Monodentate, bidentate, and tetradentate guanidine Group IV transition metal olefin copolymerization catalysts

Abstract

The process for polymerizing polyolefins comprises reacting ethylene and any one or more (C3-C 12 ) an α-olefin, wherein the catalyst system comprises a metal-ligand complex having a structure according to formula (I). [Formula 1] JPEG2022536054000077.jpg109170

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims priority to U.S. Provisional Patent Application No. 62 / 855,306, filed on May 31, 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 including monobidentate, bisbidentate, and tetradentate Group IV transition metal catalysts, and 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 are manufactured for a wide variety of articles. The polyethylene polymerization process can be varied in many respects to produce a wide variety of polyethylene resins having various physical properties suitable for use in various 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 can also be added to the reactor. The catalyst system for producing the ethylene-based typically can include a chromium-based catalyst system, a Ziegler-Natta catalyst system, and / or a molecular (either metallocene or non-metallocene) catalyst system. The reactants in the diluent and the catalyst system circulate 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 when removed from the reactor may be processed to remove the polyethylene product from the diluent and unreacted reactants, and the diluent and unreacted reactants are typically recycled into the reactor. Alternatively, the reaction mixture may be sent to a second reactor connected in series to the first reactor, where a second polyethylene fraction may be produced.

Summary of the Invention

Problems to be Solved by the Invention

[0005] Despite the number of currently available homogeneous solution olefin polymerization catalyst systems, there is a need for high-temperature polymerization catalysts having improved molecular properties that facilitate the production of high molecular weight (Mw) polymers having a narrow polydispersity (PDI), and / or high molecular weight (Mw) ethylene / comonomer copolymers having a range of comonomer incorporation (i.e., 0 to 20 mol% of 1-hexene or 1-octene, etc.), and / or high molecular weight (Mw) polymers capable of undergoing chain transfer by a chain transfer agent (CSA) to produce an olefin block copolymer (OBC).

[0006] Embodiments of the present disclosure include polymerization processes. These polymerization processes produce ethylene-based polymers. The polymerization process includes contacting ethylene and any one or more (C3-C 12 ) α-olefins in the presence of a catalyst system, and the catalyst system includes a metal-ligand complex having a structure according to formula (I).

Chemical formula

[0007] In formula (I), M is titanium, zirconium, or hafnium. Each X is independently an unsaturated (C2-C 20 ) hydrocarbon, an unsaturated (C2-C 50 ) heterohydrocarbon, a (C1-C 50 ) hydrocarbyl, a (C1-C 50 ) heterohydrocarbyl, a (C6-C 50 ) aryl, a (C6-C 50 ) heteroaryl, a cyclopentadienyl, a substituted cyclopentadienyl, a (C4-C 12 ) diene, a halogen, -OR X , -N(R X )2, or -NCOR X selected from monodentate or bidentate ligands, and each R X is a (C1-C 30 ) hydrocarbyl or -H. The subscript n of (X) n is 1, 2, or 3. The subscript m is 1 or 2, and m plus n is equal to 3 or 4 (m + n = 3 or 4).

[0008] In formula (I), each R 1 is R 1a or R 1b , each R 4 is R 4a or R 4b , and R 1a , R 1b , R 4a , and R 4b are independently -H, a (C2-C 40 ) hydrocarbyl, a (C1-C 40)heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, or a halogen.

[0009] In formula (I), each A is, independently, -NR 2 R 3 wherein each R 2 is R 2a or R 2b wherein each R 3 is R 3a or R 3b wherein R 2a , R 2b , R 3a , and R 3b are, independently, -H or (C1-C 40 )hydrocarbyl, provided that (1) when m is 2 and (2) all of R 2a , R 2b , R 3a , and R 3b are methyl, at least one of R 1a , R 1b , R 4a , and R 4b is not 2-propyl; when m is 1, each X is the same, and R 1 and R 2 , or R 2 and R 3 , or R 3 and R 4 may optionally be connected to form a ring.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

[0011] Specific embodiments of the catalyst system will be described below. It should be understood that the catalyst system of the present disclosure may be implemented in different forms and should not be construed as being limited to the specific embodiments described in 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, Z, M, X, and n: as defined above, Me: methyl, Et: ethyl, Ph: phenyl, Bn: benzyl, i-Pr: iso-propyl, t-Bu: tert-butyl, t-Oct: tert-octyl (2,4,4-trimethylpentan-2-yl), Tf: trifluoromethanesulfonate, THF: tetrahydrofuran, Et2O: diethyl ether, CH2Cl2: dichloromethane, CV: column volume (used in column chromatography), EtOAc: ethyl acetate, C6D6: deuterated benzene or benzene-d6, CDCl3: deuterated chloroform, Na2SO4: sodium sulfate, MgSO4: magnesium sulfate, HCl: hydrogen chloride, n-BuLi: butyllithium, t-BuLi: tert-butyllithium, Cu2O: copper(I) oxide, N,N’-DMEDA: N,N’-dimethylethylenediamine, K3PO4: tripotassium phosphate, Pd(AmPhos)Cl2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II), Pd(dppf)Cl2: dichloro[1,1’-bis(diphenylphosphino)ferrocene]palladium(II), AgNO3: silver nitrate, K2CO3: potassium carbonate, Cs2CO3: cesium carbonate, i-PrOBPin: 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, BrCl2CCCl2Br: 1,2-Dibromotetrachloroethane, HfCl4: hafnium(IV) chloride, HfBn4: hafnium(IV) tetrabenzyl, ZrCl4: zirconium(IV) chloride, ZrBn4: zirconium(IV) tetrabenzyl, ZrBn2Cl2(OEt2): zirconium(IV) dibenzyldichloride mono-diethyl etherate, HfBn2Cl2(OEt2): hafnium(IV) dibenzyldichloride mono-diethyl etherate, TiBn4: titanium(IV) tetrabenzyl, Zr(CH2SiMe3)4: zirconium(IV) tetrakis-trimethylsilylmethyl, Hf(CH2SiMe3)4: hafnium(IV) tetrakis-trimethylmethyl, N2: nitrogen gas, PhMe: toluene, PPR: parallel 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 : retained fraction, TLC: thin layer chromatography, rpm: revolutions per minute.

[0013] The term "independently selected" and the multiple options that follow it are used herein to indicate that the individual R 1 , R 2 , R 3 , R 4 , and R 5 groups, such as those shown before the term, may be the same or different and are independent of the identity of other groups that appear before the term.

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

[0015] When used to describe a particular carbon atom-containing chemical group, "(Cx -C y ) The bracketed expression having the form of "(Cx-Cy)" means that the unsubstituted form of the chemical group has from x to y carbon atoms including x and y. For example, (C1-C 50 ) alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, a particular chemical group may be substituted by one or more substituents such as R S . The R x -C y ) substitution version of the chemical group defined using "(C S -C S )" may contain more than y carbon atoms depending on the identity of any group R S . For example, "(C1-C S ) alkyl" substituted by exactly one group R 50 where R x -C y )" is phenyl (-C6H5) may contain 7 to 56 carbon atoms. Thus, generally, when a chemical group defined using "(C S -C S )" is substituted by one or more carbon atom-containing substituents R

[0016] The minimum and maximum total numbers of carbon atoms of the chemical group are determined by adding to both x and y the total number of carbon atoms from all carbon atom-containing substituents R S . The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R SMeans being replaced by . The term "multiple substitution" means that at least two, but less than all, of the hydrogen atoms bonded to the carbon or heteroatom of the corresponding unsubstituted compound or functional group are replaced by substituents. The term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0017] "(C1-C 50 ) hydrocarbyl" means a hydrocarbon radical having 1 to 50 carbon atoms, and "(C1-C 50 ) hydrocarbylene" means a hydrocarbon diradical having 1 to 50 carbon atoms, where each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, 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 is substituted or unsubstituted by one or more R S .

[0018] In the present disclosure, (C1-C 50 ) hydrocarbyl can be 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-(C1-C 20 ) alkylene (such as benzyl (-CH2-C6H5)).

[0019] "(C1-C 50 ) alkyl" and "(C1-C 18 ) alkyl" mean unsubstituted or one or more R Smean, respectively, a saturated straight-chain or branched hydrocarbon radical having 1 to 50 carbon atoms and a saturated straight-chain or branched hydrocarbon radical having 1 to 18 carbon atoms, each of which is replaced by. Unsubstituted (C1-C 50 ) Examples of 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, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. Examples of substituted (C1-C 40 ) alkyl are 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 containing the substituent. For example, one R S which is each (C1-C5) alkyl is substituted (C 27 -C 40 ) alkyl. Each (C1-C5) alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0020] The term "(C6-C 50 ) aryl" means an unsubstituted or (by one or more R S ) substituted 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 non-fused, aromatic or non-aromatic. Unsubstituted (C6-C50 ) Examples of 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, polyfluorophenyl, pentafluorophenyl, and fluoren-9-one-1-yl.

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

[0022] (C1-C 50)Examples of hydrocarbylenes include unsubstituted or substituted (C6-C 50 )arylenes, (C3-C 50 )cycloalkylenes, and (C1-C 50 )alkylenes (e.g., (C1-C 20 )alkylenes). The diradicals may be on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or may be separated by one, two, or more intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or α,ω-diradicals, and others include 1,2-diradicals. An α,ω-diradical is a diradical having the greatest carbon skeleton 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] The term “(C1-C 50 )alkylene” means a saturated straight-chain or branched-chain diradical having 1 to 50 carbon atoms that is unsubstituted or substituted by one or more R S (i.e., the radical is not on a ring atom). Examples of unsubstituted (C1-C 50 )alkylenes are unsubstituted (C1-C 20 )alkylenes and include unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3), where “C*” represents a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical. Substituted (C1-C50 )Examples of alkylene include substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosylene). As described above, two Rs S together can form (C1-C 18 ) alkylene, and examples of substituted (C1-C 50 ) alkylene include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0024] The term "(C3-C 50 ) cycloalkylene" means a cyclic diradical (i.e., the radical is on a ring atom) having 3 to 50 carbon atoms, unsubstituted or substituted by one or more Rs S .

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

[0026] (C1-C 50 )heterohydrocarbyl can be unsubstituted or substituted. Non-limiting examples of (C1-C 50 )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-, (C1-C 50Hydrocarbyl-N(R N )-, (C1-C 50 )Hydrocarbyl-P(R P )-, (C2-C 50 )Heterocycloalkyl, (C2-C 19 )Heterocycloalkyl-(C1-C 20 )Alkylene, (C3-C 20 )Cycloalkyl-(C1-C 19 )Heteroalkylene, (C2-C 19 )Heterocycloalkyl-(C1-C 20 )Heteroalkylene, (C1-C 50 )Heteroaryl, (C1-C 19 )Heteroaryl-(C1-C 20 )Alkylene, (C6-C 20 )Aryl-(C1-C 19 )Heteroalkylene, or (C1-C 19 )Heteroaryl-(C1-C 20 )Heteroalkylene.

[0027] The term "(C4-C 50 )heteroaryl" means an unsubstituted or (one or more R S -substituted) 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 can be independently fused or unfused and aromatic or non-aromatic. Other heteroaryl groups (e.g., generally (C x -C y )heteroaryl, (C4-C 12 )heteroaryl, etc.) have x to y carbon atoms (such as 4 to 12 carbon atoms) and are unsubstituted or substituted with one or two or more R SIt is defined in a similar manner to that replaced by. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered or 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3, 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 or 2, and the heteroatom can be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon radicals are pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radical can be a fused 5,6- or 6,6-ring system. Examples of fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radicals include indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radicals include quinolin-2-yl and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radical can be a fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring system. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridin-9-yl.

[0028] “(C1-C 50)The term "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 )The term "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 mentioned, and each of the heteroalkyl and heteroalkylene groups is unsubstituted or substituted by one or more R 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 fluoride (F - ), chloride (Cl - ), bromide (Br - ) or iodide (I -means the anionic form of the halogen atom.

[0031] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. A saturated chemical group has one or more substituents R S When substituted with, 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, 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 not including double bonds that may be present in the substituent R S (if present), or (in the case of a (hetero)aromatic ring (if present)).

[0032] Some embodiments of the present disclosure include a polymerization process. These polymerization processes produce ethylene-based polymers. The polymerization process includes contacting ethylene and any one or more (C3-C 12 ) α-olefins in the presence of a catalyst system, and the catalyst system includes a metal-ligand complex having a structure according to formula (I). [Chemical formula]

[0033] In formula (I), M is titanium, zirconium, or hafnium. Each X is independently an unsaturated (C2-C 20 ) hydrocarbon, an unsaturated (C2-C 50 ) heterohydrocarbon, a (C1-C 50 ) hydrocarbyl, a (C1-C 50 ) heterohydrocarbyl, a (C6-C 50 ) aryl, a (C6-C 50 ) heteroaryl, a cyclopentadienyl, a substituted cyclopentadienyl, a (C4-C 12 ) diene, a halogen, -OR X , -N(R X)2, or -NCOR X is a mono- or bidentate ligand selected from, and each R X is (C1-C 30 ) hydrocarbyl or -H. (X) n The subscript n is 1, 2, or 3. The subscript m is 1 or 2, and m + n is equal to 3 or 4 (m + n = 3 or 4).

[0034] In formula (I), each R 1 is R 1a or R 1b and each R 4 is R 4a or R 4b where R 1a , R 1b , R 4a , and R 4b are independently hydrogen (-H), (C2-C 40 ) hydrocarbyl, (C6-C 40 ) aryl, (C1-C 40 ) heterohydrocarbyl, (C5-C 40 ) 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)-, or halogen.

[0035] In formula (I), each A is independently -NR 2 R 3 and each R 2 is R 2a or R 2b and each R 3 is R 3a or R 3band R 2a 、R 2b 、R 3a 、and R 3b are each, independently, -H or (C1-C 40 ) hydrocarbyl, provided that (1) m is 2, and (2) when all of R 2a 、R 2b 、R 3a 、and R 3b are methyl, at least one of R 1a 、R 1b 、R 4a 、and R 4b is not 2-propyl, and when m is 1, each X is the same, and R 1 and R 2 、or R 2 and R 3 、or R 3 and R 4 may optionally be connected to form a ring.

[0036] In some embodiments of formula (I), m is 2, n is 2, and the metal-ligand complex has a structure according to formula (II).

Chemical formula

[0037] In formula (II), R 1a 、R 1b 、R 4a 、R 4b 、M, and X are as defined in formula (I). A 1 and A 2 are each, independently, A as defined in formula (I).

[0038] In one or more embodiments, in formulas (I) and (II), each R 1 、R 1a 、or R 1b and each R 4 、R 4a 、or R 4b is each, independently, (C1-C 40 ) alkyl, (C1-C 40) heteroalkyl, (C6-C 40 ) aryl, or (C5-C 40 ) heteroaryl.

[0039] In one or more embodiments, in Formulas (I) and (II), each R 1 , R 1a , or R 1b and each R 4 , R 4a , or R 4b is independently benzyl, cyclohexyl, 2,6-dimethylphenyl, tert-butyl, or ethyl.

[0040] In one or more embodiments, in Formula (III), m is 2, n is 2, and R 4a and R 4b are covalently bonded, whereby the metal-ligand complex comprises a divalent radical Q consisting of two covalent groups R 4a and R 4b . The metal-ligand complex has a structure according to Formula (III).

Chemical formula

[0041] In Formula (III), Q is (C2-C 12 ) alkylene, (C2-C 12 ) heteroalkylene, (C6-C 50 ) arylene, (C4-C 50 ) heteroarylene, (-CH2Si(R C )2CH2-), (-CH2CH2Si(R C )2CH2CH2-), (-CH2Ge(R C )2CH2-), or (-CH2CH2Ge(R C )2CH2CH2-), and R 1a , R 1b , M, and X are as defined in Formula (I), and A 1 and A 2 are as defined in Formula (II).

[0042] In one or more embodiments, in formula (III), Q is -(CH2) x selected from -, where x is from 2 to 5. In some embodiments, Q is -(CH2)4-.

[0043] In some embodiments, in formula (III), R 1a and R 1b are 2-propyl or 2,6-dimethylphenyl.

[0044] In various embodiments, in formulas (I), (II), and (III), each A is carbazolyl, imidazolyl, indolyl, pyrrolyl, or pyrazolyl. In some embodiments, each A, A 1 , and A 2 is a ring structure having one of the following structures.

Chemical formula

[0045] In formulas (I), (II), and (III), each A, A 1 , and A 2 is independently -NR 2 R 3 , and each R 2 is R 2a or R 2b , and each R 3 is R 3a or R 3b In one or more embodiments, in (I), (II), and (III), R 2a , R 2b , R 3a , and R 3b are (C1-C 20 ) alkyl, (C1-C 20 ) heteroalkyl, (C1-C 20 ) aryl, or (C1-C 20 ) heteroaryl. In some embodiments, R 2a , R 2b , R 3a , and R 3bis methyl, ethyl, 1-propyl, 2-propyl, n-butyl, tert-butyl, 2-methylpropyl (isobutyl), n-butyl, n-hexyl, cyclohexyl, n-octyl, or tert-octyl.

[0046] In various embodiments, in Formulas (I), (II), and (III), R 1a , R 1b , R 4a , and R 4b are independently selected from cyclohexyl, benzyl, 2-propyl, or 2,6-dimethylphenyl.

[0047] In one or more embodiments, when R 1 and R 4 are 2-propyl, R 2 and R 3 are not methyl. In one or more embodiments, when R 1 and R 4 are 2-propyl, R 2 and R 3 are not -N(CH3)2. In one embodiment of Formula (II), R 1a is not covalently bonded to R 2b or R 3b to form a ring.

[0048] In the metal-ligand complexes according to Formulas (I), (II), and (III), each X is bonded to M through a covalent bond, a coordination bond, or an ionic bond. In some embodiments, each X is the same. The metal-ligand complex can have six or fewer metal-ligand bonds and can be electrically neutral as a whole or can 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 (C1-C 20 ) alkyl, (C1-C 20 ) heteroalkyl, (C6-C 20 ) aryl, (C4-C 20 ) heteroaryl, (C4-C 12 ) diene, or halogen.

[0049] In some embodiments, X is a monodentate ligand, and the monodentate ligand can be a monoanionic ligand. The monoanionic ligand has a net formal oxidation state of -1. Each monoanionic ligand is independently a hydride, (C1-C 40 ) hydrocarbyl carbanion, (C1-C 40 ) heterohydrocarbyl carbanion, halide, nitrate, carbonate, phosphate, sulfate, 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 - and can be, where 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 a (C2-C 40 ) hydrocarbylene or (C1-C 20 ) heterohydrocarbylene, and R M is as defined above.

[0050] In other embodiments, at least one monodentate ligand X may be a neutral ligand, independent of any other ligand X. In certain embodiments, the neutral ligand is R Q NR K R L 、R K OR L 、R K SR L 、or R Q PR K R L and other neutral Lewis base groups, where 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 as previously defined.

[0051] Furthermore, each X can be a monodentate ligand that is, independent of any other ligand X, halogen, unsubstituted (C1-C 20 )hydrocarbyl, unsubstituted (C1-C 20 )hydrocarbylC(O)O-, or R K R L N-, where 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-, where each of R K and R L is independently unsubstituted (C1-C 10) It is hydrocarbyl. In one or more embodiments of formulas (I), (II), and (III), X is benzyl, chloro, -CH2SiMe3, or phenyl.

[0052] In a further embodiment, each X is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, or chloro. In some embodiments, each X is benzyl. Optionally, 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 different from 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.

[0053] In some embodiments, the chemical groups (e.g., X and R 1 ~R 4 ) of the metal-ligand complex of formula (I) can all be unsubstituted. In other embodiments, none, one, or two or more of the chemical groups X and R 1 ~R 4 of the metal-ligand complex of formula (I) are not substituted with one or two or more R S , or any or all of them can be substituted with one or two or more R S . When two or three or more R S are attached to the same chemical group of the metal-ligand complex of formula (I), the individual R S can 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 need to be oversubstituted with R S , and any or all of them can be oversubstituted with R S . In a chemical group oversubstituted with R S , the individual R SThey may be all the same or independently selected.

[0054] In an exemplary embodiment, the catalyst system may include a metal-ligand complex according to formula (I) having the structure of any of the following listed pre-catalysts 1-74, which are synthesized from the corresponding ligands 1-17 shown in FIGS. 3-5.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0055] 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 a 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 different comonomer selectivity from the pre-catalyst (A), and (C) a chain transfer agent or a chain shuttling agent.

[0056] 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 if the three aforementioned components (A) to (C) are 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". Thus, 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.

[0057] The chain transfer ability of the catalyst is first evaluated by performing an attempt to vary the level of a chain transfer or chain shuttle agent (CSA) to observe the expected decrease in molecular weight and narrowing of the PDI for the shuttle catalyst. The molecular weight of the polymer produced by a catalyst having the potential to be a good chain shuttling agent will be more sensitive to the addition of CSA than the polymer molecular weight produced by a poorer shuttle or a slower chain transfer rate. The Mayo equation (Equation 1) gives the number average chain length

Number

Number

[0058] 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. The chain transfer agents suitable for the processes of the present disclosure are described in U.S. Patent Application Publication No. US2007 / 0167315, which is incorporated herein by reference in its entirety.

[0059] In one or more embodiments of the polymerization process, the chain transfer agent, when present, is selected from the group consisting of diethyl zinc, di(isobutyl) zinc, di(n-hexyl) zinc, di(n-octyl) zinc, 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 bis(2,6-di-t-butylphenoxide), ... The ethylaluminum di(ethyl(l-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminum bis(2,3,6,7-dibenzo-l-azacycloheptanamide), n-octylaluminum bis(2,3,6,7-dibenzo-l-azacycloheptanamide), n-octylaluminum bis(dimethyl(t-butyl)siloxide, ethylzinc(2,6-diphenylphenoxide), ethylzinc(t-butoxide), dimethylmagnesium, dibutylmagnesium, and n-butyl-sec-butylmagnesium.

[0060] 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 precatalyst form that is neutral and a catalyst form that can be positively charged by the loss of a monoanionic ligand such as benzyl or phenyl. Suitable activating cocatalysts for use herein 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 aforementioned 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.

[0061] The Lewis acid activating cocatalyst includes group 13 metal compounds containing (C1-C 20 ) hydrocarbyl substituents 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 further embodiments, the Group 13 metal compounds are tris(fluorosubstituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tris((C1-C 20 )hydrocarbylborate (e.g., trityltetrafluoroborate) 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.

[0062] Examples of combinations of neutral Lewis acid activating cocatalysts include tri((C1-C4)alkyl)aluminum and tri((C6-C 18)Mixtures including an aryl boron compound, particularly in combination with tris(pentafluorophenyl)borane, are included. Other embodiments are combinations of such neutral Lewis acid mixtures with polymers or oligomeric aluminoxanes, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymers or oligomeric aluminoxanes. The molar ratio of (metal-ligand complex):(tris(pentafluoro-phenyl)borane):(aluminoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluoro-phenyl)borane):(aluminoxane)] is from 1:1:1 to 1:10:30, and in other embodiments from 1:1:1.5 to 1:5:10.

[0063] 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 cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, and inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, and combinations thereof.

[0064] In some embodiments, two or more of the aforementioned activating cocatalysts can be used in combination with each other. Specific examples of cocatalyst combinations are 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 not more than 10:1, and in some other embodiments, not more than 1:1. When using an alumoxane alone as the activating cocatalyst, the number of moles of the alumoxane 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 the activating cocatalyst, in some other embodiments, the number of moles 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). Polyolefin

[0065] The catalyst systems described in the previous paragraphs are utilized for the polymerization of olefins, mainly ethylene and propylene. In some embodiments, only a single type of olefin or α-olefin is present during the polymerization scheme, producing a homopolymer. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin comonomers typically have 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 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.

[0066] 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.

[0067] 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.

[0068] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50%, and in other embodiments, it comprises at least 0.5 mole percent (mol%) to 25 mol%, and in further embodiments, the amount of additional α-olefin comprises at least 5 mol% to 10 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0069] Any conventional polymerization process may be used to produce the ethylene-based polymer. Such conventional polymerization processes include solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and any combination thereof that use one or more conventional reactors, for example, loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, etc., in parallel, series, or any combination thereof, but are not limited thereto.

[0070] 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 described in this disclosure and the specification and optionally one or more other catalysts. The catalyst systems described herein can be used, optionally in combination with one or more other catalysts, in the first reactor or the second reactor. 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.

[0071] 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 systems described within this disclosure and optionally one or more cocatalysts.

[0072] The ethylene-based polymer can further contain 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 contain a filler, and such fillers can 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.

[0073] In some embodiments, the polymerization process for producing the ethylene-based polymer can include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, the catalyst system incorporating at least one metal-ligand complex of formula (I). Polymers obtained from such catalyst systems incorporating the metal-ligand complexes of formula (I) can have a density 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 in accordance with ASTM D792, which is hereby incorporated by reference in its entirety.

[0074] In another embodiment, the polymer obtained from a catalyst system containing the metal-ligand complex of formula (I) has a melt flow ratio (I 10has an Melt Index I2, where the Melt Index I2 is measured at 190 °C and a load of 2.16 kg in accordance with ASTM D1238 (which is hereby incorporated by reference in its entirety), and the Melt Index I 10 is measured at 190 °C and a load of 10 kg in accordance with ASTM D1238. In other embodiments, the Melt Flow Ratio (I 10 / I2) is from 5 to 10, and in others, the Melt Flow Ratio is from 5 to 9.

[0075] In some embodiments, the polymer obtained from the catalyst system comprising the metal-ligand complex of formula (I) has a molecular weight distribution (MWD) of from 1 to 25, where the MWD is defined as M w / M n where M w is the weight average molecular weight and M n is the number average molecular weight. In other embodiments, the polymer obtained from the catalyst system has an MWD of from 1 to 6. Another embodiment includes an MWD of from 1 to 3, and other embodiments include an MWD of from 1.5 to 2.5.

[0076] Embodiments of the catalyst systems described herein result in unique polymer properties as a result of the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer.

[0077] 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, 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 deuterated solvents 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 deuterated solvents as the reference.

[0078] 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 precatalyst 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.

[0079] 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 solutions of the reagents are added in the following order: (1) 1-octene together with 500 nmol of the scavenger MMAO-3A, (2) the activator (cocatalyst-1, cocatalyst-2, etc.), and (3) the catalyst.

[0080] 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 whichever period occurs earlier until the uptake or conversion request value is reached. Each reaction is quenched by adding 10% carbon monoxide in argon for 4 minutes at a pressure 40 - 50 psi higher than the reactor pressure. 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.

[0081] SymRAD HT-GPC analysis Molecular weight data is determined by analysis on a hybrid Symyx / Dow robotic-assisted dilution high temperature gel permeation chromatography apparatus (Sym-RAD-GPC). Polymer samples are dissolved by heating at 160 °C for 120 minutes in 1,2,4-trichlorobenzene (TCB) at a concentration of 10 mg / mL stabilized with 300 parts per million (ppm) 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.

[0082] 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 analysis of 1-octene incorporation. 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 shaken 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 nitrogen purge. The analysis of 1-octene is performed on the HT silicon wafer using a NEXUS 670 E.S.P. FT-IR.

[0083] Batch reactor polymerization procedure The polymerization reaction in the batch reactor is carried out in a 4 L Parr™ batch reactor. The reactor is heated by an electric heating mantle and cooled by an internal coiled cooling coil containing cooling water. Both the reactor and the heating / cooling system are controlled and monitored by a Camile™ TG process computer. At the bottom of the reactor, a dump valve is attached 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 Isopar E 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

Number

Number

[0084] The reactor is first charged from a shot tank that may contain Isopar E 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. When ethylene is used, ethylene is added to the reactor at a reaction temperature to maintain the reaction pressure set point. The amount of ethylene added is monitored by a Micro Motion flow meter. In some experiments, the standard conditions at 120 °C are 88 g of ethylene and 568 g of 1-octene in 1155 g of Isopar E, and the standard conditions at 150 °C are 81 g of ethylene and 570 g of 1-octene in 1043 g of Isopar E.

[0085] The procatalyst and activator are mixed with an appropriate amount of purified toluene to obtain a molar concentration solution. The procatalyst and activator are processed inside an inert glove box, drawn into a syringe, and pressured transferred into the 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 ethylene is used, it is added by Camille to maintain the reaction pressure set point inside 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 the dump pot. The contents of the dump pot are poured into a tray and placed in a fume hood where the solvent is allowed to evaporate 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 has cooled to ambient temperature, the polymer yield is measured to determine efficiency and the polymer is subjected to polymer testing.

Examples

[0086] Examples 1 - 45 are the synthetic procedures for ligand intermediates, ligands, and isolated procatalysts. The structures of ligands 1 - 17 are provided in Figures 3 - 5. Procatalysts 1 - 74 were synthesized from ligands 1 - 17. A general synthetic scheme is illustrated. One or more features of the present disclosure are illustrated in the context of the following examples.

[0087] Example 1: Synthesis of Monocarbodiimide Intermediate to Ligand 1

Chemical formula

[0088] To a clear golden solution of crude isothiourea (3.740 g, 14.252 mmol, 1.00 eq) and Et3N (1.586 g, 2.20 mL, 15.677 mmol, 1.10 eq) in MeCN-CH2Cl2 (150 mL, 1:1) in a 23 °C oven-dried brown jar was added all of the solid AgNO3 (2.542 g, 14.965 mmol, 1.05 eq) at once. After stirring for 2 h (500 rpm), the bright yellow heterogeneous mixture was taken out, diluted with hexane (100 mL), stirred vigorously for 2 min (1000 rpm), suction filtered through a pad of celite, rinsed with hexane (3 × 25 mL), concentrated to about 10 mL, hexane (25 mL) was added, concentrated to about 10 mL of dark yellow, and this process was repeated 2 more times to remove residual MeCN, CH2Cl2, grind the residual silver and ammonium salts, the resulting dark tan heterogeneous mixture was diluted with hexane (25 mL), suction filtered through a pad of celite, rinsed with hexane (3 × 25 mL), concentrated, and the monocarboimide was obtained as a clear pale yellow oil (2.510 g, 11.712 mmol, 82%). NMR showed the product.

[0089] Characterization of thiourea: 1 H NMR (500 MHz, chloroform-d) δ 7.39 - 7.27 (m, 5H), 6.16 (br s, 1H), 5.79 (br s, 1H), 4.61 (br s, 2H), 3.80 - 3.90 (m, 1H), 1.94 (dq, J = 12.6, 4.0 Hz, 2H), 1.64 (dt, J = 13.8, 3.9 Hz, 2H), 1.56 (dq, J = 12.2, 4.0 Hz, 1H), 1.37 - 1.27 (m, 2H), 1.14 (tt, J = 15.3, 7.6 Hz, 3H). 13 C NMR (126 MHz, chloroform-d) δ 180.54, 136.88, 128.92, 127.92, 127.54, 52.96, 48.38, 32.69, 25.31, 24.51.

[0090] Characterization of methyl isothiourea: 11H NMR (500 MHz, chloroform-d) δ 7.34 (dt, J = 14.8, 7.6 Hz, 4H), 7.23 (t, J = 7.3 Hz, 1H), 4.70 - 4.30 (m, 2H), 4.25 - 3.90 (m, 1H), 3.90 - 3.40 (m, 1H), 2.38 (s, 3H), 2.09 - 1.80 (m, 2H), 1.72 (dt, J = 13.4, 4.1 Hz, 2H), 1.62 (dt, J = 13.0, 4.0 Hz, 1H), 1.37 (q, J = 12.5 Hz, 2H), 1.20 (q, J = 12.2 Hz, 3H). 13 13C NMR (126 MHz, chloroform-d) δ 150.83, 141.74, 128.23, 127.35, 126.42, 54.16, 50.70, 34.61, 25.81, 24.92, 14.44. HRMS (ESI): C 15 H 22 N2S [M + H] + Calculated value 263.1577, found 263.1555.

[0091] Characterization of the monocarboimide: 1 1H NMR (500 MHz, chloroform-d) δ 7.38 - 7.24 (m, 5H), 4.35 (s, 2H), 3.15 (dp, J = 8.3, 3.8 Hz, 1H), 1.72 (ddt, J = 56.9, 13.0, 4.0 Hz, 4H), 1.55 - 1.48 (m, 1H), 1.31 - 1.09 (m, 5H). 13 13C NMR (126 MHz, chloroform-d) δ 140.72, 138.70, 128.55, 127.68, 127.43, 55.68, 50.72, 34.68, 25.37, 24.48. C 14 H 18 N2 [M + H] + HRMS (ESI) calculated value 215.1543, found 215.1536.

[0092] Example 2: Synthesis of Ligand 1

Chemical Structure

[0093] 1 H NMR (500 MHz, benzene-d6) δ 7.56 (d, J = 7.5 Hz, 2H), 7.25 (t, J = 7.6 Hz, 2H), 7.11 (d, J = 10.5 Hz, 1H), 4.45 - 4.30 (m, 2H), 3.19 (q, J = 7.1 Hz, 4H), 3.25 - 3.00 (m, 2H), 1.84 - 1.31 (m, 4H), 1.06 (q, J = 13.4, 10.2 Hz, 10H), 0.81 (dq, J = 74.8, 12.2 Hz, 2H). 13 C NMR (126 MHz, benzene-d6) δ 155.66, 143.13, 128.11, 125.95, 53.42, 51.62, 42.74, 34.50, 25.49, 25.31, 24.89, 12.66.

[0094] Example 3: Synthesis of Ligand 2

Chemical Structure

[0095] 1 H NMR (500 MHz, benzene-d6) δ 7.62 (d, J = 7.4 Hz, 2H), 7.27 (t, J = 7.6 Hz, 2H), 7.20 - 7.05 (m, 1H), 4.55 - 4.35 (m, 2H), 3.45 - 3.27 (m, 4H), 3.26 - 3.17 (m, 1H), 3.10 - 2.94 (m, 1H), 1.86 - 1.68 (m, 2H), 1.56 - 1.41 (m, 6H), 1.40 - 0.71 (m, 6H). 13 C NMR (126 MHz, benzene-d6) δ 154.99, 143.50, 128.07, 127.93, 125.90, 53.14, 51.67, 48.12, 34.74, 25.51, 25.30, 25.14.

[0096] Example 4: Synthesis of Ligand 3

Chemical formula

[0097] 1 H NMR (500 MHz, benzene-d6) δ 7.58 (d, J = 7.6 Hz, 2H), 7.24 (p, J = 11.4, 9.4 Hz, 2H), 7.10 (d, J = 16.5 Hz, 1H), (4.88 - 4.67 (m, 2H)*) 4.43 - 4.33 (m, 2H), (4.06 - 3.92 (m, 1H)*) 3.67 - 3.49 (m, 2H), 3.07 (br s, 1H) 3.01 - 2.86 (m, 1H), 2.15 - 1.86 (m, 2H), 1.86 - 1.35 (m, 4H), 1.27 (dd, J = 22.4, 6.7 Hz, 12H), 1.29 - 1.20 (m, 2H), 1.13 - 0.69 (m, 2H), (0.97 - 0.90 (m, 12H)*). 13 C NMR (126 MHz, benzene-d6) δ 155.13, 143.25, 128.10, 127.09, 125.90, (53.52*) 51.95, 49.37, 47.62 (46.99*), 34.65 (33.25*), (26.10*) 25.47 (24.92*), 21.81, 20.98.

[0098] Example 5: Synthesis of Ligand 4

Chemical formula

[0099] The product exists as a complex mixture of isomers and tautomers: (*) showing minor isomers

[0100] 1 H NMR (500 MHz, benzene-d6) δ 7.40 - 7.30 (m, 2H), 7.29 - 6.92 (m, 3H), 6.69 - 6.58 (br s, 2H), 6.25 - 6.14 (br s, 2H), 4.50 - 4.32 (br s, 2H) (4.26 (s, 2H)*), (3.76 (s, 1H)*) 3.61 - 3.43 (br s, 2H), 3.30 - 3.13 (m, 1H), 1.98 - 1.83 (m, 2H), 1.73 - 1.16 (m, 4H), 1.16 - 1.04 (m, 2H), 0.99 - 0.53 (m, 2H). 13 C NMR (126 MHz, benzene-d6) δ 142.41, (128.31*) 128.14, (127.10*) 126.08, 119.74, (110.09*) 109.26, 52.26, 50.02, (35.64*) (34.41*) 32.53, 25.74, 24.73.

[0101] Example 6: Synthesis of Ligand 5

Chemical formula

[0102] The product exists as a complex mixture of isomers and tautomers: (*) indicating minor isomers

[0103] 1 H NMR (400 MHz, benzene - d6) δ 7.26 (d, J = 7.8 Hz, 2H), 7.19 - 6.95 (m, 5H), 6.57 - 6.48 (m, 1H), 4.23 - 4.14 (br s, 2H), 3.70 (br s, 1H), 3.00 - 2.80 (m, 1H), 1.91 (m, 2H), 1.66 - 1.28 (m, 4H), 1.19 - 0.76 (m, 4H). 1313C NMR (101 MHz, benzene-d6) δ 141.65, 141.12, 135.57, 129.09, (128.29*) 128.20 (128.15*), (127.52*), 126.96, 126.27, 117.68, (56.30*) 52.13, 50.25 (45.91*), 35.40, 32.37, 25.69, 24.75 (24.23*).

[0104] Example 7: Synthesis of Ligand 6

Chemical Structure

[0105] The product exists as a complex mixture of isomers and tautomers: (*) indicates minor isomers

[0106] 11H NMR (400 MHz, benzene-d6) δ 8.42 (d, J = 2.6 Hz, 1H), 7.46 (d, J = 7.5 Hz, 2H), 7.38 - 6.95 (m, 3H), 6.22 (d, J = 9.8 Hz, 1H), 6.03 - 5.91 (m, 1H) (5.91 - 5.80 (m, J = 4.6, 2.4 Hz, 1H)*), (4.90 - 4.76 (d, J = 15.2 Hz, 2H)*) 4.64 (s, 2H), 4.58 - 4.38 (m, 1H), (4.18 - 4.10 (m, J = 6.0 Hz, 1H)*), (3.62 - 3.49 (m, 1H)*) 3.48 - 3.32 (m, 1H), 2.08 - 1.83 (m, 2H), 1.83 - 0.74 (m, 8H). 13 13C NMR (101 MHz, benzene-d6) δ 143.90, 142.03, (139.77*) 139.74, 129.61, 128.19, 127.26, 126.31, 107.39 (106.16*), (51.99*) 51.28, 33.81, (25.74*) 25.25, (24.59*) 24.20.

[0107] Example 8: Synthesis of Ligand 7 [Chemical formula] A solution of indole (27.3 mg, 0.2333 mmol, 1.00 eq) in anhydrous deoxygenated THF (2 mL) in a nitrogen-filled glove box at 22 °C was slowly added dropwise neat n-BuLi (5.0 μL, 0.0166 mmol, 0.05 eq, 2.40 M titrated in hexane) via syringe. After stirring for 2 minutes (300 rpm), a solution of carbodiimide (50.0 mg, 0.2333 mmol, 1.00 eq) in THF (0.5 mL) was slowly added dropwise. After stirring for 48 hours, the pale yellow solution was concentrated, suspended in hexane (5 mL), concentrated, and this suspension / concentration process was repeated 3 more times to remove residual THF and pyrrolidine. The resulting opaque mixture was suspended in hexane (5 mL), stirred vigorously for 1 minute (1000 rpm), filtered through a 0.45 μm PTFE filter, rinsed with hexane (3 × 5 mL), and concentrated to give the guanidine as a clear pale yellow amorphous foam (73.6 mg, 0.2221 mmol, 95%). NMR showed the product to be present as a complex mixture of isomers and tautomers.

[0108] The product exists as a complex mixture of isomers and tautomers: (*) showing the minor isomer

[0109] 1 H NMR (500 MHz, benzene-d6) δ 7.62 - 7.52 (m, 1H), 7.44 - 7.30 (br s, 1H), 7.30 - 7.06 (m, 6H), 7.06 - 6.98 (m, 1H), 6.85 - 6.71 (br s, 1H), 6.49 - 6.31 (br s, 1H), 4.35 - 4.07 (br s, 2H), (3.99 - 3.72 (m, 1H)*), 3.72 - 3.38 (m, 1H), 3.10 - 2.73 (m, 1H), 2.09 - 1.74 (m, 2H), 1.74 - 0.61 (m, 8H). 1313C NMR (126 MHz, benzene-d6) δ 141.97, 135.45, 128.14, 127.93, 127.17, 126.17, 125.88, 123.06, 122.91, 121.08, 120.94, 111.32, 103.54, (56.36*) 52.36, 50.32 (46.12*), (35.52*) (34.07*) 32.63, (26.83*) 25.57, 24.73, (24.23*).

[0110] Example 9: Synthesis of Ligand 8

Chemical Structure

[0111] The product exists as a complex mixture of isomers: (*) indicating minor isomers

[0112] 11H NMR (400 MHz, benzene-d6) δ 8.01 - 7.82 (m, 2H), 7.43 - 7.29 (m, 2H), 7.29 - 7.23 (m, 3H), 7.22 - 6.94 (m, 6H), 4.32 - 4.10 (br s, 2H) (4.05 - 3.84 (br s, 2H)*), 3.61 - 3.37 (br s, 1H), 3.07 - 2.82 (br s, 1H), 2.15 - 1.84 (m, 2H), 1.80 - 0.66 (m, 8H). 13 13C NMR (101 MHz, benzene-d6) δ 141.92, 139.10, 127.74, 127.51, 126.94, 126.34, 126.01, 123.20, 120.39, 120.27, 110.55, (56.67*) 52.66, 50.23 (46.15*), (35.48*) 32.65, 25.67, 24.80.

[0113] Example 10: Synthesis of Ligand 9

Chemical Structure

[0114] The product exists as a mixture of complex isomers: only the major isomer chemical shifts are listed.

[0115] 1 H NMR (500 MHz, benzene-d6) δ 8.01 - 7.85 (m, J = 7.7 Hz, 2H), 7.46 - 7.24 (m, 4H), 7.23 - 7.13 (m, 2H), 4.35 - 3.95 (br s, 1H), 3.44 - 3.17 (m, 1H), 3.17 - 2.93 (br s, 1H), 1.18 - 0.74 (m, 12H). 13 C NMR (126 MHz, benzene-d6) δ 139.46, 128.17, 126.28, 122.98, 120.42, 120.27, 110.04, 48.94, 42.96, 25.09, 21.94.

[0116] Example 11: Synthesis of Intermediates for Ligands 10 and 11

Chemical formula

[0117] To a stirred (500 rpm) solution of thiourea (3.285 g, 12.149 mmol, 1.00 eq) in EtOH-CH2Cl2 (100 mL, 1:1) at 23 °C, iodomethane (3.10 mL, 48.596 mmol, 4.00 eq) was added neat via syringe. After 12 h, the clear pale yellow solution was neutralized with a saturated aqueous mixture of NaHCO3 (100 mL), then aqueous NaOH (15 mL, 1 N) was added and the biphasic mixture was stirred vigorously (1000 rpm) for 2 min, poured into a separatory funnel, partitioned, and the organic layer was washed with a saturated aqueous mixture of NaHCO3 (3 × 50 mL), and the residual organic matter was extracted from the aqueous layer with CH2Cl2 (2 × 25 mL), combined, dried over solid Na2SO4, decanted, and concentrated to give methylisothiourea as a pale yellow solid (3.450 g, 12.149 mmol, 100%). This material was used in the next reaction without further purification.

[0118] Characteristic data of crude methylisothiourea: 1 H NMR (500 MHz, chloroform-d) δ 7.36 (d, J = 5.5 Hz, 3H), 7.33 - 7.27 (m, 2H), 7.04 - 6.98 (m, 2H), 6.87 (t, J = 7.5 Hz, 1H), 4.74 - 4.46 (m, 3H), 2.45 - 2.34 (m, 3H), 2.12 (s, 6H). 13 C NMR (126 MHz, chloroform-d) δ 152.80, 146.31, 138.75, 129.32, 128.63, 127.90, 127.55, 127.45, 122.71, 47.09, 18.07, 13.80.

[0119] Characteristic evaluation data of thiourea: 1 H NMR (500 MHz, chloroform-d) δ 7.65 (s, 1H), 7.32 - 7.27 (m, 2H), 7.26 - 7.22 (m, 3H), 7.16 (dd, J = 8.5, 6.5 Hz, 1H), 7.10 (d, J = 7.5 Hz, 2H), 5.72 - 5.54 (m, 1H), 4.85 (d, J = 5.4 Hz, 2H), 2.26 (s, 6H). 1313C NMR (126 MHz, chloroform-d) δ 181.26, 137.63, 137.30, 132.68, 129.04, 128.67, 127.63, 127.51, 49.17, 18.10.

[0120] Example 12: Synthesis of Monocarbodiimide Intermediates to Ligands 10 and 11

Chem.

[0121] 1 1H NMR (400 MHz, chloroform-d) δ 7.39 (d, J = 4.3 Hz, 4H), 7.35 - 7.29 (m, 1H), 7.00 (d, J = 7.9 Hz, 2H), 6.93 (dd, J = 8.5, 6.3 Hz, 1H), 4.55 (s, 2H), 2.26 (s, 6H). 13 13C NMR (101 MHz, chloroform-d) δ 138.04, 136.34, 134.33, 132.32, 128.67, 128.07, 127.62, 127.50, 124.27, 50.57, 18.84.

[0122] Example 13: Synthesis of Ligand 10 [Chemistry] To a solution of carbazole (0.144 g, 0.6094 mmol, 1.00 eq) in anhydrous deoxygenated THF (5 mL) in a nitrogen-filled glove box at 23 °C, n-BuLi (25.0 μL, 0.0609 mmol, 0.10 eq, 2.50 M titrated in hexane) was slowly added dropwise neat via syringe. After stirring for 2 minutes (300 rpm), a solution of carbodiimide (0.102 g, 0.6094 mmol, 1.00 eq) in THF (5 mL) was slowly added dropwise. After stirring for 48 hours, the pale yellow solution was concentrated, suspended in hexane / PhMe (5 mL, 1:1), concentrated, and this suspension / concentration process was repeated 3 more times to remove residual THF, crush insoluble impurities, and the resulting opaque mixture was suspended in hexane / PhMe (5 mL, 1:1), stirred vigorously for 1 minute (1000 rpm), filtered through a 0.45 μm PTFE filter, rinsed with hexane / PhH (3 × 5 mL, 1:1), and concentrated to obtain guanidine as an amorphous pale yellow foam (0.197 g, 0.4875 mmol, 80%). NMR showed the product to be a mixture of isomers and tautomers.

[0123] The product exists as a mixture of isomers: only the major isomer chemical shifts are listed.

[0124] 1 H NMR (500 MHz, benzene-d6) δ 8.05 - 7.79 (m, 4H), 7.40 - 7.24 (m, 2H), 7.24 - 7.09 (m, 4H), 7.09 - 6.69 (m, 6H), 4.64 - 4.31 (br s, 1H), 3.60 - 3.30 (br s, 2H), 2.15 (s, 6H). 13 C NMR (126 MHz, benzene-d6) δ 145.15, 139.53, 128.49, 128.32, 128.14, 127.95, 127.25, 126.30, 125.50, 124.41, 123.39, 123.28, 120.99, 120.13, 112.48, 47.76, 18.55.

[0125] Example 14: Synthesis of Ligand 11

Chemical Structure

[0126] 1 H NMR (500 MHz, benzene-d6) δ 7.07 - 7.03 (m, 2H), 7.02 - 6.97 (m, 2H), 6.97 - 6.92 (m, 1H), 6.90 - 6.81 (m, 3H), 3.81 (d, J = 6.4 Hz, 2H), 3.63 - 3.56 (m, 1H), 3.09 (q, J = 7.1 Hz, 4H), 2.16 (s, 6H), 1.00 (t, J = 7.0 Hz, 6H). 13 C NMR (126 MHz, benzene-d6) δ 152.67, 147.85, 139.70, 129.14, 128.26, 128.14, 126.91, 123.27, 121.47, 48.19, 42.60, 18.50, 12.79.

[0127] Example 15: Synthesis of Ligand 12

Chemical Structure

[0128] The product exists as a mixture of isomers: only the major isomer chemical shifts are listed.

[0129] 1 H NMR (400 MHz, benzene-d6) δ 7.92 (dt, J = 7.8, 1.0 Hz, 2H), 7.37 (d, J = 8.2 Hz, 2H), 7.29 (ddd, J = 8.2, 7.1, 1.2 Hz, 2H), 7.15 (ddd, J = 8.1, 7.1, 1.1 Hz, 2H), 3.63 - 3.44 (br s, 1H), 2.93 - 2.75 (m, 2H), 1.24 (s, 9H), 1.01 - 0.90 (m, 3H). 13 C NMR (101 MHz, benzene-d6) δ 139.49, 139.23, 126.27, 122.94, 120.41, 120.25, 110.31, 50.71, 43.62, 28.21, 17.20.

[0130] Example 16: Synthesis of Intermediates for Ligands 13, 14, and 15 [Chemical formula] To a vigorously stirred (1000 rpm) solution of isothiocyanate (2.11 mL, 19.77 mmol, 2.00 eq) in anhydrous ethyl ether (50 mL) at 23 °C under nitrogen, a solution of cadaverine (1.16 mL, 9.88 mmol, 1.00 eq) was added neat via syringe dropwise over 2 minutes. The clear colorless solution immediately changed to a white heterogeneous mixture, which was stirred vigorously (1000 rpm) for 12 hours. An aliquot was then taken, concentrated, and NMR indicated the product. The white mixture was concentrated to give bisthiourea (3.01 g, 9.88 mmol, 100%). NMR indicated the product. This material was used in the next reaction without further purification.

[0131] 1 H NMR (400 MHz, DMSO-d6) δ 7.16 (br s, 2H), 7.09 (br s, 2H), 4.18 (br s, 2H), 3.33 - 3.24 (m, 4H), 1.43 (p, J = 7.3 Hz, 4H), 1.21 (tt, J = 8.2, 6.0 Hz, 2H), 1.05 (dd, J = 6.5, 0.9 Hz, 12H). 13 C NMR (101 MHz, DMSO-d6) δ 181.25, 45.21, 43.72, 29.03, 24.29, 22.79. HRMS (ESI): C 13 H 28 N4S2 [M + H] + Calculated value for 305.2255, found 305.2285.

[0132] Example 17: Synthesis of Intermediates to Ligands 13, 14, and 15 [Chemical formula] To a mixture of bisthiourea (850.0 mg, 2.79 mmol, 1.00 eq) in CH2Cl2 and ethanol (40 mL, 1:1) at 23 °C was added iodomethane (0.70 mL, 11.16 mmol, 4.00 eq). The white mixture was stirred for 12 h (300 rpm), whereupon a clear colorless homogeneous solution was neutralized with an aqueous saturated mixture of NaHCO3 (60 mL) and CH2Cl2 (20 mL), the white mixture was stirred vigorously for 5 min (1000 rpm), and then an aqueous solution of NaOH (10 mL, 1 N) was added. The colorless transparent biphasic mixture was poured into a separatory funnel, partitioned, and the organic was washed with a saturated aqueous mixture of NaHCO3 (3 × 20 mL). The residual organic was back-extracted from the aqueous with CH2Cl2 (3 × 10 mL), combined, washed with brine (20 mL), dried over solid Na2SO4, decanted, and concentrated to give isothiourea as an off-white solid (866.7 mg, 2.61 mmol, 94%). The solid NMR showed the product. This material was used in the next reaction without further purification.

[0133] 1 1H NMR (400 MHz, chloroform-d) δ 3.82 (br s, 3H), 3.23 (br s, 5H), 2.32 (br s, 6H), 1.57 (p, J = 7.3 Hz, 4H), 1.47 - 1.34 (m, 2H), 1.11 (d, J = 6.3 Hz, 12H). 13 13C NMR (126 MHz, chloroform-d) δ 149.84, 46.11, 30.63, 24.95, 23.78, 23.59, 14.35. HRMS (ESI): C 15 H 32 N4S2 [M + H] + calcd for 333.2630, found 333.2634.

[0134] Example 18: Synthesis of Intermediates to Ligands 13, 14, and 15

Chemical Structure

[0135] 1 1H NMR (500 MHz, chloroform-d) δ 3.56 (hept, J = 6.4 Hz, 2H), 3.22 (t, J = 6.8 Hz, 4H), 1.68 - 1.51 (m, 4H), 1.51 - 1.37 (m, 2H), 1.22 (d, J = 6.4 Hz, 12H). 13 13C NMR (126 MHz, chloroform-d) δ 140.12, 48.91, 46.65, 30.90, 24.59, 24.11. HRMS (ESI): C 13 H 24 N4 [M + H] + Calculated value 237.2035, found value 237.2027.

[0136] Example 19: Synthesis of Ligand 13

Chemical Structure

[0137] The product exists as a complex mixture of isomers / tautomers: only the major isomers are listed

[0138] 1 H NMR (500 MHz, benzene-d6) δ 3.34 (tdd, J = 12.5, 6.2, 2.3 Hz, 4H), 3.11 (dq, J = 14.0, 7.1, 6.3 Hz, 8H), 2.92 (dd, J = 15.4, 9.0 Hz, 2H), 2.66 - 2.55 (m, 2H), 1.87 (p, J = 7.0 Hz, 4H), 1.41 - 1.33 (m, 2H), 1.23 (d, J = 6.1 Hz, 12H), 1.05 (tt, J = 7.0, 2.3 Hz, 12H). 13 C NMR (126 MHz, benzene-d6) δ 154.50, 47.90, 45.87, 42.72, 32.55, 25.22, 23.49, 12.65. HRMS (ESI): C 21 H 46 N6 [M + H] + calculated value 383.3857, found value 383.3855.

[0139] Example 20: Synthesis of Ligand 14

Chemical Structure

[0140] The product exists as a complex mixture of isomers / tautomers: only the major isomers are listed

[0141] 1 H NMR (500 MHz, benzene-d6) δ 3.43 - 3.34 (m, 4H), 3.31 (d, J = 6.5 Hz, 8H), 2.94 (q, J = 6.9 Hz, 2H), 1.95 (p, J = 7.1 Hz, 4H), 1.84 (q, J = 7.6 Hz, 4H), 1.75 (t, J = 8.0 Hz, 4H), 1.57 - 1.50 (m, 2H), 1.50 - 1.39 (m, 12H). 13 C NMR (126 MHz, benzene-d6) δ 154.08, 48.17, 47.98, 45.69, 32.95, 32.43, 25.72, 25.08, 23.77. HRMS (ESI): C 21 H 42 N6[M + H] + calcd for 379.3544, found 379.3556.

[0142] Example 21: Synthesis of Ligand 15

Chemical Structure

[0143] The product exists as a complex mixture of isomers: (*) showing minor isomers

[0144] 1 H NMR (500 MHz, benzene-d6) δ 8.00 - 7.87 (m, 4H), 7.44 - 7.23 (m, 8H), 7.17 (d, J = 8.3 Hz, 4H), 4.33 - 3.92 (m, 2H), 3.39 - 3.05 (m, 4H), 3.04 - 2.75 (m, 2H), 1.55 - 1.16 (m, 4H), 1.16 - 1.06 (m, 2H), 1.07 - 0.85 (m, 12H). 13 C NMR (126 MHz, benzene-d6) δ 141.00, (139.40*)139.18, 128.19, 126.23, 123.01, (120.39*)120.36(120.22*), 110.48, 48.76, 42.95(41.95*), 31.59, 25.23, 22.05.

[0145] Example 22: Synthesis of Intermediates for Ligands 16 - 18 [Chemical Formula] To a vigorously stirred (1000 rpm) solution of 2,6 - dimethylphenyl isothiocyanate (1.85 mL, 12.252 mmol, 2.00 eq) in Et2O (65 mL), cadaverine (0.72 mL, 6.126 mmol, 1.00 eq) was slowly added dropwise over 1 minute. The clear colorless solution was stirred vigorously at 23 °C for 12 hours, then the white heterogeneous mixture was placed in an ice - water bath for 1 hour, filtered under suction at low temperature, and the white filtered solid was washed with cold Et2O (3 × 20 mL) and dried in vacuo to give bisthiourea as a white powder (2.331 g, 5.438 mmol, 89%). NMR indicated the product.

[0146] 1 1H NMR (500 MHz, acetone - d6) δ 8.45 - 8.21 (br s, 1H), 7.19 - 7.04 (m, 6H), 6.64 - 6.27 (br s, 1H), 3.62 - 3.48 (m, 4H), 2.22 (s, 12H), 1.64 - 1.47 (br s, 4H), 1.36 - 1.16 (br s, 2H). 13 13C NMR (126 MHz, acetone - d6) δ 181.44, 137.22, 134.45, 128.35, 127.98, 44.44, 28.91, 23.82, 17.40.

[0147] Example 23: Synthesis of Intermediates for Ligands 16 - 18 [Chemical Formula] To a solution of bisthiourea (2.331 g, 5.438 mmol, 1.00 eq) in EtOH-CH2Cl2 (100 mL, 1:1) at 23 °C was added iodomethane (3.087 g, 1.40 mL, 21.752 mmol, 4.00 eq). After stirring (500 rpm) for 12 h, the clear pale yellow solution was neutralized with a saturated aqueous mixture of NaHCO3 (100 mL), then aqueous NaOH (15 mL, 1 N) was added dropwise, and the white two-phase heterogeneous mixture was stirred vigorously (1000 rpm) for 2 min, poured into a separatory funnel, partitioned, the organic layer was washed with a saturated aqueous mixture of NaHCO3 (3 × 50 mL), the residual organic matter was extracted from the aqueous layer with CH2Cl2 (2 × 25 mL), combined, washed with brine (1 × 50 mL), dried over solid Na2SO4, decanted, and concentrated to give bismethylisothiourea (2.483 g, 5.438 mmol, 100%). NMR showed the product as a mixture of isomers / tautomers along with a small amount of impurities. Without further purification, the crude material was used in the subsequent reaction.

[0148] 1 H NMR (500 MHz, chloroform-d) δ 7.00 (d, J = 7.5 Hz, 4H), 6.86 (t, J = 7.5 Hz, 2H), 4.40 - 4.13 (br s, 2H), 3.49 - 3.20 (br s, 4H), 2.51 - 2.27 (br s, 6H), 2.10 (s, 12H), 1.71 - 1.50 (br s, 4H), 1.46 - 1.25 (br s, 2H). 13 C NMR (126 MHz, chloroform-d) δ 152.52, 146.60, 129.25, 127.89, 122.52, 43.01, 29.90, 24.07, 18.01, 13.66.

[0149] Example 24: Synthesis of Intermediates for Ligands 16 - 18

Chemical Structure

[0150] 1 1H NMR (500 MHz, chloroform-d) δ 7.01 (dq, J = 7.3, 0.7 Hz, 4H), 6.93 (dd, J = 8.2, 6.8 Hz, 2H), 3.40 (t, J = 6.8 Hz, 4H), 2.34 (s, 12H), 1.74 - 1.66 (m, 4H), 1.59 - 1.51 (m, 2H). 13 13C NMR (126 MHz, chloroform-d) δ 136.80, 133.75, 132.19, 128.12, 124.11, 46.67, 30.72, 24.27, 18.93. HRMS (ESI): C 23 H 28 N4 [M + H] + calculated value 361.2314, found 361.2299.

[0151] Example 25: Synthesis of Ligand 16

Chemical Structure

[0152] The product exists as a complex mixture of isomers: (*) showing minor isomers

[0153] 1 H NMR (500 MHz, benzene-d6) δ (8.04 - 7.88 (m, 4H)*) 7.88 - 7.78 (m, 4H), 7.40 - 7.24 (m, 4H), 7.18 - 7.08 (m, 4H), 7.09 - 6.97 (m, 6H), 6.97 - 6.85 (m, 4H), 4.33 - 4.07 (m, 2H), 4.04 - 3.76 (br s, 4H), 2.35 - 2.15 (br s, 12H), 2.15 - 1.97 (m, 4H), 1.30 - 1.15 (m, 2H). 1313C NMR (126 MHz, benzene-d6) δ 145.44, 139.70, 128.59, 128.32, (128.17*), 127.23, 126.30, (125.49*), 124.20 (123.16*), 120.93, (120.27*) 120.22, 112.17 (110.39*), 43.22, 30.44, 25.24, 18.67.

[0154] Example 26: Synthesis of Pro-Catalyst 1 [Chemical formula] A solution of guanidine (15.0 mg, 0.0512 mmol, 1.00 eq) in C6D6 (0.60 mL) was added dropwise to a clear gold-orange solution of ZrBn4 (23.8 mg, 0.0512 mmol, 1.00 eq) in nitrogen-filled glove box in anhydrous deoxygenated C6D6 (1.0 mL) at 23 °C. Here, the bright gold solution was vigorously stirred (1000 rpm) for 1 hour, aliquots were taken, NMR showed complete conversion of the starting ligand, the solution was concentrated, suspended in anhydrous deoxygenated hexane (3 mL), concentrated, and the suspension / concentration process was repeated two more times to remove residual C6D6 and PhMe. The resulting mixture was suspended in hexane (2 mL), PhMe (2 mL) was added, the mixture was vigorously stirred (1000 rpm) for 2 minutes, filtered through a 0.20 μm PTFE filter, rinsed with hexane / PhMe (3 × 3 mL, 1:1), and the filtrate was concentrated to obtain the zirconium complex as a bright yellow foam (31.3 mg, 0.0481 mmol, 94%). NMR showed the product.

[0155] 11H NMR (400 MHz, benzene-d6) δ 7.21 - 7.17 (m, 2H), 7.15 - 7.09 (m, 3H), 7.08 - 7.03 (m, 6H), 6.89 - 6.83 (m, 3H), 6.80 - 6.75 (m, 6H), 4.13 - 4.04 (m, 2H), 3.14 - 3.00 (m, 1H), 2.58 (q, J = 7.1 Hz, 4H), 2.30 (s, 6H), 1.71 (dt, J = 30.7, 12.2 Hz, 6H), 1.53 - 1.46 (m, 1H), 1.20 - 0.99 (m, 3H), 0.58 (t, J = 7.0 Hz, 6H). 13 13C NMR (101 MHz, benzene-d6) δ 175.90, 143.85, 141.97, 130.53, 129.21, 128.36, 126.27, 125.76, 122.28, 72.74, 58.53, 51.12, 41.12, 34.64, 26.51, 25.54, 12.61.

[0156] Example 27: Synthesis of Pro-catalyst 3

Chemical Structure

[0157] 11H NMR (400 MHz, benzene-d6) δ 7.31 - 7.28 (m, 2H), 7.20 - 7.14 (m, 2H), 7.01 (t, J = 7.4 Hz, 1H), 4.52 (s, 2H), 3.03 (tt, J = 11.4, 3.8 Hz, 1H), 2.70 (q, J = 7.1 Hz, 4H), 1.89 - 1.78 (m, 2H), 1.74 - 1.64 (m, 2H), 1.63 - 1.43 (m, 4H), 1.09 (d, J = 8.2 Hz, 2H), 1.01 (s, 6H), 0.59 (t, J = 7.1 Hz, 6H), 0.28 (s, 27H). 13 13C NMR (101 MHz, benzene-d6) δ 174.64, 141.89, 128.26, 126.43, 126.22, 65.84, 56.20, 51.93, 41.75, 35.85, 26.01, 25.63, 12.58, 3.05.

[0158] Example 28: Synthesis of Procatalyst 4

Chemical Structure

[0159] 11H NMR (500 MHz, benzene-d6) δ 7.30 (d, J = 7.5 Hz, 2H), 7.18 (t, J = 7.5 Hz, 2H), 7.02 (t, J = 7.4 Hz, 1H), 4.61 (s, 2H), 3.22 (d, J = 12.1 Hz, 1H), 2.70 (q, J = 7.1 Hz, 4H), 1.82 (m, 2H), 1.68 (m, 2H), 1.60 (m, 2H), 1.49 (m, 1H), 1.09 (m, 3H), 0.58 (t, J = 7.1 Hz, 6H), 0.48 (s, 6H), 0.31 (s, 27H). 13 13C NMR (126 MHz, benzene-d6) δ 173.68, 141.70, 128.28, 126.50, 126.26, 72.71, 55.92, 51.41, 41.70, 35.71, 26.05, 25.64, 12.59, 3.44.

[0160] Example 29: Synthesis of Pro-catalyst 7

Chemical formula

[0161] 11H NMR (400 MHz, benzene-d6) δ 7.41 (d, J = 7.5 Hz, 4H), 7.14 - 7.07 (m, 4H), 7.01 (t, J = 7.3 Hz, 2H), 4.67 (s, 4H), 3.22 - 3.08 (m, 2H), 2.85 (q, J = 7.0 Hz, 8H), 1.91 - 1.48 (m, 14H), 1.27 - 1.10 (m, 6H), 0.89 (s, 4H), 0.72 (t, J = 7.0 Hz, 12H), 0.38 (s, 18H). 13 13C NMR (101 MHz, benzene-d6) δ 176.24, 142.93, 128.26, 126.65, 125.94, 56.99, 56.81, 52.46, 41.40, 35.69, 26.44, 12.85, 3.73.

[0162] Example 30: Synthesis of Pro-Catalyst 13

Chemical formula

[0163] Characterization at 23 °C: 11H NMR (500 MHz, benzene-d6) δ 7.22 - 7.05 (m, 11H), 6.92 - 6.87 (m, 3H), 6.82 - 6.78 (m, 6H), 4.33 (s, 2H), 3.40 - 3.32 (m, 1H), 3.28 (hept, J = 6.9 Hz, 2H), 2.30 (s, 6H), 1.75 - 1.62 (m, 4H), 1.18 - 0.97 (m, 6H), 0.94 (br s, 12H).

[0164] Property evaluation at 50 °C: 1 1H NMR (500 MHz, benzene-d6) δ 7.16 (dt, J = 15.2, 7.5 Hz, 5H), 7.08 (t, J = 7.6 Hz, 6H), 6.88 (t, J = 7.4 Hz, 3H), 6.82 - 6.78 (m, 6H), 4.36 (s, 2H), 3.37 (dq, J = 14.2, 6.9, 6.3 Hz, 1H), 3.29 (h, J = 6.8 Hz, 2H), 2.29 (s, 6H), 1.72 - 1.62 (m, 3H), 1.55 - 1.47 (m, 1H), 1.20 - 0.99 (m, 6H), 0.94 (d, J = 6.8 Hz, 12H). 13 13C NMR (126 MHz, benzene-d6) δ 178.01, 144.00, 141.64, 129.14, 128.27, 127.86, 126.26, 126.08, 122.35, 74.48, 57.39, 51.00, 49.79, 34.88, 26.29, 25.55, 22.91.

[0165] Example 31: Synthesis of Procatalyst 15

Chemical Structure

[0166] Chemical shifts are listed by VT-NMR at 70 °C.

[0167] 1 H NMR (500 MHz, benzene-d6) δ 7.31 (d, J = 7.6 Hz, 4H), 7.26 (d, J = 7.5 Hz, 4H), 7.17 (t, J = 7.6 Hz, 4H), 7.08 (t, J = 7.6 Hz, 4H), 6.99 (dq, J = 15.5, 8.5 Hz, 2H), 6.84 (t, J = 7.3 Hz, 2H), 4.56 (s, 4H), 3.45 (p, J = 6.9 Hz, 4H), 3.40 - 3.32 (m, 2H), 2.57 (s, 4H), 1.83 - 1.42 (m, 10H), 1.29 - 1.12 (m, 10H), 1.06 (d, J = 7.0 Hz, 24H). 13 C NMR (126 MHz, benzene-d6) δ 179.02, 149.03, 142.43, 128.79, 128.04, 128.01, 126.42, 125.74, 120.23, 56.19, 52.10, 50.07, 35.48, 26.36, 25.71, 23.51.

[0168] Example 32: Synthesis of Pre-Catalyst 17

Chemical formula

[0169] 1 H NMR (400 MHz, benzene-d6) δ 7.51 - 7.45 (m, 4H), 7.18 - 7.12 (m, 4H), 7.05 - 7.00 (m, 2H), 4.64 (s, 4H), 3.46 - 3.32 (m, 6H), 1.87 (d, J = 12.1 Hz, 4H), 1.81 - 1.67 (m, 6H), 1.60 - 1.53 (m, 2H), 1.34 - 1.07 (m, 8H), 1.02 (d, J = 6.8 Hz, 24H), 0.81 (s, 6H). 1313C NMR (101 MHz, benzene-d6) δ 176.77, 142.99, 128.01, 126.59, 125.87, 55.98, 51.22, 49.46, 43.65, 35.84, 26.28, 25.93, 23.06.

[0170] Example 33: Synthesis of Procatalyst 35 [Chemical formula] A solution of the substrate (10.0 mg, 0.0302 mmol, 1.00 eq) in C6D6 (0.20 mL) was added dropwise to a solution of tetrakis-trimethylsilylmethyldizirconium (13.3 mg, 0.0302 mmol, 1.00 eq) in C6D6 (0.26 mL) in a nitrogen-filled glove box at 23 °C. After stirring (300 rpm) for 1.5 hours, an aliquot was taken out, and NMR showed complete conversion of the starting guanidine to the desired zirconium complex. The clear pale yellow solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and this suspension / concentration process was repeated three more times to remove residual C6D6. The resulting pale yellow amorphous foam was suspended in pentane (3 mL), stirred vigorously (1000 rpm) for 1 minute, filtered through a 0.45 μm PTFE filter, rinsed with pentane (3 × 3 mL), and the filtrate was concentrated to obtain the zirconium complex as a pale yellow amorphous foam (17.0 mg, 0.0248 mmol, 82%). NMR showed the product.

[0171] 11H NMR (500 MHz, benzene-d6) δ 7.54 (d, J = 8.3 Hz, 1H), 7.49 (d, J = 7.9 Hz, 1H), 7.18 (t, J = 7.7 Hz, 1H), 7.07 (t, J = 7.5 Hz, 1H), 7.02 (t, J = 7.5 Hz, 2H), 6.94 (d, J = 7.9 Hz, 3H), 6.77 (d, J = 3.3 Hz, 1H), 6.38 (d, J = 3.3 Hz, 1H), 4.26 (d, J = 15.1 Hz, 1H), 4.16 (d, J = 15.1 Hz, 1H), 3.07 - 2.94 (m, 1H), 1.71 - 1.60 (m, 2H), 1.49 - 1.37 (m, 3H), 1.37 - 1.28 (m, 1H), 1.22 (d, J = 26.3 Hz, 6H), 0.84 (q, J = 12.5 Hz, 1H), 0.68 (dt, J = 46.7, 13.5 Hz, 1H), 0.29 (s, 27H). 13 13C NMR (126 MHz, benzene-d6) δ 165.30, 140.35, 134.89, 128.35, 128.27, 127.10, 126.80, 124.93, 123.67, 121.63, 121.39, 111.07, 105.25, 70.93, 56.08, 51.20, 35.97, 35.62, 25.15, 25.11, 25.04, 2.91.

[0172] Example 34: Synthesis of Pro-catalyst 36

Chemical Structure

[0173] 1 H NMR (400 MHz, benzene-d6) δ 7.52 (dq, J = 8.3, 0.9 Hz, 1H), 7.48 - 7.45 (m, 1H), 7.18 - 7.13 (m, 1H), 7.05 (ddd, J = 8.1, 7.2, 1.0 Hz, 2H), 7.02 - 6.97 (m, 2H), 6.93 - 6.88 (m, 2H), 6.74 (dd, J = 3.3, 0.4 Hz, 1H), 6.36 (dd, J = 3.4, 0.9 Hz, 1H), 4.31 (d, J = 15.0 Hz, 1H), 4.24 (d, J = 15.0 Hz, 1H), 3.17 (tt, J = 11.4, 4.0 Hz, 1H), 1.63 (m, 2H), 1.51 - 1.12 (m, 8H), 0.60 (s, 6H), 0.28 (s, 27H). 13 C NMR (101 MHz, benzene-d6) δ 164.78, 140.04, 134.87, 128.42, 128.25, 127.49, 126.84, 124.89, 123.70, 121.70, 121.40, 111.11, 105.47, 77.15, 55.88, 50.85, 35.79, 35.43, 25.11, 25.03, 3.27.

[0174] Example 35: Synthesis of Pro-catalyst 37 [Chemical formula] A solution of guanidine (20.0 mg, 0.0524 mmol, 1.00 eq) in C6D6 (0.80 mL) was added dropwise to a clear tangerine-colored solution of ZrBn4 (23.9 mg, 0.0524 mmol, 1.00 eq) in nitrogen-filled glove box in anhydrous deoxygenated C6D6 (1.0 mL) at 23 °C. Here, the bright golden solution was vigorously stirred (1000 rpm) for 1 hour, aliquots were taken out, NMR showed complete conversion of the starting ligand, the solution was concentrated, suspended in anhydrous deoxygenated hexane (3 mL), concentrated, and the suspension / concentration process was repeated 2 more times to remove residual C6D6 and PhMe. The resulting mixture was suspended in hexane (2 mL), PhMe (2 mL) was added, the mixture was vigorously stirred (1000 rpm) for 2 minutes, filtered through a 0.20 μm PTFE filter, rinsed with hexane / PhMe (3×3 mL, 1:1), and the filtrate was concentrated to obtain the zirconium complex as a pale amber foam (36.1 mg, 0.0485 mmol, 92%). NMR showed the product.

[0175] 1 H NMR (400 MHz, benzene-d6) δ 7.79 - 7.75 (m, 2H), 7.24 (ddd, J = 8.3, 7.1, 1.3 Hz, 2H), 7.17 - 7.08 (m, 8H), 7.03 - 6.88 (m, 6H), 6.87 - 6.82 (m, 4H), 6.80 - 6.72 (m, 4H), 6.62 - 6.57 (m, 2H), 4.09 (s, 2H), 2.83 (tt, J = 11.6, 4.1 Hz, 1H), 2.42 (s, 6H), 1.54 - 1.45 (m, 1H), 1.41 - 1.27 (m, 3H), 1.22 (d, J = 13.5 Hz, 2H), 1.02 (d, J = 13.2 Hz, 1H), 0.66 (qt, J = 13.0, 3.5 Hz, 1H), 0.41 (dddd, J = 16.8, 13.1, 8.3, 3.6 Hz, 2H). 1313C NMR (101 MHz, benzene-d6) δ 165.27, 142.64, 139.77, 138.29, 130.53, 129.66, 128.30, 128.28, 128.15, 127.12, 126.57, 126.38, 124.09, 123.29, 123.17, 121.02, 120.44, 110.69, 76.72, 57.47, 50.73, 34.69, 25.19, 24.93.

[0176] Example 36: Synthesis of Pro-Catalyst 38 [Chemical formula] A solution of guanidine (20.0 mg, 0.0524 mmol, 1.00 eq) in C6D6 (0.80 mL) was added dropwise to a clear golden solution of HfBn4 (28.5 mg, 0.0524 mmol, 1.00 eq) in nitrogen-filled glove box in anhydrous deoxygenated C6D6 (1.0 mL) at 23 °C. Here, the bright golden solution was vigorously stirred (1000 rpm) for 1 hour, aliquots were taken, NMR showed complete conversion of the starting ligand, the solution was concentrated, suspended in anhydrous deoxygenated hexane (3 mL), concentrated, and the suspension / concentration process was repeated two more times to remove residual C6D6 and PhMe. The resulting mixture was suspended in hexane (2 mL), PhMe (2 mL) was added, the mixture was vigorously stirred (1000 rpm) for 2 minutes, filtered through a 0.20 μm PTFE filter, rinsed with hexane / PhMe (3 × 3 mL, 1:1), and the filtrate was concentrated to obtain the hafnium complex as a pale amber foam (40.3 mg, 0.0484 mmol, 92%). NMR showed the product.

[0177] 11H NMR (400 MHz, benzene-d6) δ 7.75 (ddd, J = 7.8, 1.3, 0.7 Hz, 2H), 7.23 - 7.17 (m, 8H), 7.00 (dt, J = 7.6, 1.2 Hz, 6H), 6.95 (dddd, J = 8.7, 3.5, 2.5, 1.2 Hz, 6H), 6.76 (d, J = 2.0 Hz, 1H), 6.75 - 6.73 (m, 2H), 6.54 - 6.46 (m, 3H), 4.07 (s, 2H), 2.99 (tt, J = 11.5, 4.2 Hz, 1H), 2.30 (s, 6H), 1.45 - 1.14 (m, 5H), 1.02 (d, J = 13.1 Hz, 1H), 0.68 (qt, J = 13.2, 3.7 Hz, 2H), 0.38 (tdd, J = 13.1, 9.4, 3.6 Hz, 2H). 13 13C NMR (101 MHz, benzene-d6) δ 164.21, 143.05, 139.33, 138.06, 128.99, 128.54, 128.22, 128.15, 128.03, 127.29, 126.65, 126.55, 123.45, 122.94, 121.22, 120.44, 110.78, 86.80, 56.88, 50.48, 34.52, 25.05, 24.81.

[0178] Example 37: Synthesis of Pro-Catalyst 41

Chemical Structure

[0179] 1 H NMR (500 MHz, benzene-d6) δ 7.82 (d, J = 7.8 Hz, 2H), 7.53 (d, J = 8.2 Hz, 2H), 7.28 (t, J = 7.7 Hz, 2H), 7.13 - 7.08 (m, 2H), 6.86 - 6.82 (m, 2H), 6.80 - 6.76 (m, 3H), 4.21 (s, 2H), 3.10 - 3.01 (m, 1H), 1.75 - 1.68 (m, 2H), 1.48 (qd, J = 11.8, 11.1, 6.9 Hz, 2H), 1.30 (s, 6H), 1.30 - 1.25 (m, 1H), 1.12 - 1.04 (m, 1H), 0.90 - 0.73 (m, 2H), 0.57 - 0.45 (m, 2H), 0.34 (s, 27H). 13 C NMR (126 MHz, benzene-d6) δ 164.76, 140.05, 138.27, 128.17, 128.06, 126.72, 126.65, 123.61, 121.30, 120.64, 110.60, 71.46, 56.20, 51.62, 35.89, 25.04, 24.96, 2.96.

[0180] Example 38: Synthesis of Pro-Catalyst 43 [Chemical] To a solution of tetrakis-trimethylsilylmethyldizirconium (14.4 mg, 0.0328 mmol, 1.00 eq) in C6D6 (0.29 mL) in a nitrogen-filled glove box at 23 °C was added a solution of guanidine (25.0 mg, 0.0655 mmol, 2.00 eq) in C6D6 (0.50 mL). The clear pale yellow solution was stirred for 1 hour (300 rpm), at which point an aliquot was taken and NMR showed complete conversion to the desired complex. The solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and this suspension / concentration process was repeated three more times. The resulting pale yellow foam was suspended in pentane (3 mL), the resulting pale yellow mixture was stirred vigorously for 1 minute (1000 rpm), filtered through a 0.45 μm PTFE filter, rinsed with pentane (3 × 3 mL), and the filtrate was concentrated to give the zirconium complex as an off-white amorphous foam (29.4 mg, 0.0286 mmol, 87%). NMR showed the product.

[0181] 1 H NMR (500 MHz, benzene-d6) δ 7.85 (d, J = 7.8 Hz, 4H), 7.68 (d, J = 8.2 Hz, 4H), 7.30 (t, J = 7.8 Hz, 4H), 7.12 (t, J = 5.2 Hz, 4H), 6.87 (d, J = 7.4 Hz, 4H), 6.80 (t, J = 7.5 Hz, 4H), 6.73 (t, J = 7.3 Hz, 2H), 4.57 (s, 4H), 3.18 - 3.05 (m, 2H), 1.91 - 1.83 (m, 4H), 1.67 - 1.55 (m, 4H), 1.45 (s, 4H), 1.42 - 1.34 (m, 4H), 1.25 - 1.12 (m, 2H), 1.01 - 0.87 (m, 2H), 0.70 - 0.54 (m, 4H), 0.49 (s, 18H). 13 C NMR (126 MHz, benzene-d6) δ 165.34, 140.20, 138.60, 128.14, 128.05, 126.41, 126.36, 123.56, 121.09, 120.57, 111.12, 68.13, 56.49, 51.91, 35.88, 24.96, 22.32, 13.87, 3.72.

[0182] Example 39: Synthesis of the precatalyst 44

Chem.

[0183] 1 H NMR (500 MHz, benzene-d6) δ 7.84 (d, J = 7.8 Hz, 4H), 7.67 (d, J = 8.2 Hz, 4H), 7.29 (t, J = 7.7 Hz, 4H), 7.12 (d, J = 7.2 Hz, 4H), 6.86 (d, J = 7.5 Hz, 4H), 6.79 (t, J = 7.5 Hz, 4H), 6.74 (d, J = 7.3 Hz, 2H), 4.62 (s, 4H), 3.26 (t, J = 11.9 Hz, 2H), 1.92 - 1.82 (m, 4H), 1.68 - 1.58 (m, 4H), 1.42 - 1.33 (m, 4H), 1.25 - 1.12 (m, 2H), 1.01 - 0.87 (m, 2H), 0.85 (s, 4H), 0.67 - 0.54 (m, 4H), 0.51 (s, 18H). 1313C NMR (126 MHz, benzene-d6) δ 164.40, 140.01, 138.67, 128.14, 126.46, 126.34, 123.58, 121.14, 120.57, 111.17, 68.15, 56.34, 51.70, 35.86, 24.96, 4.20.

[0184] Example 40: Synthesis of Procatalyst 49 [Chemical formula] A solution of guanidine (20.0 mg, 0.0682 mmol, 1.00 eq) in C6D6 (0.80 mL) was added dropwise to a clear colorless solution of Zr(CH2SiMe3)4 (30.0 mg, 0.0682 mmol, 1.00 eq) in nitrogen-filled glove box in anhydrous deoxygenated C6D6 (1.0 mL) at 23 °C. Here, the bright golden solution was vigorously stirred (1000 rpm) for 1 hour, aliquots were taken, NMR showed complete conversion of the starting ligand, the solution was concentrated, suspended in anhydrous deoxygenated pentane (3 mL), concentrated, and the suspension / concentration process was repeated 2 more times to remove residual C6D6 and Me4Si. The resulting mixture was suspended in pentane (3 mL), filtered through a 0.20 μm PTFE filter, rinsed with pentane (3 × 3 mL), and the filtrate was concentrated to obtain the zirconium complex as a bright yellow foam (35.2 mg, 0.0545 mmol, 80%). NMR showed the product.

[0185] 1 1H NMR (400 MHz, benzene-d6) δ 7.88 (dt, J = 7.8, 1.1 Hz, 2H), 7.58 (dt, J = 8.2, 0.9 Hz, 2H), 7.32 (ddd, J = 8.3, 5.8, 1.2 Hz, 2H), 7.17 - 7.11 (m, 2H), 3.10 (q, J = 6.5 Hz, 2H), 1.32 (s, 6H), 0.90 (d, J = 6.5 Hz, 12H), 0.35 (s, 27H). 13 13C NMR (101 MHz, benzene-d6) δ 163.21, 138.78, 126.76, 123.39, 121.18, 120.79, 109.98, 71.04, 48.01, 24.89, 2.99.

[0186] Example 41: Synthesis of Pro-Catalyst 50

Chem.

[0187] 1 H NMR (500 MHz, benzene-d6) δ 7.88 (d, J = 7.7 Hz, 2H), 7.59 (d, J = 8.1 Hz, 2H), 7.37 - 7.30 (m, 2H), 7.14 (dd, J = 15.5, 7.8 Hz, 2H), 3.31 (p, J = 6.5 Hz, 2H), 0.90 (d, J = 6.4 Hz, 12H), 0.72 (s, 6H), 0.37 (s, 27H). 13 C NMR (126 MHz, benzene-d6) δ 163.07, 138.81, 126.79, 123.49, 121.29, 120.81, 110.03, 77.17, 47.83, 24.78, 3.39.

[0188] Example 42: Synthesis of Pro-Catalyst 55

Chem.

[0189] 1 H NMR (500 MHz, benzene-d6) δ 7.34 - 7.30 (m, 2H), 7.18 - 7.13 (m, 2H), 7.09 - 7.04 (m, 5H), 7.04 - 6.99 (m, 2H), 6.98 - 6.95 (m, 2H), 6.90 - 6.86 (m, 4H), 6.68 - 6.63 (m, 6H), 4.02 (s, 2H), 2.58 (q, J = 7.1 Hz, 4H), 2.31 (s, 6H), 2.11 (s, 6H), 0.39 (t, J = 7.1 Hz, 6H). 13 C NMR (126 MHz, benzene-d6) δ 174.22, 146.19, 143.48, 141.85, 132.84, 129.39, 128.82, 128.43, 128.32, 128.17, 125.80, 124.10, 122.35, 72.59, 50.69, 39.72, 19.48, 11.98.

[0190] Example 43: Synthesis of Pre-catalyst 57

Chemical formula

[0191] 1 1H NMR (500 MHz, benzene-d6) δ 7.33 - 7.29 (m, 2H), 7.18 - 7.13 (m, 2H), 7.11 - 7.08 (m, 4H), 6.95 (dq, J = 7.3, 0.6 Hz, 3H), 6.90 - 6.82 (m, 6H), 6.75 - 6.70 (m, 6H), 4.13 (s, 2H), 2.53 (q, J = 7.1 Hz, 4H), 2.30 (s, 6H), 1.91 (s, 6H), 0.35 (t, J = 7.1 Hz, 6H). 13 13C NMR (126 MHz, benzene-d6) δ 172.41, 145.18, 143.74, 141.53, 133.14, 128.94, 128.71, 128.45, 128.17, 126.47, 125.78, 124.54, 122.38, 80.43, 50.24, 39.89, 19.31, 12.00.

[0192] Example 44: Synthesis of Ligand 17

Chemical Structure

[0193] 1 1H NMR (400 MHz, benzene-d6) δ 7.07 (d, J = 7.5 Hz, 4H), 6.88 (t, J = 7.4 Hz, 2H), 3.13 (q, J = 7.0 Hz, 10H), 2.59 - 2.47 (m, 4H), 2.21 (s, 12H), 1.06 (t, J = 7.1 Hz, 12H), 0.76 (p, J = 7.5 Hz, 4H), 0.55 (p, J = 7.7, 7.2 Hz, 2H). 13 13C NMR (101 MHz, benzene-d6) δ 153.15, 148.13, 129.14, 128.07, 121.44, 44.37, 42.61, 30.19, 23.61, 18.55, 12.85.

[0194] Example 45: Synthesis of Ligand 18

Chemical Structure

[0195] The product exists as a mixture of isomers: (*) showing the minor isomer

[0196] 1 H NMR (400 MHz, benzene-d6) δ 7.06 (dd, J = 7.5, 4.7 Hz, 4H), 6.90 - 6.78 (m, 2H), 3.69 (pd, J = 6.8, 2.1 Hz, 4H), 3.21 (t, J = 6.0 Hz, 2H) (2.84 (t, J = 6.8 Hz, 2H)*), (2.50 (q, J = 6.5 Hz, 4H)*) 2.47 - 2.40 (m, 4H), (2.27 (d, J = 0.8 Hz, 6H*) (2.26 (s, 6H)*) 2.24 (s, 12H), 1.20 (d, J = 6.8 Hz, 24H), (0.91 - 0.80 (m, 4H)*) 0.75 (p, J = 7.5 Hz, 4H), 0.54 (p, J = 7.6, 7.0 Hz, 2H). 13 C NMR (101 MHz, benzene-d6) δ 152.22, 148.45, (132.07*) 128.77, 124.07, 120.84, 47.11 (46.09*), (44.03*) 44.01, (30.46*) 29.89 (29.76*), (23.83*) 23.77, 21.82, 18.87 (18.74*).

[0197] Example 46 - Polymerization Process The catalytic activity (from the viewpoints of quench time, efficiency, and polymer yield) and the resulting polymer properties were evaluated for Pro-Catalysts 1 to 74. The polymerization reactions were carried out in parallel pressure reactors (PPRs) and / or semi-batch reactors.

[0198] The PPR polymerization experiments were carried out at both 120 °C and 150 °C using [HNMe(C 18 H 37 )2][B(C6F5)4] as an activator in an amount of 1.5 molar equivalents relative to the Pro-Catalyst, and MMAO-3A (500 nmol at 120 °C or 750 nmol at 150 °C) was used as a scavenger. When the reactor temperature was 120 °C, the ethylene pressure was 150 psi. When the reactor temperature was 150 °C, the ethylene pressure was 213 psi. The reaction run time was 30 minutes, or until 50 psi conversion at 120 °C or 75 psi conversion at 150 °C. The reaction mixture was quenched with 10% CO.

Table 1-1

Table 1-2

Table 1-3

Table 2

[0199] The semi-batch reactor polymerization reactions were carried out in a 4 L semi-batch reactor at 120 °C and 150 °C first without diethylzinc (DEZ), and then with three different loadings of DEZ (in amounts of 0, 95, and 380 μmol) added at 150 °C. The activator was 1.2 molar equivalents of [HNMe(C 18 H 37 )2][B(C6F5)4], and the scavenger was MMAO-3 (19.0 μmol). The run time for each polymerization experiment was 10 minutes.

[0200] To determine the chain transfer rate of the precatalyst, semi-batch campaigns were conducted using various amounts of the chain transfer agent, Et2Zn (in amounts of 0 μmol, 95 μmol, and 380 μmol). All reactions were carried out at 150 °C using 1.2 equivalents of [HNMe(C 18 H 37 )2][B(C6F5)4] as the activator. The batch campaign was carried out at 150 °C using 34 g of ethylene, 110 g of 1-octene, and 1010 g of IsoparE under a pressure of 163 psi. The run time for each polymerization experiment was 10 minutes. The measured ethylene uptake, as well as the corresponding Mw, PDI, and comonomer incorporation of the resulting polymer, are presented in Table 3. The Mn for each run was calculated using Equation 3 with the Ca and Mn0 fit values 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. The calculated Ca values are presented in Table 4.

Table 3

Table 4

[0201] The high chain transfer constants of 1 or more for procatalysts 1, 15, and 55 at 150 °C indicate that these catalysts have a high sensitivity to chain transfer agents and undergo chain transfer by these chain transfer agents rapidly. For procatalysts 13, 37, and 56, only a moderate sensitivity (Ca ≧ 0.5) to chain shuttling agents is observed. For procatalysts 1, 13, 15, and 56, a decrease in PDI or consistently narrow PDI is observed with an increase in the amount of Et2Zn (DEZ). This trend is evidence that procatalysts 1, 13, 15, and 56 potentially undergo reversible chain transfer by chain shuttling agents, in contrast to irreversible chain transfer. These behaviors are not observed for procatalysts 37, 38, or 55, for which an increase in PDI is observed with an increasing amount of DEZ, showing behavior consistent with irreversible chain transfer by chain shuttling agents. The present invention includes the following aspects. Item 1. A process for polymerizing a polyolefin, the process comprising contacting ethylene and optionally one or more (C3-C 12 ) α-olefins in the presence of a catalyst system, the catalyst system comprising a metal-ligand structure according to formula (I), [Chemical formula] wherein M is a metal selected from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4, X is independently an unsaturated (C2-C 20 ) hydrocarbon, an unsaturated (C2-C 50 ) heterohydrocarbon, a (C1-C 50 ) hydrocarbyl, a (C6-C 50 ) aryl, a (C6-C 50 ) heteroaryl, a (C4-C 12 ) diene, a halogen, -OR C , -N(R N )2, and -NCOR C is a monodentate or bidentate ligand selected from, n is 1, 2, or 3, m is 1 or 2, m + n = 3 or 4, each R 1 is R 1a or R 1b and, each R 4 is R 4a or R 4b and, R 1a , R 1b , R 4a , and R 4b are independently -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, (C1-C 40 ) aryl, (C1-C 40 ) heteroaryl, -P(R P )2, -N(R N )2, R C S(O)-, R C S(O)2-, or (R C )2C=N- and are selected from, each A is independently -NR 1 R 2 and each R 2 is R 2a or R 2b and each R 3 is R 3a or R 3b and R 2a , R 2b , R 3a , and R 3b are independently -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, (C1-C 40 ) aryl, or (C1-C 40 ) heteroaryl, provided that, (1) when m is 2, (2) when all of R 2a , R 2b , R 3a , and R 3b are methyl, R 1a , R 1b , R 4a , and R4b at least one of which is not 2-propyl, when m is 1, each X is the same, R 1 and R 2 , or R 2 and R 3 , or R 3 and R 4 any of which may optionally be connected to form a ring, a process. Item 2. m is 2, n is 2, and the metal-ligand complex has a structure according to formula (II),

Chemical formula

Chemical formula

Chemical formula

Claims

1. A process for polymerizing a polyolefin, said process comprising contacting ethylene and optionally one or more (C ３ -C １２ ) α-olefins in the presence of a catalyst system, said catalyst system comprising a metal-ligand complex according to formula (II), [Chemical Formula 2] wherein M is a metal selected from zirconium or hafnium, and the metal has an oxidation state in the form of +2, +3, or +4, X is, independently, benzyl, -CH ２ SiMe ３ , phenyl, or (C １ -C ２０ ) a mono- or bidentate ligand selected from alkyl, and R １ａ 、R １ｂ 、R ４ａ 、and R ４ｂ is selected from benzyl, cyclohexyl, 2,6-dimethylphenyl, or (C １ -C ４０ ) alkyl, A １ is - NR ２ａ R ３ａ and A ２ is - NR ２ｂ R ３ｂ and R ２ａ R ２ｂ R ３ａ and R ３ｂ are each independently - H, (C １ -C ４０ ), hydrocarbyl, (C １ -C ４０ ), heterohydrocarbyl, (C ６ -C ４０ ), aryl, or (C ３ -C ４０ ), heteroaryl, provided that R ２ａ 、 R ２ｂ 、 R ３ａ 、 and R ３ｂ are all methyl, R １ａ 、 R １ｂ 、 R ４ａ 、 and R ４ｂ at least one of is not 2-propyl, R １ａ and R ２ａ , R ２ａ and R ３ａ , R ３ａ and R ４ａ , R １ｂ and R ２ｂ , R ２ｂ and R ３ｂ , or R ３ｂ and R ４ｂ Any of which may optionally be connected to form a ring, process.

2. R ４ａ and R ４ｂ are covalently bonded, whereby the metal-ligand complex contains the divalent radical Q consisting of the two covalent bonding groups R ４ａ and R ４ｂ and has a structure according to formula (III), 【Chemical Formula 3】 wherein Q is (C ２ -C １２ ) alkylene or (C ６ -C ５０ ) arylene, and R １ａ 、R １ｂ 、R ２ａ 、R ２ｂ 、R ３ａ 、R ３ｂ 、M, X, A １ 、and A ２ is as defined by formula (II), the process according to claim 1.

3. Each X is benzyl, -CH ２ SiMe ３ or phenyl, the process according to claim 1 or 2.

4. Each R １ａ or R １ｂ and each R ４ａ or R ４ｂ is, independently, (C １ -C ２０ ) alkyl, the process according to claim 1.

5. Each R １ａ or R １ｂ and each R ４ａ or R ４ｂ is independently benzyl, cyclohexyl, 2,6-dimethylphenyl, tert-butyl, or ethyl, the process according to claim 1.

6. R １ａ and R １ｂ is 2-propyl, the process according to claim 2.

7. Each A １ or A ２ independently has one of the following structures, the process according to any one of claims 1 to 6. [Chemical Formula 4]

8. R ２ａ 、 R ２ｂ 、 R ３ａ 、 and R ３ｂ are (C １ -C １２ ) alkyl, the process according to any one of claims 1 to 6.

9. R ２ａ 、 R ２ｂ 、 R ３ａ 、 and R ３ｂ is methyl, ethyl, 1-propyl, 2-propyl, n-butyl, tert-butyl, 2-methylpropyl (isobutyl), n-hexyl, cyclohexyl, n-octyl, or tert-octyl, the process according to claim 8.

10. R １ａ , R １ｂ , R ４ａ , and R ４ｂ is independently selected from benzyl, cyclohexyl, or 2-propyl, the process according to claim 1.

11. Q is selected from -(CH ２ ) ｘ -, and in the formula, x is 2 to 5. The process according to claim 2

12. Q is -(CH ２ ) ４ - and the process according to claim 2.

13. The process according to any one of claims 1 to 12, wherein the catalyst system further comprises a chain transfer agent.

14. The process according to claim 13, wherein the chain transfer agent is diethylzinc.

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