Spray-dried catalyst containing a germanium-bridged bis-biphenyl-phenoxy organometallic compound for the preparation of vinyl copolymers

Abstract

Embodiments of the present application relate to a main catalyst and a catalyst system, the catalyst systems comprising a main catalyst, the main catalysts comprising a metal-ligand complex having a structure of formula (Ia):

Description

[0001] Cross - reference to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 031,638, filed May 29, 2020, U.S. Provisional Patent Application No. 63 / 143,324, filed January 29, 2021, and U.S. Provisional Patent Application No. 63 / 143,333, filed January 29, 2021, the content of each of these patent applications being incorporated herein by reference in its entirety. Technical field

[0003] Embodiments of the present disclosure generally relate to processes for producing polyethylene and, in particular, contacting ethylene and optionally one or more (C3 - C 12 ) α - olefin comonomers with a germanium - bridged biphenyl phenoxy catalyst system in a gas - phase polymerization reactor. Background art

[0004] Since the discovery of heterogeneous olefin polymerization by Ziegler and Natta, the global polyolefin production reached approximately 150 million tons per year in 2015 and continues to increase due to market demand. Catalyst systems in polyolefin polymerization processes can contribute to the characteristics and properties of such polyolefins. For example, catalyst systems including biphenyl phenoxy (BPP) metal - ligand complexes can produce polyolefins having a flat or reverse short - chain branching distribution (SCBD), a relatively high level of comonomer incorporation, a high natural molecular weight, and / or a narrow medium - molecular - weight distribution (MWD).

[0005] However, when used in some polymerization processes such as gas - phase polymerization, catalyst systems including BPP metal - ligand complexes generally exhibit poor productivity. That is, catalyst systems including BPP metal - ligand complexes generally may produce less polymer relative to the amount of catalyst system used. Thus, using a catalyst system including a BPP metal - ligand complex in a gas - phase polymerization process may not be commercially viable. Summary of the invention

[0006] Accordingly, there is a continuing need for catalyst systems suitable for use in gas - phase reactors that have improved productivity when used in gas - phase polymerization processes. Embodiments of the present disclosure address these needs by providing catalyst systems that can be used in gas - phase polymerization processes and that exhibit greatly improved productivity compared to similar catalyst systems including BPP metal - ligand complexes without silicon - containing bridges.

[0007] In addition, vinyl copolymer (also known as poly(ethylene-co-1-olefin)) resins typically have a short-chain branching distribution (SCBD) or comonomer distribution. Many vinyl copolymers have an inverse SCBD or inverse comonomer distribution, where the weight percentage of the comonomer decreases as the molecular weight of the vinyl copolymer increases. However, as the molecular weight (MW) of the polymer chain increases, producing a copolymer with an increasing weight percentage (wt%) of the comonomer improves performance in many applications.

[0008] An inverse comonomer distribution is typically achieved using a dual reactor configuration and a single or dual catalyst process. In a dual reactor process, a single catalyst can be used to prepare a high molecular weight, lower density component (with a higher wt% comonomer) and a low molecular weight, higher density (lower wt% comonomer) component in separate reactors via independent processes in the two reactors. The result is a bimodal resin with a net inverse SCBD across the bimodal distribution. In the case of a dual catalyst single reactor process, one catalyst prepares the high molecular weight, lower density component while the other prepares the low molecular weight, higher density component, resulting in a bimodal product with an inverse SCBD.

[0009] Embodiments of the present disclosure include a process for producing a vinyl copolymer having an inverse comonomer distribution. In an embodiment, the process includes polymerizing ethylene and one or more (C3-C 12 ) α-olefin comonomers in a single gas phase polymerization reactor in the presence of a catalyst system, where the reactor temperature is less than or equal to 150 °C and the molar feed ratio of the one or more (C3-C 12 ) α-olefin comonomers to ethylene is less than or equal to 0.020, wherein: the catalyst system comprises an activated metal-ligand complex having a structure according to formula (Ia); and the vinyl copolymer has a unimodal molecular weight distribution as determined by gel permeation chromatography (GPC, e.g., conventional GPC) and a molecular weight comonomer distribution index greater than 0 as determined by rapid FT-IR spectroscopy on the GPC-measured dissolved polymer.

[0010] In one or more embodiments, the catalyst system includes an activated metal-ligand complex disposed on one or more support materials. The activated metal-ligand complex has a structure according to formula (Ia):

[0011]

[0012] In formula (Ia), A - is an anion; M is titanium, zirconium, or hafnium. The subscript n of (X) n is 1, 2, or 3; each X is independently selected from unsaturated (C2-C 50 ) hydrocarbons, unsaturated (C2-C50 )heterohydrocarbon, (C1-C 50 )hydrocarbyl, (C1-C 50 )heterohydrocarbyl, (C6-C 50 )aryl, (C4-C 50 )heteroaryl, halogen, –N(R N )2 and -N(R N )COR C monodentate ligands; and the metal-ligand complex of formula (I) is overall charge-neutral.

[0013] In formula (I), each Z is independently selected from –O-, -S-, N(C1-C 40 )hydrocarbyl and P(C1-C 40 )hydrocarbyl.

[0014] In formula (I), R 1 and R 16 are independently selected from (C6-C 50 )aryl, (C4-C 50 )heteroaryl, (C1-C 40 )alkyl, (C3-C 40 )heteroalkyl, a group having formula (II), a group having formula (III), and a group having formula (IV):

[0015]

[0016] In formula (II), (III) and (IV), R 31-35 , R 41-48 and R 51-59 are independently selected from –H, (C1-C 50 )hydrocarbyl, (C1-C 50 )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 N )-, (R C )2NC(O)- or halogen.

[0017] In formula (I), R2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are independently selected from -H, (C1-C 50 ) hydrocarbyl, (C1-C 50 ) 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 N )-, (R C )2NC(O)- and halogen.

[0018] In formula (I), R 19 and R 20 are independently selected from –(CR C 2) m -, where the subscript m is 1 or 2, and –(CR C 2) m 's R C is -H, (C1-C 10 ) alkyl.

[0019] In formula (I), R 17 and R 18 are independently selected from straight-chain or branched (C1-C 20 ) hydrocarbyl.

[0020] In formulas (I), (II), (III) and (IV), each R C , R P and R N are independently selected from -H, (C1-C 50 ) hydrocarbyl and (C1-C 50 ) heterohydrocarbyl.

[0021] Embodiments of the present disclosure include methods for producing catalyst systems. The method includes contacting one or more support materials, one or more activators, and a metal-ligand complex in an inert hydrocarbon solvent to produce a catalyst system.

[0022] Embodiments of the present disclosure include processes for producing polyethylene. The process includes contacting ethylene and optionally one or more (C3-C 12 ) α-olefin comonomers with a catalyst system in a gas phase polymerization reactor. The catalyst system includes a metal-ligand complex disposed on one or more support materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is a graphical depiction of the reverse comonomer distribution (slant line) and molecular weight distribution (GPC chromatogram) for Examples 6 and 8 of the present invention.

[0024] Figure 2 is a graphical depiction of the reverse comonomer distribution (slant line) and molecular weight distribution (GPC chromatogram) for Examples 7 and 10 of the present invention. DETAILED DESCRIPTION

[0025] Specific embodiments of the main catalyst, catalyst system, method for producing a catalyst system, and process for producing polyethylene will now be described. However, it should be understood that the systems, methods, and processes of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth herein. Instead, the embodiments are provided so that this disclosure will be thorough and complete, and the embodiments will fully convey the scope of the subject matter to those skilled in the art.

[0026] Common abbreviations used in the present disclosure are listed below:

[0027] Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl; i-Pr: isopropyl; t-Bu: tert-butyl; t-Oct: tert-octyl (2,4,4-trimethylpentan-2-yl); Tf: trifluoromethanesulfonate; 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; 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.

[0028] The term "halogen atom" or "halogen" means a group of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" means the anionic form of a halogen atom: fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ), or iodide ion (I - ).

[0029] The term "independently selected" means that R groups such as R 1 , R 2 , and R 3 can be the same or different (e.g., R 1 , R 2 , and R 3 can all be substituted alkyls; or R 1 and R 2 can be substituted alkyls, and R 3 can be aryl). The chemical names associated with the R groups are intended to convey the chemical structures corresponding to the chemical names that are recognized in the art. Thus, the chemical names are intended to supplement and illustrate rather than exclude the structural definitions known to those skilled in the art.

[0030] The term "procatalyst" means a compound that has catalytic activity when combined with an activator. The term "activator" means a compound that chemically reacts with the procatalyst in a manner that converts the procatalyst into a catalytically active compound. As used in this disclosure, the terms "promoter" and "activator" are interchangeable and have the same meaning unless specifically designated otherwise.

[0031] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom in the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S ). The term "-H" means a hydrogen or hydrogen group covalently bonded to another atom. As used in this disclosure, the terms "hydrogen" and "-H" are interchangeable and have the same meaning unless specifically designated otherwise.

[0032] When used to describe certain carbon-containing chemical groups, the inserted expression of the form "(C x -C y )" means that the unsubstituted form of the chemical group has x carbon atoms to y carbon atoms, inclusive of x and y. For example, (C1-C 50 ) alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups can be substituted with one or more substituents such as RS. Using "(C x -Cy )”Insert the defined R S The substituted chemical group may contain more than y carbon atoms, depending on the identity of any group R S For example, “(C1-C S ) alkyl substituted with exactly one group R 50 where R S is phenyl (-C6H5)” may contain from 7 to 56 carbon atoms. Thus, when using “(C x -C y )” to insert a defined chemical group that is substituted by one or more carbon atom-containing substituents R S , the minimum and maximum total number of carbon atoms of the chemical group is determined by adding the combined total of the carbon atoms from all carbon atom-containing substituents R S to both x and y.

[0033] The term “(C1C 50 ) hydrocarbyl” means a hydrocarbyl group having from 1 to 50 carbon atoms, and the term “(C1C 50 ) alkylene” means a hydrocarbyl divalent group having from 1 to 50 carbon atoms, wherein each hydrocarbyl group and each hydrocarbyl divalent group is aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (having three or more carbons and including monocyclic and polycyclic, fused and non-fused polycyclic and bicyclic) or acyclic, and substituted or unsubstituted with one or more R S . As used in this disclosure, (C1-C 50 ) hydrocarbyl may be unsubstituted or substituted (C1-C 50 ) alkyl, (C3-C 50 ) cycloalkyl, (C3-C 25 ) cycloalkyl-(C1-C 25 ) alkylene, (C6-C 50 ) aryl or (C6-C 25 ) aryl-(C1-C 25 ) alkylene (such as benzyl (-CH2-C6H5)).

[0034] The term “(C1-C 50 ) alkyl” means a saturated straight-chain or branched-chain hydrocarbyl group having from 1 to 50 carbon atoms. Each (C1-C 50 ) alkyl may be unsubstituted or substituted with one or more R S . In some embodiments, each hydrogen atom in the hydrocarbyl group may be substituted with R S , such as, for example, trifluoromethyl. Examples of unsubstituted (C1-C 50 ) alkyl are unsubstituted (C1-C 20 ) alkyl; unsubstituted (C1-C10 )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 50 )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 group including the substituents, and is, for example, a (C1-C5) alkyl (such as, for example, methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl) R S substituted (C 27 -C 40 )alkyl.

[0035] The term “(C3-C 50 )cycloalkyl” means a saturated cyclic hydrocarbon group having 3 to 50 carbon atoms, which is unsubstituted or substituted by one or more R S . Other cycloalkyl groups (e.g., (C x –C y )cycloalkyl) are defined in a similar manner as having x to y carbon atoms and being unsubstituted or substituted by one or more R S . Examples of unsubstituted (C3-C 50 )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 50 )cycloalkyl are substituted (C3–C 20 )cycloalkyl, substituted (C3–C 10 )cycloalkyl, and 1-fluorocyclohexyl.

[0036] The term “(C6-C 50 )aryl” means an unsubstituted or (substituted by one or more R S)A substituted monocyclic, bicyclic or tricyclic aromatic hydrocarbon group, wherein at least 6 to 14 carbon atoms are aromatic ring carbon atoms. The monocyclic aromatic hydrocarbon group includes one aromatic ring; the bicyclic aromatic hydrocarbon group has two rings; and the tricyclic aromatic hydrocarbon group has three rings. When a bicyclic or tricyclic aromatic hydrocarbon group is present, at least one of the rings in the group is aromatic. The other one or more rings of the aromatic group can independently be fused or unfused and can be aromatic or non-aromatic. Unsubstituted (C6-C 50 )Examples of aryl groups include: unsubstituted (C6-C 20 )aryl, unsubstituted (C6-C 18 )aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; dicyclopentadienylphenyl; hexahydrodicyclopentadienylphenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (C6-C 50 )aryl groups 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.

[0037] 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 an unsubstituted (C1-C 18 )hydrocarbon group or -H, and where each R N is an unsubstituted (C1-C 18 )hydrocarbon group. The term "heterohydrocarbon" refers to a molecule or molecular backbone in which one or more carbon atoms of a hydrocarbon are replaced by heteroatoms. The term "(C1-C 50 )heterohydrocarbyl" means a heterohydrocarbon group having 1 to 50 carbon atoms, and the term "(C1-C 50 )heteroalkylene" means a heterohydrocarbon divalent group having 1 to 50 carbon atoms. T(C1-C 50 )heterohydrocarbyl or (C1-C 50)The heteroatom of a heteroalkylene has one or more heteroatoms. The groups of a heteroalkylene can be on a carbon atom or a heteroatom. The two groups of a heteroalkenylene can be on a single carbon atom or on a single heteroatom. Additionally, one of the two groups of a divalent group can be on a carbon atom and the other group can be on a different carbon atom; one of the two groups can be on a carbon atom and the other group can be on a heteroatom; or one of the two groups can be on a heteroatom and the other group can be on a different heteroatom. Each (C1-C 50 )heteroalkylene and (C1-C 50 )heteroalkenylene can be unsubstituted or substituted with (one or more R S ), aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0038] The term “(C4-C 50 ) heteroaryl” means an unsubstituted or substituted (with one or more R S ) monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon group having a total of 4 to 50 carbon atoms and 1 to 10 heteroatoms. A monocyclic heteroaromatic hydrocarbon group includes one heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon group has two rings; and a tricyclic heteroaromatic hydrocarbon group has three rings. When a bicyclic heteroaromatic hydrocarbon group or a tricyclic heteroaromatic hydrocarbon group is present, at least one of the rings in the group is heteroaromatic. The other one or more rings of the heteroaromatic group can be independently fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., typically (C x -C y ) heteroaryl, such as (C4-C 12 ) heteroaryl) are defined in a similar manner as having x to y carbon atoms (such as 4 to 12 carbon atoms) and being unsubstituted or substituted with one or more than one R SSubstituted. The monocyclic heteroaromatic hydrocarbon group is a 5-membered or 6-membered ring. The 5-membered ring has 5 - h carbon atoms, where h is the number of heteroatoms and can be 1, 2, 3, or 4, and each heteroatom can be O, S, N, or P. Examples of the 5-membered ring heteroaromatic hydrocarbon group include: pyrrol-1-yl; piperidin-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 - h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatoms can be N or P. Examples of the 6-membered ring heteroaromatic hydrocarbon group include pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon group can be a fused 5,6- or 6,6-ring system. Examples of the fused 5,6-ring system bicyclic heteroaromatic hydrocarbon group are indol-1-yl; and benzimidazol-1-yl. Examples of the fused 6,6-ring system bicyclic heteroaromatic hydrocarbon group are quinolin-2-yl; and isoquinolin-1-yl. The bicyclic heteroaromatic hydrocarbon group can be a fused 5,6,5-ring system; 5,6,6-ring system; 6,5,6-ring system; or 6,6,6-ring system. Examples of the fused 5,6,5-ring system are 1,7-dihydropyrrolo[3,2-f]indol-1-yl. Examples of the fused 5,6,6-ring system are 1H-benzo[f]indol-1-yl. Examples of the fused 6,5,6-ring system are 9H-carbazol-9-yl. Examples of the fused 6,6,6-ring system are acridin-9-yl.

[0039] The term "polymer" refers to a polymeric compound prepared by polymerizing the same or different types of monomers. Thus, the general term polymer includes homopolymers, which are polymers prepared by polymerizing only one type of monomer, and copolymers, which are polymers prepared by polymerizing two or more different monomers.

[0040] The term "interpolymer" refers to a polymer prepared by polymerizing at least two different types of monomers. Thus, the general term interpolymer includes copolymers and other polymers prepared by polymerizing more than two different monomers (such as terpolymers).

[0041] The terms "polyolefin", "polyolefin polymer", and "polyolefin resin" refer to polymers prepared by polymerizing simple olefins (also called olefins, which have the general formula C n H 2n) Polymers prepared by the polymerization of monomers. Thus, the general term polyolefin includes polymers prepared by polymerizing ethylene monomers with or without one or more comonomers (such as polyethylene) and polymers prepared by polymerizing propylene monomers with or without one or more comonomers (such as polypropylene).

[0042] The terms "vinyl copolymer", "polyethylene", and "vinyl polymer" refer to polyolefins containing more than 50 mole percent (%) of ethylene monomer-derived units, including polyethylene homopolymers and copolymers. Common forms of polyethylene known in the art include Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), Ultra Low Density Polyethylene (ULDPE), Very Low Density Polyethylene (VLDPE), Medium Density Polyethylene (MDPE), and High Density Polyethylene (HDPE).

[0043] The term "monomodal" means a molecular weight distribution that includes a single maximum. A monomodal molecular weight distribution can be characterized by a single peak in a plot of dW / dLog(MW) on the y-axis versus Log(MW) on the x-axis of a GPC chromatogram.

[0044] The term "molecular weight distribution" means the ratio of two different molecular weights of a polymer. The general term molecular weight distribution includes the ratio of the weight-average molecular weight (M w ) of a polymer to the number-average molecular weight (M n ) of the polymer, which ratio can also be referred to as "molecular weight distribution (M w / M n )", and the ratio of the z-average molecular weight (M z ) of a polymer to the weight-average molecular weight (M w ) of the polymer, which ratio can also be referred to as "molecular weight distribution (M z / M w )".

[0045] The term "composition" means a mixture of materials that make up the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0046] The terms "comprising", "including", "having" and their derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed by use of the term "comprising" may include any additional additive, adjuvant or compound, whether polymeric or otherwise. In contrast, the term "consisting essentially of" excludes any other component, step or procedure from the scope of any subsequent recitation, except those that are not essential to the operability. The term "consisting of" excludes any component, step or procedure not specifically recited or listed.

[0047] In an embodiment of the process of the present disclosure, the catalyst system includes a main catalyst. The main catalyst includes a metal-ligand complex. The metal-ligand complex may have a structure according to formula (I):

[0048]

[0049] In one or more embodiments, the catalyst system comprises an activated metal-ligand complex having a structure according to formula (Ia):

[0050]

[0051] Formula (Ia) is an illustrative depiction of the active catalyst. When the metal-ligand complex of formula (I) has catalytic activity through an activator, the metal of the metal-ligand complex may have a formal charge of plus one (+1). In an embodiment where the main catalyst includes a metal-ligand complex, the metal-ligand complex has a structure according to formula (I) and is overall electrically neutral. In an embodiment where the catalyst system includes a metal-ligand complex, the metal-ligand complex may have a structure according to formula (Ia) and have a total formal charge of plus one (+1):

[0052] In formulas (I) and (Ia), M is titanium (Ti), zirconium (Zr) or hafnium (Hf). In an embodiment, M is titanium, zirconium or hafnium, each independently in a formal oxidation state of +2, +3 or +4.

[0053] In formulas (I) and (Ia), (X) n the subscript n is 1, 2 or 3, and each X is independently selected from unsaturated (C2-C 50 ) hydrocarbon, unsaturated (C2-C 50 ) heterohydrocarbon, (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C6-C 50 ) aryl, (C4-C 50 ) heteroaryl, halogen, –N(RN )2 and –N(R N )COR C monodentate ligands. In embodiments, each X is independently selected from methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chloro. In some embodiments, (X) n has a subscript n of 2, and each X is the same. In other embodiments, at least two Xs are different. For example, (X) n has a subscript n that can be 2, and each X can be a different group from the following: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chloro. In embodiments, (X) n has a subscript n of 1 or 2, and at least two Xs are independently monoanionic monodentate ligands, and if present, the third X is a neutral monodentate ligand. In one or more embodiments, (X) n has a subscript n of 2. In formula (I), the metal-ligand complex is electrically neutral as a whole.

[0054] In formulas (I) and (Ia), each Z is independently selected from –O–, –S–, N(C1-C 50 )hydrocarbyl, and P(C1-C 50 )hydrocarbyl. In embodiments, each Z is the same. For example, each Z can be –O–.

[0055] In formulas (I) and (Ia), R 1 and R 16 are independently selected from (C6-C 50 )aryl, (C4-C 50 )heteroaryl, (C1-C 50 )alkyl, (C3-C 40 )heteroalkyl, a group having formula (II), a group having formula (III), and a group having formula (IV):

[0056]

[0057] In formula (II), R 31 , R 32 , R 33 , R 34 , R 35 are independently selected from –H, (C1-C 50 )hydrocarbyl, (C1-C 50 )heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(RN ) 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 N )-, (R C )2NC(O)- or halogen

[0058] In formula (III), R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 are independently selected from –H, (C1-C 50 ) hydrocarbyl, (C1-C 50 ) 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 N )-, (R C )2NC(O)- or halogen

[0059] In formula (IV), R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 and R 59 are independently selected from –H, (C1-C 50 ) hydrocarbyl, (C1-C 50 ) 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 N )-, (R C )2NC(O)- or a halogen.

[0060] The groups R in the metal-ligand complexes of formula (I) and (Ia) 1 and R 16 are each independently selected. For example, R 1 may be selected from groups having formula (II), (III) or (IV), and R 16 may be (C4-C 50 ) heteroaryl; or R 1 may be selected from groups having formula (II), (III) or (IV), and R 16 may be selected from groups having formula (II), (III) or (IV) that are the same as or different from R 1 . In an embodiment, R 1 and R 16 are both groups having formula (II), wherein the group R 31-35 is the same as or different in R 1 and R 16 . In some embodiments, R 1 and R 16 are both groups having formula (III), wherein the group R 41-48 is the same as or different in R 1 and R 16 . In other embodiments, R 1 and R 16 are both groups having formula (IV), wherein the group R 51-59 is the same as or different in R 1 and R 16 .

[0061] In an embodiment, at least one of R 1 and R 16 is a group having formula (II), wherein at least one of R 32 and R 34 is tert-butyl. In some embodiments, when R 1or R 16 When at least one of them is a group having the formula (III), R 43 and R 46 one or both of them are tert-butyl, and R 41-42 、R 44-45 and R 47-48 are -H. In some embodiments, R 42 and R 47 one or both of them are tert-butyl, and R 41 、R 43-46 and R 48 are -H. In some embodiments, R 42 and R 47 both are -H. In some embodiments, R 41-48 is –H.

[0062] In formulas (I) and (Ia), R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 and R 15 are independently selected from -H, (C1-C 50 ) hydrocarbyl, (C1-C 50 ) 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)- and halogen.

[0063] In some embodiments, R 5 、R 6 、R 7 and R 8 at least one of them is a halogen atom; and R9 , R 10 , R 11 and R 12 at least one of them is a halogen atom. In some embodiments, R 5 , R 6 , R 7 and R 8 at least two of them are halogen atoms; and R 9 , R 10 , R 11 and R 12 at least two of them are halogen atoms. In various embodiments, R 5 , R 6 , R 7 and R 8 at least three of them are halogen atoms; and R 9 , R 10 , R 11 and R 12 at least three of them are halogen atoms.

[0064] In an embodiment, R 3 and R 14 are (C1-C 24 ) alkyl. In various embodiments, R 3 and R 14 are (C1-C 20 ) alkyl. In some embodiments, R 3 and R 14 are (C4-C 24 ) alkyl. In one or more embodiments, R 3 and R 14 are (C8-C 12 ) alkyl. In some embodiments, R 3 and R 14 are 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpentan-2-yl), nonyl and decyl. In an embodiment, R 3 and R 14 are -OR C , where R C is (C1-C 20 ) hydrocarbon, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl) or 1,1-dimethylethyl.

[0065] In an embodiment, R 3 and R14 is methyl. In other embodiments, R 3 and R 14 are (C4-C 24 ) alkyl. In some embodiments, R 8 and R 9 are 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpentan-2-yl), nonyl, and decyl.

[0066] In some embodiments, R 6 and R 11 are halogen. In other embodiments, R 6 and R 11 are (C1-C 24 ) alkyl. In some embodiments, R 6 and R 11 are independently selected from methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. In some embodiments, R 6 and R 11 are tert-butyl. In an embodiment, R 6 and R 11 are -OR C , where R C is (C1-C 20 ) hydrocarbyl, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), or 1,1-dimethylethyl. In other embodiments, R 6 and R 11 are -SiR C 3, where each R C is independently (C1-C 20 ) hydrocarbyl, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), or 1,1-dimethylethyl.

[0067] In some embodiments, R 3 and R 14 are methyl; and R 6 and R 11 are halogen. In other embodiments, R 6 and R11 is tert-butyl. In other embodiments, R 3 and R 14 are tert-octyl or n-octyl.

[0068] In Formulas (I) and (Ia), R 19 and R 20 are independently selected from –(CR C 2) m -, where the subscript m is from 1 to 10. In one or more embodiments, each subscript m is 1 or 2. In some embodiments, the R of –(CR C 2) m - is selected from the group consisting of: –H and (C1-C C )alkyl. 10 )alkyl.

[0069] In Formulas (I) and (Ia), R 17 and R 18 are independently selected from straight-chain or branched (C1-C 20 )alkyl. In some embodiments, R 17 and R 18 are independently selected from straight-chain or branched (C2-C 20 )alkyl or (C3-C7)alkyl.

[0070] In Formulas (I), (Ia), (II), (III), and (IV), each R C , R P and R N is independently selected from -H, (C1-C 50 )hydrocarbyl, and (C1-C 50 )heterohydrocarbyl.

[0071] In an embodiment, the main catalyst can have catalytic activity by contacting with or in combination with an activator. The main catalyst having catalytic activity by contacting with or binding to an activator can be referred to as a "catalyst system". That is, as used in the present disclosure, the catalyst system can include a main catalyst and one or more activators. The term "activator" can include any combination of reagents that increase the rate of oligomerization or polymerization of unsaturated monomers (such as olefins) by a transition metal compound. The activator can also affect the molecular weight, degree of branching, comonomer content, or other properties of the oligomer or polymer. The transition metal compound can be activated for oligomerization and / or polymerization catalysis in any manner sufficient to allow coordination or cationic oligomerization and / or polymerization.

[0072] Aluminoxane activators can be used as activators for one or more of the catalyst compositions. Aluminoxanes or alkylaluminums are generally oligomeric compounds containing --Al(R)--O-- subunits, where R is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, especially when the extractable ligand is a halide. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. For further description, see U.S. Patent Nos. 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP 0 561 476, EP 0 279586, EP 0 516 476, EP 0 594218, and WO 94 / 10180.

[0073] When the activator is an aluminoxane (modified or unmodified), the maximum amount of the activator can be selected to be 5000-fold molar excess of Al / M relative to the catalyst precursor (per metal catalytic site). Alternatively or additionally, the minimum amount of the activator and the catalyst precursor can be set at a 1:1 molar ratio.

[0074] Alkylaluminum or organoaluminum compounds that can be used as activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like.

[0075] In an embodiment, the metal-ligand complex, activator, or both can be disposed on one or more support materials. For example, the metal-ligand complex can be deposited on, contacted with, vaporized with, bonded to, or incorporated into one or more support materials, adsorbed or absorbed onto or into them. One of the support methods well known in the art or described below can be used, and the metal-ligand complex, activator, or both can be combined with one or more support materials. As used in the present disclosure, the metal-ligand complex, activator, or both are in a supported form, e.g., when deposited on, contacted with, or incorporated into one or more support materials, adsorbed or absorbed onto or into them.

[0076] Suitable carrier materials, such as inorganic oxides, include metal oxides of Groups 2, 3, 4, 5, 13 or 14 of the IUPAC Periodic Table. In embodiments, the carrier material includes silica, fumed silica, alumina (e.g., as described in International Patent Application No. 1999 / 060033), silica-alumina, and mixtures thereof, which may or may not be dehydratable. The fumed silica can be hydrophilic (untreated), alternatively hydrophobic (treated). In embodiments, the carrier material is hydrophobic fumed silica, which can be prepared by treating untreated fumed silica with a treating agent such as dimethyldichlorosilane, polydimethylsiloxane fluid, or hexamethyldisilazane. In some embodiments, the carrier material includes magnesium oxide, titanium dioxide, zirconium oxide, magnesium chloride (e.g., as described in U.S. Patent No. 5,965,477), montmorillonite (e.g., as described in European Patent No. 0 511 665), phyllosilicate, zeolite, talc, clay (e.g., as described in U.S. Patent No. 6,034,187), and mixtures thereof. In other embodiments, combinations of these carrier materials can be used, such as, for example, silica-chromium, silica-alumina, silica-titanium dioxide, and combinations thereof. Additional carrier materials can also include those porous acrylic polymers described in European Patent No. 0 767184. Other carrier materials can also include the nanocomposites described in International Patent Application No. 1999 / 047598; the aerogels described in International Patent Application No. 1999 / 048605; the spherulites described in U.S. Patent No. 5,972,510; and the polymer beads described in International Patent Application No. 1999 / 050311.

[0077] In embodiments, the surface area of the carrier material is from 10 square meters per gram (m 2 / g) to 700 m 2 / g, the pore volume is from 0.1 cubic centimeter per gram (cm 3 / g) to 4.0 cm 3 / g, and the average particle size is from 5 micrometers (μm) to 500 μm. In some embodiments, the surface area of the carrier material is from 50 m 2 / g to 500 m 2 / g, the pore volume is from 0.5 cm 3 / g to 3.5 cm 3 / g, and the average particle size is from 10 μm to 200 μm. In other embodiments, the surface area of the carrier material can be from 100 m 2 / g to 400 m 2 / g, the pore volume is from 0.8 cm 3 / g to 3.0 cm 3 / g, and the average particle size is from 5 μm to 100 μm. The average pore diameter of the carrier material is typically 10 angstroms to such as to or to

[0078] There are various suitable methods for producing the catalyst systems of the present disclosure. In one or more embodiments, methods for producing a catalyst system include contacting one or more support materials, one or more activators, and a metal-ligand complex in an inert hydrocarbon solvent to produce a catalyst system. In some embodiments, methods for producing a catalyst system may include disposing the one or more activators on the one or more support materials to produce a supported activator, and contacting the supported activator with a solution of the metal-ligand complex in an inert hydrocarbon solvent (commonly referred to as "fine-tuning the catalyst" or "fine-tuning the feed"). For example, in some embodiments, methods for producing a catalyst system include contacting a spray-dried supported activator (i.e., a supported activator produced via spray drying) with a solution of the metal-ligand complex in an inert hydrocarbon solvent. In some embodiments, the supported activator may be included in a slurry, such as, for example, a mineral oil slurry.

[0079] In some embodiments, methods for producing a catalyst system may include mixing one or more support materials, one or more activators, and a metal-ligand complex to produce a catalyst system precursor. These methods may further include drying the catalyst system precursor to produce a catalyst system. More specifically, these methods may include preparing a mixture of the metal-ligand complex, one or more support materials, one or more activators, or combinations thereof, and an inert hydrocarbon solvent. The inert hydrocarbon solvent may then be removed from the mixture to produce the metal-ligand complex, the one or more activators, or combinations thereof disposed on the one or more support materials. In embodiments, the removal step may be accomplished by conventional evaporation of the inert hydrocarbon solvent from the mixture (i.e., conventional concentration methods), which produces an evaporated / supported catalyst system. In other embodiments, the removal step may be accomplished by spray drying the mixture, which produces spray-dried particles. It should be understood that the drying and / or removal steps may not result in complete removal of liquid from the resulting catalyst system. That is, the catalyst system may include a residual amount (i.e., 1 wt% to 3 wt%) of the inert hydrocarbon solvent.

[0080] As described above, the catalyst systems of the present disclosure can be used in methods for producing polymers (such as polyethylene) via the polymerization of olefins (such as ethylene). In an embodiment, one or more olefins can be contacted with the catalyst systems of the present disclosure in a gas-phase polymerization reactor, such as a gas-phase fluidized bed polymerization reactor. Exemplary gas-phase systems are described in U.S. Patent Nos. 5,665,818; 5,677,375; and 6,472,484; and European Patent Nos. 0 517 868 and 0 794 200. For example, in some embodiments, ethylene and optionally one or more (C3-C 12 ) α-olefin comonomers can be contacted with the catalyst systems of the present disclosure. The catalyst systems can be fed to the gas-phase polymerization reactor in pure form (i.e., as a dry solid), as a solution, or as a slurry. For example, in some embodiments, spray-dried particles of the catalyst systems can be fed directly to the gas-phase polymerization reactor. In other embodiments, a solution or slurry of the catalyst systems in a solvent (such as an inert hydrocarbon or mineral oil) can be fed to the reactor. For example, the main catalyst can be fed to the reactor in an inert hydrocarbon solution, and the activator can be fed to the reactor in a mineral oil slurry.

[0081] In an embodiment, the gas-phase polymerization reactor comprises a fluidized bed reactor. The fluidized bed reactor can comprise a "reaction zone" and a "velocity reduction zone". The reaction zone can comprise a bed of growing polymer particles, forming polymer particles, and a small amount of the catalyst system, which is fluidized by the continuous flow of gaseous monomers and diluents to remove the heat of polymerization through the reaction zone. Optionally, some recycle gas can be cooled and compressed to form a liquid, which, when re-entering the reaction zone, increases the heat removal capacity of the recycle gas stream. Suitable gas flow rates can be easily determined by simple experiments. The rate of replenishment of the gaseous monomer to the recycle gas stream can be equal to the rate at which the particulate polymer product and the monomer associated therewith can be withdrawn from the reactor, and the composition of the gas passing through the reactor can be adjusted to maintain a substantially steady-state gaseous composition within the reaction zone. The gas leaving the reaction zone can be transferred to a velocity reduction zone for removing entrained particles. Finer entrained particles and dust can be removed in a cyclone and / or a fine filter. The gas can pass through a heat exchanger, where the heat of polymerization can be removed, be compressed in a compressor, and then returned to the reaction zone. Additional reactor details and ways of operating the reactor are described, for example, in U.S. Patent Nos. 3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,882,400; 5,352,749; and 5,541,270; European Patent No. 0 802 202; and Belgian Patent No. 839,380.

[0082] In an embodiment, the reactor temperature of the gas phase polymerization reactor is less than or equal to 150 °C. For example, the reactor temperature of the gas phase polymerization reactor can be 30 °C to 120 °C, 30 °C to 110 °C, 30 °C to 100 °C, 30 °C to 90 °C, 30 °C to 50 °C, 30 °C to 40 °C, 40 °C to 150 °C, 40 °C to 120 °C, 40 °C to 110 °C, 40 °C to 100 °C, 40 °C to 90 °C, 40 °C to 50 °C, 50 °C to 150 °C, 50 °C to 120 °C, 50 °C to 110 °C, 50 °C to 100 °C, 50 °C to 90 °C, 90 °C to 150 °C, 90 °C to 120 °C, 90 °C to 110 °C, 90 °C to 100 °C, 100 °C to 150 °C, 100 °C to 120 °C, 100 °C to 110 °C, 110 °C to 150 °C, 110 °C to 120 °C, or 120 °C to 150 °C. Generally, considering the sintering temperature of the polymer product in the reactor, the gas phase polymerization reactor can be operated at the highest feasible temperature. Regardless of the process used to manufacture polyethylene, the reactor temperature should be below the melting temperature or "sintering" temperature of the polymer product. Thus, the upper temperature limit can be the melting temperature of the polymer product.

[0083] In an embodiment, the reactor pressure of the gas phase polymerization reactor is 690 kPa (100 psig) to 3,448 kPa (500 psig). For example, the reactor pressure of the gas phase polymerization reactor can be 690 kPa (100 psig) to 2,759 kPa (400 psig), 690 kPa (100 psig) to 2,414 kPa (350 psig), 690 kPa (100 psig) to 1,724 kPa (250 psig), 690 kPa (100 psig) to 1,379 kPa (200 psig), 1,379 kPa (200 psig) to 3,448 kPa (500 psig), 1,379 kPa (200 psig) to 2,759 kPa (400 psig), 1,379 kPa (200 psig) to 2,414 kPa (350 psig), 1,379 kPa (200 psig) to 1,724 kPa (250 psig), 1,724 kPa (250 psig) to 3,448 kPa (500 psig), 1,724 kPa (250 psig) to 2,759 kPa (400 psig), 1,724 kPa (250 psig) to 2,414 kPa (350 psig), 2,414 kPa (350 psig) to 3,448 kPa (500 psig), 2,414 kPa (350 psig) to 2,759 kPa (400 psig), or 2,759 kPa (400 psig) to 3,448 kPa (500 psig).

[0084] In an embodiment, hydrogen gas may be used during polymerization to control the final properties of the polyethylene. The amount of hydrogen in the polymerization may be expressed as a molar ratio relative to the total polymerizable monomers (such as, for example, ethylene or a blend of ethylene and 1-hexene). The amount of hydrogen gas used in the polymerization process may be an amount required to achieve the desired properties of the polyethylene, such as, for example, the melt flow rate (MFR). In an embodiment, the molar ratio of hydrogen to total polymerizable monomers (H2: monomer) is greater than 0.0001. For example, the molar ratio of hydrogen to total polymerizable monomers (H2: monomer) may be from 0.0001 to 10, from 0.0001 to 5, from 0.0001 to 3, from 0.0001 to 0.10, from 0.0001 to 0.001, from 0.0001 to 0.0005, from 0.0005 to 10, from 0.0005 to 5, from 0.0005 to 3, from 0.0005 to 0.10, from 0.0005 to 0.001, from 0.001 to 10, from 0.001 to 5, from 0.001 to 3, from 0.001 to 0.10, from 0.10 to 10, from 0.10 to 5, from 0.10 to 3, from 3 to 10, from 3 to 5, or from 5 to 10.

[0085] In one or more embodiments, the process produces greater than or equal to 2,500 grams of polyethylene per gram of catalyst system per hour (g 聚合物 / g 催化剂 ·h). In some embodiments, the process produces greater than or equal to 3,000 g 聚合物 / g 催化剂 ·h; 4,000 g 聚合物 / g 催化剂 ·h or 5,000 g 聚合物 / g 催化剂 ·h.

[0086] In an embodiment, the catalyst system of the present disclosure may be used to polymerize a single type of olefin to produce a homopolymer. However, in other embodiments, additional α-olefins may be incorporated into the polymerization procedure. Such additional α-olefin comonomers generally have no more than 20 carbon atoms. For example, the catalyst system of the present disclosure may be used to polymerize ethylene and one or more (C3-C 12 ) α-olefin comonomers. 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, selected from the group consisting of 1-hexene and 1-octene.

[0087] In one or more embodiments, the process produces a vinyl copolymer, wherein the ratio of the weight average molecular weight of the vinyl copolymer to the weight percentage of the comonomer content of the vinyl copolymer is greater than or equal to 10,000, 20,000, or 30,000.

[0088] In some embodiments, the process produces a vinyl copolymer that further comprises a molecular weight greater than 500,000 g / mol. In some embodiments, the molecular weight of the produced vinyl copolymer is greater than 600,000 g / mol, greater than 700,000 g / mol, or greater than 750,000 g / mol.

[0089] In various embodiments, when the reactor temperature is from 85 °C to 105 °C, the molecular weight comonomer distribution is greater than 0. In one or more embodiments, when the molecular weight is greater than 200,000 g / mol, the molecular weight comonomer distribution is greater than 0.

[0090] In an embodiment, the vinyl copolymer further comprises less than 30 wt% comonomer incorporation, as determined by rapid FT-IR (Fourier transform infrared) spectroscopy as part of GPC measurement. In some embodiments, the comonomer incorporation is less than 20 wt%.

[0091] The comonomer content of most vinyl copolymers (i.e., the weight fraction of the constitutional units derived from the 1-olefin in the copolymer) varies with the molecular weight of its constitutional macromolecules. Substantially, if the higher molecular weight fractions of the macromolecules have a lower weight % of comonomer content, then this is a normal comonomer distribution with respect to molecular weight. The normal comonomer distribution may also be referred to as the normal short chain branching distribution (normal SCBD) or the normal molecular weight comonomer distribution index (normal MWCDI). If the MWCDI is less than 0, then there is a normal MWCDI or normal SCBD. If the MWCDI = 0, then there is a flat MWCDI or flat SCBD. The MWCDI value is determined by the plot of SCB per 1000 carbon atoms versus Log(weight average molecular weight) (Log(M w ))). See US2017 / 008444 A1.

[0092] When the higher molecular weight fractions have a higher weight % of comonomer content, then it can be said that it has an inverse comonomer distribution with respect to molecular weight. This phenomenon is also referred to as the inverse short chain branching distribution (inverse SCBD), the inverse molecular weight comonomer distribution index (inverse MWCDI), or the broad orthogonal composition distribution (BOCD). If the MWCDI is greater than 0, then there is an inverse comonomer distribution or inverse SCBD.

[0093] The content distribution of these comonomers in terms of molecular weight is shown by plotting the linear regression of the comonomer content expressed as weight percentage (wt%) on the y-axis against Log(M) on the x-axis. The wt% comonomer content is determined by performing Fourier Transform Infrared (FT-IR) spectroscopy on the dissolved copolymer measured by Gel Permeation Chromatography (GPC) using an infrared detector. M is the specific x-axis molecular weight point of the Flory distribution of the molecular weight (10^[Log(M)]), as measured by GPC. In such a graph, a normal comonomer distribution has a negative slope (i.e., the line fitting the data points from lower Log(M) values to higher Log(M) values (from left to right on the x-axis) slopes downward).

[0094] In an embodiment, the one or more (C3-C 12 ) α-olefin comonomers may not be derived from propylene. That is, the one or more (C3-C 12 ) α-olefin comonomers may be substantially free of propylene. The term "substantially free of" for a compound means that the material or mixture contains less than 1.0 wt% of the compound. For example, the one or more (C3-C 12 ) α-olefin comonomers that may be substantially free of propylene may include less than 1.0 wt% of propylene, such as less than 0.8 wt% of propylene, less than 0.6 wt% of propylene, less than 0.4 wt% of propylene, or less than 0.2 wt% of propylene.

[0095] In an embodiment, the produced polyethylene, such as homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers, may include at least 50 mole percent (mol.%) of monomer units derived from ethylene. For example, the polyethylene may include at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, or at least 90 mol% of monomer units derived from ethylene. In an embodiment, the polyethylene includes 50 mol.% to 100 mol.% of monomer units derived from ethylene. For example, the polyethylene may include 50 mol.% to 90 mol.%, 50 mol.% to 80 mol.%, 50 mol.% to 70 mol.%, 50 mol.% to 60 mol.%, 60 mol.% to 100 mol.%, 60 mol.% to 90 mol.%, 60 mol% to 80 mol.%, 60 mol% to 70 mol%, 70 mol% to 100 mol%, 70 mol% to 90 mol%, 70 mol% to 80 mol%, 80 mol% to 100 mol%, 80 mol% to 90 mol.%, or 90 mol.% to 100 mol.% of monomer units derived from ethylene.

[0096] In an embodiment, the produced polyethylene comprises at least 90 mol.% of monomer units derived from ethylene. For example, the polyethylene may comprise at least 93 mol.%, at least 96 mol.%, at least 97 mol.%, or at least 99 mol.% of monomer units derived from ethylene. In an embodiment, the polyethylene comprises from 90 mol.% to 100 mol.% of monomer units derived from ethylene. For example, the polyethylene may comprise from 90 mol.% to 99.5 mol.%, from 90 mol.% to 99 mol.%, from 90 mol.% to 97 mol.%, from 90 mol.% to 96 mol.%, from 90 mol.% to 93 mol.%, from 93 mol.% to 100 mol.%, from 93 mol.% to 99.5 mol.%, from 93 mol.% to 99 mol.%, from 93 mol% to 97 mol%, from 93 mol% to 96 mol%, from 96 mol.% to 100 mol.%, from 96 mol.% to 99.5 mol.%, from 96 mol.% to 99 mol.%, from 96 mol.% to 97 mol.%, from 97 mol.% to 100 mol.%, from 97 mol.% to 99.5 mol.%, from 97 mol.% to 99 mol.%, from 99 mol.% to 100 mol.%, from 99 mol.% to 99.5 mol.%, or from 99.5 mol.% to 100 mol.% of monomer units derived from ethylene.

[0097] In an embodiment, the produced polyethylene comprises less than 50 mol.% of monomer units derived from additional α-olefins. For example, the polyethylene can comprise less than 40 mol.%, less than 30 mol.%, less than 20 mol.%, or less than 10 mol.% of monomer units derived from additional α-olefins. In an embodiment, the polyethylene comprises from 0 mol.% to 50 mol.% of monomer units derived from additional α-olefins. For example, the polyethylene can comprise from 0 mol.% to 40 mol.%, from 0 mol.% to 30 mol.%, from 0 mol.% to 20 mol.%, from 0 mol.% to 10 mol.%, from 0 mol.% to 5 mol.%, from 0 mol.% to 1 mol.%, from 1 mol.% to 50 mol.%, from 1 mol.% to 40 mol.%, from 1 mol.% to 30 mol.%, from 1 mol.% to 20 mol.%, from 1 mol.% to 10 mol.%, from 1 mol.% to 5 mol.%, from 5 mol.% to 50 mol.%, from 5 mol.% to 40 mol.%, from 5 mol.% to 30 mol.%, from 5 mol.% to 20 mol.%, from 5 mol.% to 10 mol.%, from 10 mol.% to 50 mol.%, from 10 mol.% to 40 mol.%, from 10 mol.% to 30 mol.%, from 10 mol.% to 20 mol.%, from 20 mol.% to 50 mol.%, from 20 mol.% to 40 mol.%, from 20 mol.% to 30 mol.%, from 30 mol.% to 50 mol.%, from 30 mol.% to 40 mol.%, or from 40 mol.% to 50 mol.% of monomer units derived from additional α-olefins.

[0098] In an embodiment, the produced polyethylene further comprises 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 (UV) stabilizers, and combinations thereof. The polyethylene can comprise any amount of additives. In an embodiment, the produced polyethylene further comprises fillers, which can include, but are not limited to, organic or inorganic fillers such as, for example, calcium carbonate, talc, or Mg(OH)2.

[0099] The polyethylene produced can be used in a variety of products and end-use applications. The polyethylene produced can also be blended and / or co-extruded with any other polymer. Non-limiting examples of other polymers include linear low density polyethylene, elastomers, plastomers, high pressure low density polyethylene, high density polyethylene, polypropylene, etc. In a variety of other end-uses, the polyethylene produced and blends including the polyethylene produced can be used to produce blow molded components or products. The polyethylene produced and blends including the polyethylene produced can be used to form operations such as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding, and rotational molding. Films include blown or cast films formed by co-extrusion or lamination, and the films can be used as shrink films, food wrap, stretch films, seal films, oriented films, snack packaging, heavy duty bags, grocery sacks, bakery and frozen food packaging, medical packaging, industrial liners, and membranes in food contact and non-food contact applications. Fibers can include melt spinning, solution spinning, and melt blown fiber operations and are used in woven or non-woven form to manufacture filter paper, diaper fabrics, medical garments, and geotextiles. Extruded articles can include medical catheters, wire and cable coatings, pipes, geomembranes, and pond liners. Molded articles can include single and multi-layer constructions in the form of bottles, jars, large hollow articles, rigid food containers, and toys.

[0100] Testing method

[0101] Polymerization activity

[0102] Unless otherwise noted, all polymerization activities (also known as productivity) currently disclosed are determined as the ratio of the polymer produced to the amount of catalyst added to the reactor and are recorded in grams of polymer / gram of catalyst / hour (gPE / gcat / hr).

[0103] Comonomer content

[0104] Unless otherwise indicated, all comonomer contents (i.e., the amount of comonomer incorporated into the polymer) currently disclosed are measured by performing rapid FT-IR spectroscopy on the dissolved polymer in gel permeation chromatography (GPC) measurements and are recorded as weight percentages (wt%). In GPC measurements, the comonomer content of the polymer can be determined relative to the polymer molecular weight by using an infrared detector such as an IR5 detector, as described by Lee et al. in: Toward absolute chemical composition distribution measurement of polyolefins by high-temperature liquid chromatography hyphenated with infrared absorbance and light scattering detectors, Volume 86, A NAL .C HEM .Page 8649, 2014.

[0105] Uptake ratio

[0106] Unless otherwise indicated, all uptake ratios disclosed herein are determined as the ratio of the amount of monomer units derived from a comonomer (e.g., (C3-C 12 ) α-olefin comonomer) to the amount of monomer units derived from ethylene.

[0107] Molecular weight

[0108] Unless otherwise indicated, all molecular weights disclosed herein, including the weight-average molecular weight (M w ), number-average molecular weight (M n ), and z-average molecular weight (M z ), are measured using conventional GPC measurements and are recorded in grams per mole (g / mol).

[0109] The chromatographic system consists of a high-temperature gel permeation chromatography (Polymer Laboratories) equipped with a differential refractive index detector (DRI). Three Polymer Laboratories PLgel 10μm Mixed-B chromatographic columns are used. The nominal flow rate is 1.0 mL / min, and the nominal injection volume is 300 μL. All kinds of transfer pipelines, chromatographic columns and differential refractometers (DRI detectors) are placed in an oven maintained at 160 °C. The solvent for the experiment was prepared by dissolving 6 grams of butylated hydroxytoluene in 4 liters of Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.1μm Teflon filter. Then, the TCB was degassed with an on-line degasser before entering the GPC instrument.

[0110] The polymer solution was prepared by placing the dried polymer in a glass bottle, adding the required amount of TCB, and then heating the mixture at 160 °C and shaking continuously for about 2 hours. All amounts were measured by gravimetric analysis. The injection concentration was 0.5 mg / ml to 2.0 mg / ml, and the lower concentration was used for higher molecular weight samples. Before running each sample, the DRI detector was purged. Then the flow rate in the device was increased to 1.0 mL / min, and the DRI was stabilized for 8 hours before injecting the first sample. The molecular weight was determined by combining the universal calibration relationship with column calibration, which was carried out with a series of monodisperse polystyrene (PS) standards. The MW for each elution volume was calculated using the following equation:

[0111]

[0112] where the variables with subscript "X" support the test sample, while the variables with subscript "PS" support PS. In this method, a PS = 0.67 and K PS = 0.000175, while a X and K X were obtained from published literature. Specifically, for (PE), a / K = 0.695 / 0.000579, and for PP, it is 0.705 / 0.0002288.

[0113] The concentration c at each point in the chromatography was calculated from the DRI signal IDRI minus the baseline using the following equation:

[0114]

[0115] where KDRI is a constant determined by calibrating the DRI, and (dn / dc) is the refractive index increment of the system. Specifically, for polyethylene, dn / dc = 0.109.

[0116] The mass recovery rate is calculated from the ratio of the integrated area of the concentration chromatogram to the elution volume and the injection mass, which is equal to the predetermined concentration multiplied by the injection loop volume.

[0117] Example

[0118] These examples include the synthetic procedures of intermediates of ligands, ligands, and isolated main catalysts, as well as polymerization processes including the main catalysts (also known as metal-ligand complexes). One or more features of the present disclosure are illustrated according to the following examples:

[0119]

[0120] Synthesis of metal-ligand complex 1 (MLC-1)

[0121]

[0122] Degassed toluene (15 mL) and degassed water (5 mL) were added to a 40 mL vial containing 3,6 - di - tert - butyl - 9 - [2 - (tetrahydropyran - 2 - yloxy) - 5 - (1,1,3,3 - tetramethylbutyl) - 3 - (4,4,5,5 - tetramethyl - 1,3,2 - dioxaborolan - 2 - yl)phenyl]carbazole (4.14 g, 5.97 mmol), bis[(2 - bromo - 4 - tert - butyl - phenoxy)methyl] - diisopropylgermane (1.6 g, 2.49 mmol), tBu3P - PdG2 (0.05 g, 0.1 mmol) and NaOH (0.5 g, 12.4 mmol). The reaction was heated to 50 °C and maintained at this temperature for 18 h. Thereafter, the reaction was cooled to room temperature. The mixture was transferred to a separatory funnel, Et2O (20 mL) and H2O (10 mL) were added, and the layers were separated. The aqueous phase was extracted with additional Et2O (10 mL). The combined organic matter was washed with brine (10 mL), dried (Na2SO4) and filtered into a 100 mL round - bottom flask. The solvent was removed under reduced pressure. The crude residue was dissolved in MeOH / THF (1:1, 20 mL), concentrated HCl (5 drops, from a glass pipette) was added, a reflux condenser was fitted to the flask, and then the solution was heated to 70 °C with stirring. After 18 h, the solvent was removed under reduced pressure. The yellow oil was rotary - evaporated from MeOH (3×3 mL) and a brown solid was formed. MeOH (20 mL) was added to the solid, which was then collected by filtration. The solid was washed with MeOH (2×8 mL). Acetone (10 mL) was added to the solid in the filter funnel to give a heterogeneous solution. The heterogeneous mixture was stirred with a spatula and then acetone was drawn through the filter using vacuum. Acetone (10 mL) was again added to the solid in the filter. The heterogeneous mixture was stirred with a spatula and then acetone was drawn through the filter using vacuum. The material was dried under vacuum to give 2.1 g (58%) of the desired product as a brown solid:

[0123] 1 1H NMR (400 MHz, chloroform - d) δ 8.22 (br s, 4H), 7.47–7.30 (m, 4H), 7.26 (d, J = 2.5 Hz, 2H), 7.22 (d, J = 2.4 Hz, 2H), 7.11–6.86 (m, 6H), 6.72 (br s, 2H), 5.78–5.19 (m, 4H), 3.80–3.44 (m, 4H), 1.66 (s, 4H), 1.45 (s, 36H), 1.30 (s, 12H), 1.24–1.11 (m, 20H), 0.87 (d, J = 7.4 Hz, 12H), 0.76 (s, 18H).

[0124] (Synthesis of MLC-1)

[0125]

[0126] 3 M MeMgBr in Et2O (1.96 mL) was added to a -30 °C mixture of hafnium tetrachloride (0.46 g, 1.43 mmol) in toluene (30 mL). After stirring for 3 minutes, solid 2-[5-tert-butyl-2-[[[4-tert-butyl-2-[3-(3,6-di-tert-butylcarbazol-9-yl)-2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl]phenoxy]methyl-diisopropyl-germaniumyl]methoxy]phenyl]-6-(3,6-di-tert-butylcarbazol-9-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (2.05 g, 1.42 mmol) was added.

[0127] After 18 h, additional 3 M MeMgBr in Et2O (200 uL) was added and the reaction mixture was stirred for 1 h. Thereafter, the solvent was removed under reduced pressure to give a dark solid.

[0128] Hexane / toluene (2:1, 30 mL) was added to a wide-mouth bottle and the solution was stirred at room temperature for 5 minutes, then the material was passed through a CELITE plug in a sintered funnel. The frit was extracted with hexane / toluene (2:1, 15 mL). The combined organics were dried under vacuum to give MLC-1 as an off-white solid (2.10 g, yield: 89%):

[0129] 1 H NMR (400 MHz, benzene-d6) δ 8.71 (t, J = 1.3 Hz, 2H), 8.37 (dd, J = 2.0, 0.7 Hz, 2H), 7.70–7.62 (m, 6H), 7.53 (dd, J = 7.4, 2.5 Hz, 4H), 7.47 (dd, J = 8.7, 0.6 Hz, 2H), 7.30 (dd, J = 8.7, 1.9 Hz, 2H), 7.19–7.11 (m, 2H), 5.29 (d, J = 8.7 Hz, 2H), 4.52 (d, J = 12.2 Hz, 2H), 3.52 (d, J = 12.2 Hz, 2H), 1.81 (d, J = 14.5 Hz, 2H), 1.64 (d, J = 14.5 Hz, 2H), 1.58 (s, 18H), 1.42 (s, 6H), 1.36 (s, 6H), 1.30 (s, 18H), 1.22 (s, 18H), 0.93 (s, 18H), 0.74–0.61 (m, 8H), 0.59 (d, J = 6.6 Hz, 6H), -1.20 (s, 6H).

[0130] Synthesis of metal-ligand complex 2 (MLC-2)

[0131]

[0132] Degassed THF (3 mL) and degassed water (1 mL) were added to a 40 mL vial containing 9-[5-methyl-2-(tetrahydro-2H-pyran-2-yloxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbazole (as described in International Publication No. WO 2016 / 003879 A1; 0.72 g, 1.49 mmol), bis[(2-bromo-4-fluorophenoxy)methyl]diisopropylgermane (0.36 g, 0.64 mmol), tBu3P-PdG2 (0.013 g, 0.03 mmol) and NaOH (0.13 g, 3.18 mmol). The resulting mixture was warmed to 50 °C and maintained at this temperature for 18 h. Thereafter, the reaction was cooled to room temperature. Et2O (10 mL) and brine (3 mL) were added to the mixture. The resulting solution was shaken and, after the layers had settled, the organic phase was removed using a pipette and transferred to a 40 mL vial. MeOH (6 mL) was added, followed by concentrated HCl (5 drops, from a glass pipette). The resulting solution was stirred at room temperature for 3 h and then the solvent was removed under reduced pressure.

[0133] The resulting yellow oil was rotary evaporated from CH3CN (3 × 3 mL) to form a tan solid. CH3CN (6 mL) was added to the solid, which was then collected by filtration. The solid was washed with CH3CN (2 × 3 mL). The material was dissolved in Et2O (4 mL) and passed through a silica plug. The plug was washed with additional Et2O (20 mL). The combined Et2O was concentrated to dryness to afford 2-carbazol-9-yl-6-[2-[[[2-(3-carbazol-9-yl-2-hydroxy-5-methylphenyl)-4-fluorophenoxy]methyl]diisopropylgermyl]methoxy]-5-fluorophenyl]-4-methylphenol as a white solid (0.430 g, yield: 71%):

[0134] 11H NMR (400 MHz, chloroform-d) δ 8.20 (ddd, J = 7.7, 1.3, 0.7 Hz, 4H), 7.34 (ddd, J = 8.1, 7.2, 1.4 Hz, 4H), 7.29 (td, J = 7.4, 1.2 Hz, 4H), 7.18 (d, J = 2.2 Hz, 2H), 7.14–7.10 (m, 4H), 7.04 (dd, J = 2.2, 0.7 Hz, 2H), 6.92 (dd, J = 8.8, 3.1 Hz, 2H), 6.50–6.36 (m, 2H), 5.95–5.81 (m, 2H), 5.49 (s, 2H), 3.60 (s, 4H), 2.31 (s, 6H), 1.13 (h, J = 7.3 Hz, 2H), 0.81 (d, J = 7.5 Hz, 12H).

[0135] 19 19F NMR (376 MHz, CDCl3) δ -123.49.

[0136]

[0137] In a glove box, an ethereal solution of MeMgBr (3 M, 0.37 mL) was added to a -30 °C suspension of ZrCl4 (0.06 g, 0.27 mmol) in anhydrous toluene (5 mL). After stirring the resulting mixture for 3 minutes, a solution of 2-carbazol-9-yl-6-[2-[[[2-(3-carbazol-9-yl-2-hydroxy-5-methyl-phenyl)-4-fluoro-phenoxy]methyl-diisopropyl-germyl]methoxy]-5-fluoro-phenyl]-4-methyl-phenol (0.25 g, 0.26 mmol) in toluene / CH2Cl2 (2:1, 3 mL) was added. The resulting mixture was stirred for four hours and then the solvent was removed in vacuo to give a dark residue. Hexane (4 mL) was added to the dark residue and the mixture was then passed through a CELITE pad. The residue was washed with additional hexane (4 mL). A fresh collection vial was placed and the residue was then extracted with toluene (3 × 8 mL). The combined toluene extracts were concentrated to dryness to give a tan semi-solid. The solid was evaporated from pentane (3 × 2 mL) to give a metal-ligand complex as a tan solid (0.150 g, yield: 53%):

[0138] 11H NMR (400 MHz, benzene-d6) δ 8.12 (dt, J = 7.7, 0.9 Hz, 2H), 8.03 (dt, J = 7.7, 1.0 Hz, 2H), 7.48 (dq, J = 8.3, 1.0 Hz, 4H), 7.36 (ddd, J = 8.2, 7.1, 1.3 Hz, 2H), 7.25 (ddd, J = 8.4, 7.2, 1.2 Hz, 4H), 7.20–7.11 (m, 2H), 7.03 (dd, J = 2.4, 0.8 Hz, 2H), 6.88–6.80 (m, 4H), 6.66 (ddd, J = 9.0, 7.3, 3.2 Hz, 2H), 4.91 (dd, J = 9.0, 4.8 Hz, 2H), 4.30 (d, J = 12.1 Hz, 2H), 3.26 (d, J = 12.1 Hz, 2H), 2.07 (s, 6H), 1.31–1.15 (m, 1H), 0.61–0.48 (m, 14H), -0.93 (s, 6H).

[0139] 19 19F NMR (376 MHz, C6D6) δ -117.32.

[0140] Synthesis of metal-ligand complex 5 (MLC-5)

[0141]

[0142] Degassed toluene (6 mL) and degassed water (3 mL) were added to a 40 mL vial containing 2,7 - di - tert - butyl - 9 - [2 - (tetrahydro - 2H - pyran - 2 - yloxy) - 5 - (1,1,3,3 - tetramethylbutyl) - 3 - (4,4,5,5 - tetramethyl - 1,3,2 - dioxaborolan - 2 - yl)phenyl]carbazole (1.62 g, 2.33 mmol), bis[(2 - bromo - 4 - tert - butylphenoxy)methyl]diisopropylgermane (as described in International Publication No. WO 2018 / 183056 A1; 0.6 g, 0.93 mmol), tBu3P - PdG2 (0.02 g, 0.04 mmol) and NaOH (0.19 g, 4.67 mmol). The resulting mixture was heated to 75 °C and maintained at this temperature for 18 h. Thereafter, the reaction was cooled to room temperature. The mixture was transferred to a separatory funnel, Et2O (20 mL) and H2O (10 mL) were added, and the layers were separated. The aqueous phase was extracted with additional Et2O (10 mL). The combined organic layers were washed with brine (10 mL), dried (Na2SO4) and filtered into a 100 mL round - bottom flask. The solvent was removed under reduced pressure. The crude residue was dissolved in MeOH / THF (1:1, 20 mL), concentrated HCl (5 drops, from a glass pipette) was added, a reflux condenser was fitted to the flask, and then the solution was heated to 70 °C with stirring. After 4 h, the solvent was removed under reduced pressure. The yellow oil was rotary - evaporated from CH3CN (3 × 5 mL) and a tan solid was formed. CH3CN (15 mL) was added to the solid, which was then collected by filtration. The solid was washed with CH3CN (2 × 4 mL). The solid was isolated and dried under vacuum to give 6',6'''-(((diisopropylgermanediyl)bis(methylene))bis(oxy))bis(3'-(tert - butyl)-3-(2,7 - di - tert - butyl - 9H - carbazol - 9 - yl)-5-(2,4,4 - trimethylpentan - 2 - yl)-[1,1'-biphenyl]-2 - ol) (0.7 g, yield: 52%) as a tan powder:

[0143] 1 H NMR (400 MHz, chloroform - d) δ 8.05 (d, J = 8.2 Hz, 4H), 7.35–7.29 (m, 6H), 7.24 (d, J = 2.5 Hz, 2H), 7.21–7.10 (m, 6H), 6.71 (d, J = 8.6 Hz, 2H), 6.25 (d, J = 7.2 Hz, 2H), 5.35 (s, 2H), 3.78 (s, 4H), 1.67 (s, 4H), 1.33 (s, 12H), 1.30 (s, 36H), 1.23–1.12 (m, 20H), 0.79 (d, J = 7.4 Hz, 12H), 0.77 (s, 18H).

[0144]

[0145] In a glove box, an ethereal solution of MeMgBr (3 M, 0.30 mL) was added to a -30 °C suspension of ZrCl4 (0.05 g, 0.22 mmol) in anhydrous toluene (8 mL). After stirring the resulting mixture for 3 minutes, a -30 °C solution of 6',6'''-(((diisopropylgermylene)bis(methylene))bis(oxy))bis(3'-(tert-butyl)-3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol) (0.3 g, 0.21 mmol) in toluene (2 mL) was added. The resulting mixture was stirred for 2 hours and then the solvent was removed in vacuo to give a dark residue. Hexane (10 mL) was added to the vial and the solution was shaken at room temperature for a few minutes, and then the material was passed through a CELITE plug in a sintered funnel. The frit was extracted with hexane (5 mL), the vial was replaced, and the CELITE plug was extracted with toluene (2 × 10 mL). The toluene was removed using vacuum to give a metal-ligand complex as a tan powder (0.18 g, yield: 55%):

[0146] 1 H NMR (400 MHz, benzene-d6) δ 8.40 (d, J = 8.2 Hz, 2H), 8.09 (dd, J = 8.2, 0.6 Hz, 2H), 7.75 (d, J = 1.6 Hz, 2H), 7.68–7.63 (m, 4H), 7.61–7.55 (m, 4H), 7.50 (d, J = 2.5 Hz, 2H), 7.29 (dd, J = 8.3, 1.7 Hz, 2H), 7.09 (dd, J = 8.7, 2.6 Hz, 2H), 5.19 (d, J = 8.6 Hz, 2H), 4.64 (d, J = 12.2 Hz, 2H), 3.67 (d, J = 12.2 Hz, 2H), 1.79–1.61 (m, 4H), 1.48–1.43 (m, 24H), 1.40 (s, 6H), 1.22 (s, 18H), 1.16 (s, 18H), 0.94 (s, 20H), 0.75 (d, J = 7.4 Hz, 6H), 0.64 (d, J = 7.5 Hz, 6H), -1.01 (s, 6H).

[0147] Synthesis of metal-ligand complex 6 (MLC-6)

[0148]

[0149] In a glove box, an ethereal solution of MeMgBr (3 M, 0.30 mL) was added to a -30 °C suspension of HfCl4 (0.07 g, 0.21 mmol) in anhydrous toluene (8 mL). After stirring the resulting mixture for 3 minutes, a -30 °C solution of 6',6'''-(((diisopropylgermandiyl)bis(methylene))bis(oxy))bis(3'-(tert-butyl)-3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol) (0.3 g, 0.21 mmol) in toluene (2 mL) was added. The resulting mixture was stirred for 18 hours and then the solvent was removed in vacuo to give a dark residue. Hexane (5 mL) was added to the vial, the solution was shaken at room temperature for a few minutes, and then the material was passed through a CELITE plug in a sintered funnel. The frit was extracted with hexane (3 mL), the vial was replaced, and the CELITE plug was extracted with toluene (2 × 10 mL). The toluene was removed using vacuum to give a metal-ligand complex as a tan powder (0.14 g, yield: 41%):

[0150] 1 H NMR (400 MHz, benzene-d6) δ 8.41 (d, J = 8.4 Hz, 2H), 8.10 (dd, J = 8.2, 0.6 Hz, 2H), 7.75 (d, J = 1.6 Hz, 2H), 7.66 (d, J = 2.5 Hz, 2H), 7.63–7.60 (m, 4H), 7.57 (dd, J = 8.3, 1.7 Hz, 2H), 7.49 (d, J = 2.5 Hz, 2H), 7.29 (dd, J = 8.3, 1.7 Hz, 2H), 7.10 (dd, J = 8.2, 2.1 Hz, 2H), 5.19 (d, J = 8.7 Hz, 2H), 4.74 (d, J = 12.3 Hz, 2H), 3.74 (d, J = 12.4 Hz, 2H), 1.78–1.60 (m, 4H), 1.47–1.44 (m, 24H), 1.40 (s, 6H), 1.21 (s, 18H), 1.15 (s, 18H), 0.93 (s, 20H), 0.75 (d, J = 7.4 Hz, 6H), 0.63 (d, J = 7.5 Hz, 6H), -1.23 (s, 6H).

[0151] Synthesis of metal-ligand complex 7 (MLC-7)

[0152]

[0153] In a glove box, an ethereal solution of MeMgBr (methylmagnesium bromide, 3.0 M, 0.88 mmol, 4.4 equiv) was added to a -30 °C suspension of HfCl4 (64 mg, 0.2 mmol, 1.0 equiv) in anhydrous toluene (6.0 mL). After stirring the resulting mixture for 2 minutes, the ligand (described in International Publication No. WO 2018 / 183056 A1; 0.254 g, 0.2 mmol, 1.0 equiv) was added in portions. The resulting mixture was stirred overnight and then the solvent was removed in vacuo to give a dark residue, which was extracted with hexane (12 mL) and then with toluene (12 mL). The hexane extract was concentrated to approximately 3 mL to 4 mL, then kept in a refrigerator for one day, and then the top solution was decanted and the white solid was dried in vacuo to give a white solid (150 mg). The toluene extract was dried in vacuo to give a white solid (60 mg). Then the hexane extract and the toluene extract were combined to give a metal-ligand complex as a white powder (210 mg, yield: 71%):

[0154] 1H NMR (400 MHz, C6D6) δ 8.14 (br s, 2H), 7.80 (t, J = 1.8 Hz, 2H), 7.65 (br s, 2H), 7.58 (d, J = 2.5 Hz, 2H), 7.42–7.29 (m, 4H), 7.22 (dd, J = 8.6, 2.5 Hz, 2H), 5.71 (d, J = 8.6 Hz, 2H), 4.97 (d, J = 11.8 Hz, 2H), 3.78 (d, J = 11.8 Hz, 2H), 2.74–2.53 (m, 4H), 1.75–1.61 (m, 4H), 1.59–1.20 (m, 74H), 0.94–0.88 (m, 6H), 0.82–0.78 (m, 2H), 0.70–0.60 (m, 12H), -0.23 (s, 6H).

[0155] Preparation of the effective catalyst for spray drying of the present invention :

[0156] Production of catalyst system

[0157] Various catalyst systems are produced via spray drying. Specifically, fumed silica (which can Obtained commercially from Cabot Corporation (available from W.R.Grace) and methylaluminoxane (10 wt% in toluene solution) were slurried and mixed in toluene for 15 minutes. The metal-ligand complex was added to the resulting slurry and mixed for an additional 30 to 60 minutes. Then the resulting catalyst system precursor was dried using a spray dryer (commercially available from BUCHI Corporation as Mini Spray Dryer B-290) at an inlet temperature of 185 °C, an outlet temperature of 100 °C, a suction speed of 95 revolutions per minute (rpm), and a pump speed of 150 rpm.

[0158] Table 1: Preparation of catalyst system

[0159]

[0160] Gas-phase batch reactor test :

[0161] The spray-dried catalyst prepared above was used for ethylene / 1-hexene copolymerization in the gas phase in a 2 L semi-batch autoclave polymerization reactor. The individual test conditions and the polymer properties produced in these tests are listed in the test performance results.

[0162] Gas-phase batch reactor catalyst test procedure :

[0163] The gas-phase reactor used was a 2-liter stainless-steel autoclave equipped with a mechanical stirrer. For the experimental runs, the reactor was first dried for 1 hour, 200 g of NaCl was added, and it was dried by heating at 100 °C under nitrogen for 30 minutes. After the baking process of the reactor, 3 g of SDMAO (supported methylaluminoxane) (only 5 g of SDMAO was used for sd-Cat1) was introduced under nitrogen pressure as a scavenger. After adding SDMAO, the reactor was sealed and the components were stirred. Then hydrogen and 1-hexene pressurized with ethylene were added to the reactor. Once the system reached a steady state, the catalyst was loaded into the reactor at 80 °C to start the polymerization. The reactor temperature was brought to the desired reaction temperature and maintained at that temperature, and the feed ratios of ethylene, 1-hexene, and hydrogen were maintained throughout the 1-hour run. At the end of the run, the reactor was cooled, vented, and opened. The resulting product mixture was washed with water and methanol and then dried. The polymerization productivity (grams of polymer / gram of catalyst-hour) was determined as the ratio of the polymer produced to the amount of catalyst added to the reactor.

[0164] Production of polyethylene

[0165] The reaction conditions used for each test are reported in Table 2. The properties of the poly(ethylene-co-1-hexene) copolymer (vinyl copolymer) produced in each test are reported in Table 3.

[0166] Table 2: Batch gas-phase reactor conditions

[0167]

[0168] Table 3: Characteristics of vinyl copolymers prepared in a gas-phase polymerization batch reactor (see Table 2) 。

[0169]

[0170] As the molecular weight (MW) of the polymer chain increases, polymers in which the weight percentage (wt%) of comonomer increases have improved properties in many applications. This is also referred to as a polymer having a broad orthogonal composition distribution (BOCD). Quantitatively, a measure of the "reverse" or "BOCD" is the molecular weight comonomer distribution index (MWCDI). If the MWCDI is greater than 0, the polymer is called BOCD, or has a reverse comonomer distribution, while a polymer with an MWCDI less than 0 is called having a normal (or Ziegler-Natta) type comonomer distribution, and when the MCDWI equals 0, the comonomer distribution is called flat. As the comonomer distribution goes from normal to flat to reverse, certain polymer properties generally improve.

[0171] The results in Table 3 show that the vinyl copolymers of Examples 1 to 11 prepared in a gas phase polymerization batch reactor independently have a reverse comonomer distribution and a unimodal molecular weight distribution. The molecular weight distribution (MWD) and MWCDI were determined by the conventional GPC analysis described previously. The MWCDI and MWD of Examples 6 and 8 of the present invention are graphically depicted in Figure 1 ; Examples 7 and 10 are graphically depicted in Figure 2 . Figure 1 and Figure 2 further show that based on the single maximum of the MWD curve, the vinyl copolymers are unimodal. In addition, as shown in Figures 1 to 2 , the MWCDI line has a slope greater than 0, indicating the presence of reverse comonomer incorporation.

Claims

1. A process for producing a vinyl copolymer having a reverse comonomer distribution, the process comprising polymerizing ethylene and one or more C3-C 12 α-olefin comonomers in a single gas phase polymerization reactor in the presence of a catalyst system, the reactor temperature being from 60 °C to less than or equal to 150 °C, and the molar feed ratio of the one or more C3-C 12 α-olefin comonomers to the ethylene being less than or equal to 0.020, wherein: The catalyst system comprises an activated metal-ligand complex disposed on one or more support materials; and the metal-ligand complex has a structure according to formula (Ia): Wherein: A - is an anion; M is titanium, zirconium or hafnium; n is 2; Z is –O-; Each X is a monodentate ligand independently selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl and chlorine; R 1 and R 16 are identical and are selected from a group having formula (II) and a group having formula (III): wherein R 31 、R 32 、R 33 、R 34 、R 35 、R 41 、R 42 、R 43 、R 44 、R 45 、R 46 、R 47 、R 48 is –H; or R 32 、R 34 、R 43 、R 46 is tert-butyl, and R 31 、R 33 、R 35 、R 41 、R 42 、R 44 、R 45 、R 47 、R 48 is –H; or R 32 、R 34 、R 42 、R 47 is tert-butyl, and R 31 、R 33 、R 35 、R 41 、R 43 、R 44 、R 45 、R 46 、R 48 is –H; R 2 、R 4 、R 5 、R 7 、R 8 、R 9 、R 10 、R 12 、R 13 and R 15 is –H; R 3 、R 6 、R 11 、R 14 are independently selected from -H, C1-C 50 hydrocarbyl, and halogen; R 19 and R 20 is –CH2-; R 17 and R 18 are independently selected from linear or branched C1-C 20 alkyl; and The vinyl copolymer has a unimodal molecular weight distribution as determined by gel permeation chromatography (GPC) and a molecular weight comonomer distribution index greater than 0 as measured by fast Fourier transform infrared (FT-IR) spectroscopy using the gel permeation chromatography (GPC).

2. The process according to claim 1, wherein R 17 and R 18 are independently selected from branched C3-C7 alkyl groups.

3. The process according to claim 1, wherein R 1 and R 16 are groups having the formula (II), and R 32 and R 34 are tert-butyl groups.

4. The process according to claim 1, wherein R 3 , R 6 , R 11 , R 14 are independently selected from methyl, 1-butyl, n-octyl, tert-octyl.

5. The process according to any one of claims 1 to 4, wherein R 1 and R 16 are groups having the formula (III).

6. The process according to any one of claims 1 to 4, wherein the one or more carrier materials comprise fumed silica.

7. The method according to any one of claims 1 to 4, wherein the catalyst system is in the form of spray-dried particles, and the spray-dried particles are prepared by spray-drying the metal-ligand complex onto the one or more support materials.

8. The method according to any one of claims 1 to 4, wherein the method produces greater than or equal to 2,500 grams of the vinyl copolymer per gram of the catalyst system per hour.

9. The method according to any one of claims 1 to 4, wherein the ratio of the weight-average molecular weight of the vinyl copolymer to the weight percentage (wt%) of the comonomer in the vinyl copolymer is greater than or equal to 10,000.

10. The method according to any one of claims 1 to 4, wherein the vinyl copolymer further has a weight-average molecular weight greater than 500,000 g / mol.

11. The method according to any one of claims 1 to 4, wherein the ratio of the weight-average molecular weight of the vinyl copolymer to the weight percentage (wt%) of the comonomer in the vinyl copolymer is greater than or equal to 20,000.

12. The method according to any one of claims 1 to 4, wherein the ratio of the weight-average molecular weight of the vinyl copolymer to the weight percentage (wt%) of the comonomer in the vinyl copolymer is greater than or equal to 30,000.

13. The method according to claim 1, wherein the catalyst system further comprises one or more activators.

14. The method according to claim 13, wherein the one or more activators include methylaluminoxane (MAO).

15. The method according to any one of claims 1 to 4, wherein the catalyst system is fed into the gas-phase polymerization reactor in pure form, as a solution, as a slurry, or a combination thereof.

16. The method according to any one of claims 1 to 4, wherein the reactor temperature is less than or equal to 120 °C.

17. The method according to any one of claims 1 to 4, wherein the reactor temperature is 75 °C to 105 °C.

18. The method according to any one of claims 1 to 4, wherein the reactor temperature is 80 °C to 100 °C.

19. The method according to any one of claims 1 to 4, wherein the reactor temperature is 85 °C to 95 °C.

20. The method according to any one of claims 1 to 4, wherein the weight-average molecular weight of the vinyl copolymer is greater than 200,000 g / mol.

21. The method according to any one of claims 1 to 4, wherein the vinyl copolymer further comprises less than 30% by weight of comonomer incorporation, determined by rapid FT-IR spectroscopy on the dissolved polymer measured by GPC.

Images