Bidentate biaryl phenoxy Group 4 transition metal catalysts for olefin polymerization using a chain transfer agent

Abstract

Processes for polymerizing olefins include ethylene, (C3-C 40 ) contacting an alpha-olefin comonomer, and a solvent in the presence of a chain transfer agent and a catalyst system, the catalyst system comprising a metal-ligand complex according to formula (I). [Formula 1] JPEG2022549073000018.jpg103170

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims priority to U.S. Provisional Patent Application No. 62 / 907,954, filed on September 30, 2019, the entire disclosure of which is incorporated herein by reference.

[0002] Embodiments of the present disclosure generally relate to olefin polymerization catalyst systems and processes, and more specifically, to olefin polymerization catalyst systems containing thiazole, imidazole, or biphenoxy Group IV transition metal catalysts, and to olefin polymerization processes incorporating such catalyst systems.

Background Art

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

[0004] Ethylene-based polymers and propylene-based polymers are manufactured for a wide variety of articles. The polyethylene and polypropylene polymerization processes can be varied in several respects to produce a wide variety of resulting polyethylene resins having different physical properties that are suitable for use in different applications. Ethylene monomer and optionally one or more comonomers are present in a liquid diluent (such as a solvent), an alkane or isoalkane, for example isobutene. Hydrogen may also be added to the reactor. Catalyst systems for producing ethylene-based polymers can typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (metallocene or non-metallocene (molecular)) catalyst systems. The reactants in the diluent and catalyst system are circulated in the reactor at a high polymerization temperature, thereby producing an ethylene-based homopolymer or copolymer. Periodically or continuously, a portion of the reaction mixture containing the polyethylene product dissolved in the diluent is removed from the reactor together with unreacted ethylene and one or more optional comonomers. The reaction mixture may be processed to remove the polyethylene product from the diluent and unreacted reactants when removed from the reactor, and the diluent and unreacted reactants typically are recycled into the reactor. Alternatively, the reaction mixture may be sent to a second reactor connected in series with the first reactor, where a second polyethylene fraction may be produced. Despite research efforts to develop catalyst systems suitable for olefin polymerization such as polyethylene or polypropylene polymerization, there remains a need to improve the efficiency of catalyst systems capable of producing polymers having high molecular weight and narrow molecular weight distribution. SUMMARY OF THE INVENTION

[0005] Despite currently available olefin polymerization catalyst systems, there is a need for high-temperature polymerization catalysts with improved molecular properties that promote the production of high molecular weight (Mw) polymers with narrow polydispersity (PDI) and / or high comonomer incorporation (e.g., greater than 20% comonomer). There is a further need for high-temperature polymerization catalysts that have the ability to produce olefin block copolymers by participating in chain transfer. Olefin block copolymers (OBCs) exhibit excellent performance differentiating attributes not achievable in polymer blends.

[0006] Embodiments of the present disclosure include a process for polymerizing olefins. The process includes contacting ethylene, a (C3-C 40 ) alpha-olefin comonomer, and a solvent in the presence of a chain transfer agent and a catalyst system, the catalyst system including a metal-ligand complex according to formula (I). [Chemical Formula]

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

[0008] In formula (I), each R 1is independently selected from (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 )2NC(O)-, halogen, and -H. Each R 2 is independently selected from (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C6-C 50 ) aryl, (C4-C 50 ) heteroaryl, -Si(R C )3, and -Ge(R C )3.

[0009] In formula (I), each A is independently selected from -z3-z4-z5- or -C(R 3 )C(R 4 )C(R 5 )C(R 6 )-. For each of z3, z4, and z5 of each A, provided that exactly one of z3, z4, or z5 is -C(R A )- or exactly two of z3, z4, or z5 are -C(R A )-, it is selected from the group consisting of sulfur, oxygen, -N(R A )-, and -C(R A )-. Each R A of -C(R A )- is independently (C1-C50 )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)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, or -H, and any two R groups bonded to adjacent atoms are optionally linked. Each R of each A A , R 3 , R 4 , R 5 , and R 6 is independently selected from (C1-C 50 )hydrocarbyl, (C1-C 50 )heterohydrocarbyl, halogen, or -H.

[0010] In formula (I), each B is independently selected from -z6-z7- or -C(R 7 )C(R 8 )C(R 9 )-. Each of z6 and z7 of B is independently selected from the group consisting of sulfur, oxygen, -N(R B )-, and -C(R B )-, provided that at most one of z6 or z7 is -C(R B )-. Each R of -C(R B )- is independently (C1-C B )hydrocarbyl, (C1-C 50 )heterohydrocarbyl, (C6-C 50 )aryl, (C4-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)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, or -H, and any two R B groups bonded to adjacent atoms are optionally linked. Each R 7 , R 8 , and R 9 is independently (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)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, or -H. In formula (I), each R C , R N , and R P is independently (C1-C 50 )hydrocarbyl.

Best Mode for Carrying Out the Invention

[0011] Here, specific embodiments of the catalyst system will be described. It should be understood that the catalyst system of the present disclosure may be implemented in different forms and should not be construed as limited to the specific embodiments described in the present disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0012] Common abbreviations are listed below. R C 、R Z 、R 1 、R 2 、R 3 、R 4 、Z1, Z2, Z3, X, Y, Q, and W: 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), THF: tetrahydrofuran, Et2O: diethyl ether, CH2Cl2: dichloromethane, EtOAc: ethyl acetate, C6D6: deuterated benzene or benzene-d6, CDCl3: deuterated chloroform, Na2SO4: sodium sulfate, MgSO4: magnesium sulfate, HCl: hydrogen chloride, n-BuLi: butyllithium, t-BuLi: tert-butyllithium, K2CO3: potassium carbonate, N2: nitrogen gas, PhMe: toluene, PPR: parallel pressure reactor, MAO: methylaluminoxane, MMAO: modified methylaluminoxane, GC: gas chromatography, LC: liquid chromatography, NMR: nuclear magnetic resonance, MS: mass spectrometry, mmol: millimole, mL: milliliter, M: molar, min or mins: minute, h or hrs: hour, d: day, R f : retention fraction, TLC: thin layer chromatography, rpm: revolutions per minute.

[0013] The term "independently selected" and the multiple options that follow it refer to R 1 、R 2 、R 3 、R 4 、and R Cetc. are used herein to indicate that the individual groups appearing before the term may be the same or different and there is no dependency as to the identity of any other group appearing before the term.

[0014] The term "procatalyst" refers to a compound that has catalytic activity after activation, for example, upon removal of a Lewis base coordinated to a Ni or Pd metal center.

[0015] When used to describe certain carbon atom-containing chemical groups, "(C x -C y A parenthetical expression having the form "(C1-C2)" means that the unsubstituted form of the chemical group has x carbon atoms to y carbon atoms, inclusive, x and y. For example, (C1-C2) 50 ) Alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, specific chemical groups are R S and R S Generally, represents any substituent defined in this application. x -C y ) for chemical groups defined using S The substitution can be carried out by any group R S Depending on the identity of R, R may contain more than y carbon atoms. For example, S Exactly one group R is phenyl (-C6H5) S (C1-C 50 "(C)alkyl" can contain from 7 to 56 carbon atoms. Thus, the parenthetical "(C)alkyl" is generally used. x -C y )" is a group defined as one or more carbon atom-containing substituents R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group are both x and y, respectively, all of the carbon atom-containing substituents R S The total number of carbon atoms derived from the aryl group is determined by adding the total number of carbon atoms derived from the aryl group.

[0016] The term "substituted" means that at least one heteroatom (-H) attached to the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S ). The prefix "per" has its usual meaning of "completely" or "entirely", e.g., the terms "per-substituted" or "per-substituted compound" mean that all hydrogen atoms (H) attached to the carbon or hetero atoms of the corresponding unsubstituted compound or functional group are replaced by a substituent (e.g., R S ), and similarly, in the case of "perfluorinated alkyl", it means that all hydrogens of the alkyl group are replaced by fluorine atoms. The term "poly-substituted" means that at least two, but less than all, of the hydrogen atoms attached to the carbon or hetero atoms of the corresponding unsubstituted compound or functional group are replaced by a substituent. The term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. "Hydrogen" and "--H" are interchangeable and have the same meaning unless otherwise specified.

[0017] The term "(C1-C 50 ) hydrocarbyl" means a hydrocarbon radical having from 1 to 50 carbon atoms, and the term "(C1-C 50 ) hydrocarbylene" means a hydrocarbon diradical having from 1 to 50 carbon atoms, each of said hydrocarbon radicals and each of said hydrocarbon diradicals being aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (having 3 or more carbons, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and being unsubstituted or substituted by one or more R S .

[0018] In the present disclosure, (C1-C 50 ) hydrocarbyl is unsubstituted or substituted (C1-C 50 ) alkyl, (C3-C 50 ) cycloalkyl, (C3-C 20 ) cycloalkyl-(C1-C 20 ) alkylene, (C6-C 40)Aryl, or (C6-C 20 )Aryl-(C 1- C 20 ) alkylene (such as benzyl (-CH2-C6H5)) may be.

[0019] “(C1-C 50 ) alkyl” and “(C1-C 18 ) alkyl” terms mean, respectively, a saturated straight-chain or branched hydrocarbon radical of 1 to 50 carbon atoms, and a saturated straight-chain or branched hydrocarbon radical of 1 to 18 carbon atoms, which is unsubstituted or substituted by one or more R S . Examples of unsubstituted (C1-C 50 ) alkyl are unsubstituted (C1-C 20 ) alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 2,2-dimethylpropyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. Examples of substituted (C1-C 40 ) alkyl include substituted (C1-C 20 ) alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 alkyl. The term “[C 45 alkyl” means that there are up to 45 carbon atoms in the radical including substituents, for example, each (C1-C5) alkyl is substituted by one R S which is (C 27 -C 40 ) alkyl. Each (C1-C5) alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, 2,2-dimethylpropyl, or 1,1-dimethylethyl.

[0020] “(C6-C 50The term "aryl" means an unsubstituted or (substituted by one or more R S ) monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical having 6 to 40 carbon atoms, at least 6 to 14 of which are aromatic ring carbon atoms. A monocyclic aromatic hydrocarbon radical contains one aromatic ring, a bicyclic aromatic hydrocarbon radical has two rings, and a tricyclic aromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other one or more rings of the aromatic radical can be independently fused or unfused and aromatic or non-aromatic. Examples of unsubstituted (C6-C 50 ) aryl include unsubstituted (C6-C 20 ) aryl, unsubstituted (C6-C 18 ) aryl, 2-(C1-C5)alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. Examples of substituted (C6-C 40 ) aryl include substituted (C1-C 20 ) aryl, substituted (C6-C 18 ) aryl, 2,4-bis([C 20 alkyl)-phenyl, 3,5-bis([C 20 alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-one-1-yl.

[0021] The term "(C3-C 50 ) cycloalkyl" means an unsubstituted or substituted by one or more R S saturated cyclic hydrocarbon radical having 3 to 50 carbon atoms. Other cycloalkyl groups (e.g., (C x -C y ) cycloalkyl) are defined in a similar manner as having x to y carbon atoms and being unsubstituted or substituted by one or more R S . Examples of unsubstituted (C3-C40 )Examples of cycloalkyl include unsubstituted (C3-C 20 ) cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3-C 40 ) cycloalkyl include substituted (C3-C 20 ) cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanone-2-yl, and 1-fluorocyclohexyl.

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

[0023] "(C1-C 50 The term "alkylene" may be unsubstituted or may contain one or more R S means a saturated straight or branched diradical of 1 to 50 carbon atoms (i.e., the radical is not on a ring atom) substituted by 50 Examples of alkylenes include unsubstituted (C1-C)alkylenes, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)CH3. 20 ) alkylene, where "C*" represents a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical. 50 Examples of alkylenes are substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted 1,20-eicosylene). As mentioned above, the two R S Together, (C1-C 18 ) alkylene, substituted (C1-C 50 Examples of alkylenes include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0024] "(C3-C 50 The term "cycloalkylene" may be unsubstituted or may contain one or more R S "R" means a cyclic diradical (i.e., the radicals are on ring atoms) of 3 to 50 carbon atoms substituted by

[0025] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include -O-, -S-, -S(O)-, -S(O)2-, -Si(R C)2-, -P(R P )-, -P(R P )2, -N(R N )-, -N(R N )2-, -N=C(R C )2, -N=C(NR2 N )(R C ) 、 -Ge(R C )2-、or -Si(R C )3 is present, where each R C and each R P is an unsubstituted (C1-C 18 ) hydrocarbyl or -H, and each R N is an unsubstituted (C1-C 18 ) 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. The term "(C1-C 50 ) heterohydrocarbyl" means a heterohydrocarbon radical having 1 to 50 carbon atoms, and the term "(C1-C 50 ) heterohydrocarbylene" means a heterohydrocarbon diradical having 1 to 50 carbon atoms. (C1-C 50 ) heterohydrocarbyl or (C1-C 50 ) heterohydrocarbylene heterohydrocarbons have one or more heteroatoms. The radicals of heterohydrocarbyl may be present on a carbon atom or on a heteroatom. The two radicals of heterohydrocarbylene may be present on a single carbon atom or on a single heteroatom. In addition, one of the two radicals of the diradical may be present on a carbon atom, and the other radical may be present on a different carbon atom, or one of the two radicals may be present on a carbon atom and the other may be present on a heteroatom, or one of the two radicals may be present on a heteroatom and the other radical may be present on a different heteroatom. (C1-C 50 ) heterohydrocarbyl and (C1-C 50 ) heterohydrocarbylene are each unsubstituted or (one or more R Smay be replaced by), and may be aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0026] (C1-C 50 ) The heterohydrocarbyl may be unsubstituted or may be substituted. (C1-C 50 ) Non-limiting examples of heterohydrocarbyl include (C1-C 50 ) heteroalkyl, (C1-C 50 ) hydrocarbyl-O-, (C1-C 50 ) hydrocarbyl-S-, (C1-C 50 ) hydrocarbyl-S(O)-, (C1-C 50 ) hydrocarbyl-S(O)2-, (C1-C 50 ) hydrocarbyl-Si(R C )2-, (C l -C 50 ) hydrocarbyl-N(R N )-, (C l -C 50 ) hydrocarbyl-P(R P )-, (C2-C 50 ) heterocycloalkyl, (C2-C 19 ) heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 ) cycloalkyl-(C1-C 19 ) heteroalkylene, (C2-C 19 ) heterocycloalkyl-(C1-C 20 ) heteroalkylene, (C1-C 50 ) heteroaryl, (C1-C 19 ) heteroaryl-(C1-C 20 ) alkylene, (C6-C 20 ) aryl-(C1-C 19 ) heteroalkylene, or (C1-C 19 ) heteroaryl-(C1-C 20 ) heteroalkylene. Additional examples include, but are not limited to, -Si(R C ) 3-Q (OR C ) Q, -OSi(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -NH(R C )2, -OR C , -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C , -S(O)2R C , -OS(O)2R C , -N=C(R C )2, -N=P(R C )3, -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C , and -C(O)N(R C )2 are included.

[0027] The term "(C4-C 50 ) heteroaryl" means an unsubstituted or (substituted by one or more R S ) monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical having a total of 4 to 50 carbon atoms and 1 to 10 heteroatoms. A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring, a bicyclic heteroaromatic hydrocarbon radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other one or more rings of the heteroaromatic radical may be independently fused or unfused and aromatic or non-aromatic. Other heteroaryl groups (e.g., (C4-C 12(C such as heteroaryl x -C y ), heteroaryl in general, has x to y carbon atoms (such as 4 to 12 carbon atoms), and is unsubstituted or substituted with one or more R S and is defined in a similar manner. Monocyclic heteroaromatic hydrocarbon radicals are 5-membered or 6-membered rings. The 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, 3, or 4, and each heteroatom can be O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. The 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3, and the heteroatom can be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, pyrazin-2-yl, 1,3,5-triazin-2-yl. Bicyclic heteroaromatic hydrocarbon radicals can be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl and isoquinolin-1-yl. Tricyclic heteroaromatic hydrocarbon radicals can be fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridin-9-yl.

[0028] “(C1-C 50 ) heteroalkyl” means a saturated straight-chain or branched-chain radical containing from 1 to 50 carbon atoms, or fewer carbon atoms, and one or more of the heteroatoms. “(C1-C 50 ) heteroalkylene” means a saturated straight-chain or branched-chain diradical containing from 1 to 50 carbon atoms and one or two or more heteroatoms. The heteroatoms of the 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 ., S(O), and S(O)2 may be included, and each of the heteroalkyl and heteroalkylene groups is unsubstituted or substituted by one or more R S s.

[0029] Examples of unsubstituted (C2-C 40 ) heterocycloalkyl include unsubstituted (C2-C 20 ) heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thia-cyclononyl, and 2-aza-cyclodecyl.

[0030] The term “halogen atom” or “halogen” means a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term “halide” means the anionic form of a halogen atom (fluoride (F -) chloride (Cl - ) bromide (Br - ) or iodide (I - ).

[0031] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and carbon-nitrogen, carbon-phosphorus, nitrogen-nitrogen, nitrogen-phosphorus, and carbon-silicon double bonds (in heteroatom-containing groups). If a saturated chemical group is substituted with one or more substituents R S , one or more double and / or triple bonds may or may not be present in the substituent R S . The term "unsaturated" means containing one or more carbon-carbon double bonds or carbon-carbon triple bonds, or one or more carbon-nitrogen, carbon-phosphorus, nitrogen-nitrogen, nitrogen-phosphorus, or carbon-silicon double bonds (in heteroatom-containing groups), and, if any, does not include any double bonds that may be present in the substituent R S or, if any, in a (hetero)aromatic ring.

[0032] In one or more embodiments, the process involves contacting ethylene, a (C3-C 40 ) alpha-olefin comonomer, and a solvent in the presence of a chain transfer agent and a catalyst system. In various embodiments, the catalyst system includes a metal-ligand complex according to formula (I).

Chemical formula

[0033] 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 independently an unsaturated (C2-C 50 ) hydrocarbon, an unsaturated (C2-C 50 ) heterohydrocarbon, a (C1-C 50 ) hydrocarbyl, a (C6-C 50 ) aryl, a (C6-C 50)heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 )diene, halogen, -N(R N )2, and -NCOR C is a monodentate or bidentate ligand selected from. Subscript n is 1, 2, or 3. Subscript m is 1 or 2, and the metal-ligand complex has 6 or fewer ligand bonds. - Each Y is independently selected from oxygen or sulfur.

[0034] In formula (I), each R 1 is (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 )2NC(O)-, halogen, and -H. Each R 2 is independently selected from (C1-C 50 )hydrocarbyl, (C1-C 50 )heterohydrocarbyl, (C6-C 50 )aryl, (C4-C 50 )heteroaryl, -Si(R C )3, and -Ge(R C )3.

[0035] In formula (I), each A is independently -z3-z4-z5- or -C(R 3 )C(R 4 )C(R5 )C(R 6 )- selected from. For each A, each of z3, z4, and z5, exactly one of z3, z4, or z5 is -C(R A )- or exactly two of z3, z4, or z5 are -C(R A )- is a condition, and is selected from the group consisting of sulfur, oxygen, -N(R A )-, and -C(R A )-. Each R of -C(R A )- A is independently (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)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, or -H, and any two R A groups bonded to adjacent atoms are optionally linked. Each R of each A 3 , R 4 , R 5 , and R 6 is independently (C1-C 50 )hydrocarbyl, (C1-C 50 )heterohydrocarbyl, halogen, or -H.

[0036] In formula (I), each B is independently -z6-z7- or -C(R 7 )C(R 8 )C(R 9)-selected from. Each of z6 and z7 of B is such that no more than one of z6 or z7 is -C(R B )-and is selected from the group consisting of sulfur, oxygen, -N(R B )-, and -C(R B )-. Each R B of -C(R B )-is independently (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)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, or -H, and any two R B groups bonded to adjacent atoms are optionally linked. Each R 7 , R 8 , and R 9 of B is (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)-, R C S(O)2-, (R C )2C=N-, R CC(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, or -H. Each R in formula (I) C , R N , and R P is, independently, (C1-C 50 )hydrocarbyl.

[0037] In some embodiments, M is zirconium or hafnium, and each X is, independently, (C6-C 20 )aryl, (C4-C 20 )heteroaryl, (C4-C 12 )diene, or halogen.

[0038] In various embodiments, each Y is oxygen. In other embodiments, Y is sulfur.

[0039] In one or more embodiments, each B is -z6-z7-, where one of z6 and z7 is sulfur and the other is -C(H)-. Thus, in such embodiments, B is -S-C(H)- or -C(H)-S-. In other embodiments, each A is -C(R 3 )C(R 4 )C(R 5 )C(R 6 )-, where R 3 , R 4 , R 5 , and R 6 is -H, and thus, in such embodiments, each A is -C(H)C(H)C(H)C(H)-.

[0040] In embodiments, each R 1 is, independently, selected from (C1-C 50 )aryl or (C4-C 50 )heteroaryl. In some embodiments, each R 1 is carbazolyl or substituted carbazolyl. Substituted carbazolyl is di-(C1-C 12) It can be an alkylcarbazolyl. In various embodiments, R 1 is 2,7-di(tert-butyl)carbazolyl or 3,6-di(tert-butyl)carbazolyl. In one or more embodiments, each R 1 is phenyl or substituted phenyl. In various embodiments, each R 1 is a substituted phenyl selected from 2,4,6-trimethylphenyl, 2,4,6-tri(isopropyl)phenyl, 3,5-di-tert-butylphenyl, or 3,5-diphenylphenyl.

[0041] In one or more embodiments, each R 2 is independently (C1-C 10 ) alkyl. In various embodiments, each R 2 is methyl, ethyl, propyl, 2-propyl, n-butyl, tert-butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl.

[0042] In some embodiments, each B is -C(R 7 )C(R 8 )C(R 9 )-, where R 7 , R 8 , and R 9 are -H. In other embodiments, each B is -C(R 7 )C(R 8 )C(R 9 )-, where R 7 and R 9 are -H and R 8 is (C1-C 20 ) alkyl.

[0043] In various embodiments, R 1 is selected from the group consisting of a radical having formula (II), a radical having formula (III), and a radical having formula (IV). [Chemical formula]

[0044] In formulas (II), (III), and (IV), R 31 ~R 35 、R 41 ~R 48 、and R 51 ~R 59 are independently (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R T )3, -Ge(R T )3, -P(R T )2, -N(R T )2, -N=CHR T 、-OR T 、-SR T 、-NO2、-CN、-CF3、R T S(O)-、R T S(O)2-、(R T )2C=N-、R T C(O)O-、R T OC(O)-、R T C(O)N(R T )-、(R T )2NC(O)-、halogen, or -H, and each R T is (C1-C 30 ) hydrocarbyl or -H.

[0045] In various embodiments of formula (I), R 1 is a radical having formula (IV), and R 52 and R 58 in formula (IV) are independently (C1-C 12 ) alkyl or (C1-C 20 ) aryl. In one or more embodiments, R 1 is a radical having formula (IV), and R 53 and R 58 in formula (IV) are independently (C1-C 12 ) alkyl or (C1-C 20 ) aryl. In some embodiments, R 1 is a radical having formula (IV), and R 53 and R 57 in formula (IV) are independently (C1-C 12) is alkyl or (C1-C 20 ) is aryl. In some embodiments, R 1 is a radical having the formula (IV), and R in the formula (IV) 53 , R 55 and R 57 are independently (C1-C 12 ) alkyl or (C1-C 20 ) aryl.

[0046] R 31 ~R 35 , R 41 ~R 48 and R 51 ~R 59 is (C1-C 12 ) alkyl in any embodiment, (C1-C 12 ) alkyl can be methyl, ethyl, propyl, 2-propyl, n-butyl, tert-butyl, 2-methylpropyl, pentyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, n-octyl, tert-octyl, nonyl, decyl, undecyl, or dodecyl.

[0047] In one or more embodiments, the subscript m of the formula (I) is 2, and the metal-ligand complex has a structure according to the formula (II). [Chemical formula]

[0048] In the formula (II), R 1 , R 2 , M, A, B, Y, and X are as defined in the formula (I), and n is 1 or 2. All compounds according to the formula (II) are also compounds according to the formula (I). Therefore, unless otherwise specified, it should be understood that the general reference to the metal-ligand complex having the formula (I) in this specification includes all metal-ligand complexes having the formula (II), but is not necessarily limited thereto.

[0049] In some embodiments, in formula (II), M is zirconium or hafnium, and each X is independently (C6-C 50 ) aryl, (C6-C 50 ) heteroaryl, (C4-C 12 ) diene, or halogen. Each Y is oxygen, and each R 1 and R 2 are independently (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C6-C 50 ) aryl, (C4-C 50 ) heteroaryl, halogen, and hydrogen.

[0050] In one or more embodiments, each B is -z6-z7-, where one of z6 and z7 is sulfur and the other is -C(H)-. In some embodiments, each R 1 is carbazolyl and each R 2 is methyl.

[0051] In one or more embodiments, each R 1 is independently 3,6-di-tert-butylcarbazol-9-yl or 2,7-di-tert-butylcarbazol-9-yl. In some embodiments, each R 1 is 3,5-di-tert-butylphenyl. In various embodiments, each R 1 is 2,4,6-trimethylphenyl.

[0052] In some embodiments, each B of formula (II) is -C(R 7 )C(R 8 )C(R 9 )-, where R 7 , R 8 , and R 9 are -H. In other embodiments, each B of formula (II) is such that each B is -C(R 7 )C(R 8 )C(R 9 )-, where R 7 and R 9 are -H and R8 is (C1-C 20 ) alkyl.

[0053] In one or more embodiments, the metal-ligand complex of formula (I) has a structure according to formula (Ia), (Ib), or (Ic).

Chemical formula

[0054] In formula (Ia), formula (Ib), and formula (Ic), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , z3, z4, z5, z6, z7, n, M, Y, and X are as defined in formula (I). All compounds according to formula (Ia), (Ib), and (Ic) are also compounds according to formula (I). Thus, unless otherwise specified, it should be understood that a general reference to a metal-ligand complex having formula (I) herein encompasses all metal-ligand complexes having formula (Ia), (Ib), and (Ic).

[0055] In some embodiments, in formula (Ia) or formula (Ib), R 5 is (C1-C 12 ) alkyl, (C6-C 20 ) aryl, or halogen. In some embodiments, R 5 is fluorine.

[0056] In one or more embodiments, in formula (Ia) or (Ic), R 8 is (C1-C 20 ) alkyl. In some embodiments, R 8is methyl, ethyl, 1-propyl, 2-propyl, n-butyl, tert-butyl, 2-methylpropyl (isobutyl), n-butyl, n-hexyl, cyclohexyl, n-octyl, or tert-octyl, nonyl, decyl, undecyl, or dodecyl.

[0057] In the metal-ligand complex according to formula (I) or formula (II), each X is bonded to M via a covalent bond, a coordination bond, or an ionic bond. In some embodiments, each X has the same identity. The metal-ligand complex has six or fewer metal-ligand bonds and may be electrically neutral as a whole or have a positive charge associated with the metal center. In some embodiments, the catalyst system comprises a metal-ligand complex according to formula (I), wherein M is zirconium or hafnium, and each X is independently selected from (C1-C 20 )alkyl, (C1-C 20 )heteroalkyl, (C6-C 20 )aryl, (C4-C 20 )heteroaryl, (C4-C 12 )diene, or halogen. In one or more embodiments, each X is independently benzyl, phenyl, or chloro.

[0058] In some embodiments, the monodentate ligand can be a monoanionic ligand. The monoanionic ligand has a net formal oxidation state of -1. Each monoanionic ligand is independently hydride, (C1-C 40 )hydrocarbyl carbanion, (C1-C 40 )heterohydrocarbyl carbanion, halide, nitrate, HC(O)O - , HC(O)N(H) - , (C1-C 40 )hydrocarbyl C(O)O - , (C1-C 40 )hydrocarbyl C(O)N((C1-C 20 )hydrocarbyl) - , (C1-C 40 )hydrocarbyl C(O)N(H) - , R K R LB - 、 R K R L N - 、 R K O - 、 R K S - 、 R K R L P - 、 or R M R K R L Si - may also be, each R K 、 R L 、 and R M is independently hydrogen, (C1-C 40 ) hydrocarbyl, or (C1-C 40 ) heterohydrocarbyl, or R K and R L together form (C2-C 40 ) hydrocarbylene or (C1-C 20 ) heterohydrocarbylene, and R M is as defined above.

[0059] In other embodiments, at least one monodentate ligand X can be, independently of any other ligand X, a neutral ligand. In certain embodiments, the neutral ligand is a neutral Lewis base such as R Q NR K R L 、 R K OR L 、 R K SR L 、 or R Q PR K R L etc., wherein each R Q is independently hydrogen, [(C1-C 10 ) hydrocarbyl]3Si(C1-C 10 ) hydrocarbyl, (C1-C 40 ) hydrocarbyl, [(C1-C 10 ) hydrocarbyl]3Si, or (C1-C 40 ) heterohydrocarbyl, and each R K and R L are independently as previously defined.

[0060] Additionally, each X, independently of any other ligand X, is halogen, unsubstituted (C1-C 20 )hydrocarbyl, unsubstituted (C1-C 20 )hydrocarbylC(O)O-, or R K R L N- which may be a monodentate ligand, and each of R K and R L is, independently, unsubstituted (C1-C 20 )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 )hydrocarbylC(O)O-, or R K R L N-, and each of R K and R L is, independently, unsubstituted (C1-C 10 )hydrocarbyl. In one or more embodiments of formulas (I) and (II), X is benzyl, chloro, -CH2SiMe3, or phenyl.

[0061] In a further embodiment, each X is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, chloro, bromo, or iodo. In some embodiments, each X is the same. In other embodiments, at least two Xs are different from each other. In embodiments where at least two Xs are different from at least one X, X is one of the different ones of methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, and chloro. In a further embodiment, the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

[0062] In some embodiments, the chemical groups of the metal-ligand complex of formula (I) (e.g., X and R 1 ~R4 ) Any or all of them may be unsubstituted. In other embodiments, the chemical groups X and R of the metal-ligand complex of formula (I) 1 ~R 4 None of them, or any or all of them, may be substituted with one or more R S s, or any or all of them may be substituted with one or more R S s. When two or more R S s are attached to the same chemical group of the metal-ligand complex of formula (I), the individual R S s may be attached to the same carbon atom or heteroatom, or to different carbon atoms or heteroatoms. In some embodiments, none of the chemical groups X and R 1 ~R 4 s are oversubstituted with R S s, or any or all of them may be oversubstituted with R S s. For a chemical group oversubstituted with R S s, the individual R S s may all be the same or may be independently selected.

[0063] In an exemplary embodiment, the catalyst system may include a metal-ligand complex according to any of formulas (I) or (II) having the structure of any of precatalysts 1-11.

Chemical formula

Chemical formula

[0064] In an exemplary embodiment, precatalysts 1-11 may be generated from ligands 1-7.

Chemical formula

[0065] Chain shuttling and / or chain transfer agent In one or more embodiments, the polymerization process of the present disclosure comprises contacting ethylene and / or one or more (C3-C 12 ) α-olefins in a reactor in the presence of a catalyst system and a chain transfer agent or chain shuttling agent. In such embodiments, the polymerization process comprises three components: (A) a pre-catalyst comprising a metal-ligand complex having the structure of formula (I), and optionally a co-catalyst, (B) an olefin polymerization catalyst having a comonomer selectivity different from that of the pre-catalyst (A), and (C) a chain transfer agent or chain shuttling agent.

[0066] As an addition to the catalyst system, a chain transfer agent and a chain shuttling agent are compounds that can transfer polymer chains between two catalyst molecules in a single polymerization reactor. The catalyst molecules can have the same structure or different structures. When the catalyst molecules have different structures, they can have different monomer selectivities. Whether a compound functions as a chain transfer agent or a chain shuttling agent depends on the type of polymerization reactor, even though the three components (A) to (C) described above can be chemically identical in any type of polymerization reactor. For example, in a batch reactor equipped with a single catalyst system or a dual catalyst system, the compound functions as a chain transfer agent. In a continuous reactor equipped with a dual catalyst system, the compound functions as a chain shuttling agent. Generally, a compound that functions as a chain transfer agent in a batch reactor can also function as a chain shuttling agent in a continuous reactor, and conversely, a molecule that functions as a chain shuttling agent can also function as a chain transfer agent. Therefore, in the embodiments of the polymerization process in the present disclosure, it should be understood that the disclosure of a compound as a "chain transfer agent" further constitutes the disclosure of the same compound as a "chain shuttling agent". Therefore, the terms "chain transfer agent" and "chain shuttling agent" are interchangeable with respect to a compound, but are distinguishable when the process is specified to be carried out in a particular type of polymerization reactor.

[0067] The chain transfer ability of the catalyst is first evaluated by performing an attempt to vary the level of a chain transfer or shuttling agent (CSA) in order to observe the predicted molecular weight decrease and overall impact on PDI for the shuttling catalyst. The molecular weight of the polymer produced by a catalyst having the potential to be a good chain shuttle agent will be more sensitive to the addition of CSA than the polymer molecular weight produced by a poorer shuttle or slower chain transfer rate. The Mayo equation (Equation 1) represents how the chain transfer agent decreases the number average chain length from the natural number average chain length [Number] to the number average chain length [Number] Equation 2 defines the chain transfer constant or chain shuttling constant Ca as the ratio of the chain transfer constant and the propagation rate constant. By assuming that most of the chain propagation occurs by ethylene insertion rather than comonomer incorporation, Equation 3 represents the predicted Mn of the polymerization. Mn0 is the natural molecular weight of the catalyst in the absence of the chain shuttling agent, and Mn is the molecular weight observed in the presence of the chain shuttling agent (Mn = Mn0 without the chain shuttling agent). [Number]

[0068] Typically, the chain transfer agent contains a metal that is Al, B, or Ga in a +3 formal oxidation state or a metal that is Zn or Mg in a +2 formal oxidation state. Chain transfer agents suitable for the processes of the present disclosure are described in U.S. Patent Application Publication No. 2007 / 0167315, which is incorporated herein by reference in its entirety.

[0069] In one or more embodiments of the polymerization process, the chain transfer agent, if present, may be selected from di(isobutyl)zinc, di(n-hexyl)zinc, di(n-octyl)zinc, trimethylaluminum, triethylaluminum, trioctylaluminum, triethylgallium, isobutylaluminum bis(dimethyl(t-butyl)siloxane), isobutylaluminum bis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide), bis(n-octadecyl)isobutylaluminum, isobutylaluminum bis(di(n-pentyl)amide), n-octylaluminum bis(2,6-di-t-butylphenoxide), n-octylaluminum di(ethyl(l-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminum bis(2,3,6,7-dibenzo-l-azacycloheptaneamide), n-octylaluminum bis(2,3,6,7-dibenzo-l-azacycloheptaneamide), n-octylaluminum bis(dimethyl(t-butyl)siloxide), ethylzinc(2,6-diphenylphenoxide), ethylzinc(t-butoxide), dimethylmagnesium, dibutylmagnesium, and n-butyl-sec-butylmagnesium.

[0070] In some embodiments, the chain transfer agent is a dialkylzinc or a trialkylaluminum. In various embodiments, the chain transfer agent is diethylzinc, trimethylaluminum, triethylaluminum, or trioctylaluminum.

[0071] Cocatalyst component The catalyst system comprising the metal-ligand complex of formula (I) can be catalytically activated by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, the precatalyst with the metal-ligand complex of formula (I) can be catalytically activated by contacting the complex with an activating cocatalyst or by combining the complex with an activating cocatalyst. Further, the metal-ligand complex according to formula (I) includes both a neutral precatalyst form and a positively charged catalyst form that can be positively charged by the loss of a monoanionic ligand such as benzyl or phenyl. Suitable activating cocatalysts for use in the present invention include alkylaluminum, polymeric or oligomeric aluminoxanes (also known as aluminoxanes), neutral Lewis acids, and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidative conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the foregoing activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means monoalkylaluminum dihydride or monoalkylaluminum dihalide, dialkylaluminum hydride or dialkylaluminum halide, or trialkylaluminum. Examples of polymeric aluminoxane or oligomeric aluminoxane include methylaluminoxane, triisobutylaluminum-modified methylaluminoxane, and isobutylaluminoxane.

[0072] The Lewis acid activating cocatalyst includes a Group 13 metal compound containing a (C1-C 20 ) hydrocarbyl substituent as described herein. In some embodiments, the Group 13 metal compound is a tri((C1-C 20 ) hydrocarbyl)-substituted aluminum or a tri((C1-C 20 ) hydrocarbyl)-boron compound. In other embodiments, the Group 13 metal compound is a tri(hydrocarbyl)-substituted aluminum, a tri((C1-C 20 ) hydrocarbyl)-boron compound, a tri((C1-C 10 ) alkyl)aluminum, a tri((C6-C 18)They are aryl boron compounds and their halogenated (including perhalogenated) derivatives. In a further embodiment, the Group 13 metal compound is tris(fluorine-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tris((C1-C 20 )hydrocarbyl borate (e.g., trityl tetrafluoroborate) or tri((C1-C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)borane (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term "ammonium" means a nitrogen cation that is ((C1-C 20 )hydrocarbyl)4N + , ((C1-C 20 )hydrocarbyl)3N(H) + , ((C1-C 20 )hydrocarbyl)2N(H)2 + , (C1-C 20 )hydrocarbylN(H)3 + , or N(H)4 + , and each (C1-C 20 )hydrocarbyl may be the same or different if more than one is present.

[0073] Examples of combinations of neutral Lewis acid activating cocatalysts include tri((C1-C4)alkyl)aluminum and tri((C6-C 18)Mixtures comprising an (aryl)boron compound, particularly in combination with tris(pentafluorophenyl)borane, are included. Other embodiments are combinations of such neutral Lewis acid mixtures with a polymer or oligomeric alumoxane, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with a polymer or oligomeric alumoxane. The molar ratio of (metal-ligand complex):(tris(pentafluoro-phenyl)borane):(alumoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluoro-phenyl)borane):(alumoxane)] is from 1:1:1 to 1:10:30, and in other embodiments from 1:1:1.5 to 1:5:10.

[0074] An active catalyst composition can be formed by activating a catalyst system comprising a metal-ligand complex of formula (I) and combining it with one or more cocatalysts, such as a cation-forming cocatalyst, a strong Lewis acid, or a combination thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, and inert, compatible, non-coordinating, ion-forming compounds. Examples of suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, and combinations thereof.

[0075] In some embodiments, two or more of the foregoing activating cocatalysts can be used in combination with each other. Specific examples of combinations of cocatalysts are tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or a mixture of an ammonium borate and an oligomeric or polymeric alumoxane compound. The ratio of the total molar amount of one or more metal-ligand complexes of formula (I) to the total molar amount of one or more 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 10:1 or less, and in still some other embodiments, 1:1 or less. When using an alumoxane alone as the activating cocatalyst, the molar amount of the alumoxane used is preferably at least 100 times the molar amount of the metal-ligand complex of formula (I). When using tris(pentafluorophenyl)borane alone as the activating cocatalyst, in some other embodiments, the molar amount of tris(pentafluorophenyl)borane used relative to the total molar amount 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).

[0076] Polyolefin The catalyst system according to the embodiment is used for the polymerization of olefins, mainly ethylene and propylene. In some embodiments, only a single type of olefin or α-olefin is present in the polymerization scheme to produce a homopolymer. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin comonomer typically has 20 or fewer carbon atoms. For example, the α-olefin comonomer may have 3 to 10 carbon atoms, or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, one or more α-olefin comonomers can be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively from the group consisting of 1-hexene and 1-octene.

[0077] Ethylene-based polymers, such as homopolymers and / or interpolymers (including copolymers) of ethylene, and optionally one or more comonomers such as α-olefins, may contain at least 50 weight percent of monomer units derived from ethylene. All individual values and subranges encompassed by "at least 50 weight percent" are disclosed herein as separate embodiments. For example, ethylene-based polymers, homopolymers and / or interpolymers (including copolymers) of ethylene, and optionally one or more comonomers such as α-olefins, may contain at least 60 weight percent of monomer units derived from ethylene, at least 70 weight percent of monomer units derived from ethylene, at least 80 weight percent of monomer units derived from ethylene, 50 to 100 weight percent of monomer units derived from ethylene, or 80 to 100 weight percent of monomer units derived from ethylene.

[0078] In some embodiments, the ethylene-based polymer may comprise at least 90 mole percent of monomer units derived from ethylene. All individual values and subranges from at least 90 mole percent are included herein and are disclosed herein as separate embodiments. For example, the ethylene-based polymer may comprise at least 93 mole percent of units derived from ethylene, at least 96 mole percent of units, at least 97 mole percent of units derived from ethylene, or alternatively, 90 to 100 mole percent of units derived from ethylene, 90 to 99.5 mole percent of units derived from ethylene, or 97 to 99.5 mole percent of units derived from ethylene.

[0079] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50%, other embodiments comprise at least 1 mole percent (mol%) to 25 mol%, and in further embodiments, the amount of additional α-olefin is at least 5 mol% to 100 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0080] The ethylene-based polymer can further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color intensifiers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, ultraviolet stabilizers, and combinations thereof. The ethylene-based polymer can contain any amount of additives. The ethylene-based polymer can contain a total of about 0 to about 10 weight percent of such additives, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further comprise a filler, and examples of such fillers include, but are not limited to, organic or inorganic fillers. The ethylene-based polymer can contain about 0 to about 20 weight percent of a filler, such as calcium carbonate, talc, or Mg(OH)2, based on the total weight of the ethylene-based polymer and all additives or fillers. The ethylene-based polymer can be further blended with one or more polymers to form a blend.

[0081] Coincidence condition In one or more embodiments, polymerization processes include, but are not limited to, solution polymerization processes, particle formation polymerization processes, and combinations thereof using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed reactors, stirred tank reactors, parallel, series, and / or any combination of batch reactors.

[0082] In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, such as a dual loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized in the presence of the catalyst system described herein and optionally one or more cocatalysts. In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, such as a dual loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized in the presence of the catalyst systems of the present disclosure and the present specification and optionally one or more other catalysts. The catalyst systems described herein can be used in the first reactor or the second reactor, optionally in combination with one or more other catalysts. In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, such as a dual loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized in both reactors in the presence of the catalyst system described herein.

[0083] In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single reactor system, such as a single loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized as described in the previous paragraph in the presence of the catalyst system described within the present disclosure and optionally one or more cocatalysts.

[0084] Generally, the solution phase polymerization process is carried out in one or more well-stirred reactors, such as one or more loop reactors or one or more spherical isothermal reactors, at a temperature in the range of 30 to 300 °C, for example 120 to 215 °C, and at a pressure in the range of 300 to 1500 psi, for example 400 to 750 psi. The residence time in the solution phase polymerization process is typically in the range of 2 to 30 minutes, for example 10 to 20 minutes. Ethylene, one or more solvents, one or more Group III metal / lanthanide-based catalyst systems, and optionally one or more comonomers are continuously fed to one or more reactors in the absence of any activator. Exemplary solvents include, but are not limited to, isoparaffin. For example, such a solvent is commercially available under the name ISOPAR E from ExxonMobil Chemical Co., Houston, Texas. The resulting mixture of the ethylene-based polymer and the solvent is then removed from the reactor and the ethylene-based polymer is isolated. The solvent is typically recovered via a solvent recovery unit, i.e., a heat exchanger and a vapor-liquid separation drum, and then recycled to the polymerization system.

[0085] In some embodiments, the polymerization process for producing an ethylene-based polymer comprises polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, the catalyst system incorporating at least one metal-ligand complex of formula (I), (II), or (III). Polymers obtained from such catalyst systems incorporating metal-ligand complexes of formula (I), (II), or (III) have a density, according to ASTM D792 (which is hereby incorporated by reference in its entirety), of, for example, 0.850 g / cm 3 ~0.950 g / cm 3 , 0.880 g / cm 3 ~0.920 g / cm 3 , 0.880 g / cm 3 ~0.910 g / cm 3 or 0.880 g / cm 3 ~0.900 g / cm 3 and may have.

[0086] In another embodiment, the polymer obtained from a polymerization process comprising a metal-ligand complex of either formula (I) or (II) has a melt flow ratio (I 10 / I2) of 5 to 15, where the melt index I2 is measured according to ASTM D1238 at 190 °C and under a load of 2.16 kg (incorporated herein by reference in its entirety), and the melt index I 10 is measured according to ASTM D1238 at 190 °C and under a load of 10 kg. In other embodiments, the melt flow ratio (I 10 / I2) is from 5 to 10, and in other embodiments, the melt flow ratio is from 5 to 9.

[0087] In some embodiments, the polymer obtained from a polymerization process comprising a metal-ligand complex of either formula (I) or (II) has a molecular weight distribution (MWD) of 1 to 25, where the MWD is defined as M w / M n , M w being the weight average molecular weight and M n being the number average molecular weight. In other embodiments, the polymer obtained from the catalyst system has an MWD of 1 to 6. Another embodiment includes an MWD of 1 to 3. Another embodiment includes an MWD of 1.5 to 2.5.

[0088] The embodiments of the catalyst systems described in this disclosure result in unique polymer properties as a result of the high molecular weight of the polymers formed and the amount of comonomer incorporated into the polymers.

[0089] All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passage through activated alumina and, in some cases, Q-5 reactant. Solvents used in experiments conducted in a nitrogen-filled glove box were further dried by storage over activated 4 Å molecular sieves. Glassware for moisture-sensitive reactions was dried in an oven overnight before use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. 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 was carried out on an Xbridge C18 3.5 μm 2.1×50 mm column using a gradient of acetonitrile and water from 5:95 to 100:0 (containing 0.1% formic acid as the ionizing agent). HRMS analysis was performed using an Agilent 1290 Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm 2.1×50 mm column combined with an Agilent 6230 TOF mass spectrometer equipped with electrospray ionization. 1 1H NMR data are reported as follows: chemical shift (multiplicity (br = broad line, s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sex = sextet, sept = septet, and m = multiplet), integration value, and assignment). Residual protons in the deuterated solvent were used as the reference substance to 1 report the chemical shift of 1H NMR data in ppm (TMS, δ scale) at low magnetic field from the inside of tetramethylsilane. 13 13C NMR data were 1 determined using 1H decoupling, and the chemical shift was reported as ppm at low magnetic field from tetramethylsilane (TMS, δ scale) using residual carbon in the deuterated solvent as the reference.

[0090] General Procedure for PPR Screening Experiments Polyolefin catalyst screening is carried out in a high-throughput parallel polymerization reactor (PPR) system. The PPR system consists of an array of 48 single-cell (6×8 matrix) reactors within an inert atmosphere glove box. Each cell is equipped with a glass insert having an internal working liquid volume of approximately 5 mL. Each cell has independent pressure control and continuously stirs the liquid within the cell at 800 rpm. The catalyst solution is prepared by dissolving an appropriate amount of procatalyst in toluene, unless otherwise described. All liquids (e.g., solvent, 1-octene, chain shuttling agent solution appropriate for the experiment, and catalyst solution) are added to the single-cell reactor via a robotic syringe. Gaseous reagents (i.e., ethylene, H2) are added to the single-cell reactor via a gas injection port. Prior to each run, the reactor is heated to 80 °C, purged with ethylene, and aerated.

[0091] A portion of Isopar-E is added to the reactor. The reactor is heated to the operating temperature and pressurized with ethylene to the appropriate psig. The toluene solution of the reagents is added in the order of (1) 1-octene together with 500 nmol of scavenger MMAO-3A, (2) activator (cocatalyst-1, cocatalyst-2, etc.), and (3) catalyst.

[0092] After adding each liquid, a small amount of Isopar-E is added to make the total reaction volume 5 mL after the final addition. When the catalyst is added, the PPR software starts monitoring the pressure of each cell. The pressure (within approximately 2 - 6 psig) is maintained by additional addition of ethylene gas by opening the valve at the setpoint minus 1 psi and closing the valve when the pressure exceeds 2 psi. All pressure drops are cumulatively recorded as "uptake" or "conversion" of ethylene over the course of the run, or at the earliest time period that occurs before reaching the uptake or conversion demand value. Each reaction is quenched for 4 minutes at a pressure 40 - 50 psi higher than the reactor pressure by addition of 10% carbon monoxide in argon. A shorter "quench time" means the catalyst is more active. To prevent the formation of excess polymer in any given cell, the reaction is quenched when a predetermined uptake level (50 psig for runs at 120 °C, 75 psig for runs at 150 °C) is reached. After quenching all reactions, the reactor is cooled to 70 °C. The reactor is vented and purged with nitrogen for 5 minutes to remove carbon monoxide, and the tube is removed. The polymer sample is dried in a centrifugal evaporator at 70 °C for 12 hours, weighed to determine the polymer yield, and subjected to IR (incorporation of 1-octene) and GPC (molecular weight) analysis.

[0093] SymRAD HT-GPC analysis Molecular weight data is determined by analysis on a hybrid Symyx / Dow robotic-assisted dilution high temperature gel permeation chromatography (Sym-RAD-GPC) apparatus. Polymer samples are dissolved by heating at 160 °C for 120 minutes in 1,2,4-trichlorobenzene (TCB) at a concentration of 10 mg / mL stabilized with 300 parts per million (ppm) of butylated hydroxytoluene (BHT). Each sample is diluted to 1 mg / mL immediately prior to injection of a 250 μL aliquot. The GPC is equipped with two Polymer Labs Plgel 10 μm MIXED-B columns (300 × 10 mm) at a flow rate of 2.0 mL / min at 160 °C. Sample detection is performed using a PolyChar IR4 detector in concentration mode. Conventional calibration with narrow polystyrene (PS) standards is utilized in apparent units adjusted to homopolyethylene (PE) using known Mark-Houwink coefficients for PS and PE in TCB at this temperature.

[0094] 1-Octene incorporation IR analysis The execution of samples for HT-GPC analysis precedes IR analysis. For IR analysis, a 48-well HT silicon wafer is utilized for sample deposition and 1-octene incorporation analysis. In the analysis, the sample is heated to 160 °C for up to 210 minutes, the sample is reheated to remove the magnetic GPC stir bar, and agitation is performed using a glass rod stir bar in a J-KEM Scientific heated robotic shaker. The sample is deposited while heating using the 75 deposition stations of a Tecan MiniPrep, and 1,2,4-trichlorobenzene is evaporated from the deposition wells of the wafer at 160 °C under a nitrogen purge. The 1-octene analysis is performed on the HT silicon wafer using a NEXUS 670 E.S.P. FT-IR.

[0095] Batch reactor polymerization procedure The polymerization reaction in the batch reactor is carried out in a 2 L Parr (trademark) batch reactor. The reactor is heated by an electric heating mantle and cooled by an internal coil cooling coil containing cooling water. Both the reactor and the heating / cooling system are controlled and monitored by a Camile (trademark) TG process computer. At the bottom of the reactor, a dump valve is installed to transfer the contents of the reactor to a stainless-steel dump pot. The dump pot is pre-filled with a catalyst deactivation solution (typically, a 5 mL mixture of Irgafos / Irganox / toluene). Both the pot and the tank are purged with nitrogen, and the dump pot is vented to a 30-gallon blowdown tank. All solvents used for polymerization or catalyst replenishment are passed through a solvent purification column to remove any impurities that could affect the polymerization. 1-Octene and IsoparE are passed through two columns, a first column containing A2 alumina and a second column containing Q5. Ethylene is passed through two columns, a first column containing A204 alumina and 4 Å molecular sieves and a second column containing Q5. The N2 used for transfer is passed through a single column containing A204 alumina, 4 Å molecular sieves, and Q5.

[0096] The reactor is first charged from a shot tank that may contain IsoparE solvent and / or 1-octene, depending on the reactor load. The shot tank is filled to the load set point using a laboratory scale attached to the shot tank. After adding the liquid feed, the reactor is heated to the polymerization temperature set point. If ethylene is used, ethylene is added to the reactor at the reaction temperature to maintain the reaction pressure set point. The amount of ethylene added is monitored by a Micro Motion flow meter. For some experiments, the standard conditions at 120 °C are 46 g of ethylene and 303 g of 1-octene in 611 g of IsoparE, and the standard conditions at 150 °C are 43 g of ethylene and 303 g of 1-octene in 547 g of IsoparE.

[0097] The procatalyst and activator are mixed with an appropriate amount of purified toluene to obtain a solution of molar concentration. The procatalyst and activator are processed in an inert glove box, drawn into a syringe, and pressuredly transferred into a catalyst shot tank. The syringe is rinsed three times with 5 mL of toluene. Immediately after the catalyst is added, the run timer starts. When using ethylene, it is added by Kamir to maintain the reaction pressure set point in the reactor. The polymerization reaction is run for 10 minutes, then the stirrer is stopped and the bottom dump valve is opened to transfer the contents of the reactor to a dump pot. The contents of the dump pot are poured into a tray and placed in a fume hood where the solvent is evaporated overnight. The tray containing the remaining polymer is transferred to a vacuum oven and heated to 140 °C under vacuum to remove any remaining solvent. After the tray is cooled to ambient temperature, the polymer yield is measured to determine efficiency and the polymer is subjected to polymer testing.

Example

[0098] Procatalysts 1-11 were synthesized from ligands 1-7. Examples 1-2 include results from polymerization reactions in a batch reactor and a parallel pressure reactor. One or more features of the present disclosure are illustrated in view of the following examples.

[0099] Ligands 1-7 and procatalysts 1-11 were synthesized using the protocols found in patent application publications WO2013 / 052585 A2, WO2013 / 036546 A2, and WO2013 / 013111.

[0100] Example 1: Polymer Obtained from Procatalyst The catalyst efficiency (grams of polymer obtained per gram of metal) and the properties of the polymer obtained were evaluated for procatalysts 1-11. The polymerization reaction was carried out in a 2-L semi-batch reactor first without using diethylzinc (DEZ) and then with the addition of three different amounts of DEZ (0, 50 μmol, and 200 μmol). The activator was [HNMe(C 18 H 37)2][B(C6F5)4].

[0101] The procatalysts in Table 1 produced polymers at temperatures up to 190 °C. The bidentate procatalysts Procatalyst 1, 6, and 10 were the most active above 150 °C compared to the other procatalysts. [Table 1]

[0102] The procatalysts produced ethylene / octene copolymers with molecular weights in the range of 14,940 - 374,211 g / mol. Procatalysts 2 and 8 produced polymers with the highest molecular weights of 372,026 g / mol and 374,211 g / mol, respectively. Procatalysts 3, 7, and 8 produced polymers with the highest comonomer incorporation, specifically 11.4, 18.6, and 21.5, respectively. Procatalysts 1 - 7 and 9 - 11 produced polymers with a narrow polydispersity (3.0 or less).

[0103] Example 2 - Chain Transfer Study To determine the chain transfer rates of Procatalysts 1 - 11, semi - batch experiments were conducted using various amounts of the chain transfer agent Et2Zn (0, 50 μmol, and 200 μmol). All reactions were carried out at 150 °C, and 1.2 equivalents of [HNMe(C 18 H 37 )2][B(C6F5)4] was used as the activator for the procatalysts. The semi - batch experiments were carried out at 150 °C using 12.1 g of ethylene, 57 g of 1 - octene, and 555 g of IsoparE under a pressure of 136 psi. The catalyst efficiency, as well as the Mw, PDI, and comonomer incorporation of the corresponding polymers produced, are shown in Table 2. M n for each run was calculated using Equation 3 with the values of Ca and M n0 fit using Microsoft Excel Solver to minimize the sum of the squared deviations between the fitted molecular weight data and the experimental molecular weight data for all runs using a particular catalyst. [Table 2]

Table 3

[0104] The high chain transfer constants (Ca ≥ 0.5) of procatalysts 1 to 5 and 11 at 150 °C indicate that these catalysts have a high sensitivity to the chain transfer agent and rapidly undergo chain transfer with these agents. The narrow PDI that did not change or decrease as the amount of Et2Zn increased, as observed for each procatalyst, is evidence that these procatalysts may undergo reversible chain transfer by CSA rather than irreversible chain transfer. The present specification includes the following aspects. Item 1. A process for polymerizing an olefin, comprising contacting ethylene, a (C3-C 40 ) alpha-olefin comonomer, and a solvent in the presence of a chain transfer agent and a catalyst system, wherein the catalyst system comprises a metal-ligand complex according to formula (I),

Chemical formula

Chemical formula

Claims

1. A process for polymerizing an olefin, comprising contacting ethylene, (C ３ -C ４０ ) an alpha-olefin comonomer, and a solvent in the presence of a chain transfer agent and a catalyst system, wherein the chain transfer agent comprises a dialkyl zinc, and the catalyst system comprises a metal-ligand complex according to formula (Ia), formula (Ib), or formula (Ic). 【Chemical Formula 3】 wherein 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, independently, an unsaturated (C ２ -C ５０ ) hydrocarbon, an unsaturated (C ２ -C ５０ ) heterohydrocarbon, a (C １ -C ５０ ) hydrocarbyl, a (C ６ -C ５０ ) aryl, a (C ６ -C ５０ ) heteroaryl, a cyclopentadienyl, a substituted cyclopentadienyl, a (C ４ -C １２ ) diene, a halogen, -N(R Ｎ ) ２ , and -NOCOR Ｃ selected from monodentate or bidentate ligands, n is 1 or 2, m is 2, the metal-ligand complex has 6 or fewer metal-ligand bonds, each Y is oxygen, Each R １ is independently selected from carbazolyl or substituted carbazolyl, Each R ２ is independently selected from (C1-C10)alkyl, z ３ 、z ４ 、and z ５ is z ３ 、z ４ 、or z ５ such that exactly one of them is -C(R Ａ )-, or z ３ 、z ４ 、or z ５ such that exactly two of them are -C(R Ａ )- is selected from the group consisting of sulfur, oxygen, -N(R Ａ )-, and -C(R Ａ )- R ３ 、R ４ 、R ５ 、and R ６ are each independently selected from (C １ -C ５０ ), (C １ -C ５０ ), hydrocarbyl, hetero hydrocarbyl, halogen, or -H, z ６ and z ７ is z ６ and z ７ both being -C(R Ｂ )-, on the condition that, sulfur, oxygen, -N(R Ｂ )-, and -C(R Ｂ )- are selected from the group consisting of, R ７ 、R ８ 、and R ９ are each independently (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)-, R Ｃ S(O) ２ -, (R Ｃ ), ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ), ２ NC(O)-, halogen, or -H, and R8 in formula (Ia) is methyl, Each R Ａ is independently (C １ -C ５０ ), a hydrocarbyl, (C １ -C ５０ ), a heterohydrocarbyl, (C ６ -C ５０ ), an aryl, (C ４ -C ５０ ), a 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) ２ -, R Ｃ S(O) ２ (R Ｃ ) ２ C = N -, R Ｃ C(O)O -, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ NC(O)-, a halogen, or -H, and any two R Ａ groups bonded to adjacent atoms are optionally bonded, Each R Ｂ is independently (C １ -C ５０ ), a hydrocarbyl, (C １ -C ５０ ), a hetero hydrocarbyl, (C ６ -C ５０ ), an aryl, (C ４ -C ５０ ), a 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)-, R Ｃ S(O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ NC(O)-, a halogen, or -H, and any two R Ｂ groups bonded to adjacent atoms are optionally bonded, Each R Ｃ , R Ｎ , and R Ｐ is independently (C １ -C ５０ ) hydrocarbyl, a polymerization process.

2. M is zirconium or hafnium, Each X is independently selected from (C ６ -C ２０ ), aryl, (C ４ -C ２０ ), heteroaryl, (C ４ -C １２ ), diene, or halogen, and the polymerization process according to claim 1.

3. The polymerization process according to claim 1, wherein the metal-ligand complex has the structure of formula (Ib), z6 is sulfur, z7 is -C(H)-, or z6 is -C(H)- and z7 is sulfur.

4. The polymerization process according to claim 1, wherein the metal-ligand complex has the structure of formula (Ia) or formula (Ib), and R3, R4, R5, and R6 are -C(H)-.

5. The polymerization process according to claim 1, wherein R2 is methyl.

6. In formula (Ic), the polymerization process according to claim 1, wherein R7 and R9 are -C(H)- and R8 is (C1-C20) alkyl.

7. The polymerization process according to claim 1, wherein each R1 is carbazolyl.

8. Each R １ is independently 3,6-di-tert-butylcarbazol-9-yl or 2,7-di-tert-butylcarbazol-9-yl, the polymerization process according to claim 1.

9. The polymerization process according to claim 1, wherein the chain transfer agent is diethylzinc.

10. The polymerization process according to any one of claims 1 to 9, wherein the polymerization process is carried out in a reactor.

11. The polymerization process according to any one of claims 1 to 9, wherein the polymerization process is carried out at a reaction temperature of 120°C to 190°C.

12. The polymerization process according to any one of claims 1 to 9, wherein the catalyst system further comprises a cocatalyst.

13. The polymerization process according to any one of claims 1 to 9, wherein each X is independently benzyl, phenyl, or chloro.

14. The polymerization process according to claim 1, wherein the metal-ligand complex has one of the following structures. 【Chemical Formula 4】

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