Catalyst system and method for producing polyethylene using the same

Abstract

Embodiments of the present application relate to procatalysts and catalyst systems comprising procatalysts comprising metal-ligand complexes having a structure of formula (I).

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 031,638 filed on May 29, 2020 and U.S. Provisional Patent Application No. 63 / 143,333 filed on January 29, 2021, both of which are incorporated herein by reference in their entirety. Technical Field

[0003] Embodiments of the present disclosure relate generally to processes for producing polyethylene, and in particular to the polymerization of ethylene and optionally one or more (C 3 -C 12 ) an alpha-olefin comonomer is contacted with a germanium-bridged bisphenylphenoxy catalyst system. Background Art

[0004] Since the discovery of heterogeneous olefin polymerization by Ziegler and Natta, 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 bisphenylphenoxy (BPP) metal-ligand complexes can produce polyolefins with flat or reverse short chain branching distribution (SCBD), relatively high levels of comonomer incorporation, high native molecular weight and / or narrow medium molecular weight distribution (MWD).

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

[0006] Therefore, there is a continuing need for catalyst systems suitable for use in gas phase reactors, and these catalyst systems have improved productivity when used in gas phase polymerization processes. Embodiments of the present disclosure address these needs by providing catalyst systems that include BPP metal-ligand complexes having germanium-containing bridges. These catalyst systems exhibit greatly improved productivity when used in gas phase polymerization processes when compared to similar catalyst systems that include BPP metal-ligand complexes that do not have germanium-containing bridges.

[0007] Embodiments of the present disclosure include a procatalyst. The procatalyst includes a metal-ligand complex disposed on one or more support materials. The metal-ligand complex has a structure according to formula (I):

[0008]

[0009] In formula (I), M is titanium, zirconium or hafnium; (X) n The subscript n is 1, 2 or 3; each X is independently selected from unsaturated (C 2 -C 50 ) hydrocarbons, unsaturated (C 2 -C 50 ) heterohydrocarbons, (C 1 -C 50 ) alkyl, (C 1 -C 50 ) heteroalkyl, (C 6 -C 50 ) aryl, (C 4 -C 50 )heteroaryl, halogen, -N(R N ) 2 and -N(R N )COR C The monodentate ligand of formula (I) is neutrally charged overall.

[0010] In formula (I), each Z is independently selected from -O-, -S-, (C 6 -C 50 ) aryl, (C 4 -C 50 ) heteroaryl, N(C 1 -C 40 ) alkyl and P(C 1 -C 40 ) hydrocarbon group.

[0011] In formula (I), R 1 and R 16 Independently selected from (C 6 -C 50 ) aryl, (C 4 -C 50 ) heteroaryl, (C 1 -C 40 ) alkyl, (C 3 -C 40 ) heteroalkyl, a group having formula (II), a group having formula (III), and a group having formula (IV):

[0012]

[0013] In formula (II), (III) and (IV), R 31-35 , R 41-48 and R 51-59 are independently selected from -H, (C 1-C 50 ) alkyl, (C 1 -C 50 ) heteroalkyl, -Si(R C ) 3 , -Ge(R C ) 3 、-P(R P ) 2 、-N(R N ) 2 、-OR C 、-SR C 、-NO 2 、-CN、-CF 3 , R C S(O)-、R C S(O) 2 -、(R C ) 2 C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C ) 2 NC(O)- or halogen.

[0014] In formula (I), 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, (C 1 -C 50 ) alkyl, (C 1 -C 50 ) heteroalkyl, -Si(R C ) 3 , -Ge(R C ) 3 、-P(R P ) 2 、-N(R N ) 2 、-OR C 、-SR C 、-NO 2 、-CN、-CF 3 , R CS(O)-、R C S(O) 2 -、(R C ) 2 C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C ) 2 NC(O)- and halogen.

[0015] In formula (I), R 23 and R 24 Independently selected from -(CR C 2 ) m -, wherein the subscript m is 1 to 10.

[0016] In formula (I), R 17 and R 18 Independently selected from linear or branched (C 1 -C 20 )alkyl.

[0017] In formulas (I), (II), (III) and (IV), each R C , R P and R N are independently selected from -H, (C 1 -C 50 ) alkyl and (C 1 -C 50 ) heteroalkyl.

[0018] Embodiments of the present disclosure include methods for producing a catalyst system. 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 the catalyst system.

[0019] Embodiments of the present disclosure include processes for producing polyethylene. The process comprises reacting ethylene and optionally one or more (C 3 -C 12 ) an alpha-olefin comonomer is contacted with a catalyst system. The catalyst system comprises a metal-ligand complex disposed on one or more support materials.

[0020] These and additional features provided by embodiments of the present disclosure will be more fully understood from the following detailed description. DETAILED DESCRIPTION

[0021] The specific embodiments of the primary catalyst, catalyst system, method for producing the catalyst system and the process for producing polyethylene will now be described. However, it should be understood that the system, method and process of the present disclosure can be embodied in different forms and should not be construed as being limited to the specific embodiments set forth in the present disclosure. On the contrary, embodiments are provided so that the present disclosure will be thorough and complete, and the embodiments will fully convey the scope of the subject matter to those skilled in the art.

[0022] The following is a list of common abbreviations used in this disclosure:

[0023] 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; Et 2 O: ether; CH 2 Cl 2 : dichloromethane; CV: column volume (used in column chromatography); EtOAc: ethyl acetate; C 6 D 6 : Deuterated benzene or benzene-d6; CDCl 3 : deuterated chloroform; Na 2 SO 4 :Sodium sulfate; MgSO 4 : magnesium sulfate; HCl: hydrogen chloride; n-BuLi: butyl lithium; t-BuLi: tert-butyl lithium; MAO: methylaluminoxane; MMAO: modified methylaluminoxane; GC: gas chromatography; LC: liquid chromatography; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimole; mL: milliliter; M: mole; min or mins: minutes; h or hrs: hours; d: day.

[0024] The term "halogen atom" or "halogen" refers to a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to the anionic form of a halogen atom: fluoride ion (F-), chloride ion (Cl-), bromide ion (Br-), or iodide ion (I-).

[0025] 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 may all be substituted alkyl; or R 1 and R 2 may be a substituted alkyl group, and R 3The chemical names associated with the R groups are intended to convey chemical structures that are recognized in the art to correspond to the chemical structures of the chemical names. Thus, the chemical names are intended to supplement and illustrate rather than exclude structural definitions known to those skilled in the art.

[0026] 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 "cocatalyst" and "activator" are interchangeable and have the same meaning unless expressly specified.

[0027] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom in a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S ) is replaced by the term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. As used in this disclosure, the terms "hydrogen" and "-H" are interchangeable and have the same meaning unless expressly specified.

[0028] When used to describe certain chemical groups containing carbon atoms, it has the form "(C x -C y )" means that the unsubstituted form of the chemical group has from x to y carbon atoms, including x and y. For example, (C 1 -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 may be substituted with one or more substituents such as RS. x -C y )″ insert the defined R S The substituted chemical group may contain more than y carbon atoms, depending on the number of any group R S For example, "with exactly one group R S Replaced (C 1 -C 50 ) alkyl, wherein R S It is phenyl (-C 6 H 5 )" may contain from 7 to 56 carbon atoms. Thus, when "(C x -C y )" is inserted into the chemical group defined by one or more carbon-containing substituents R S When substituted, both x and y are added to the substituent R from all carbon atoms. S The combined sum of the number of carbon atoms is used to determine the minimum and maximum total number of carbon atoms in a chemical group.

[0029] The term " 1 C 50 )alkyl" means a hydrocarbon group having 1 to 50 carbon atoms, and the term "(C 1 C 50 )alkylene" means a hydrocarbon diradical having from 1 to 50 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched, cyclic (having three carbons or more, and including monocyclic and polycyclic, fused and non-fused polycyclic and bicyclic) or acyclic, and is substituted by one or more R S Substituted or unsubstituted. As used in this disclosure, (C 1 -C 50 ) The hydrocarbon group may be unsubstituted or substituted (C 1 -C 50 ) alkyl, (C 3 -C 50 )cycloalkyl, (C 3 -C 25 )cycloalkyl-(C 1 -C 25 ) alkylene, (C 6 -C 50 ) aryl or (C 6 -C 25 )Aryl-(C 1 -C 25 ) alkylene (such as benzyl (-CH 2 -C 6 H 5 )).

[0030] The term " 1 -C 50 ") alkyl" means a saturated straight or branched hydrocarbon group of 1 to 50 carbon atoms. Each (C 1 -C 50 ) The alkyl group may be unsubstituted or substituted with one or more R S In some embodiments, each hydrogen atom in the hydrocarbon group may be replaced by R S Substituted, such as, for example, trifluoromethyl. Unsubstituted (C 1 -C 50 Examples of alkyl groups are unsubstituted (C 1 -C 20 ) alkyl; unsubstituted (C 1 -C 10 ) alkyl; unsubstituted (C 1 -C 5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Substituted (C 1 -C 50 Examples of alkyl groups are substituted (C 1 -C 20 ) alkyl, substituted (C 1 -C 10 ) alkyl, trifluoromethyl and [C 45 ] alkyl. The term "[C 45 "] alkyl" means that there are a maximum of 45 carbon atoms in the group including the substituents, and for example (C 1 -C 5 ) alkyl (such as, for example, methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl or 1,1-dimethylethyl) S Replaced (C 27 -C 40 )alkyl.

[0031] The term " 3 -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 Substitution. Other cycloalkyl groups (e.g., (C x -C y )cycloalkyl) is defined in a similar manner as having x to y carbon atoms and being unsubstituted or substituted with one or more R S Substituted. Unsubstituted (C 3 -C 50 Examples of cycloalkyl groups are unsubstituted (C 3 -C 20 )cycloalkyl, unsubstituted (C 3 -C 10 )cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. 3 -C 50 Examples of cycloalkyl groups are substituted (C 3 -C 20 )cycloalkyl, substituted (C 3 -C 10 )cycloalkyl and 1-fluorocyclohexyl.

[0032] The term " 6 -C 50 ) aryl" means an unsubstituted or substituted (one or more R S) substituted monocyclic, bicyclic or tricyclic aromatic hydrocarbon groups, wherein at least 6 to 14 carbon atoms are aromatic ring carbon atoms. Monocyclic aromatic hydrocarbon groups include one aromatic ring; bicyclic aromatic hydrocarbon groups have two rings; and tricyclic aromatic hydrocarbon groups have three rings. When bicyclic or tricyclic aromatic hydrocarbon groups are present, at least one of the rings of the group is aromatic. The other one or more rings of the aromatic group may independently be fused or non-fused and be aromatic or non-aromatic. Unsubstituted (C 6 -C 50 Examples of aryl groups include: unsubstituted (C 6 -C 20 ) aryl, unsubstituted (C 6 -C 18 ) aryl; 2-(C 1 -C 5 )alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; dicyclopentadienylphenyl; hexahydrodicyclopentadienylphenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C 6 -C 50 Examples of aryl groups include: substituted (C 1 -C 20 ) aryl; substituted (C 6 -C 18 ) aryl; 2,4-bis([C 20 ] alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-on-1-yl.

[0033] 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 (C 1 -C 18 )alkyl or -H, and each R N is unsubstituted (C 1 -C 18 ) hydrocarbon group. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by a heteroatom. 1 -C 50)heteroalkyl" means a heteroalkyl group having 1 to 50 carbon atoms, and the term "(C 1 -C 50 "Heteroalkylene" means a heteroalkylene radical having 1 to 50 carbon atoms. 1 -C 50 ) heteroalkyl or (C 1 -C 50 The heteroalkylene group has one or more heteroatoms. The radicals of the heteroalkylene group can be on carbon atoms or heteroatoms. The two radicals of the heteroalkylene group can be on a single carbon atom or on a single heteroatom. In addition, one of the two radicals of the diradical can be on a carbon atom and the other can be on a different carbon atom; one of the two radicals can be on a carbon atom and the other can be on a heteroatom; or one of the two radicals can be on a heteroatom and the other can be on a different heteroatom. Each (C 1 -C 50 ) heteroalkyl and (C 1 -C 50 ) heteroalkylene may be unsubstituted or substituted with (one or more R S ) substituted, aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0034] The term " 4 -C 50 )heteroaryl" means an unsubstituted or substituted (one or more R S ) substituted monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon radicals. Monocyclic heteroaromatic hydrocarbon groups include one heteroaromatic ring; bicyclic heteroaromatic hydrocarbon groups have two rings; and tricyclic heteroaromatic hydrocarbon groups have 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 may independently be fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., typically (C x -C y ) heteroaryl, such as (C 4 -C 12 ) heteroaryl) is defined in a similar manner as having x to y carbon atoms (such as 4 to 12 carbon atoms) and being unsubstituted or substituted by one or more than one R SSubstituted. The monocyclic heteroaromatic hydrocarbon group is a 5-membered ring or a 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 heteroaromatic hydrocarbon groups include: pyrrol-1-yl; piperidin-2-yl; furan-3-yl; thien-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazole-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazole-1-yl; 1,3,4-oxadiazole-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 heteroatoms can be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon groups include pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. Bicyclic heteroaromatic hydrocarbon groups can be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring system bicyclic heteroaromatic hydrocarbon groups are indol-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-ring system bicyclic heteroaromatic hydrocarbon groups are quinolin-2-yl; and isoquinolin-1-yl. Bicyclic heteroaromatic hydrocarbon groups can be fused 5,6,5-ring systems; 5,6,6-ring systems; 6,5,6-ring systems; or 6,6,6-ring systems. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridin-9-yl.

[0035] The term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different type. 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.

[0036] The term "interpolymer" refers to polymers prepared by polymerizing at least two different types of monomers. Thus, the generic term interpolymer includes copolymers and other polymers prepared by polymerizing two or more different monomers (such as terpolymers).

[0037] The terms "polyolefin", "polyolefin polymer" and "polyolefin resin" refer to polyolefins prepared by reacting simple olefins (also known as olefins) with the general formula C n H 2nThus, the generic 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).

[0038] The terms "polyethylene" and "ethylene-based polymers" 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).

[0039] The term "molecular weight distribution" refers to the ratio of two different molecular weights of a polymer. The general term molecular weight distribution includes the weight average molecular weight (M) of a polymer. w ) and the number average molecular weight (M n ) ratio, which can also be called "molecular weight distribution (M w / M n )″, and the z-average molecular weight of the polymer (M z ) and the weight average molecular weight (M w ) ratio, which can also be called "molecular weight distribution (M z / M w )″.

[0040] The term "composition" is intended to mean a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0041] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of excludes from the scope of any subsequently recited component, step, or procedure, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically recited or listed.

[0042] In an embodiment, the catalyst system includes a procatalyst. The procatalyst includes a metal-ligand complex. The metal-ligand complex may have a structure according to formula (I):

[0043]

[0044] In formula (I), M is titanium (Ti), zirconium (Zr) or hafnium (Hf). In embodiments, M is titanium, zirconium or hafnium, each independently in a formal oxidation state of +2, +3 or +4.

[0045] In formula (I), (X) n The subscript n is 1, 2 or 3, and each X is independently selected from unsaturated (C 2 -C 50 ) hydrocarbons, unsaturated (C 2 -C 50 ) heterohydrocarbons, (C 1 -C 50 ) alkyl, (C 1 -C 50 ) heteroalkyl, (C 6 -C 50 ) aryl, (C 4 -C 50 )heteroaryl, halogen, -N(R N ) 2 and -N(R N )COR C In some embodiments, each X is independently selected from methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chlorine. In some embodiments, (X) n The subscript n is 2, and each X is the same. In other embodiments, at least two X are different. For example, (X) nThe subscript n of 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 an embodiment, (X) n The subscript n is 1 or 2, and at least two X are independently monoanionic monodentate ligands, and if present, the third X is a neutral monodentate ligand. In one or more embodiments, (X) n The subscript n of is 2. In formula (I), the metal-ligand complex is electrically neutral as a whole.

[0046] In formula (I), each Z is independently selected from -O-, -S-, (C 6 -C 50 ) aryl, (C 4 -C 50 ) heteroaryl, N(C 1 -C 50 ) alkyl and P(C 1 -C 50 ) alkyl. In an embodiment, each Z is the same. For example, each Z can be -O-.

[0047] In formula (I), R 1 and R 16 Independently selected from (C 6 -C 50 ) aryl, (C 4 -C 50 ) heteroaryl, (C 1 -C 50 ) alkyl, (C 3 -C 40 ) heteroalkyl, a group having formula (II), a group having formula (III), and a group having formula (IV):

[0048]

[0049] In formula (II), R 31 , R 32 , R 33 , R 34 , R 35 are independently selected from -H, (C 1 -C 50 ) alkyl, (C 1 -C 50 ) heteroalkyl, -Si(R C ) 3 , -Ge(R C ) 3 、-P(R P ) 2 、-N(R N) 2 、-OR C 、-SR C 、-NO 2 、-CN、-CF 3 , R C S(O)-、R C S(O) 2 -、(R C ) 2 C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C ) 2 NC(O)- or halogen.

[0050] In formula (III), R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 are independently selected from -H, (C 1 -C 50 ) alkyl, (C 1 -C 50 ) heteroalkyl, -Si(R C ) 3 , -Ge(R C ) 3 、-P(R P ) 2 、-N(R N ) 2 、-OR C 、-SR C 、-NO 2 、-CN、-CF 3 , R C S(O)-、R C S(O) 2 -、(R C ) 2 C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C ) 2 NC(O)- or halogen.

[0051] In formula (IV), R 51 、R5 2 , R53 , R 54 , R 55 , R 56 , R 57 , R 58 and R 59 are independently selected from -H, (C 1 -C 50 ) alkyl, (C 1 -C 50 ) heteroalkyl, -Si(R C ) 3 , -Ge(R C ) 3 、-P(R P ) 2 、-N(R N ) 2 、-OR C 、-SR C 、-NO 2 、-CN、-CF 3 , R C S(O)-、R C S(O) 2 -、(R C ) 2 C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C ) 2 NC(O)- or halogen.

[0052] The group R in the metal-ligand complex of formula (I) 1 and R 16 are chosen independently of each other. For example, R 1 can be selected from groups having formula (II), (III) or (IV), and R 16 It can be (C 4 -C 50 ) heteroaryl; or R 1 can be selected from free radicals having formula (II), (III) or (IV), and R 16 Can be selected from R 1 The same or different free radicals having formula (II), (III) or (IV). In an embodiment, R 1 and R 16 Both are radicals of formula (II) in which the radical R 31-35 In R 1 and R 16 In some embodiments, R 1 and R16 Both are groups of formula (III) in which the group R 41-48 In R 1 and R 16 In other embodiments, R 1 and R 16 Both are radicals of formula (IV) in which the radical R 51-59 In R 1 and R 16 The same or different.

[0053] In an embodiment, R 1 and R 16 At least one of them is a group having formula (II), wherein R 32 and R 34 In some embodiments, when R 1 or R 16 When at least one of them is a group having 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 is -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 is -H. In some embodiments, R 42 and R 47 Both are -H. In some embodiments, R 41-48 Yes -H.

[0054] In formula (I), 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, (C 1 -C 50 ) alkyl, (C 1 -C 50 ) heteroalkyl, -Si(R C ) 3 , -Ge(R C) 3 、-P(R P ) 2 、-N(R N ) 2 、-OR C 、-SR C 、-NO 2 、-CN、-CF 3 , R C S(O)-、R C S(O) 2 -、(R C ) 2 C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C ) 2 NC(O)- and halogen.

[0055] In some embodiments, R 5 , R 6 , R 7 and R 8 At least one of is a halogen atom; and R 9 , R 10 , R 11 and R 12 At least one of is a halogen atom. 5 , R 6 , R 7 and R 8 At least two of are halogen atoms; and R 9 , R 10 , R 11 and R 12 At least two of are halogen atoms. In various embodiments, R 5 , R 6 , R 7 and R 8 At least three of are halogen atoms; and R 9 , R 10 , R 11 and R 12 At least three of them are halogen atoms.

[0056] In an embodiment, R 3 and R 14 Yes (C 1 -C 24 ) alkyl. In various embodiments, R 3 and R 14 Yes (C 1 -C 20In some embodiments, R 3 and R 14 Yes (C 4 -C 24 ) alkyl. In one or more embodiments, R 3 and R 14 Yes (C 8 -C 12 In some embodiments, R 3 and R 14 is 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-trimethylpent-2-yl), nonyl, and decyl. In an embodiment, R 3 and R 14 For-OR C , where R C For (C 1 -C 20 ) hydrocarbon, and in some embodiments, R C It is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl) or 1,1-dimethylethyl.

[0057] In an embodiment, R 3 and R 14 In other embodiments, R 3 and R 14 Yes (C 4 -C 24 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-trimethylpent-2-yl), nonyl and decyl.

[0058] In some embodiments, R 6 and R 11 is halogen. In other embodiments, R 6 and R 11 Yes (C 1 -C 24 In some embodiments, R 6 and R 11R is 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-trimethylpent-2-yl), nonyl, and decyl. In some embodiments, R 6 and R 11 In the embodiment, R 6 and R 11 For-OR C , where R C For (C 1 -C 20 ) alkyl, 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 -SiR C 3 , where each R C Independently (C 1 -C 20 ) alkyl, and in some embodiments, R C It is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl) or 1,1-dimethylethyl.

[0059] In some embodiments, R 3 and R 14 is methyl; and R 6 and R 11 is halogen. In other embodiments, R 6 and R 11 In other embodiments, R 3 and R 14 It is tert-octyl or n-octyl.

[0060] In formula (I), R 23 and R 24 Independently selected from -(CR C 2 ) m -, wherein the subscript m is 1 to 10. In one or more embodiments, each subscript m is 1 or 2.

[0061] In formula (I), R 17 and R 18 Independently selected from linear or branched (C 1 -C 20 In some embodiments, R 17 and R 18Independently selected from linear or branched (C 2 -C 20 ) alkyl, (C 3 -C 7 ) alkyl or (C 4 -C 7 )cycloalkyl.

[0062] In formulas (I), (II), (III) and (IV), each R C , R P and R N are independently selected from -H, (C 1 -C 50 ) alkyl and (C 1 -C 50 ) heteroalkyl.

[0063] In embodiments, the primary catalyst may be catalytically active by contact with or in combination with an activator. A primary catalyst that is catalytically active by contact with or in combination with an activator may be referred to as a "catalyst system". That is, as used in the present disclosure, a catalyst system may include a primary catalyst and one or more activators. The term "activator" may include any combination of reagents that increase the rate of oligomerization or polymerization of unsaturated monomers (such as olefins) of a transition metal compound. The activator may also affect the molecular weight, degree of branching, comonomer content or other properties of an oligomer or polymer. The transition metal compound may be activated for oligomerization and / or polymerization catalysis in any manner sufficient to allow coordination or cationic oligomerization and / or polymerization.

[0064] Aluminoxane activators can be used as activators for one or more of the catalyst compositions. Aluminoxanes or alkylaluminums are typically oligomeric compounds containing --Al(R)--O--subunits, wherein 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, particularly 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 0 594 218, and WO 94 / 10180.

[0065] When the activator is an alumoxane (modified or unmodified), the maximum amount of activator can be selected to be a 5000-fold molar excess of Al / M relative to the catalyst precursor (per metal catalytic site). Alternatively or additionally, the minimum amount of activator to catalyst precursor can be set at a 1:1 molar ratio.

[0066] Aluminum alkyl or organoaluminum compounds that can be used as activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like.

[0067] When the metal-ligand complex is catalytically active by an activator, the metal of the metal-ligand complex may have a formal charge of positive one (+1). In embodiments where the primary catalyst comprises a metal-ligand complex, the metal-ligand complex has a structure according to formula (I) and is overall electrically neutral. In embodiments where the catalyst system comprises a metal-ligand complex, the metal-ligand complex may have a structure according to formula (Ia) and have an overall formal charge of positive one (+1):

[0068]

[0069] In formula (Ia), A- is an anion, and M, (X) n The subscript n, each X, each Z, R i -R 16 , R 17-18 and R 23-24 As previously described for the metal-ligand complex of formula (I).

[0070] Formula (Ia) is an exemplary depiction of an active catalyst.

[0071] In embodiments, the metal-ligand complex, the activator, or both may be disposed on one or more support materials. For example, the metal-ligand complex may be deposited on, contacted with, vaporized with, bonded with, incorporated into, adsorbed or absorbed therein or thereon, one or more support materials. One of the support methods well known in the art or as described below may be used, and the metal-ligand complex may be combined with one or more support materials. As used in the present disclosure, the metal-ligand complex is in a supported form, for example, when deposited on, contacted with, incorporated into, adsorbed or absorbed therein or thereon, one or more support materials.

[0072] Suitable support 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 support material includes dehydrated or non-dehydrated silica, fumed silica, alumina (e.g., as described in International Patent Application No. 1999 / 060033), silica-alumina, and mixtures of these. The fumed silica may be hydrophilic (untreated), alternatively hydrophobic (treated). In embodiments, the support material is hydrophobic fumed silica, which may be prepared by treating untreated fumed silica with a treating agent such as dimethyldichlorosilane, polydimethylsiloxane fluid, or hexamethyldisilazane. In some embodiments, the support 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), phyllosilicates, zeolites, talc, clays (e.g., as described in U.S. Patent No. 6,034,187), and mixtures of these. In other embodiments, combinations of these support materials may be used, such as, for example, silica-chromium, silica-alumina, silica-titania, and combinations of these. Additional support materials may also include those porous acrylic polymers described in European Patent No. 0767184. Other support materials may also include nanocomposites described in International Patent Application No. 1999 / 047598; aerogels described in International Patent Application No. 1999 / 048605; spherulites described in U.S. Patent No. 5,972,510; and polymer beads described in International Patent Application No. 1999 / 050311.

[0073] In an embodiment, the surface area of ​​the support material is 10 m2 / g (m 2 / g) to 700m 2 / g, pore volume is 0.1 cubic meter / gram (cm 3 / g) to 4.0cm 3 / g, and the average particle size is 5 micrometers (μm) to 500 μm. In some embodiments, the surface area of ​​the support material is 50m 2 / g to 500m 2 / g, pore volume 0.5cm 3 / g to 3.5cm 3 / g, and the average particle size is 10 μm to 200 μm. In other embodiments, the surface area of ​​the support material can be 100 m 2 / g to 400m 2 / g, pore volume 0.8cm 3 / g to 3.0cm 3 / g, and the average particle size is 5μm to 100μm. The average pore size of the support material is usually 10 angstroms to Such as to or to

[0074] There are various suitable methods to produce the catalyst system of the present disclosure. In one or more embodiments, the method for producing the catalyst system includes contacting one or more support materials, one or more activators, and a metal-ligand complex in an inert hydrocarbon solvent to produce the catalyst system. In some embodiments, the method for producing the 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, the method for producing the catalyst system includes 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.

[0075] In some embodiments, the method 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 a catalyst system precursor to produce a catalyst system. More specifically, these methods may include preparing a mixture of a metal-ligand complex, one or more support materials, one or more activators, or a combination of these and an inert hydrocarbon solvent. The inert hydrocarbon solvent may then be removed from the mixture to produce a metal-ligand complex, one or more activators, or a combination of these disposed on the one or more support materials. In an embodiment, the removal step may be achieved by conventionally evaporating the inert hydrocarbon solvent from the mixture (i.e., conventional concentration methods), which produces an evaporation / supported catalyst system. In other embodiments, the removal step may be achieved 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 the 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 an inert hydrocarbon solvent.

[0076] As described above, the catalyst systems of the present disclosure can be used in a process for producing a polymer (such as polyethylene) via the polymerization of an olefin (such as ethylene). In an embodiment, one or more olefins can be contacted with the catalyst system 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 (C 3 -C 12 ) α-olefin comonomer is contacted with the catalyst system of the present disclosure. The catalyst system can be fed into 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 system can be fed directly into the gas phase polymerization reactor. In other embodiments, a solution or slurry of the catalyst system in a solvent (such as an inert hydrocarbon or mineral oil) can be fed into the reactor. For example, the primary catalyst can be fed into the reactor in an inert hydrocarbon solution, and the activator can be fed into the reactor in a mineral oil slurry.

[0077] In an embodiment, the gas phase polymerization reactor comprises a fluidized bed reactor. The fluidized bed reactor may include a "reaction zone" and a "speed reduction zone". The reaction zone may include a bed of growing polymer particles, forming polymer particles and a small amount of a catalyst system, which is fluidized by a continuous flow of gaseous monomers and diluents to remove the heat of polymerization through the reaction zone. Optionally, some recycle gases may be cooled and compressed to form liquids, which increase the heat removal capacity of the circulating gas stream when re-entering the reaction zone. Suitable gas flow rates can be easily determined by simple experiments. The replenishment rate of gaseous monomers to the circulating gas stream may be equal to the rate at which the particulate polymer product and the monomers associated therewith can be taken out of the reactor, and the composition of the gas passing through the reactor may be adjusted to maintain a substantially stable gaseous composition in the reaction zone. The gas leaving the reaction zone may be transferred to a speed reduction zone for removing entrained particles. Finer entrained particles and dust may be removed in a cyclone dust collector and / or a fine filter. The gas may pass through a heat exchanger, where the heat of polymerization may be removed, compressed in a compressor, and then returned to the reaction zone. Additional reactor details and means for 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.

[0078] In an embodiment, the reactor temperature of the gas phase polymerization reactor is from 30° C. to 150° C. For example, the reactor temperature of the gas phase polymerization reactor may be from 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., 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. 0°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. Typically, a gas phase polymerization reactor can be operated at the highest temperature feasible, taking into account the sintering temperature of the polymer product in the reactor. Regardless of the process used to make polyethylene, the reactor temperature should be below the melting temperature or "sintering" temperature of the polymer product. Therefore, the upper temperature limit can be the melting temperature of the polymer product.

[0079] 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 may 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). sig), 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).

[0080] In an embodiment, hydrogen can be used during polymerization to control the final properties of the polyethylene. The amount of hydrogen in the polymerization can 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 used in the polymerization process can be the amount required to achieve the desired properties of the polyethylene, such as, for example, the melt flow rate (MFR). In an embodiment, the ratio of hydrogen to total polymerizable monomers (H 2 The molar ratio of hydrogen to total polymerizable monomers (H 2 The molar ratio of : monomer may be 0.0001 to 10, 0.0001 to 5, 0.0001 to 3, 0.0001 to 0.10, 0.0001 to 0.001, 0.0001 to 0.0005, 0.0005 to 10, 0.0005 to 5, 0.0005 to 3, 0.0005 to 0.10, 0.0005 to 0.001, 0.001 to 10, 0.001 to 5, 0.001 to 3, 0.001 to 0.10, 0.10 to 10, 0.10 to 5, 0.10 to 3, 3 to 10, 3 to 5, or 5 to 10.

[0081] In embodiments, the catalyst system of the present disclosure can be used to polymerize a single type of olefin to produce a homopolymer. However, additional α-olefins can be incorporated into the polymerization process in other embodiments. Such additional α-olefin comonomers typically have no more than 20 carbon atoms. For example, the catalyst system of the present disclosure can be used to polymerize ethylene and one or more (C 3 -C 12 ) α-olefin comonomer polymerization. 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, the one or more α-olefin comonomers can 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.

[0082] In an embodiment, the one or more (C 3 -C 12 ) α-olefin comonomers may not be derived from propylene. That is, the one or more (C 3 -C 12 ) α-olefin comonomers may be substantially free of propylene. The term "substantially free" of a compound means that the material or mixture contains less than 1.0 wt. % of the compound. For example, the one or more (C 3 -C 12) The α-olefin comonomer may include less than 1.0 wt% propylene, such as less than 0.8 wt% propylene, less than 0.6 wt% propylene, less than 0.4 wt% propylene, or less than 0.2 wt% propylene.

[0083] In embodiments, the polyethylene produced, such as homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers, may include at least 50 mole % (mol.%) 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.% monomer units derived from ethylene. In embodiments, the polyethylene includes 50 mol.% to 100 mol.% 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.

[0084] In embodiments, the polyethylene produced includes at least 90 mol.% of monomer units derived from ethylene. For example, the polyethylene may include at least 93 mol.%, at least 96 mol.%, at least 97 mol.%, or at least 99 mol.% of monomer units derived from ethylene. In embodiments, the polyethylene includes 90 mol.% to 100 mol.% of monomer units derived from ethylene. For example, the polyethylene may include 90 mol.% to 99.5 mol.%, 90 mol.% to 99 mol.%, 90 mol.% to 97 mol.%, 90 mol.% to 96 mol.%, 90 mol.% to 93 mol.%, 93 mol.% to 100 mol.%, 93 mol.% to 99.5 mol.%, 93 mol.% to 99 mol.%, 93 mol.% to 97 mol.%, 93 mol.% to 96 mol.%, 96 mol.% to 98 mol.%, 99 mol.% to 99 mol.%, 9 ... % to 100 mol.%, 96 mol.% to 99.5 mol.%, 96 mol.% to 99 mol.%, 96 mol.% to 97 mol.%, 97 mol.% to 100 mol.%, 97 mol.% to 99.5 mol.%, 97 mol.% to 99 mol.%, 99 mol.% to 100 mol.%, 99 mol.% to 99.5 mol.%, or 99.5 mol.% to 100 mol.% of monomer units derived from ethylene.

[0085] In embodiments, the polyethylene produced includes less than 50 mol.% of monomer units derived from additional α-olefins. For example, the polyethylene may include 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 embodiments, the polyethylene includes 0 mol.% to 50 mol.% of monomer units derived from additional α-olefins. For example, polyethylene may include 0 mol.% to 40 mol.%, 0 mol.% to 30 mol.%, 0 mol.% to 20 mol.%, 0 mol.% to 10 mol.%, 0 mol.% to 5 mol.%, 0 mol.% to 1 mol.%, 1 mol.% to 50 mol.%, 1 mol.% to 40 mol.%, 1 mol.% to 30 mol.%, 1 mol.% to 20 mol.%, 1 mol.% to 10 mol.%, 1 mol.% to 5 mol.%, 5 mol.% to 50 mol.%, 5 mol.% to 40 mol.%, 5m % to 30 mol.%, 5 mol.% to 20 mol.%, 5 mol.% to 10 mol.%, 10 mol.% to 50 mol.%, 10 mol.% to 40 mol.%, 10 mol.% to 30 mol.%, 10 mol.% to 20 mol.%, 20 mol.% to 50 mol.%, 20 mol.% to 40 mol.%, 20 mol.% to 30 mol.%, 30 mol.% to 50 mol.%, 30 mol.% to 40 mol.%, or 40 mol.% to 50 mol.% of monomer units derived from additional α-olefins.

[0086] In an embodiment, the polyethylene produced further includes one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, ultraviolet (UV) stabilizers, and combinations of these. The polyethylene may include any amount of additives. In an embodiment, the polyethylene produced further includes fillers, which may include, but are not limited to, organic or inorganic fillers, such as, for example, calcium carbonate, talc, or Mg(OH) 2 .

[0087] The polyethylene produced can be used in various products and end-use applications. The polyethylene produced can also be blended and / or coextruded 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 various other end uses, the polyethylene produced and blends including the polyethylene produced can be used to produce blow molding 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 coextrusion and blow molding, injection molding and rotational molding. The film includes a blown or cast film formed by coextrusion or lamination, which can be used as shrink film, cling film, stretch film, sealing film, oriented film, snack packaging, heavy-duty bags, grocery store sacks, baked and frozen food packaging, medical packaging, industrial pads and films in food contact and non-food contact applications. Fibers can include melt spinning, solution spinning and melt-blown fiber operations, which are used to make filter paper, diaper fabrics, medical clothing and geotextiles in woven or non-woven forms. Extruded articles may include medical catheters, wire and cable coatings, pipes, geomembranes, and pond liners. Molded articles may include single and multilayer constructions in the form of bottles, cans, large hollow articles, rigid food containers, and toys.

[0088] Test Method

[0089] Polymerization activity

[0090] Unless otherwise stated, all polymerization activities (also referred to as productivity) disclosed herein are determined as the ratio of polymer produced to the amount of catalyst charged to the reactor and are reported as grams polymer per gram catalyst per hour (gPE / gcat / hr).

[0091] Comonomer content

[0092] Unless otherwise indicated, all comonomer contents disclosed herein (i.e., the amount of comonomer incorporated into a polymer) are determined by rapid FT-IR spectroscopy of dissolved polymers in gel permeation chromatography (GPC) measurements and are reported as weight percent (wt%). In GPC measurements, the comonomer content of a 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, Vol. 86, A NAL .C HEM .Page 8649, 2014.

[0093] High load melt index (I 21 )

[0094] Unless otherwise stated, all high load melt indexes (I 21 ) are measured according to ASTM D1238-10 Method B at 190°C and 21.6 kg load and are reported in decigrams per minute (dg / min).

[0095] Melting temperature (T m )

[0096] Unless otherwise stated, all melting temperatures (T m ) are measured according to ASTM D3418-08 and are reported in degrees Celsius (°C). Unless otherwise stated, a scan rate of 10 degrees Celsius / minute (°C / min) is used for 10 milligrams (mg) of sample, and the second heating cycle is used to determine the melting temperature (T m ).

[0097] Intake ratio

[0098] Unless otherwise stated, all uptake ratios disclosed herein are based on the ratio derived from the comonomer (e.g., (C 3 -C 12 )α-olefin comonomer) to the amount of monomer units derived from ethylene.

[0099] Molecular weight

[0100] Unless otherwise indicated, all molecular weights disclosed herein, including weight average molecular weight (M) w ), number average molecular weight (M n ) and z-average molecular weight (M z ), are measured using conventional GPC and are reported in grams per mole (g / mol).

[0101] 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 10 μm Mixed-B chromatographic columns are used. The nominal flow rate is 1.0 mL / min, and the nominal injection volume is 300 μL. Various transmission lines, chromatographic columns and differential refractometers (DRI detectors) are placed in an oven maintained at 160 ° C. The solvent for the experiment is prepared by dissolving 6 grams of butylated hydroxytoluene in 4 liters of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.1 μm Teflon filter. Then, before entering the GPC instrument, TCB is degassed with an online degasser.

[0102] 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 continuously shaking for about 2 hours. All quantities were measured gravimetrically. The injection concentration was 0.5 mg / ml to 2.0 mg / ml, with lower concentrations used for higher molecular weight samples. Before running each sample, the DRI detector was purged. The flow rate in the device was then increased to 1.0 mL / molecule, and the DRI was stabilized for 8 hours before injecting the first sample. The molecular weight was determined by combining a universal calibration relationship with a column calibration, which was performed with a series of monodisperse polystyrene (PS) standards. The MW of each elution volume was calculated using the following equation:

[0103]

[0104] The variables with the subscript "X" support the test sample, and the variables with the subscript "PS" support the PS. In this method, a PS =0.67 and K PS =0.000175, and a X and K X is obtained from publicly published literature. Specifically, for (PE), a / K=0.695 / 0.000579, and for PP, it is 0.705 / 0.0002288.

[0105] The concentration c at each point in the chromatogram was calculated from the baseline-subtracted DRI signal IDRI using the following equation:

[0106]

[0107] 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.

[0108] The mass recovery was calculated from the ratio of the integrated area of ​​the concentration chromatogram to the elution volume and the injected mass, which was equal to the predetermined concentration multiplied by the injection loop volume.

[0109] Example

[0110] Synthesis of Metal-Ligand Complex 1 (MLC-1)

[0111] Synthesis of 2-[5-tert-butyl-2-[[[4-tert-butyl-2-[3-(3,6-di-tert-butylcarbazole-9-yl)-2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl]phenoxy]methyl-diisopropyl-germanyl]methoxy]phenyl]-6-(3,6-di-tert-butylcarbazole-9-yl)-4-(1,1,3,3-tetramethylbutyl)phenol

[0112]

[0113] Degassed toluene (15 mL) and degassed water (5 mL) were added to a mixture 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), tBu 3 P-PdG2 (0.05 g, 0.1 mmol) and NaOH (0.5 g, 12.4 mmol) were placed in a 40 mL vial. The reaction was heated to 50 °C and maintained at this temperature for 18 hours. Thereafter, the reaction was cooled to room temperature. The mixture was transferred to a separatory funnel and Et 2 O (20 mL) and H 2 O (10 mL) and the layers were separated. The aqueous phase was washed with additional Et 2 O (10 mL). The combined organics were washed with brine (10 mL), dried (Na 2 SO 4) and filtered into a 100mL round-bottom flask. The solvent was removed under reduced pressure. The crude residue was dissolved in MeOH / THF (1:1, 20mL), concentrated HCl (5 drops from a glass pipette) was added, a reflux condenser was assembled on the flask, and the solution was then heated to 70°C under stirring. After 18 hours, the solvent was removed under reduced pressure. Yellow oil was rotary evaporated from MeOH (3×3mL) and a tan solid was formed. MeOH (20mL) was added to the solid and then collected by filtration. The solid was washed with MeOH (2×8mL). Acetone (10mL) was added to the solid in the filter funnel to obtain a heterogeneous solution. The heterogeneous mixture was stirred with a spatula, and the acetone was then pulled through the filter using a vacuum. Acetone (10mL) was added to the solid in the filter again. The heterogeneous mixture was stirred with a spatula, and the acetone was then pulled through the filter using a vacuum. The material was dried under vacuum to obtain 2.1g (58%) of the desired product as a tan solid:

[0114] 1 H NMR (400MHz, chloroform-d) δ8.22 (br s, 4H), 7.47-7.30 (m, 4H), 7.26 (d, J=2.5Hz, 2H), 7.22 (d, J=2.4Hz, 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=7.4Hz, 12H), 0.76 (s, 18H).

[0115] Synthesis of (MLC-1)

[0116]

[0117] Et 2 3M MeMgBr in 2-(4-(tert-butyl)-2-[[[4-tert-butyl-2-[3-(3,6-di-tert-butylcarbazole-9-yl)-2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl]phenoxy]methyl-diisopropyl-germanyl]methoxy]phenyl]-6-(3,6-di-tert-butylcarbazole-9-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (2.05 g, 1.42 mmol) was added to a mixture of hafnium tetrachloride (0.46 g, 1.43 mmol) in toluene (30 mL) at -30°C. After stirring for 3 minutes, solid 2-[5-tert-butyl-2-[[[4-tert-butyl-2-[3-(3,6-di-tert-butylcarbazole-9-yl)-2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl]phenoxy]methyl-diisopropyl-germanyl]methoxy]phenyl]-6-(3,6-di-tert-butylcarbazole-9-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (2.05 g, 1.42 mmol) was added.

[0118] After 18 h, additional 23M MeMgBr (200 uL) in 4% CO was added and the reaction was stirred for 1 hour. After that, the solvent was removed under reduced pressure to give a dark solid.

[0119] Hexane / toluene (2: 1, 30 mL) was added to the jar and the solution was stirred at room temperature for 5 minutes, then the material was passed through the CELITE plug of the sintered funnel. The glass frit was extracted with hexane / toluene (2: 1, 15 mL). The combined organics were dried under vacuum to give IMLC-1 (2.10 g, yield: 89%) as an off-white solid:

[0120] 1 H NMR (400MHz, benzene-d6) δ8.71 (t, J=1.3Hz, 2H), 8.37 (dd, J=2.0, 0.7Hz, 2H), 7.70-7.62 (m, 6H), 7.53 (dd, J=7.4, 2.5Hz , 4H), 7.47 (dd, J=8.7, 0.6Hz, 2H), 7.30 (dd, J=8.7, 1.9Hz, 2H), 7.19-7.11 (m, 2H), 5.29 (d, J=8.7Hz, 2H), 4.52 (d, J=12.2Hz, 2H), 3.52 (d, J=12.2Hz, 2H), 1.81 (d, J=14.5Hz, 2H), 1.64 (d, J=14.5Hz, 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=6.6Hz, 6H), -1.20 (s, 6H).

[0121] Synthesis of Metal-Ligand Complex 2 (MLC-2)

[0122]

[0123] In a glove box, a 40 mL vial equipped with a stir bar was charged with 3,5-difluorophenol (1.58 g, 12.2 mmol, 1.0 equiv), concentrated MeSO 3H (0.79 mL, 12.2 mmol, 1.0 eq) and 1,2-dichloroethane (1.2 mL). The resulting mixture was stirred at ambient temperature until 3,5-difluorophenol was completely dissolved and then cooled in an ice bath before 1-methylcyclohexanol (1.51 mL, 12.2 mmol, 1.0 eq) was added dropwise over 20 minutes. The resulting reaction mixture was stirred at 0°C for 1 hour and at room temperature for 16 hours before being cooled back to 0°C and additional 1-methylcyclohexanol (0.5 mL) was added over 5 minutes. After stirring the resulting mixture at 0°C for 10 minutes, the vial was removed from the cold bath and stirred at room temperature for 4 hours before being washed with Et 2 O (15 mL) and neutralized with 1N NaOH aqueous solution. The resulting mixture was then transferred to a separatory funnel and Et 2 O (10 mL), the layers were separated and washed with Et 2 The aqueous phase was further extracted with 10 mL of 0.5% ethanol. The combined organics were washed with brine (10 mL) and purified by Na 2 SO 4 Dry, filter and concentrate to dryness. 2 O (10 mL) was added to the concentrate, and then The solvent was removed under reduced pressure and the resulting solid material was directly loaded onto a pre-column and purified using flash column chromatography (40 g SiO 2 , 40 mL / min, 0% EtOAc to 10% EtOAc / hexanes in 18 minutes) to give 3,5-difluoro-4-(1-methylcyclohexyl)phenol (1.00 g, yield: 35%) as a white solid:

[0124] 1 H NMR (400 MHz, CDCl 3 )δ6.37-6.27(m, 2H), 5.01(s, 1H), 2.47-2.35(m, 2H), 1.67-1.30(m, 8H), 1.29(s, 3H).

[0125] 19 F{1H}NMR(376MHz, CDCl3)δ-104.67.

[0126]

[0127] NBS (0.787 g, 4.42 mmol, 1.0 eq) was slowly added to a 0°C solution of 3,5-difluoro-4-(1-methylcyclohexyl)phenol (1.00 g, 4.42 mmol, 1.0 eq) and 4-methylbenzenesulfonic acid hydrate (0.841 g, 4.42 mmol, 1.0 eq) in acetonitrile (10 mL). The resulting mixture was stirred for 3 days. The solvent was removed under reduced pressure and then flash chromatography (12 g glass slide, 40 g SiO 2 The resulting residue was directly purified by HPLC (40 mL / min, 0% ethyl acetate to 10% ethyl acetate / hexane over 17 minutes) to give 2-bromo-3,5-difluoro-4-(1-methylcyclohexyl)phenol (1.00 g, yield: 74%) as a light yellow oil:

[0128] 1 H NMR (400 MHz, CDCl 3 ) δ6.57 (dd, J=14.3, 2.3Hz, 1H), 5.60 (d, J=1.3Hz, 1H), 2.42 (dt, J=13.3, 3.4Hz, 2H), 1.62 (ddt, J=9.1, 6.2, 3.2Hz, 2H), 1.55-1.26 (m, 9H).

[0129] 19 F{1H}NMR (376 MHz, CDCl 3 )δ-97.78 (d, J=6.2Hz), -105.01 (d, J=6.2Hz).

[0130]

[0131] In a glove box, a 40 mL vial was charged with a germanium bridge (described in International Publication No. WO 2018 / 183056 A1; 0.385 g, 1.50 mmol, 0.48 equiv), phenol (0.95 g, 3.11 mmol, 1.0 equiv), K 3 PO 4 (1.98 g, 9.34 mmol, 3.0 equiv) and DMF (3 mL). The resulting mixture was stirred at 80 ° C overnight. After cooling to room temperature, the reaction mixture was purified by column chromatography to give bis((2-bromo-3,5-difluoro-4-(1-methylcyclohexyl)phenoxy)methyl)diisopropylgermane (1.24 g, yield: 68%) as a colorless oil:

[0132] 1 H NMR (400 MHz, CDCl 3)δ6.60 (dd, J=15.1, 2.0Hz, 2H), 4.12 (s, 4H), 2.43 (dd, J=13.3, 6.0Hz, 4H), 1 .70 (p, J=7.4Hz, 2H), 1.60 (ddq, J=12.7, 6.8, 3.1Hz, 4H), 1.53-1.16 (m, 32H).

[0133] 19 F NMR (376 MHz, CDCl 3 )δ-97.35 (d, J=5.9Hz, 2F), -104.75 (d, J=6.4Hz, 2F).

[0134]

[0135] In a glove box, a 40 mL vial was charged with 2-(3′,5′-di-tert-butyl-5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)-[1,1′-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.256 g, 2.48 mmol, 3.0 equiv), bis((2-bromo-3,5-difluoro-4-(1-methylcyclohexyl)phenoxy)methyl)diisopropylgermane (0.657 g, 0.83 mmol, 1.0 equiv), tBu 3 P Pd G2 (0.066g, 0.08mmol, 0.08 equivalent), toluene (4mL) and KOH solution (4m, 0.83mL, 3.30mmol, 4.0 equivalent). The vial was heated at 80 ° C overnight under nitrogen. Upon completion, the top organic layer was transferred to another 40mL vial by rinsing the reaction vial with THF (5mL). MeOH (10mL) and concentrated HCl (1mL) were then added. The resulting mixture was stirred at 85 ° C for 2 hours. After cooling to room temperature, the reaction mixture was filtered through a short plug of silica gel (rinsed with ether). The solvent was removed under reduced pressure, and the residue was purified by reverse phase column chromatography to obtain the ligand (0.24g, yield: 23%) as a white solid:

[0136] 1 H NMR (400 MHz, CDCl 3)δ7.41 (q, J=1.8Hz, 2H), 7.31-7.28 (m, 4H), 7.12-7.08 (m, 2H), 6.90-6.86 (m, 2H), 6.50-6.41 (m, 2H), 5.06 (d, J=6.3Hz, 2H), 3.77-3.6 8(m, 4H), 2.50-2.42(m, 4H), 2.30(s, 6H), 1.64-1.56(m, 4H), 1.43(s, 6H), 1.40-1.28(m, 48H), 1.20-1.11(m, 2H), 0.88-0.78(m, 12H).

[0137] 19 F NMR (376 MHz, CDCl 3 )δ-104.34 (dd, J=18.1, 6.5Hz, 2F), -105.19 (dd, J=15.4, 6.3Hz, 2F).

[0138]

[0139] In a glove box, MeMgBr in ether (3 M, 0.281 mL, 0.86 mmol, 4.3 equiv) was added to ZrCl 4 The mixture was stirred overnight and then the solvent was removed under reduced pressure overnight to give a dark residue, which was extracted with hexane (12 mL) and filtered. Any remaining solids were then extracted with toluene (10 mL). The hexane extract was concentrated to approximately 2 mL and placed in a refrigerator for one day. Any remaining solvent was decanted and the remaining material (98 mg) was dried under vacuum and combined with the toluene extract (dried under vacuum; 141 mg) to give the metal-ligand complex as a white powder (0.239 g, yield: 91%):

[0140] 1 H NMR (400 MHz, C 6 D 6)δ8.07(br s, 2H), 7.82(q, J=1.5Hz, 2H), 7.54(br s, 2H), 7.28-7.19 (m, 4H), 5.37 (dd, J=13.4, 1.7Hz, 2H), 4.72 (d, J=11.5Hz, 2H), 3.65 (d, J=11. 5Hz, 2H), 2.72-2.55(m, 4H), 2.19(s, 6H), 1.69-1.26(m, 56H), 0.63-0.42(m, 14H), 0.14(s, 6H).

[0141] 19 F{1H}NMR (376 MHz, C 6 D 6 )δ-101.44 (d, J=5.5Hz, 2F), -104.43 (d, J=5.7Hz, 2F).

[0142] Synthesis of Metal-Ligand Complex 3 (MLC-3)

[0143]

[0144] In a glove box, MeMgBr (methylmagnesium bromide) in diethyl ether (3.0 M, 0.88 mmol, 4.4 equiv) was added to HfCl 4 (64mg, 0.2mmol, 1.0 equivalent) in anhydrous toluene (6.0mL) solution at -30°C suspension. After the resulting mixture was stirred for 2 minutes, the ligand (described in International Publication No. WO 2018 / 183056 A1; 0.254g, 0.2mmol, 1.0 equivalent) was added in batches. The resulting mixture was stirred overnight, and the solvent was then removed under vacuum to give a dark residue, which was extracted with hexane (12mL) and then extracted with toluene (12mL). The hexane extract was concentrated to approximately 3mL to 4mL and then kept in a refrigerator for one day, then the top solution was decanted and the white solid was dried under vacuum to give a white solid (150mg). The toluene extract was dried under vacuum to give a white solid (60mg). The hexane extract and the toluene extract were then combined to give a metal-ligand complex (210mg, yield: 71%) in the form of a white powder:

[0145] 1H NMR (400MHz, C6D6) δ8.14 (br s, 2H), 7.80 (t, J=1.8Hz, 2H), 7.65 (br s, 2H), 7.58 (d, J=2.5Hz, 2H), 7.42-7.29 (m, 4H), 7.22 (dd, J=8.6, 2.5Hz, 2H), 5.71 (d, J=8.6Hz, 2H), 4.97 (d, J=11.8Hz, 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).

[0146] Synthesis of Metal-Ligand Complex 4 (MLC-4)

[0147]

[0148] The metal-ligand complex was prepared in the manner described in International Publication No. WO 2018 / 183056 A1:

[0149] 1 H NMR (400 MHz, C 6 D 6 )δ8.04(br s, 2H), 7.76 (t, J=1.9Hz, 2H), 7.61 (brs, 2H), 7.43 (t, J=2.8Hz, 2H), 7.34 (d , J=2.4Hz, 2H), 7.08 (t, J=8.8Hz, 2H), 5.50 (dd, J=8.8, 1.1Hz, 2H), 4.75 (d, J=11.5Hz, 2H), 3.69(d, J=11.4Hz, 2H), 2.69-2.49(m, 4H), 1.71-1.60(m, 4H ), 1.58-1.19 (m, 74H), 0.96-0.87 (m, 6H), 0.73-0.57 (m, 14H), -0.04 (s, 6H). 19 F{1H}NMR (376 MHz, C 6 D 6 )δ-108.63(m, 2F).

[0150] Synthesis of Metal-Ligand Complex 5 (MLC-5)

[0151]

[0152] Degassed THF (3 mL) and degassed water (1 mL) were added to a mixture containing 9-[5-methyl-2-tetrahydropyran-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-fluoro-phenoxy)methyl]-diisopropyl-germane (0.36 g, 0.64 mmol), tBu 3 P-PdG2 (0.013 g, 0.03 mmol) and NaOH (0.13 g, 3.18 mmol) were placed in a 40 mL vial. The resulting mixture was heated to 50 °C and maintained at this temperature for 18 hours. Thereafter, the reaction was cooled to room temperature. Et 2 O (10mL) and saline (3mL) are added to the mixture. Shake the resulting solution, and after precipitation of each layer, use a pipette to remove the organic phase and transfer to a 40mL bottle. Add MeOH (6mL), followed by concentrated HCl (5 drops from a glass pipette). The resulting solution was stirred at room temperature for 3 hours, and then the solvent was removed under reduced pressure.

[0153] From CH 3 The resulting yellow oil was rotary evaporated from CN (3×3 mL) to form a tan solid. 3 CN (6 mL) was added to the solid, which was then collected by filtration. 3 The solid was washed with CN (2×3 mL). The material was dissolved in Et 2 O (4 mL) and passed through a silica plug. The plug was treated with additional Et 2 O (20 mL). 2 O was concentrated to dryness to give 2-carbazol-9-yl-6-[2-[[[2-(3-carbazol-9-yl-2-hydroxy-5-methyl-phenyl)-4-fluoro-phenoxy]methyl-diisopropyl-germanyl]methoxy]-5-fluoro-phenyl]-4-methyl-phenol (0.430 g, yield: 71%) as a white solid:

[0154] 1H 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 = 8.1, 7.2, 1.4 Hz, 4H). =2.2, 0.7Hz, 2H), 6.92 (dd, J = 8.8, 3.1Hz, 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=7.3Hz, 2H), 0.81 (d, J=7.5Hz, 12H).

[0155] 19 F NMR (376MHz, CDCl3) δ-123.49.

[0156]

[0157] In a glove box, MeMgBr in ether (3 M, 0.37 mL) was added to ZrCl 4 (0.06 g, 0.27 mmol) in anhydrous toluene (5 mL) at -30°C. After stirring the resulting mixture for 3 minutes, 2-carbazol-9-yl-6-[2-[[[2-(3-carbazol-9-yl-2-hydroxy-5-methyl-phenyl)-4-fluoro-phenoxy]methyl-diisopropyl-germanyl]methoxy]-5-fluoro-phenyl]-4-methyl-phenol (0.25 g, 0.26 mmol) in toluene / CH 2 Cl 2 (2:1, 3mL) solution. The resulting mixture was stirred for four hours, then the solvent was removed in vacuo to give a dark residue. Hexanes (4mL) were added to the dark residue, and the mixture was then passed through a CELITE pad. The residue was washed with additional hexanes (4mL). A new collection vial was placed, and the residue was extracted with toluene (3×8mL). The combined toluene extracts were concentrated to dryness to give a tan semisolid. The solid was evaporated from pentane (3×2mL) to give the metal-ligand complex as a tan solid (0.150g, yield: 53%):

[0158] 1H NMR (400MHz, benzene-d6) δ8.12 (dt, J=7.7, 0.9Hz, 2H), 8.03 (dt, J=7.7, 1.0Hz, 2H), 7.48 (dq, J=8.3, 1.0Hz, 4H) , 7.36 (ddd, J=8.2, 7.1, 1.3Hz, 2H), 7.25 (ddd, J=8.4, 7.2, 1.2Hz, 4H), 7.20-7.11 (m, 2H), 7.03 (dd, J=2.4 , 0.8Hz, 2H), 6.88-6.80 (m, 4H), 6.66 (ddd, J=9.0, 7.3, 3.2Hz, 2H), 4.91 (dd, J=9.0, 4.8Hz, 2H), 4.30 (d, J =12.1Hz, 2H), 3.26 (d, J = 12.1Hz, 2H), 2.07 (s, 6H), 1.31-1.15 (m, 1H), 0.61-0.48 (m, 14H), -0.93 (s, 6H).

[0159] 19 F NMR (376MHz, C6D6) δ-117.32.

[0160] Synthesis of Metal-Ligand Complex 6 (MLC-6)

[0161]

[0162] Degassed toluene (6 mL) and degassed water (3 mL) were added to a mixture containing 2,7-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 (1.62 g, 2.33 mmol), bis[(2-bromo-4-tert-butyl-phenoxy)methyl]-diisopropylgermane (as described in International Publication No. WO 2018 / 183056 A1; 0.6 g, 0.93 mmol), tBu 3 P-PdG2 (0.02 g, 0.04 mmol) and NaOH (0.19 g, 4.67 mmol) were placed in a 40 mL vial. The resulting mixture was heated to 75 °C and maintained at this temperature for 18 hours. Thereafter, the reaction was cooled to room temperature. The mixture was transferred to a separatory funnel and Et 2 O (20 mL) and H 2 O (10 mL) and the layers were separated. The aqueous phase was washed with additional Et 2 O (10 mL). The combined organics were washed with brine (10 mL), dried (Na 2 SO 4) 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 the solution was then heated to 70°C with stirring. After 4 hours, the solvent was removed under reduced pressure. 3 CN (3 × 5 mL) to rotary evaporate the yellow oil and form a tan solid. 3 CN (15 mL) was added to the solid which was then collected by filtration. 3 CN (2×4 mL) and washed the solid. The solid was separated 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:

[0163] 1 H NMR (400MHz, chloroform-d) δ8.05 (d, J=8.2Hz, 4H), 7.35-7.29 (m, 6H), 7.24 (d, J=2.5Hz, 2H), 7.21-7.10 (m, 6H), 6.71 (d, J=8.6Hz, 2H), 6.25 (d, J= 7.2Hz, 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=7.4Hz, 12H), 0.77 (s, 18H).

[0164]

[0165] In a glove box, MeMgBr in ether (3 M, 0.30 mL) was added to ZrCl 4(0.05 g, 0.22 mmol) in anhydrous toluene (8 mL) at -30 °C. After the resulting mixture was stirred for 3 minutes, a -30°C solution of 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) (0.3 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. Hexanes (10 mL) were added to the vial and the solution was shaken at room temperature for several minutes before the material was passed through a CELITE plug of a sintered funnel. The frit was extracted with hexanes (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 the metal-ligand complex as a tan powder (0.18 g, yield: 55%):

[0166] 1 H NMR (400MHz, benzene-d6) δ8.40 (d, J=8.2Hz, 2H), 8.09 (dd, J=8.2, 0.6Hz, 2H), 7.75 (d, J=1.6Hz, 2H), 7.68-7.63 (m, 4H), 7.61-7.55 (m, 4H), 7.50 (d, J=2.5Hz, 2H), 7.29 (dd, J=8.3, 1.7Hz, 2H), 7.09 (dd, J=8.7, 2.6Hz, 2H), 5.19 ( d, J=8.6Hz, 2H), 4.64 (d, J=12.2Hz, 2H), 3.67 (d, J=12.2Hz, 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=7.4Hz, 6H), 0.64 (d, J=7.5Hz, 6H), -1.01 (s, 6H).

[0167] Synthesis of Metal-Ligand Complex 7 (MLC-7)

[0168]

[0169] In a glove box, MeMgBr in ether (3 M, 0.30 mL) was added to HfCl 4(0.07 g, 0.21 mmol) in anhydrous toluene (8 mL) at -30 °C. After the resulting mixture was stirred for 3 minutes, a -30°C solution of 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) (0.3 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. Hexanes (5 mL) were 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 of a sintered funnel. The frit was extracted with hexanes (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 the metal-ligand complex as a tan powder (0.14 g, yield: 41%):

[0170] 1 H NMR (400MHz, benzene-d6) δ8.41 (d, J=8.4Hz, 2H), 8.10 (dd, J=8.2, 0.6Hz, 2H), 7.75 (d, J=1.6Hz, 2H), 7.66 (d, J=2.5Hz, 2H), 7.63-7.60 (m, 4H), 7.57 (dd, J=8.3, 1.7Hz, 2H), 7.49 (d, J=2.5Hz, 2H), 7.29 (dd, J=8.3, 1.7Hz, 2H), 7.10 (dd, J=8.2, 2. 1Hz, 2H), 5.19 (d, J=8.7Hz, 2H), 4.74 (d, J=12.3Hz, 2H), 3.74 (d, J=12.4Hz, 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 = 7.4Hz, 6H), 0.63 (d, J = 7.5Hz, 6H), -1.23 (s, 6H).

[0171] Synthesis of Metal-Ligand Complex 8 (MLC-8)

[0172]

[0173] A 1 L glass bottle was charged with acetonitrile (400 mL), 4-fluoro-6-methylphenol (50 g, 396.4 mmol) and p-toluenesulfonic acid (monohydrate; 75.6 g, 396 mmol), ensuring that all contents were in solution. The solution was cooled to 0 °C with ice for 25 minutes to give a precipitate. Over the course of approximately 5 minutes, the cooled solution was slowly treated with N-bromosuccinimide (70.55 g, 396.4 mmol) and allowed to reach room temperature while stirring overnight. The volatiles were removed in vacuo, and the resulting solid was treated with dichloromethane (600 mL), cooled in a refrigerator (0 °C), and filtered through a large plug of silica gel. The silica gel was washed with cold CH 2 Cl 2 Wash several times. Remove the volatiles under vacuum to obtain 2-bromo-4-fluoro-6-methyl-phenol (46 g, yield: 56%):

[0174] 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.05 (ddd, J = 7.7, 3.0, 0.7 Hz, 1H), 6.83 (ddt, J = 8.7, 3.0, 0.8 Hz, 1H), 5.35 (s, 1H), 2.29 (d, J = 0.7 Hz, 3H).

[0175] 19 F NMR (376 MHz, chloroform-d) δ -122.84.

[0176]

[0177] In a glove box, in a 250 mL flask equipped with a magnetic stir bar, 95% NaH (1.76 g) (be careful to generate H 2 ) was slowly added to a solution of 2-bromo-4-fluoro-6-methyl-phenol (15 g, 73.2 mmol) in N,N-dimethylformamide (DMF) (35 mL) until hydrogen evolution ceased. The mixture was stirred at room temperature for 30 minutes. Thereafter, diisopropylgermane dichloride (6.29 g, 24.4 mmol) was added. The mixture was heated to 55°C and maintained at this temperature for 18 hours. The reactants were taken out of the glove box and washed with saturated NH 4 Cl aqueous solution (20 mL) and H 2 O (8 mL) was added. 2 O (30 mL), transfer each phase to a separatory funnel and separate. 2 O (20 mL), and the combined organic extracts were washed with brine (10 mL). The organic layer was then dried (MgSO 4), filtered and concentrated to dryness. The crude residue was dried and loaded onto silica gel, then purified using rapid column chromatography (100 mL / min, pure hexane, plus ethyl acetate rose to 10% in 20 minutes) to obtain the product in the form of a light yellow oil. All clean fractions (some fractions containing <10% of the starting phenol) were combined, and the final product was dried overnight under vacuum to obtain bis((2-bromo-4-fluoro-6-methylphenoxy)methyl)diisopropylgermane (9 g, yield: 62%):

[0178] 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.10 (dd, J = 7.7, 3.0 Hz, 2H), 6.84 (ddd, J = 8.8, 3.1, 0.8 Hz, 2H), 4.14 (s, 4H), 2.33 (s, 6H), 1.74 (hept, J = 7.4 Hz, 2H), 1.35 (d, J = 7.4 Hz, 12H).

[0179] 19 F NMR (376 MHz, chloroform-d) δ -118.03.

[0180]

[0181] A 500 mL glass bottle equipped with a stir bar was charged with 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (as described in International Patent No. WO 2014 / 105411A1; 29.0 g, 41.9 mmol), bis((2-bromo-4-fluoro-6-methylphenoxy)methyl)diisopropylgermane (6.00 g, 8.65 mmol, containing 10% 2-bromo-4-fluoro-2-methyl-phenol) and THF (80 mL). The solution was heated to 55° C. and stirred with chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) (tBu 3P-PdG2) (199 mg, 0.346 mmol, 4 mol%) was treated. NaOH aqueous solution (17.3 mL, 51.9 mmol, 3 M) was purged with nitrogen for 20 minutes and then added to the THF solution. The reactant was stirred at 55 ° C overnight. The aqueous phase was separated and discarded, and the remaining organic phase was diluted with ether and washed twice with brine. The solution was passed through a short silica gel plug. The filtrate was dried on a rotary evaporator, dissolved in THF / methanol (40 mL / 40 mL), treated with HCl (2 mL), and stirred at 70 ° C overnight. The solution was dried under vacuum and purified by C18 reverse phase column chromatography to obtain the ligand (6.5 g, yield: 54%) as an off-white solid:

[0182] 1 H NMR (400MHz, chloroform-d) δ8.01 (d, J=8.2Hz, 4H), 7.42 (dd, J=25.5, 2.4Hz, 4H), 7.32 (dd, J=8.2, 1.6Hz, 4H), 7.17 (s, 4H), 6.87 (ddd, J=16.4 , 8.8, 3.0Hz, 4H), 6.18 (s, 2H), 3.79 (s, 4H), 2.12 (s, 6H), 1.71 (s, 6H), 1.56 (s, 4H), 1.38 (s, 12H), 1.31 (s, 36H), 0.83-0.73 (m, 30H).

[0183] 19 F NMR (376 MHz, chloroform-d) δ -119.02.

[0184]

[0185] In a glove box, MeMgBr in ether (3 M, 2.4 mL, 7.1 mmol) was added to ZrCl 4 The mixture was stirred for 3 minutes and then filtered through a sintered plastic funnel. The filtrate was dried under vacuum, dissolved in toluene (40 mL), filtered through a plug of CELITE again, and dried again under vacuum. The solid was washed with pentane (approximately 5 mL) and dried under vacuum to give a metal-ligand complex (2.1 g, yield: 84%) in an off-white powder form:

[0186] 1 H NMR (400 MHz, benzene-d 6)δ8.20 (dd, J=8.2, 0.5Hz, 2H), 8.11 (dd, J=8.2, 0.6Hz, 2H), 7.88-7.82 (m, 4H), 7.77 (d, J=2.6Hz, 2H), 7.50 (dd, J=8.3, 1.7Hz, 2H), 7.42-7.37 (m, 4H), 6.99 (dd, J=8.7, 3.1Hz, 2H), 6.20-6.10 (m, 2H), 4.29 ( d, J=12.2Hz, 2H), 3.90 (d, J=12.2Hz, 2H), 1.56 (s, 4H), 1.53 (s, 18H), 1.29 (s, 24H), 1.27 (s, 6H), 1.18 (s, 6H), 1.04-0.94 (m, 2H), 0.81 (d, J=7.4Hz, 6H), 0.80 (s, 18H), 0.74 (d, J=7.4Hz, 6H), -0.47 (s, 6H).

[0187] 19 F NMR (376 MHz, benzene-d 6 )δ-116.24.

[0188] Production of catalyst systems

[0189] Various catalyst systems are produced by spray drying. Specifically, fumed silica (which can be Commercially available from Cabot Corporation) and methylaluminoxane (10 wt% in toluene solution) were dissolved in toluene and mixed for 15 minutes. The metal-ligand complex was added to the resulting slurry and mixed for another 30 to 60 minutes. The resulting catalyst system precursor was then dried using a spray dryer (commercially available from BUCHI Corporation as Mini Spray Dryer B-290) with 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.

[0190] The structures of the different metal-ligand complexes are reported in Table 1. The specific metal-ligand complexes used to produce each catalyst system are reported in Table 2 along with the amounts of each component.

[0191] Table 1

[0192]

[0193]

[0194]

[0195] Table 2

[0196]

[0197]

[0198] Polyethylene production

[0199] Various polyethylene samples were produced in a gas phase polymerization reactor by contacting ethylene and 1-hexene with the catalyst systems reported in Table 2. Specifically, a gas phase polymerization reactor (i.e., a 2-liter stainless steel autoclave equipped with a mechanical stirrer) was dried for 1 hour, charged with sodium chloride (200 grams), and dried again at 100°C under nitrogen for 30 minutes. Supported methylaluminoxane (SMAO; 3 grams) was then introduced into the reactor under nitrogen pressure, the reactor was sealed, and the components were stirred. Hydrogen and 1-hexene pressurized with ethylene were then added to the reactor. Once steady-state operation was achieved, the catalyst system was charged into the reactor at 80°C to initiate polymerization. The reactor was then heated to the desired reaction temperature and maintained for the desired test time. After the test was completed, the reactor was cooled, vented, and opened. The resulting poly(ethylene-co-1-hexene) copolymer was collected, washed with water and methanol, and dried.

[0200] The reaction conditions used for each run are reported in Table 3. The reactor data for each run are reported in Table 4. The properties of the poly(ethylene-co-1-hexene) copolymers produced for each run are reported in Table 5.

[0201] Table 3

[0202]

[0203] Table 4

[0204]

[0205]

[0206] a Temperature: 90℃, H 2 / C 2 Ratio: 0.05, C 2 Partial pressure: 220psi

[0207] Table 5

[0208]

[0209]

[0210] As shown in Table 4, catalyst systems including metal-ligand complexes having germanium-containing bridges provide higher productivity than catalyst systems including metal-ligand complexes having carbon bridges (i.e., bridges containing only carbon connecting atoms). In more simple terms, the catalyst systems of the present disclosure provide higher productivity than the comparative catalyst systems. This increase in productivity is unexpected because corresponding changes in the bridge structure do not generally improve productivity or efficiency in unsupported catalyst systems including such metal-ligand complexes (typically used in solution phase polymerization processes).

[0211] When comparing experiments performed under similar conditions and using compounds comprising R 1 and R 16 ) of the catalyst system, the influence of the metal-ligand complex on the catalyst system is more clearly indicated. For example, experiments 1 to 5 were each carried out under condition 1, and the catalyst system including 3,6-tBu 2 -carbazolyl groups as the two top groups of the metal-ligand complex. However, compared to Runs 1 and 3 using Comparative Samples 1 and 3, Run 4 using Sample 1 produced 60,000 more grams of polymer per gram of catalyst system, and Run 2 produced no polymer at all. When comparing Runs 18 to 22 (using the same catalyst system as Runs 1 to 5), a greater improvement in productivity can be seen, but conducted under Condition 2. By comparing Runs 6 to 11 and 23 to 28 (using the same catalyst system as Runs 1 to 5, but conducted under Condition 2), the productivity can be improved. 2 phenyl as two top groups), and runs 12 to 15 and 29 to 32 (using a catalyst system comprising a metal-ligand complex having unsubstituted carbazolyl as two top groups), demonstrate similar improvements in productivity provided by metal-ligand complexes having germanium-containing bridges.

[0212] Additional polyethylene samples were produced in a gas phase polymerization reactor by contacting ethylene and 1-hexene with the catalyst system reported in Table 2 in a manner consistent with that previously described. Reaction conditions and reactor data for each run are reported in Table 6. Properties of the poly(ethylene-co-1-hexene) copolymers produced in each run are reported in Table 7.

[0213] Table 6

[0214]

[0215]

[0216] Table 7

[0217]

[0218] As shown in Table 6, under the same and / or similar conditions and relatively low ethylene partial pressure, the catalyst system including the metal-ligand complex having the germanium bridge provides higher productivity than the catalyst system including the metal-ligand complex having the carbon bridge. For example, when under the same reaction conditions, the test using Sample 4 provides higher productivity than the test using Comparative Sample 1. The increased productivity is important for use in dual reactor applications with a relatively low ethylene partial pressure in the first reactor, which is used to increase the life of the catalyst system to produce polymer in both reactors.

[0219] Additional polyethylene samples were produced in a gas phase polymerization reactor by contacting ethylene with the catalyst system reported in Table 2 in a manner consistent with that previously described, except for the inclusion of 1-hexene. Reaction conditions and reactor data for each run are reported in Table 8. Properties of the poly(ethylene-co-1-hexene) copolymers produced in each run are reported in Table 9.

[0220] Table 8

[0221]

[0222]

[0223] Table 9

[0224]

[0225] Additional polyethylene samples were produced in a gas phase polymerization reactor by contacting ethylene and 1-hexene in a manner consistent with that previously described with the catalyst system reported in Table 2. The reaction conditions and reactor data for each run are reported in Table 10.

[0226] Table 10

[0227]

[0228]

[0229] In Table 10, each of Experiments 71 to 74 was conducted under similar conditions; however, Experiments 71 and 72 used Sample 4, and Experiments 73 and 74 used Comparative Sample 4. The main difference between the metal-ligand complexes of Sample 4 and Comparative Sample 4 is the bridge. Specifically, the metal-ligand complex of Comparative Sample 4 has -CH 3 CH 3 CH 3 -bridge, and the metal-ligand complex of sample 4 has -CH 2Ge(iPr) 2 CH 2 However, due to this difference, the productivity of Runs 71 and 72 is at least nineteen times higher than the productivity of Runs 73 and 74, and the efficiency is at least twenty-two times higher than the efficiency of Runs 73 and 74. That is, given similar conditions, a catalyst system including a metal-ligand complex having a germanium-containing bridge can result in a polymerization process that is significantly more productive and efficient than a polymerization process utilizing a catalyst system including a similar metal-ligand complex having a carbon bridge.

[0230] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Indeed, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding the recited value. For example, a disclosure of "40 g / cm 3 The size of " is intended to mean "about 40g / cm 3 ″.

[0231] Notations used in equations included herein refer to their standard meanings as understood in the mathematical arts. For example, "=" means equal to, "×" represents a multiplication operation, "+" represents an addition operation, "-" represents a subtraction operation, ">" is a "greater than" symbol, "<" is a "less than" symbol, and " / " represents a division operation.

[0232] Unless expressly excluded or otherwise limited, each document cited herein, if any, including any cross-referenced or related patent or patent application to which this application claims priority or rights, and any patent or patent application in its entirety, is incorporated by reference. The citation of any document does not admit that it is prior art with respect to any embodiment disclosed or claimed, or that it alone or in combination with any other reference document or multiple reference documents teaches, suggests or discloses any such embodiment. In addition, in the event of any meaning or definition of a term in this document that conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to the term in this document shall prevail.

Claims

1. A procatalyst comprising a metal-ligand complex disposed on one or more support materials, wherein the metal-ligand complex has a structure according to formula (I): in: M is zirconium or hafnium; n is 1, 2, or 3; Each X is independently selected from unsaturated (C2-C 50 ) hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, (C6-C 50 ) aryl, (C4-C 50 )heteroaryl, halogen, –N(R N )2 and –N(R N )COR C Monodentate ligands; The metal-ligand complex is overall electrically neutral; Each Z is independently selected from -O-; R 1 and R 16 Independently selected from a group having formula (II), a group having formula (III): Where R 31-35 and R 41-48 are independently selected from -H, (C1-C 50 ) alkyl; 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 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -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 )2NC(O)- and halogen; R 23 and R 24 Independently selected from – (CR C 2) m -, where the subscript m is 1 to 10; R 17 and R 18 are independently selected from branched (C3-C7) alkyl groups; and Each R C , R P and R N are independently selected from -H, (C1-C 50 ) alkyl and (C1-C 50 ) heteroalkyl.

2. The main catalyst according to claim 1, wherein R 1 and R 16 are the same.

3. The main catalyst according to claim 1, wherein R 1 and R 16 At least one of is a group having formula (II), and R 32 and R 34 At least one of them is tert-butyl.

4. The main catalyst according to claim 2, wherein R 1 and R 16 At least one of is a group having formula (II), and R 32 and R 34 At least one of them is tert-butyl.

5. The main catalyst according to claim 1, wherein R 1 and R 16 At least one of them is a group having formula (III).

6. The main catalyst according to claim 2, wherein R 1 and R 16 At least one of them is a group having formula (III).

7. The main catalyst according to claim 5 or 6, wherein R 42 , R 43 , R 46 and R 47 At least one of them is tert-butyl.

8. The main catalyst according to any one of claims 1 to 6, wherein R 41-48 Yes – H.

9. The procatalyst according to any one of claims 1 to 6, wherein the one or more support materials comprise fumed silica.

10. A catalyst system comprising the procatalyst according to any one of claims 1 to 8 and one or more activators.

11. The catalyst system of claim 10, wherein the activator comprises methylaluminoxane (MAO).

12. A method for producing a catalyst system, the method comprising: One or more support materials, one or more activators and a metal-ligand complex are contacted in an inert hydrocarbon solvent to produce the catalyst system, wherein the metal-ligand complex has a structure according to formula (Ia): in: A - It is an anion; M is zirconium or hafnium; n is 1, 2, or 3; Each X is independently selected from unsaturated (C2-C 50 ) hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, (C6-C 50 ) aryl, (C4-C 50 )heteroaryl, halogen, –N(R N )2 and –N(R N )COR C Monodentate ligands; Each Z is independently selected from -O-; R 1 and R 16 Independently selected from a group having formula (II), a group having formula (III): Where R 31-35 and R 41-48 are independently selected from -H, (C1-C 50 ) alkyl; 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 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -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 )2NC(O)- and halogen; R 23 and R 24 Independently selected from – (CR C 2) m -, where the subscript m is 1 to 10; R 17 and R 18 are independently selected from branched (C3-C7) alkyl groups; and Each R C , R P and R N are independently selected from -H, (C1-C 50 ) alkyl and (C1-C 50 ) heteroalkyl.

13. The method of claim 12, wherein the activator comprises methylaluminoxane (MAO).

14. The method according to any one of claims 12 or 13, wherein the method further comprises: mixing the one or more support materials, the one or more activators, and the metal-ligand complex in the inert hydrocarbon solvent to produce a catalyst system precursor; as well as The catalyst system precursor is dried to produce the catalyst system.

15. The method of claim 14, wherein the catalyst system precursor is spray dried to produce the catalyst system; and the catalyst system comprises spray dried particles.

16. The method according to any one of claims 12 or 13, wherein the method further comprises: disposing the one or more activators on the one or more support materials to produce a supported activator; as well as The supported activator is contacted with a solution of the metal-ligand complex in the inert hydrocarbon solvent.

17. The method of claim 16, wherein disposing the one or more activators on the one or more support materials comprises spray drying to produce a spray-dried supported activator.

18. A process for producing polyethylene, comprising reacting ethylene and optionally one or more (C3-C 12 ) an α-olefin comonomer is contacted with a catalyst system, wherein the catalyst system comprises a metal-ligand complex disposed on one or more support materials; and the metal-ligand complex has a structure according to formula (Ia): in: A - It is an anion; M is zirconium or hafnium; (X) n The subscript n is 1, 2, or 3; Each X is independently selected from unsaturated (C2-C 50 ) hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, (C6-C 50 ) aryl, (C4-C 50 )heteroaryl, halogen, –N(R N )2 and –N(R N )COR C Monodentate ligands; Each Z is independently selected from -O-; R 1 and R 16 Independently selected from a group having formula (II), a group having formula (III): Where R 31-35 and R 41-48 are independently selected from -H, (C1-C 50 ) alkyl; 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 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -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 )2NC(O)- and halogen; R 23 and R 24 Independently selected from – (CR C 2) m -, where the subscript m is 1 to 10; R 17 and R 18 are independently selected from branched (C3-C7) alkyl groups; and Each R C , R P and R N are independently selected from -H, (C1-C 50 ) alkyl and (C1-C 50 ) heteroalkyl.

19. The method of claim 18, wherein the catalyst system further comprises an activator.

20. The method of claim 19, wherein the activator comprises methylaluminoxane (MAO).

21. The process according to any one of claims 18 to 20, wherein the catalyst system is fed into the gas phase polymerization reactor in pure form, as a solution or as a slurry.

22. The process of any one of claims 18 to 20, wherein the catalyst system comprises spray-dried particles.

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