mixture was stirred in 1C for 16 hours. The reaction product was diluted with H2O (6 mL), extracted with ethyl acetate (2 × 8 mL), and washed with brine (5 mL). The combined organic layer was dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was subjected to column chromatography on silica (Hex / DCM 8:2 → Hex / DCM 4:6) to obtain the product (111.1 mg) as a yellow solid in 66% yield.

[0152] 1 H NMR (500MHz, CDCl3)δ 9.31(s, 1H), 8.39(s, 1H), 8.01-7.99(m, 2H), 7.96(d, J=8.9Hz, 2H), 7.88(d, J=2.6Hz, 1H), 7.55(dd, J=8.9, 1.9Hz, 2H), 6.84(d, J=2.2Hz) , 2H), 6.82(dd, J=3.5, 2.6Hz, 1H), 6.69(d, J=2.6Hz, 1H), 6.54(dd, J=3.5, 2.7Hz, 1H), 6.32(t, J=2.2Hz, 1H), 3.80(s, 6H), 1.36(s, 18H).

[0153] 13C NMR (126MHz, CDCl3)δ 161.52, 148.08, 146.95, 141.73, 131.83, 129.92, 128.76, 128.21, 128.17, 127.77, 126. 36, 125.83, 124.54, 121.01, 112.64, 108.04, 104.27, 98.43, 97.20, 55.73, 35.29, 31.08.

[0154] Example 9: For the synthesis of MLC-10 4-(3-bromo-1H-pyrazole-1-yl)-N,N-dimethylaniline 3-bromo-1H-pyrazole (500 mg, 3.40 mmol, 100 mol%), 4-iodo-N,N-dimethylaniline (1000 mg, 4.05 mmol, 120 mol%), trans-cyclohexane-1,2-diamine (163 μL, 1.36 mmol, 40 mol%), CuI (130 mg, 0.68 mmol, 20 mol%), and K2CO3 (705 mg, 5.10 mmol, 150 mol%) were weighed in vials. Toluene (3.4 mL) was added, and the mixture was stirred overnight at 110°C. The reaction product was diluted with hexane (3 mL), filtered, and the solvent was removed under reduced pressure. The residue was subjected to column chromatography on silica (Hex→Hex / DCM 4:6) to obtain the product (182 mg) in 20% yield.

[0155] 1 H NMR (400MHz, CDCl3) δ 7.66(d, J=2.4Hz, 1H), 7.49-7.44(m, 2H), 6.75(d, J=8.6Hz, 2H), 6.41(d, J=2.4Hz, 1H), 2.99(s, 6H).

[0156] 13 C NMR (101MHz, CDCl3) δ 149.77, 128.76, 126.93, 120.95, 112.74, 109.73, 40.82.

[0157] For the synthesis of 4-(3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1H-pyrazole-1-yl)-N,N-dimethylaniline:MLC-10 4-(3-bromo-1H-pyrazole-1-yl)-N,N-dimethylaniline (81 mg, 0.30 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracene-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (179 mg, 0.37 mmol, 125 mol%), Pd(PPh3)4 (34 mg, 0.03 mmol, 10 mol%), and K3PO4 (189 mg, 0.89 mmol, 300 mol%) were weighed in vials. 1,4-dioxane (5 mL) and H2O (2 mL) were added, and the mixture was heated to 90°C. o The mixture was stirred in 1C for 16 hours. The reaction product was diluted with H2O (6 mL), extracted with ₹ (2 × 8 mL), and washed with brine (5 mL). The combined organic layer was dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was subjected to column chromatography on silica (Hex / DCM 8:2 → Hex / DCM 4:6) to obtain the product (90.6 mg) as a yellow solid in 56% yield.

[0158] 1 H NMR (500MHz, CDCl3)δ 9.20(s, 1H), 8.37(s, 1H), 8.04-8.02(m, 2H), 7.96(d, J=8.9Hz, 2H), 7.81(d, J=2.5Hz, 1H), 7.55(dd, J=8.9, 1.9Hz, 2H), 7.51(d, J=9.0 Hz, 2H), 6.80(dd, J=3.4, 2.6Hz, 1H), 6.78-6.72(m, 2H), 6.67(d, J=2.5Hz, 1H), 6.54(dd, J=3.4, 2.7Hz, 1H), 2.96(s, 6H), 1.36(s, 18H).

[0159] 13C NMR (126MHz, CDCl3)δ 148.01, 146.37, 131.84, 129.93, 128.16, 128.13, 127.96, 127.86, 126.51, 126.2 2, 124.51, 121.10, 120.51, 113.06, 112.51, 107.16, 103.26, 40.96, 35.28, 31.09.

[0160] Example 10: For the synthesis of MLC-1 Synthesis of 3-bromo-1-(p-tolyl)-1H-indazole 3-Bromo-1H-indazole (500 mg, 2.54 mmol, 100 mol%), 4-iodotoluene (830 mg, 3.81 mmol, 150 mol%), trans-cyclohexane-1,2-diamine (70 μL, 0.58 mmol, 23 mol%), CuI (53 mg, 0.28 mmol, 11 mol%), and K2CO3 (526 mg, 3.81 mmol, 150 mol%) were weighed in vials. DMF (10 mL) was added, and the mixture was stirred overnight at 120°C. The reaction product was diluted with water (50 mL). The organic matter was extracted with ethyl acetate (30 mL x 3). The combined organic matter was washed with water (30 mL x 3 times) and brine (30 mL). The organic matter was dried over magnesium sulfate, filtered, and concentrated. The residue was subjected to column chromatography on silica (Hex / DCM 9:1 → Hex / DCM 6.5:3.5) to obtain the product (671 mg) in 92% yield.

[0161] 1 H NMR (400MHz, chloroform-d)δ 7.73-7.62(m, 2H), 7.59-7.54(m, 2H), 7.47(ddt, J=8.8, 6.9, 1.0Hz, 1H), 7.35-7.31(m, 2H), 7.29(dq, J=8.1, 1.0Hz, 1H), 2.44(s, 3H).

[0162] 13C NMR (101MHz, CDCl3)δ 139.88, 137.12, 137.04, 130.03, 130.01, 128.18, 128.10, 124.82, 123.37 , 122.80, 122.74, 122.09, 121.90, 120.65, 110.62, 110.49, 21.09, -0.01.

[0163] 3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1-(p-tolyl)-1H-indazole: For the synthesis of MLC-1 3-Bromo-1-(p-tolyl)-1H-indazole (49 mg, 0.171 mmol, 100 mol%), 2-(2,7-di-tert-butylanthracene-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole (120 mg, 0.209 mmol, 123 mol%, purity 85%), Pd(PPh3)4 (12 mg, 0.010 mmol, 6 mol%), and K3PO4 (109 mg, 0.512 mmol, 300 mol%) were weighed in vials. Dioxane (5 mL) and H2O (2 mL) were added, and the mixture was stirred overnight at 90°C. The reaction product was diluted with H2O (15 mL) and brine (15 mL) and extracted with  (2 × 30 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. The residue was subjected to column chromatography on silica (Hex / DCM 9:1 → Hex / DCM 7:3) to obtain the product (83 mg) as a yellow solid in 87% yield.

[0164] 1 H NMR (400MHz, chloroform-d)δ 9.50(s, 1H), 8.43(s, 1H), 8.27(d, J=8.1Hz, 1H), 8.12(s, 2H), 8.01(d, J=8.9Hz, 2H), 7.78(d, J=8.5Hz, 1H), 7.68-7.55 (m, 4H), 7.54-7.46(m, 1H), 7.42-7.28(m, 3H), 7.26(d, J=3.5Hz, 1H), 6.73(t, J=3.1Hz, 1H), 2.43(s, 3H), 1.41(s, 18H).

[0165] 13 C NMR (101MHz, CDCl3)δ 148.04, 140.17, 139.57, 137.78, 136.19, 131.74, 129.95, 129.82, 128.85, 128.11, 127.48, 127.23, 126.3 5, 125.43, 124.45, 122.56, 122.17, 121.69, 121.59, 120.88, 112.78, 110.62, 108.63, 35.19, 30.98, 21.07.

[0166] HRMS(ESI)[M+H] + =562.325 Example 11: Synthesis of metal-ligand complex 1 (MLC-1) In a glove box, a solution of 3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1-(p-tolyl)-1H-indazole (15.0 mg, 0.03 mmol, 100 mol%) dissolved in C6D6 (500 μL) was added dropwise to HfBn4 (14.0 mg, 0.03 mmol, 100 mol%), which is solid at room temperature. To ensure thorough mixing, the vial was swirled after each drop. Five minutes after addition, the solution was transferred to an NMR tube. 1 H and 13 This was checked by 13C NMR. Complete conversion to the desired complex was observed.

[0167] 1H NMR (400MHz, C6D6)δ 8.41(s, 1H), 8.36-8.31(m, 2H), 7.94(d, J=9.0Hz, 2H), 7.76(dt, J=8.2, 1.1Hz, 1H), 7.46( dd, J=8.9, 1.9Hz, 2H), 7.31(d, J=3.2Hz, 1H), 7.25(d, J=1.9Hz, 1H), 7.20-6.98(m, 13H), 6. 98-6.82(m, 4H), 6.63(t, J=7.7Hz, 4H), 6.56-6.50(m, 1H), 6.39(tt, J=7.3, 1.3Hz, 2H), 6.1 9-6.10(m, 4H), 2.13(s, 3H), 1.78(d, J=11.7Hz, 2H), 1.36(d, J=11.7Hz, 2H), 1.25(s, 18H).

[0168] 13 C NMR (101MHz, C6D6)δ 191.22, 148.19, 146.19, 145.78, 142.69, 139.56, 138.56, 137.58, 137.52, 137.32 , 136.16, 133.32, 131.83, 130.87, 130.46, 130.18, 129.92, 129.31, 128.96, 128.6 1, 128.49, 128.27, 128.20, 127.00, 125.33, 124.81, 124.39, 122.98, 122.86, 121.80, 121.76, 119.32, 114.70, 111.87, 111.52, 110.98, 84.19, 34.94, 30.58, 21.07.

[0169] Example 12: Synthesis of metal-ligand complex 2 (MLC-2) In a glove box, a solution of 3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1-(3,5-dimethylphenyl)-1H-indazole (11.7 mg, 0.020 mmol, 100 mol%) dissolved in C6D6 (600 μL) was added dropwise to HfBn4 (11.0 mg, 0.020 mmol, 100 mol%), which is solid at room temperature. To ensure thorough mixing, the vial was swirled after each drop. Five minutes after addition, the solution was transferred to an NMR tube. 1 H and 13The solution was checked by 13C NMR. A mixture of the [3,2] complex and the mono-[2,1] complex was observed. The solution was then subjected to 80°C in an NMR tube. o It was heated at ℃ for 2 hours.

[0170] 1 H NMR (400MHz, C6D6) δ8.45(s, 1H), 8.42-8.40(m, 2H), 7.99(d, J=9.0Hz, 2H), 7.84(dt, J=8.2, 1.1Hz, 1 H), 7.47(dd, J=9.0, 1.9Hz, 2H), 7.41(d, J=3.1Hz, 1H), 7.35(d, J=8.9Hz, 1H), 7.07(q, J=1.4Hz, 1H), 6.99(d, J=3.1Hz, 1H), 6.94-6.89(m, 1H), 6.81(s, 1H), 6.62-6.56(m, 4H), 6.51-6.42(m, 5H), 6.24-6 .16(m, 2H), 2.29(s, 3H), 2.17(d, J=11.9Hz, 2H), 2.06(s, 3H), 1.31(d, J=11.9Hz, 2H), 1.24(s, 18H). 13 ¹¹C NMR (10¹ MHz, C6D6) δ 188.89, 148.51, 147.70, 145.76, 144.39, 142.82, 140.25, 137.44, 136.63, 136.04, 133.65, 131.28, 130.61, 130.09, 128.81, 128.45, 128.21, 127.27, 126.29, 125.24, 123.67, 122.84, 122.19, 122.01, 119.84, 114.74, 111.67, 111.51, 110.46, 86.44, 35.36, 30.83, 23.89, 21.69.

[0171] Example 13: Synthesis of metal-ligand complex 3 (MLC-3) In a glove box, a solution of 3-(5-(2,6-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1-(3,5-dimethoxyphenyl)-1H-indazole (12.2 mg, 0.020 mmol, 100 mol%) dissolved in C6D6 (600 μL) was added dropwise to HfBn4 (11.0 mg, 0.020 mmol, 100 mol%), which is solid at room temperature. To ensure thorough mixing, the vial was swirled after each drop. Five minutes after addition, the solution was transferred to an NMR tube. 1 H and 13 This was checked by 13C NMR.

[0172] 1 H NMR (400MHz, C6D6)δ 8.55-8.52(m, 1H), 8.43(t, J=4.5Hz, 2H), 8.03-7.95(m, 2H), 7.78(dt, J=8.2, 1.1Hz, 1H), 7.50(td, J=9.1, 1.9H) z, 2H), 7.36(d, J=3.2Hz, 1H), 7.21(d, J=8.7Hz, 1H), 6.96(d, J=3.2Hz, 1H), 6.91-6.85(m, 1H), 6.68-6.51(m, 9H) ), 6.43(d, J=1.6Hz, 1H), 6.32(tt, J=6.3, 2.1Hz, 1H), 6.24(tt, J=6.8, 1.9Hz, 1H), 5.99(d, J=1.6Hz, 1H), 3.30( s, 3H), 3.22(s, 3H), 2.16-2.11(m, 2H), 1.49(d, J=6.4Hz, 1H), 1.42(d, J=11.2Hz, 1H), 1.29(s, 9H), 1.27(s, 9H). 13C NMR (101MHz, C6D6)δ 171.47, 167.78, 162.50, 148.62, 148.21, 147.67, 146.53, 143.17, 140.45, 138.46, 13 7.26, 136.50, 132.98, 132.38, 132.00, 131.17, 131.08, 130.35, 130.30, 128.98, 128.7 8, 127.63, 125.71, 125.36, 123.18, 122.97, 122.96, 122.26, 122.13, 119.98, 114.89, 111.96, 111.19, 91.95, 91.93, 88.64, 86.92, 54.79, 53.94, 35.37, 34.87, 30.93, 30.92.

[0173] Example 14: Synthesis of metal-ligand complex 4 (MLC-4) In a glove box, a solution of 3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1-(4-methoxyphenyl)-1H-pyrazole (10.6 mg, 0.020 mmol, 100 mol%) dissolved in C6D6 (600 μL) was added dropwise to ZrBn4 (9.1 mg, 0.020 mmol, 100 mol%), which is solid at room temperature. The vial was swirled after each drop to ensure thorough mixing. After addition, the solution was transferred to an NMR tube, and the sample was reacted overnight at room temperature. Two equivalents of toluene were clearly detected by NMR.

[0174] 1 H NMR (400MHz, C6D6)δ 8.35(s, 1H), 8.26-8.14(m, 2H), 7.91(d, J=8.9Hz, 2H), 7.45(dd, J=8.9, 1.9Hz, 2H), 6.80(d, J=2.5Hz, 1H), 6.75-6.65(m, 7H), 6.56 -6.45(m, 4H), 6.05(d, J=2.5Hz, 1H), 5.93-5.87(m, 4H), 3.32(s, 3H), 2.05(d, J=10.0Hz, 2H), 1.24(s, 18H), 1.17(d, J=10.0Hz, 2H).

[0175] 13C NMR (101MHz, C6D6)δ 181.58, 156.55, 151.57, 148.45, 140.16, 139.34, 138.30, 136.19, 133.64, 132.25, 130.52, 130.41, 129.15, 128.39, 1 27.32, 127.03, 125.18, 123.73, 122.30, 120.79, 113.73, 113.24, 111.51, 109.32, 100.16, 74.81, 54.95, 35.26, 30.94.

[0176] Example 15: Synthesis of metal-ligand complex 5 (MLC-5) In a glove box, a solution of 3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1-(3,4-dimethoxyphenyl)-1H-pyrazole (11.2 mg, 0.020 mmol, 100 mol%) dissolved in C6D6 (600 μL) was added dropwise to ZrBn4 (9.1 mg, 0.020 mmol, 100 mol%), which is solid at room temperature. The vial was swirled after each drop to ensure thorough mixing. After addition, the solution was transferred to an NMR tube, and the sample was reacted overnight at room temperature. Two equivalents of toluene were clearly detected by NMR.

[0177] 1 H NMR (400MHz, C6D6)δ 8.37(s, 1H), 8.24-8.20(m, 2H), 7.92(d, J=9.0Hz, 2H), 7.47(dd, J=8.9, 1.9Hz, 2H) , 7.19(d, J=3.1Hz, 1H), 6.76(d, J=3.1Hz, 1H), 6.73-6.68(m, 5H), 6.59(d, J=2.5Hz, 1H), 6.58-6.52(m, 2H), 6.17(s, 1H), 6.05(d, J=2.5Hz, 1H), 5.93-5.89(m, 4H), 3.42 (s, 3H), 3.38(s, 3H), 2.06(d, J=10.1Hz, 2H), 1.25(s, 18H), 1.19(d, J=10.1Hz, 2H).

[0178] 13C NMR (101MHz, C6D6)δ 173.43, 151.86, 149.76, 148.44, 146.07, 140.29, 139.67, 138.76, 136.11, 133.67, 132.25, 130.53, 130.23, 129.09, 128. 39, 127.44, 127.02, 125.19, 123.60, 122.37, 119.51, 113.73, 109.42, 100.18, 96.41, 74.43, 55.86, 55.82, 35.27, 30.94.

[0179] Example 16: Synthesis of metal-ligand complex 6 (MLC-6) In a glove box, a solution of 1-(benzo[d][1,3]dioxol-5-yl)-3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1H-pyrazole (10.8 mg, 0.020 mmol, 100 mol%) dissolved in C6D6 (600 μL) was added dropwise to ZrBn4 (9.1 mg, 0.020 mmol, 100 mol%), which is solid at room temperature. To ensure thorough mixing, the vial was swirled after each drop. After addition, the solution was transferred to an NMR tube, and the sample was reacted overnight at room temperature. Two equivalents of toluene were clearly detected by NMR.

[0180] 1 H NMR(500MHz, C6D6)δ 8.39(s, 1H), 8.20-8.18(m, 2H), 7.95(d, J=9.0Hz, 2H), 7.45(dd, J=8.9, 2.0Hz, 2H), 6.76 (d, J=2.5Hz, 1H), 6.70(d, J=3.1Hz, 1H), 6.69-6.63(m, 4H), 6.52-6.48(m, 2H), 6.40-6.36 (m, 1H), 6.34(d, J=8.1Hz, 1H), 6.22-6.17(m, 4H), 6.06(d, J=2.5Hz, 1H), 5.99(d, J=8.1H) z, 1H), 5.13(s, 2H), 1.86(d, J=9.6Hz, 2H), 1.59(d, J=9.5Hz, 2H), 1.23(d, J=1.7Hz, 18H).

[0181] 13C NMR (126MHz, C6D6)δ 157.23, 151.32, 148.34, 143.49, 141.17, 140.78, 137.78, 135.88, 133.63, 132.63, 131.04, 130.60, 130.49, 128.95, 128.4 7, 128.35, 127.63, 126.74, 125.16, 124.16, 122.21, 114.05, 109.25, 106.50, 103.93, 100.27, 99.05, 74.79, 35.24, 30.93.

[0182] Example 17: Synthesis of metal-ligand complex 7 (MLC-7) In a glove box, a solution of 1-(4-(tert-butyl)phenyl)-3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1H-pyrazole (11.1 mg, 0.020 mmol, 100 mol%) dissolved in C6D6 (600 μL) was added dropwise to ZrBn4 (9.1 mg, 0.020 mmol, 100 mol%), which is solid at room temperature. To ensure thorough mixing, the vial was swirled after each drop. After addition, the solution was transferred to an NMR tube, and the sample was reacted overnight at room temperature. Two equivalents of toluene were clearly detected by NMR.

[0183] 1 H NMR(500MHz, C6D6)δ 8.37(s, 1H), 8.21-8.18(m, 2H), 7.92(d, J=8.9Hz, 2H), 7.46(dd, J=8.9, 1.9Hz, 2H), 7 .22(d, J=2.1Hz, 1H), 7.18(d, J=3.1Hz, 1H), 6.94(dd, J=8.3, 2.2Hz, 1H), 6.75-6.70(m , 6H), 6.55(t, J=7.4Hz, 2H), 6.51(d, J=8.3Hz, 1H), 6.07(d, J=2.5Hz, 1H), 5.91(d, J=7 .5Hz, 4H), 2.01(d, J=10.0Hz, 2H), 1.24(s, 18H), 1.22(d, J=10.3Hz, 2H), 1.18(s, 9H).

[0184] 13C NMR (126MHz, C6D6)δ 180.30, 151.87, 148.45, 146.26, 143.08, 140.38, 138.55, 136.21, 133.65, 132.94, 132.28, 130.53, 130.32, 129.05, 128. 35, 127.69, 126.99, 125.20, 124.34, 123.62, 122.31, 113.69, 110.13, 109.43, 100.46, 74.51, 35.25, 34.61, 31.68, 30.92.

[0185] Example 18: Synthesis of metal-ligand complex 8 (MLC-8) In a glove box, a solution of 3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1-(3,5-dimethylphenyl)-1H-pyrazole (10.5 mg, 0.020 mmol, 100 mol%) dissolved in C6D6 (600 μL) was added dropwise to ZrBn4 (9.1 mg, 0.020 mmol, 100 mol%), which is solid at room temperature. The vial was swirled after each drop to ensure thorough mixing. After addition, the solution was transferred to an NMR tube, and the sample was reacted overnight at room temperature. Two equivalents of toluene were clearly detected by NMR.

[0186] 1 H NMR(500MHz, C6D6)δ 8.41(s, 1H), 8.32(s, 2H), 7.96(dd, J=8.9, 2.3Hz, 2H), 7.45(d, J=9.0Hz, 2H), 7.20-7.17(m, 1H), 6.87-6.84(m, 1H), 6.74-6.72(m, 1H), 6.65-6.59(m, 4H), 6. 52-6.47(m, 4H), 6.41-6.36(m, 2H), 6.28(s, 1H), 6.10-6.05(m, 2H), 2.32(d, J =10.7Hz, 2H), 1.98(s, 3H), 1.94(s, 3H), 1.57(d, J=10.8Hz, 2H), 1.24(s, 18H).

[0187] 13C NMR (126MHz, C6D6)δ 179.77, 150.86, 148.36, 144.20, 143.54, 140.55, 136.96, 136.84, 136.09, 133.68, 132.02, 130.61, 129.07, 128.68, 127. 76, 127.63, 126.99, 126.65, 125.15, 123.58, 122.12, 113.34, 109.01, 108.65, 100.43, 76.71, 35.30, 30.84, 24.08, 21.20.

[0188] Example 19: Synthesis of metal-ligand complex 9 (MLC-9) In a glove box, a solution of 3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1-(3,5-dimethoxyphenyl)-1H-pyrazole (11.2 mg, 0.020 mmol, 100 mol%) dissolved in C6D6 (600 μL) was added dropwise to ZrBn4 (9.1 mg, 0.020 mmol, 100 mol%), which is solid at room temperature. The vial was swirled after each drop to ensure thorough mixing. After addition, the solution was transferred to an NMR tube, and the sample was reacted overnight at room temperature. Two equivalents of toluene were clearly detected by NMR.

[0189] 1 H NMR(500MHz, C6D6)δ 8.40(s, 1H), 8.31(s, 2H), 7.95(d, J=8.6Hz, 2H), 7.45(dd, J=9.0, 2.1Hz, 2H), 7.20-7.17(m, 1H), 6.84-6.81(m, 1H), 6.71-6.60(m, 5H), 6.50-6.44(m, 2H), 6 .40-6.35(m, 4H), 6.06-6.02(m, 1H), 5.79(dd, J=15.1, 2.6Hz, 2H), 3.27(s, 3H) ), 3.02(s, 3H), 2.03(d, J=10.1Hz, 2H), 1.87(d, J=10.2Hz, 2H), 1.25(s, 18H).

[0190] 13C NMR (126MHz, C6D6)δ 167.20, 162.47, 161.78, 151.64, 148.25, 145.85, 141.05, 137.92, 135.99, 133.71, 132.43, 130.62, 129.01, 128.59, 128 .40, 128.35, 126.97, 125.09, 123.29, 122.27, 113.60, 109.33, 100.53, 93.06, 89.13, 76.45, 54.85, 53.51, 35.29, 30.91.

[0191] Example 20: Synthesis of metal-ligand complex 10 (MLC-10) In a glove box, a solution of 4-(3-(5-(2,7-di-tert-butylanthracene-9-yl)-1H-pyrrole-2-yl)-1H-pyrazole-1-yl)-N,N-dimethylaniline (10.8 mg, 0.020 mmol, 100 mol%) dissolved in C6D6 (600 μL) was added dropwise to ZrBn4 (9.1 mg, 0.020 mmol, 100 mol%), which is solid at room temperature. The vial was swirled after each drop to ensure thorough mixing. After addition, the solution was transferred to an NMR tube, and the sample was reacted overnight at room temperature. Two equivalents of toluene were clearly detected by NMR.

[0192] 1 H NMR(500MHz, C6D6)δ 8.37(s, 1H), 8.26-8.23(m, 2H), 7.92(d, J=8.9Hz, 2H), 7.46(dd, J=8.9, 1.9Hz, 2H ), 7.16(s, 1H), 6.76-6.71(m, 5H), 6.70(d, J=2.5Hz, 1H), 6.62(d, J=2.7Hz, 1H), 6 .60-6.54(m, 3H), 6.31(dd, J=8.7, 2.7Hz, 1H), 6.05(d, J=2.5Hz, 1H), 5.96-5.92( m, 4H), 2.53(s, 6H), 2.10(d, J=10.0Hz, 2H), 1.25(s, 18H), 1.19(d, J=10.0Hz, 2H).

[0193] 13C NMR (126MHz, C6D6)δ 181.54, 151.11, 148.39, 147.79, 139.89, 138.59, 136.86, 136.47, 133.71, 132.45, 130.55, 130.15, 129.30, 128.37, 1 26.99, 126.71, 125.16, 123.49, 122.44, 119.96, 113.65, 111.86, 111.21, 108.99, 99.81, 74.55, 40.89, 35.26, 30.96.

[0194] Example 21: Batch reactor screening of metal-ligand complexes 1-3 and 4-10

[0195] [Table 1]

[0196] Half-batch reactor conditions at 120°C: 46g ethylene, 300g 1-octene, 610g IsoparE, 1.2 equivalents of RIBS-II activator relative to the catalyst, 10μmol MMAO-3A, ​​reactor pressure of 310psi. Half-batch reactor conditions at 150°C: 43g ethylene, 300g 1-octene, 546g IsoparE, 1.2 equivalents of RIBS-II activator relative to the catalyst, 10μmol MMAO-3A, ​​reactor pressure of 360psi. Half-batch reactor conditions at 190°C: 43g ethylene, 300g 1-octene, 520g IsoparE, 1.2 equivalents of RIBS-II activator relative to the catalyst, 10μmol MMAO-3A, ​​reactor pressure of 420psi.

[0197] [ka]

[0198] The polymer produced by Comparative Example C1 has a high level of comonomer incorporation. Therefore, the expected melting temperature is very low, as indicated by the negative numbers in Table 1. The efficiency of Comparative Example C1 is not significantly higher at higher temperatures, such as 150°C, compared to Examples MLC-1 to MLC-3 of the present invention. The examples are more efficient at 150°C. Examples MLC-1 to MLC-3 of the present invention also have a much higher reactivity ratio than Comparative Example C1.

[0199] [Table 2]

[0200] At 120°C, the half-batch reactor conditions include: 46 g ethylene, 300 g 1-octene, 610 g IsoparE, 1.2 equivalents of RIBS-II activator relative to the catalyst, 10 μmol MMAO-3A, ​​and a reactor pressure of 310 psi. At 150°C, the half-batch reactor conditions are: 43 g ethylene, 300 g 1-octene, 546 g IsoparE, 1.2 equivalents of RIBS-II activator relative to the catalyst, 10 μmol MMAO-3A, ​​and a reactor pressure of 360 psi. At 190°C, the half-batch reactor conditions include: 43 g ethylene, 300 g 1-octene, 520 g IsoparE, 1.2 equivalents of RIBS-II activator relative to the catalyst, 10 μmol MMAO-3A, ​​and a reactor pressure of 420 psi.

Claims

1. A metal-ligand complex according to formula (I), 【Chemistry 1】 During the ceremony, M is a metal selected from titanium, zirconium, or hafnium, wherein the metal has a formal oxidation state of +2, +3, or +4. Each X is a monodentate ligand or bidentate ligand independently selected from (C １ ~C ５０ ), hydrocarbyl, halogen, -(CH ２ ), ｗ Si(R Ｘ ), ３ -N(R Ｎ ), ２ and -NOCOR Ｃ . In the formula, w is from 1 to 10, and R Ｘ is (C １ ~C ２０ ) alkyl. If X is a single seat, n is 2, and if X is a double seat, n is 1 or 2. z １ Independently, N or C(R) １ ) is selected from, R １ and R １１ It forms an aromatic or non-aromatic ring without covalent bonding. z ２ Independently, N or C(R) ２ ) is selected from, R １ and R ２ These may form aromatic or non-aromatic rings through covalent bonding. z ３ These are independently O, S, N, R Ｎ , or C(R ３ ) is selected from, R ３ and R ４ These may form aromatic or non-aromatic rings through covalent bonding. z ４ These are independently O, S, N, NR Ｎ , or C(R ４ ) is selected from, R ４ and R ３ These may form aromatic or non-aromatic rings through covalent bonding. z ５ It is selected independently of N or C, R １ , R ２ , R ３ , R ４ , R １１ , R １２ , R １３ , R １４ , and R １５ (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, where R １２ and R １３ They are optionally joined to form a ring, R １３ and R １４ They are optionally joined to form a ring, and R １４ and R １５ They are optionally joined to form a ring, In the formula, each R Ｎ , R Ｃ , and R Ｐ (C １ ~C ２０ ) Hydrocarbyl, (C １ ~C ２０ A metal-ligand complex selected from the group consisting of heterohydrocarbyl and -H.

2. z ３ is CR ３ and z ４ is CR ４ and R ３ and R ４ are combined to form an aromatic ring, and the metal-ligand structure has a structure according to formula (II). 【Chemistry 2】 where z １ and z ２ and R １１ and R １２ and R １３ and R １４ and R １５ and X, n, and M are defined as in formula (I), R ｚ１ , R ｚ２ , R ｚ３ , R ｚ４ is hydrogen, (C １ ~C ２０ ) alkyl, (C ６ ~C ５０ ) Aryl, (C １ ~C １０ ) Heterohydrocarbyl, -NR Ｎ , -OR Ｃ , -SR Ｃ , halogen, CF ３ - NO ２ Selected from the group consisting of , or -CN, in the formula, R Ｃ is (C １ ~C ２０ ) alkyl, (C ６ ~C ２０ ) is an aryl, and z ５ The metal-ligand complex according to claim 1, wherein is N.

3. X is benzyl, methyl, -CH ２ Si[(C １ ~C ２０ ) Alkyl] ３ , -N[(C １ ~C ２０ ) Alkyl] ３ The metal-ligand complex according to any one of claims 1 to 2, wherein the ligand is , or chloro.

4. R １１ The metal-ligand complex according to any one of claims 1 to 3, wherein is 2,4,6-triisopropylphenyl, mesityl, substituted and unsubstituted anthracenyl, 3,5-di-tert-butylphenyl, and naphthyl.

5. R １１ is the radical of equation (III), 【Transformation 3】 In the formula, R ２１ , R ２２ , R ２３ , R ２４ , and R ２５ is, (C １ ~C １０ ) alkyl, (C ６ ~C １０ A metal-ligand complex according to any one of claims 1 to 3, selected from aryl or -H.

6. R ２１ , R ２２ , R ２３ , R ２４ , and R ２５ The metal-ligand complex according to claim 5, wherein is independently selected from tert-butyl, 3,5-di-tert-butylphenyl, or -H.

7. z １ and z ２ A metal-ligand complex according to any one of claims 1 to 6, wherein only one of them is N.

8. z ２ N is z １ CR １ If R １ and R １１ The metal-ligand complex according to any one of claims 1 to 7, wherein the complex forms an aromatic ring or a non-aromatic ring without covalent bonding.

9. R １２ , R １３ , R １４ , and R １５ is hydrogen, chloro, fluoro, benzyl, (C １ ~C １０ ) alkyl, cyclic (C １ ~C １０ ) Heteroalkyl, -OR Ｃ , -NR Ｎ ２ Selected from the group consisting of, in the formula, R Ｃ and R Ｎ is (C １ ~C １２ The metal-ligand complex according to any one of claims 1 to 8, wherein the ligand is alkyl.

10. R １２ and R １３ The metal-ligand complex according to any one of claims 1 to 9, wherein the two elements bond to form a heterocycle.

11. R １３ and R １５ is chloro or fluoro, or (C １ ~C １０ The metal-ligand complex according to any one of claims 1 to 9, wherein the ligand is alkyl.

12. R １３ and R １４ ha-OR Ｃ And R Ｃ is (C １ ~C ８ The metal-ligand complex according to any one of claims 1 to 9, wherein the ligand is alkyl.

13. R １４ is, (C １ ~C １０ ) alkyl, cyclic (C １ ~C １０ ) Heteroalkyl, -OR Ｃ , -NR Ｎ ２ Selected from the group consisting of, in the formula, R Ｃ and R Ｎ is (C １ ~C ８ The metal-ligand complex according to any one of claims 1 to 9, wherein the ligand is alkyl.

14. R １３ and R １４ The two compounds covalently bond to form an aromatic ring, and the metal-ligand complex is given by formula (IV): 【Chemistry 4】 A metal-ligand complex according to any one of claims 1 to 13, having the structure described herein.

15. A polymerization process comprising contacting ethylene with one or more optionally selected α-olefin monomers in the presence of a catalytic system, wherein the catalytic system comprises one or more procatalysts and a cocatalyst, and the procatalyst is a metal-ligand complex according to any one of claims 1 to 14, and producing an ethylene-based polymer.

Images