Catalyst system and process for producing polyethylene using the same

Abstract

Embodiments of the present application are directed to procatalysts and catalyst systems that include the procatalysts, including metal-ligand complexes having the structure of formula (I). [Formula 1] JPEG2023528187000045.jpg45145

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority to U.S. Provisional Patent Application No. 63 / 031,638, filed on 29 May 2020, and U.S. Provisional Patent Application No. 63 / 143,333, filed on 29 January 2021, both of which are invoked by reference in their entirety.

[0002] (Field of Invention) Embodiments of the present disclosure generally relate to a gas-phase polymerization reactor for producing polyethylene, specifically, ethylene and one or more (C3-C3) in a gas-phase polymerization reactor. 12 This relates to a process for contacting an α-olefin comonomer with a germanium-bridged bis-phenylphenoxy catalyst system. [Background technology]

[0003] 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. Catalytic systems in polyolefin polymerization processes can contribute to the characteristics and properties of such polyolefins. For example, catalytic systems containing bis-phenylphenoxy (BPP) metal-ligand complexes can produce polyolefins with a flat or inverted short-chain branching distribution (SCBD), relatively high levels of comonomer incorporation, high native molecular weight, and / or a narrow to medium molecular weight distribution (MWD).

[0004] However, when used in some polymerization processes, such as gas-phase polymerization, catalyst systems containing BPP metal-ligand complexes typically exhibit 1) operability problems related to rapid light-off, and / or 2) insufficient productivity. In other words, catalyst systems containing BPP metal-ligand complexes generally contaminate reactors and / or produce less polymer relative to the amount of catalyst system used. As a result, the use of catalyst systems containing BPP metal-ligand complexes may not be commercially viable in gas-phase polymerization processes.

SUMMARY OF THE INVENTION

[0005] Thus, when utilized in a gas phase polymerization process, there is a continuing need for catalyst systems suitable for use in gas phase reactors that have improved light-off and / or productivity characteristics. Embodiments of the present disclosure address these needs by providing a catalyst system that includes a BPP metal-ligand complex having a germanium-containing bridge. The catalyst system exhibits improved light-off and productivity characteristics when compared to similar catalyst systems that include bis-phenylphenoxy metal-ligand complexes that do not contain a germanium-containing bridge when utilized in a gas phase polymerization process.

[0006] Embodiments of the present disclosure include a process for producing polyethylene. The process includes contacting ethylene and optionally one or more (C3-C 12 ) α-olefin comonomers in a gas phase polymerization reactor at a reactor temperature of 70° C to 150° C or less, with an ethylene partial pressure of 150 psi or more and a molar feed ratio of the one or more (C3-C 12 ) α-olefin comonomers to ethylene of 0.030 or less, with a catalyst system that includes an activated metal-ligand complex disposed on one or more carrier materials. The metal-ligand complex has a structure according to formula (Ia):

[0007] [Chemical formula] In formula (Ia), A - is an anion, M is titanium, zirconium, or hafnium, and n is 1, 2, or 3. Each X is a monodentate ligand independently selected from the group consisting of (C1-C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, (C6-C 50 ) aryl, (C4-C 50 ) heteroaryl, and halogen.

[0008] In formula (Ia), R 1 and R 8is independently selected from the group consisting of radicals having formula (II) and radicals having formula (III):

[0009] [ka] In formula (II), R 9~13 is -H, (C1~C 50 ) Hydrocarbyl, (C1~C 50 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , or selected independently from halogens. In formula (III), R 14~21 is -H, (C1~C 50 ) Hydrocarbyl, (C1~C 50 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C or selected independently of halogens.

[0010] In formula (Ia), R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 is -H, (C1~C 50 ) Hydrocarbyl, (C1~C 50 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C It is selected independently of halogens.

[0011] The process disclosed herein involves determining the amount of ethylene consumed in the first 5 minutes when the catalyst system is injected into the gas-phase polymerization reactor, and the average residence time t at the initial addition of the catalyst system. R This includes less than 25% of the total ethylene consumed over the entire time, and the time during which 25% of the total ethylene is taken up (t 25% ) is calculated by the formula given by equation (IV):

[0012]

number

[0013] [Figure 1] This is a diagram of the ethylene uptake curves for Examples 4 and 7 from Table 1. [Figure 2] This is a graphical representation of the reactor temperature profiles for Examples 1-3. [Figure 3] This graph shows the reactor temperature profiles for Examples 4-6, in which the polymerization reaction was carried out under condition 2b. [Figure 4] This graph shows the reactor temperature profiles for Examples 7-9, in which the polymerization reaction was carried out under condition 3. [Figure 5] This figure shows the ethylene uptake curves for Examples 7 and 9, where the polymerization reaction was carried out under condition 3. [Figure 6] This is a graph showing the ethylene and total ethylene uptake curves of catalyst system 2 in Example 14. [Figure 7] This figure shows the ethylene uptake curve and internal reactor profile of catalyst system 2 in Example 16. [Figure 8] This is a graph showing the ethylene and total ethylene uptake curves of catalyst system 2 in Example 19. [Modes for carrying out the invention]

[0014] Next, specific embodiments of procatalysts, catalyst systems, methods for producing catalyst systems, and processes for producing polyethylene will be described. However, it should be understood that the systems, methods, and processes of this disclosure may be embodied in different forms and should not be construed as being limited to the specific embodiments described herein. Rather, embodiments are provided so that this disclosure may be thorough and complete and so as to convey to those skilled in the art the scope of the disclosed subject matter.

[0015] The following is a list of common abbreviations used in this disclosure:

[0016] Me: Methyl; Et: Ethyl; Ph: Phenyl; Bn: Benzyl; i-Pr: Isopropyl; t-Bu: Tert-butyl; t-Oct: Tert-octyl(2,4,4-trimethylpentan-2-yl); Tf: Trifluoromethanesulfonate; THF: Tetrahydrofuran; Et2O: Diethyl ether; CH2Cl2: Dichloromethane; CV: Column volume (used in column chromatography); Depositphotos: Ethyl acetate; C6D6: Deuterated benzene or benzene-d6; CDCl3: Deuterated chloroform; Na2SO4: Sodium sulfate; MgSO4: Magnesium sulfate; HCl: Hydrogen chloride; n-BuLi: Butyllithium; t-BuLi: Tert-butyllithium; MAO: Methylaluminoxane; MMAO: Modified methylaluminoxane; GC: Gas chromatography; LC: Liquid chromatography; NMR: Nuclear magnetic resonance; MS: Mass spectrometry; mmol: Millimole mL: milliliter; M: molar concentration; min or mins: minute; h or hrs: hour; d: day.

[0017] The terms "halogen atom" or "halogen" refer to the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I). The term "halide" refers to the anionic form of a halogen atom: fluoride (F). - ), chloride (Cl - ), bromide (Br - ), or iodide (I -) means.

[0018] The term "independently selected" refers to the R group, for example, R 1 , R 2 , and R 3 However, this means that they may be the same or different (for example, R 1 , R 2 , and R 3 All of them may be substituted alkyl groups, or R 1 and R 2 is a substituted alkyl, and R 3 (This may also be an aryl group.) Chemical names associated with the R group are intended to convey the chemical structure recognized in the art as corresponding to that chemical name. As a result, chemical names are intended to supplement and illustrate, and not to exclude, structural definitions known to those skilled in the art.

[0019] The term "procatalyst" refers to a compound that exhibits catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with a procatalyst in such a way that it 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.

[0020] The term "substituted" means that at least one hydrogen atom (-H) bonded to the carbon atom of the corresponding unsubstituted compound or functional group is a substituent (e.g., R S This means that it is replaced by ). The term "-H" means 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.

[0021] When used to describe a specific carbon-carbon-containing chemical group, "(C x ~C y The parenthetical expression in the form of ")" means that the unsubstituted form of the chemical group has x to y carbon atoms. For example, (C1~C50 ) Alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups are R S It can be replaced by one or more substituents such as (C x ~C y R defined using ")" S A chemical group substituted with any group R S Depending on the identity, it may contain more than y carbon atoms. For example, "exactly one R S Substituted with (C1~C 50 )alkyl(R S "(C6H5)" can contain 7 to 56 carbon atoms. x ~C y A chemical group defined using ) contains one or more carbon-carbon substituents R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group is, for both x and y, all carbon-carbon-containing substituents R S It can be determined by adding up the total number of carbon atoms derived from each element.

[0022] (C1~C 50 The term "hydrocarbyl" refers to a hydrocarbon radical consisting of 1 to 50 carbon atoms. 50 The term "hydrocarbylene" means a hydrocarbon diradical having 1 to 50 carbon atoms, and each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (having 3 or more carbon atoms, including monocyclic and polycyclic, condensed and non-condensed polycyclic, and bicyclic) or acyclic, and contains 1 or more R S It is replaced by or not replaced by. When used in this disclosure, (C1~C 50 Hydrocarbyl is either unsubstituted or substituted (C1-C 50 ) alkyl, (C3~C 50 )Cycloalkyl, (C3~C 25 )Cycloalkyl-(C1~C 25 ) Alkilen, (C6~C 50)Aryl, or (C6-C 25 )Aryl-(C1-C 25 )Alkylene (such as benzyl (~CH2-C6H5), etc.) may be.

[0023] “(C1-C 50 )Alkyl” means a saturated straight-chain or branched-chain hydrocarbon radical containing 1 to 50 carbon atoms. Each (C1-C 50 )Alkyl may be unsubstituted or substituted by one or more R S . In an embodiment, each hydrogen atom in the hydrocarbon radical may be substituted by R S such as trifluoromethyl. Examples of unsubstituted (C1-C 50 )Alkyl are unsubstituted (C1-C 20 )Alkyl, unsubstituted (C1-C 10 )Alkyl, unsubstituted (C1-C5)alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. Examples of substituted (C1-C 50 )Alkyl are substituted (C1-C 20 )Alkyl, substituted (C1-C 10 )Alkyl, trifluoromethyl, and [C 45 Alkyl. The term “[C 45 Alkyl” means that there are up to 45 carbon atoms in the radical (including substituents), for example, (C1-C5)alkyl such as methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl, substituted by one R S of (C 27 ~C 40 )Alkyl.

[0024] “(C3-C 50 )Cycloalkyl” means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms that is unsubstituted or substituted by one or more R S . Other cycloalkyl groups (such as (C x~C y Similarly, cycloalkyl groups have x to y carbon atoms and are either unsubstituted or have one or more R atoms. S It is defined as being replaced by (C3~C). Non-replacement (C3~C 50 Examples of cycloalkyl groups include unsubstituted (C3~C) 20 ) Cycloalkyl, unsubstituted (C3~C 10 These are cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substitutions (C3~C 50 Examples of cycloalkyl groups include substitutions (C3~C 20 )Cycloalkyl, substituted (C3~C 10 These are cycloalkyl and 1-fluorocyclohexyl compounds.

[0025] (C6~C 50 The term "aryl" refers to a carbon atom having 6 to 50 carbon atoms, of which at least 6 to 14 are aromatic ring carbon atoms, and is unsubstituted or (1 or more R S This refers to monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radicals that are substituted (by C6~C6). A monocyclic aromatic hydrocarbon radical contains one aromatic ring, a bicyclic aromatic hydrocarbon radical has two rings, and a tricyclic aromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical exists, at least one of the rings of the radical is aromatic. The other one or more rings of the aromatic hydrocarbon radical can independently be condensed or uncondensed, and aromatic or non-aromatic. Unsubstituted (C6~C6) 50 Examples of aryl compounds include unsubstituted (C6~C) 20 ) Aryl, unsubstituted (C6~C 18 Examples include aryl, 2-(C1~C5) alkylphenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. Substitutions (C6~C 50 Examples of aryl substitutions include (C1~C 20 ) Aryl, substitution (C6~C 18)aryl, 2,4-bis([C 20 Examples include alkyl)phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0026] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include O, S, S(O), S(O)2, and Si(R). C )2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2-, or -Si(R C )- are listed, and each R C and each R P is non-substitutable (C1~C 18 ) Hydrocarbyl or -H, each R N is non-substitutable (C1~C 18 ) is a hydrocarbyl. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by heteroatoms. (C1~C 50 The term "heterohydrocarbyl" refers to a heterohydrocarbon radical consisting of 1 to 50 carbon atoms. 50 The term "heterohydrocarbylene" refers to a heterohydrocarbon diradical consisting of 1 to 50 carbon atoms. (C1~C 50 ) Heterohydrocarbyl or (C1~C 50 A heterohydrocarbylene heterohydrocarbon has one or more heteroatoms. The groups of a heterohydrocarbylene can be located on a carbon atom or on a heteroatom. The two groups of a heterohydrocarbylene can be located on a single carbon atom or on a single heteroatom. In addition, one of the two divalent groups can be located on a carbon atom and the other on a different carbon atom, one of the two groups can be located on a carbon atom and the other on a heteroatom, or one of the two groups can be located on a heteroatom and the other on a different heteroatom. Each (C1~C 50 )heterohydrocarbyl and (C1~C 50) Heterohydrocarbylene may be unsubstituted, (one or more R S They may be substituted by, and may be aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, condensed and non-condensed polycyclic) or acyclic.

[0027] (C2~C 50 The term "heteroaryl" refers to a compound consisting of a total of 2 to 50 carbon atoms and 1 to 10 heteroatoms, which are either unsubstituted or (one or more R) atoms. S This refers to monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radicals substituted by (C). A monocyclic heteroaromatic hydrocarbon radical has one heteroaromatic ring, a bicyclic heteroaromatic hydrocarbon radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. If a bicyclic or tricyclic heteroaromatic hydrocarbon radical exists, at least one of the rings in the radical is heteroaromatic. One or more other rings in the heteroaromatic radical may independently be condensed or uncondensed, and aromatic or nonaromatic. Other heteroaryl groups (generally (C)) x ~C y ) Heteroaryls, for example, (C4~C 12 Similarly, heteroaryl compounds have x to y carbon atoms (for example, 4 to 12 carbon atoms) and are either unsubstituted or have one or more R atoms. SIt is defined as being substituted by a monocyclic heteroaromatic hydrocarbon radical. A monocyclic heteroaromatic hydrocarbon radical is a five-membered or six-membered ring. A five-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms, which can be 1, 2, or 3, and each heteroatom can be O, S, N, or P. Examples of five-membered heteroaromatic hydrocarbon radicals include pyrrole-1-yl, pyrrole-2-yl, furan-3-yl, thiophen-2-yl, pyrazole-1-yl, isoxazole-2-yl, isothiazol-5-yl, imidazole-2-yl, oxazole-4-yl, thiazol-2-yl, 1,2,4-triazole-1-yl, 1,3,4-oxadiazole-2-yl, 1,3,4-thiadiazole-2-yl, tetrazole-1-yl, tetrazole-2-yl, and tetrazole-5-yl. A six-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms, which can be 1 or 2, and the heteroatoms can be N or P. Examples of six-membered ring heteroaromatic hydrocarbon radicals include pyridine-2-yl, pyrimidine-2-yl, and pyrazine-2-yl. Bicyclic heteroaromatic hydrocarbon radicals can be condensed 5,6- or 6,6-ring systems. Examples of condensed 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indole-1-yl and benzimidazole-1-yl. Examples of condensed 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinoline-2-yl and isoquinoline-1-yl. Tricyclic heteroaromatic hydrocarbon radicals can be condensed 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. An example of a condensed 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indole-1-yl. An example of a condensed 5,6,6-ring system is 1H-benzo[f]indole-1-yl. An example of a condensed 6,5,6-ring system is 9H-carbazole-9-yl. An example of a condensed 6,6,6-ring system is acridine-9-yl.

[0028] The term "polymer" refers to polymer compounds prepared by polymerizing monomers, whether of the same or different types. Therefore, 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.

[0029] The term "interpolymer" refers to a polymer prepared by polymerizing at least two different monomers. Therefore, the general term interpolymer includes copolymers and other polymers prepared by polymerizing more than two different monomers, such as terpolymers.

[0030] The terms "polyolefin," "polyolefin polymer," and "polyolefin resin" refer to simple olefins (also called alkenes, with general formula C11). n H 2n This refers to polymers prepared by polymerizing monomers (containing a comonomer). Therefore, the general term polyolefin includes polymers prepared by polymerizing ethylene monomer with or without one or more comonomers such as polyethylene, and polymers prepared by polymerizing propylene monomer with or without one or more comonomers such as polypropylene.

[0031] The terms "polyethylene" and "ethylene polymer" refer to polyolefins containing units derived from more than 50 mole percent (%) of ethylene monomer, including polyethylene homopolymers and copolymers. Common forms of polyethylene known in the art include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (ULDPE), extremely low-density polyethylene (VLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE).

[0032] The term "molecular weight distribution" refers to the ratio of two different molecular weights of a polymer. The general term "molecular weight distribution" refers to the weight-average molecular weight (M) of a polymer. w The number average molecular weight (M) of the polymer in question. n ) Ratio to ("Molecular weight distribution (M w / M n ) (sometimes referred to as "), and the z-average molecular weight (M) of the polymer. z The weight-average molecular weight (M) of the polymer in question. w ) Ratio to ("Molecular weight distribution (M z / M w This includes (sometimes referred to as ")").

[0033] The term "composition" means a mixture of materials constituting a composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0034] The terms “comprising,” “including,” and “having,” and their derivatives, are not intended to exclude the existence of any additional components, steps, or procedures, whether or not they are specifically disclosed. To avoid any doubt, all compositions claimed through the use of the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless otherwise stated. In contrast, the term “essentially consisting of” excludes any other components, steps, or procedures from any subsequent enumerated scope, except those not essential to operability. The term “consisting of” excludes any components, steps, or procedures not specifically described or enumerated.

[0035] In the 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):

[0036] [ka]

[0037] 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.

[0038] In formula (I), (X) n The subscript n is 1, 2, or 3, and each X is unsaturated (C2~C 50 ) hydrocarbons, unsaturated (C2~C 50 ) Heterocarbons, (C1~C 50 ) Hydrocarbyl, (C1~C 50 ) Heterohydrocarbyl, (C6~C 50 )aryl, (C2~C 50 ) Heteroaryl, halogen, -N(R N )2, and -N(R N )COR C A monodentate ligand independently selected from the following. In embodiments, each X is independently selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2,-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, or chloro. In some embodiments, (X) n The subscript n is 2, and each X is identical. In other embodiments, at least two Xs are different. For example, (X) n The subscript n may be 2, and each X may be different from the following: methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2,-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, and chloro. In embodiments, (X) n The subscript n is 1 or 2, and at least two X are independently monoanionic monodentate ligands, and if present, a third X is a neutral monodentate ligand. Or in further embodiments, (X) n The subscript n is 2. In equation (I), the metal-ligand complex is charge-neutral overall.

[0039] In formula (I), R 1 and R8 This is independently selected from radicals having formula (II) and radicals having formula (III):

[0040] [ka]

[0041] In formula (II), R 9 , R 10 , R 11 , R 12 , R 13 is -H, (C1~C 50 ) Hydrocarbyl, (C1~C 50 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, ~CN, ~CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or selected independently from halogens.

[0042] In formula (III), R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , and R 21 is -H, (C1~C 50 ) Hydrocarbyl, (C1~C 50 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C, -NO2, ~CN, ~CF 3 , R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or selected independently from halogens.

[0043] The group R in the metal-ligand complex of formula (I) 1 and R 8 These are selected independently of each other. For example, R 1 R may be selected from radicals having formula (II) or (III), 8 (C2~C 50 ) may be a heteroaryl, or R 1 R may be selected from radicals having formula (II), (III), or (IV), 16 R may be selected from radicals having formula (II) or (III), 1 It may be the same as or different from. In this embodiment, R 1 and R 8 Both are radicals having formula (II), and R 1 and R 8 Base R in 9~13 They are the same or different. In some embodiments, R 1 and R 8 Both are radicals having formula (III), and R 1 and R 8 Base R in 14~21 They are either the same or different.

[0044] In this embodiment, R 1 and R 8 At least one of them is a radical having formula (II), and R 10 and R 12 At least one of them is tert-butyl. In some embodiments, R 1 or R 8If at least one of them is a radical having formula (III), then R 16 and R 19 One or both of them are tert-butyl, and R 14~15 , R 17~18 , and R 20~21 In other embodiments, R 15 and R 20 If one or both of them are tert-butyl, 14 , R 16~19 , and R 21 is -H. In some embodiments, R 15 and R 20 Both are -H. In some embodiments, R 14~21 It is -H.

[0045] In formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is -H, (C1~C 50 ) Hydrocarbyl, (C1~C 50 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, ~CN, ~CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(RN)-, (R C )2NC(O)-, and halogens are selected independently.

[0046] In some embodiments, R 3 or R 4 At least one of them is a halogen atom, R 5 or R 6At least one of them is a halogen atom. In some embodiments, R 3 and R 4 Both are halogen atoms, and both or R 5 or R 6 It is a halogen atom.

[0047] In this embodiment, R 2 and R 7 (C1~C 24 ) is alkyl. In various embodiments, R 2 and R 7 (C1~C 20 ) is alkyl. In some embodiments, R 2 and R 7 (C4~C 24 ) is alkyl. In one or more embodiments, R 2 and R 7 (C8~C 12 ) is alkyl. In some embodiments, R 2 and R 7 These are 1-propyl, 2-propyl (also called isopropyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. In embodiments, R 2 and R 7 is -OR C (In the formula, R C (C1~C 20 ) is a hydrocarbon, and in some embodiments, R C These are methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), or 1,1-dimethylethyl.

[0048] In some embodiments, R 4 and R 5 (C1~C 20 ) is alkyl. In some embodiments, R 4 and R 5These are 1-propyl, 2-propyl (also called isopropyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. In embodiments, R 4 and R 5 It is methyl.

[0049] In some embodiments, R 3 and R 6 is a halogen. In other embodiments, R 3 and R 6 (C1~C 24 ) is alkyl. In some embodiments, R 3 and R 6 R is independently selected from methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. In some embodiments, R 6 and R 11 is tert-butyl. In the embodiment, R 3 and R 6 is -OR C (In the formula, R C (C1~C 20 ) is hydrocarbyl, and in some embodiments, R C R is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), or 1,1-dimethylethyl. In other embodiments, R 3 and R 6 -SiR C 3 (in the formula, each R C (C1~C 20 ) is hydrocarbyl, and in some embodiments, R CThese are methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), or 1,1-dimethylethyl.

[0050] In some embodiments, R 2 and R 7 It is methyl, and R 3 and R 6 is a halogen. In other embodiments, R 3 and R 6 is tert-butyl. In other embodiments, R 2 and R 7 It is either tert-octyl or n-octyl.

[0051] In equations (I), (Ia), (II), and (III), each R C , R P , and R N is -H, (C1~C 50 ) Hydrocarbyl, and (C1~C 50 ) Selected independently from heterohydrocarbyl.

[0052] In embodiments, a procatalyst can be catalytically activated by contacting or combining it with an activator. A procatalyst catalytically activated by contacting or combining it with an activator may be referred to as a “catalytic system.” That is, as used in the present disclosure, a catalytic system may comprise a procatalyst and one or more activators. The term “activator” may include any combination of reagents that increase the rate at which a transition metal compound oligomerizes or polymerizes an unsaturated monomer, such as an olefin. The activator may also affect the molecular weight, degree of branching, comonomer content, or other properties of the oligomer or polymer. The transition metal compound may be activated for oligomerization and / or polymerization catalysis in any way sufficient to enable coordination or cationic oligomerization and / or polymerization.

[0053] Alumoxane activators can be used as one or more activators in a catalyst composition. Alumoxanes are generally oligomeric compounds containing the --Al(R)--O-- subunit (wherein R is an alkyl group). Examples of alumoxanes include methyl alumoxane (MAO), modified methyl alumoxane (MMAO), ethyl alumoxane, and isobutyl alumoxane. Alkyl alumoxanes and modified alkyl alumoxanes are particularly suitable as catalyst activators when the abstractable ligand is a halide. Mixtures of different alumoxanes and / or modified alumoxanes may also be used. For further explanation, see U.S. Patents 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 European Patents Nos. 0561,476, 0279,586, 0516,476, and 0 See publication 594-218 and international publication 94 / 10180.

[0054] When the activator is an almoxane (modified or unmodified), the maximum amount of activator may be selected such that Al / M is in 10,000-fold molar excess relative to the catalyst precursor (per metal catalyst site). Alternatively, the minimum amount of activator to catalyst precursor may be set to a 1:1 molar ratio. In embodiments, the amounts of activator to catalyst precursor may be selected from 10,000:1 Al / M, 5,000:1 Al / M, 1,000:1 Al / M, 500:1 Al / M, 250:1 Al / M, 150:1 Al / M, 120:1 Al / M, 100:1 Al / M, 50:1 Al / M, 20:Al / M, 10:1 Al / M, 5:1 Al / M, and 1:1 Al / M.

[0055] Examples of aluminum alkyl or organoaluminum compounds that can be used as activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.

[0056] When a neutral metal-ligand complex is catalytically activated by an activator, the metal in the metal-ligand complex may have a formal charge of +1 (+1). In embodiments where the procatalyst includes a metal-ligand complex, the metal-ligand complex has the structure of formula (I) and is charge-neutral overall. In embodiments where the catalyst system includes a metal-ligand complex, the metal-ligand complex may have the structure of formula (Ia) and has a formal charge of +1 (+1) overall:

[0057] [ka]

[0058] In equation (Ia), A - is an anion, M, (X) n The subscripts n, each X, each Z, and R 1 ~R 8 This is as previously described regarding the metal-ligand complex of formula (I).

[0059] Equation (Ia) is an exemplary description of the activated catalyst.

[0060] In embodiments, a metal-ligand complex, an activator, or both may be placed on one or more carrier materials. For example, a metal-ligand complex may be attached to, in contact with, vaporized in, bound to, or incorporated into one or more carrier materials, or adsorbed or absorbed in or on the carrier materials. A metal-ligand complex can be combined with one or more carrier materials using one of the well-known supporting methods in the art, or as described below. When used in this disclosure, a metal-ligand complex is in a supported form when, for example, it is attached to, in contact with, or incorporated into one or more carrier materials, or adsorbed or absorbed in or on the carrier materials.

[0061] Suitable carrier materials include oxides of metals in groups 2, 3, 4, 5, 13, or 14 of the IUPAC periodic table. In embodiments, the carrier material may be dehydrated silica, fumed silica, alumina (e.g., as described in International Application No. 1999 / 060033), silica-alumina, and mixtures thereof, or not. The fumed silica may be hydrophilic (untreated) or hydrophobic (treated). In embodiments, the carrier material is hydrophobic fumed silica, which can be prepared by treating untreated fumed silica with a treatment agent such as dimethyldichlorosilane, polydimethylsiloxane fluid, or hexamethyldisilazane. In some embodiments, the carrier material may be magnesia, titania, zirconia, magnesium chloride (e.g., U.S. Patent No. 5,965,477), montmorillonite (e.g., European Patent No. 0511665), phyllosilicate, zeolite, talc, clay (e.g., U.S. Patent No. 6,034,187), and mixtures thereof. In other embodiments, combinations of these carrier materials may be used, such as silica-chromium, silica-alumina, silica-titania, and combinations thereof. Additional carrier materials may include porous acrylic polymers as described in European Patent No. 0767184. Other carrier materials may include nanocomposites as described in International Application No. 1999 / 047598, aerogels as described in International Application No. 1999 / 048605, spherulites as described in U.S. Patent No. 5,972,510, and polymer beads as described in International Application No. 1999 / 050311.

[0062] In the embodiment, the carrier material is 10 square meters / gram (m 2 ( / g) ~ 700m 2 Surface area per gram, 0.1 cubic meters / gram (cm³) 3 (g) ~ 4.0cm 3 It has a pore volume of / g and an average particle size of 5 micrometers (μm) to 500 μm. In some embodiments, the carrier material is 50m 2 / g~500m 2 Surface area per g, 0.5 cm² 3 / g~3.5cm 3 It has a pore volume of / g and an average particle size of 10μm to 200μm. In other embodiments, the carrier material is 100m 2 / g~400m 2 Surface area per g, 0.8 cm² 3 / g~3.0cm 3 It may have a pore volume of / g and an average particle size of 5 μm to 100 μm. The average pore size of the carrier material is typically 10 angstroms (Å) to 1,000 Å, for example, 50 Å to 500 Å or 75 Å to 350 Å.

[0063] Various preferred methods exist for producing the catalyst systems of this disclosure. In one or more embodiments, a method for producing a catalyst system comprises contacting one or more support materials, one or more activators, and a metal-ligand complex in an inert hydrocarbon solvent to produce a catalyst system. In some embodiments, a method for producing a catalyst system may include arranging one or more activators on 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 (often referred to as a "trim catalyst" or "trim feed"). For example, in some embodiments, a method for producing a catalyst system comprises contacting a spray-dried supported activator (i.e., a supported activator produced by spray drying) with a solution of the metal-ligand complex in an inert hydrocarbon solvent. In some embodiments, the supported activator may be contained in a slurry, such as a mineral oil slurry.

[0064] In some embodiments, a 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. The method may further include drying the catalyst system precursor to produce a catalyst system. More specifically, the method may include preparing a mixture of a metal-ligand complex, one or more support materials, one or more activators, or a combination thereof, with 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 thereof, and placed on one or more support materials. In embodiments, the removal step can be achieved by conventionally evaporating the inert hydrocarbon solvent from the mixture (i.e., conventional concentration methods), resulting in an evaporated / supported catalyst system. In other embodiments, the removal step can be achieved by spray-drying the mixture, resulting in the production of spray-dried particles. It should be understood that the drying and / or removal step does not necessarily require the complete removal of the liquid from the resulting catalyst system. That is, the catalyst system may contain a residual amount (i.e., 1% to 3% by weight) of the inert hydrocarbon solvent.

[0065] As described above, the catalyst systems of this disclosure can be used in processes for producing polymers such as polyethylene via the polymerization of olefins such as ethylene. When used in some polymerization processes such as gas-phase polymerization, catalyst systems containing BPP metal-ligand complexes typically exhibit 1) operability problems related to rapid light-off and / or 2) insufficient productivity. For example, catalyst systems containing BPP metal-ligand complexes may light-off too quickly in the gas-phase polymerization reactor, i.e., they may consume ethylene too quickly upon injection, which can lead to the particles overheating, melting, and agglomerating, resulting in the formation of catalyst balls, chunking, and other "rubber" that can contaminate the gas-phase polymerization reactor.

[0066] In embodiments, one or more olefins may be brought into contact 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. Patents 5,665,818, 5,677,375, and 6,472,484, and European Patents 0517,868 and 0794,200. For example, in some embodiments, ethylene and optionally one or more (C3-C) are used. 12 The α-olefin comonomer may be brought into contact with the catalyst system of this disclosure in a gas-phase polymerization reactor. The catalyst system may be supplied to the gas-phase polymerization reactor in its as-is 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 may be supplied directly to the gas-phase polymerization reactor. In other embodiments, a solution or slurry of the catalyst system may be supplied to the reactor in a solvent such as an inert hydrocarbon or mineral oil. For example, the pro-catalyst may be supplied to the reactor in an inert hydrocarbon solution, and the activator may be supplied to the reactor in a mineral oil slurry.

[0067] In embodiments, the gas-phase polymerization reactor includes a fluidized bed reactor. The fluidized bed reactor may include a “reaction zone” and a “deceleration zone.” The reaction zone may include a bed of growing polymer particles, formed polymer particles, and a trace amount of catalyst system, fluidized by a continuous flow of gaseous monomer and diluent to remove the heat of polymerization through the reaction zone. Optionally, a portion of the recirculating gas may be cooled and compressed to form a liquid, which increases the heat removal capacity of the circulating gas flow when it re-enters the reaction zone. A suitable gas flow rate can be easily determined by simple experiments. The supply of gaseous monomer to the circulating gas flow may be at a rate equal to the rate at which particulate polymer products and associated monomers can be extracted from the reactor and the composition of the gas passing through the reactor can be adjusted to maintain an essentially steady-state gaseous composition within the reaction zone. The gas leaving the reaction zone may be sent to a deceleration zone, where transport particles are removed. Finer transport particles and dust can be removed in a cyclone and / or microfilter. The gas may pass through a heat exchanger, where the heat of polymerization is removed, then compressed in a compressor, and subsequently returned to the reaction area. Details of additional reactors and means for operating the reactors are described, for example, in U.S. Patents 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. 0802202, and Belgian Patent No. 839,380.

[0068] Catalyst systems with rapid light-off may contaminate the gas-phase polymerization reactor by forming "catalyst balls" or chunks, which can hinder catalyst injection and polymer particle removal, or lead to other problems detrimental to operability. Chunking and "catalyst ball" formation are phenomena that are thought to be exacerbated by the overheating and fusion of polymer particles due to the rapid light-off of the catalyst. Light-off of a catalyst system can be conveniently expressed in terms of ethylene uptake or consumption, and the ethylene uptake ratio Ut shown by equation (IV).

[0069]

number

[0070] In the equations, the total ethylene uptake of the catalyst system over the average residence time tR of the polymerization process is given by equation (V), and the ethylene uptake of the catalyst system at a given time after injection into the polymerization reactor is given by equation (VI):

[0071]

number

[0072] Light-off can be controlled in the process by increasing or decreasing the catalyst supply, or by increasing or decreasing the ethylene partial pressure in the reactor. However, reducing the catalyst supply or decreasing the ethylene partial pressure to mitigate the severity of catalyst light-off and associated reactor operability issues reduces the reactor yield and the amount of polymer produced per unit time, ultimately making it uneconomical in production-scale polymerization reactors and therefore often impractical. Furthermore, a major component of catalyst system light-off is inherent to the activated metal-ligand complex of the catalyst system. In this specification, the structural features of the activated organometallic components of a catalyst system are described as improving catalyst operability by altering the inherent light-off of the catalyst system.

[0073] In this disclosure, a catalyst system having a preferred light-off is quantified by formula (VII), where the amount of ethylene consumed in the first 5 minutes of the catalyst lifetime is given by the average residence time t at the time of initial addition to the catalyst system. R Less than 25% of the total ethylene consumed over the entire time, and the time (t) in which 25% of the total ethylene is taken up. 25% ) is calculated by the formula given by equation (IV):

[0074]

number

[0075] Alternatively, the light-off is the ratio of ethylene uptake consumed at a specified time t after the catalyst system has been delivered to the polymerization reactor (U t ) or a percentage, catalyst lifetime or average residence time t R It can be quantified when compared to the total ethylene consumed during the shorter of the two periods and can be calculated according to equation (IV). For example, U in the catalyst system t The concentration is less than 0.02 (2 percent) at 0.5 minutes (30 seconds) after the catalyst system is supplied to the reactor, as shown by equations (X) and (XI): Data acquisition in 30 seconds (0.5 minutes),

[0076]

number

[0077]

number

[0078] The ethylene uptake and ethylene uptake ratio of the catalyst system can be measured by the light-off batch reactor test method.

[0079] In some embodiments, the reactor temperature of a gas-phase polymerization reactor is 70°C to 150°C. For example, the reactor temperature of a gas-phase polymerization reactor may be 70°C to 120°C, 70°C to 110°C, 70°C to 100°C, 90°C to 150°C, 90°C to 120°C, 90°C to 110°C, 90°C to 100°C, 100°C to 150°C, 100°C to 120°C, 100°C to 110°C, 110°C to 150°C, 110°C to 120°C, or 120°C to 150°C. Generally, a gas-phase polymerization reactor can be operated at the highest feasible temperature, taking into account the sintering temperature of the polymer product in the reactor. Regardless of the process used to produce polyethylene, the reactor temperature must be below the melting or "sintering" temperature of the polymer product. As a result, the temperature upper limit may be the melting temperature of the polymer product.

[0080] In some embodiments, the process of the present disclosure further includes an internal reactor temperature, which is approximately the reactor temperature ± 5°C. In various embodiments, the internal reactor temperature is the reactor temperature ± 3°C or the reactor temperature ± 2°C, and in one or more embodiments, the internal reactor temperature is the reactor temperature ± 1°C.

[0081] Rapid light-off causes operability problems due to the rapid consumption of ethylene and / or comonomers, which leads to overheating of the particles, and presumably the internal reactor temperature (T), which is a measure of the heat of polymerization and an indirect measure of the catalyst particle temperature. int It can be quantified more effectively from the perspective of T. int This is a convenient method for quantifying and comparing the severity of light-off of different catalysts in a semi-batch gas-phase polymerization process.

[0082] In some embodiments, the reactor pressure of the gas-phase polymerization reactor is 50 psi to 150 psi (345 kPa to 1035 kPa). For example, the reactor pressure of the gas-phase polymerization reactor may be 80 psi to 115 psi (552 kPa to 793 kPa), 90 psi to 130 psi (620.5 kPa to 896 kPa), or 100 psi to 150 psi (690 kPa to 1035 kPa).

[0083] In one or more embodiments, the reactor pressure of the gas-phase polymerization reactor is 150 psi (1035 kPa) or higher. In various embodiments, the reactor pressure of the gas-phase polymerization reactor is 180 psi (1241 kPa) or higher, 190 psi (1310 kPa) or higher, 200 psi (1379 kPa) or higher, or 230 psi (1586 kPa) or higher.

[0084] In some embodiments, the amount of ethylene consumed in the first 5 minutes when the catalyst system is injected into the gas-phase polymerization reactor is such that the average residence time t is determined at the time of initial addition of the catalyst system. R Less than 25% of the total ethylene consumed over the entire time, and the time (t) in which 25% of the total ethylene is taken up. 25% ) is calculated by the formula given by equation (IV):

[0085]

number

[0086] In one or more embodiments, the amount of ethylene consumed in the first 25 minutes when the catalyst system is injected into the gas-phase polymerization reactor is such that the average residence time t is determined at the time of initial addition of the catalyst system. R Less than 50% of the total ethylene consumed over the entire time period (t) is taken up by 25% of the total ethylene. 25% ) is calculated by the formula given by equation (IV):

[0087]

number

[0088] In embodiments, hydrogen gas may be used during polymerization to control the final properties of polyethylene. The amount of hydrogen in polymerization can be expressed as a molar ratio to the total polymerizable monomer, such as ethylene or a blend of ethylene and 1-hexene. The amount of hydrogen used in the polymerization process may be the amount necessary to obtain the desired properties of polyethylene, such as the melt flow rate (MFR). In embodiments, the molar ratio of hydrogen to the total polymerizable monomer (H2:monomer) is greater than 0.0001. For example, the molar ratio of hydrogen to the total polymerizable monomer (H2:monomer) can be 0.0001~10, 0.0001~5, 0.0001~3, 0.0001~0.10, 0.0001~0.001, 0.0001~0.0005, 0.0005~10, 0.0005~5, 0.0005~3, 0.0005~0.10, 0.0005~0.001, 0.001~10, 0.001~5, 0.001~3, 0.001~0.10, 0.10~10, 0.10~5, 0.10~3, 3~10, 3~5, or 5~10.

[0089] In embodiments, the catalyst system of the present disclosure may be used to polymerize a single type of olefin to produce a homopolymer. However, in other embodiments, additional α-olefins may be incorporated into the polymerization scheme. The additional α-olefin comonomers typically have 20 or fewer carbon atoms. For example, the catalyst system of the present disclosure may use ethylene and one or more (C3-C3) 12 These can be used to polymerize α-olefin comonomers. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, one or more α-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-hexene and 1-octene.

[0090] In the embodiment, one or more (C3~C 12 The α-olefin comonomer does not have to be derived from propylene. That is, one or more (C3~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 the compound in an amount of less than 1.0% by weight. For example, one or more (C3~C) which may be substantially free of propylene. 12 The α-olefin comonomer may contain less than 1.0% by weight of propylene, for example, less than 0.8% by weight of propylene, less than 0.6% by weight of propylene, less than 0.4% by weight of propylene, or less than 0.2% by weight of propylene.

[0091] In embodiments, the polyethylene produced, for example, ethylene homopolymers and / or interpolymers (including copolymers), and optionally one or more comonomers, may contain at least 50 mol percent (mol%) of ethylene-derived monomer units. For example, polyethylene may contain at least 60 mol%, at least 70 mol%, at least 80 mol%, or at least 90 mol% of ethylene-derived monomer units. In embodiments, polyethylene may contain 50 mol% to 100 mol% of ethylene-derived monomer units. For example, polyethylene may contain ethylene-derived monomer units in amounts of 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%.

[0092] In embodiments, the polyethylene produced contains at least 90 mol% of ethylene-derived monomer units. For example, the polyethylene may contain at least 93 mol%, at least 96 mol%, at least 97 mol%, or at least 99 mol% of ethylene-derived monomer units. In embodiments, the polyethylene contains 90 mol% to 100 mol% of ethylene-derived monomer units. For example, polyethylene may contain ethylene-derived monomer units in the following proportions: 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 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%.

[0093] In embodiments, the polyethylene produced contains less than 50 mol% of additional α-olefin-derived monomer units. For example, polyethylene may contain less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol% of additional α-olefin-derived monomer units. In embodiments, polyethylene contains 0 mol% to 50 mol% of additional α-olefin-derived monomer units. For example, polyethylene may contain 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%, and 5 mol% to 30 mol%. It may contain additional α-olefin-derived monomer units in amounts of 10%, 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%.

[0094] In embodiments, the produced polyethylene further comprises 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 thereof. The polyethylene may contain any amount of additives. In embodiments, the produced polyethylene further comprises fillers, which may include, but are not limited to, organic or inorganic fillers such as calcium carbonate, talc, or Mg(OH)2.

[0095] The produced polyethylene can be used in a wide variety of products and end uses. The produced polyethylene may also be blended with and / or co-extruded with any other polymer. Non-limiting examples of other polymers include linear low-density polyethylene, elastomers, plastomers, high-pressure low-density polyethylene, high-density polyethylene, and polypropylene. The produced polyethylene and blends containing the produced polyethylene can be used to produce blow-molded parts or products, among other things, in a variety of end uses. The produced polyethylene and blends containing the produced polyethylene may be useful in molding operations such as extrusion and co-extrusion of films, sheets, and fibers, as well as in blow molding, injection molding, and rotational molding. Films may include blown or cast films formed by co-extrusion or lamination, which are useful as shrink films, wraps, stretch films, sealing films, stretched films, snack packaging, heavy-duty paper bags, shopping bags, packaging for baked and frozen foods, medical packaging, industrial liners, and membranes in applications that come into contact with food and applications that do not come into contact with food. Fibers may include melt spinning, solution spinning, and meltblown fiber operations for use in woven or nonwoven forms to produce filters, diaper fabrics, medical clothing, and geotextiles. Extruded articles may include coatings for medical tubes, wires, and cables, pipes, geomembranes, and pond liners. Molded articles may include single-layer and multi-layer structures in the form of bottles, tanks, large hollow articles, hard food containers, and toys.

[0096] Test method Polymerization activity Unless otherwise specified, all polymerization activity (also referred to as productivity) in this disclosure is determined as the ratio of the polymer produced to the amount of catalyst added to the reactor, and is reported in grams of polymer per gram of catalyst per hour (gPE / gcat / hr).

[0097] Comonomer content Unless otherwise specified, all comonomer contents (i.e., the amount of comonomer incorporated into the polymer) of the present disclosure are determined by rapid FT-IR spectroscopy for the dissolved polymer in gel permeation chromatography (GPC) measurements and are reported in weight percent (wt%). The comonomer content of the polymer can be determined with respect to the polymer molecular weight by using an infrared detector such as an IR5 detector in GPC measurements, as described in Lee et al., Toward absolute chemical composition distribution measurement of polyolefins by high-temperature liquid chromatography hyphenated with infrared absorbance and light scattering detectors, 86 Anal. Chem. 8649 (2014).

[0098] High load melt index (I 21 ) Unless otherwise indicated, all high load melt indices (I 21 ) disclosed herein are measured according to ASTM D1238-10, Method B at 190 °C and a 21.6 kg load and are reported in decigrams per minute (dg / min).

[0099] Melting temperature (T m ) Unless otherwise indicated, all melting temperatures (T m ) disclosed herein are measured according to ASTM D3418-08 and are reported in degrees Celsius (°C). Unless otherwise indicated, a scan rate of 10 degrees Celsius per minute (°C / min) was used for a 10 milligram (mg) sample and the second heating cycle was used to determine the melting temperature (T m ).

[0100] Incorporation ratio Unless otherwise indicated, all incorporation ratios of the present disclosure are for comonomers (e.g., (C3-C12 This was determined as the ratio of the amount of monomer units derived from α-olefin comonomers to the amount of monomer units derived from ethylene.

[0101] molecular weight Unless otherwise specified, weight-average molecular weight (M w ), number average molecular weight (M n ), and z-average molecular weight (M z All molecular weights disclosed herein, including those listed above, were measured using conventional GPC and are reported in grams per mole (g / mol).

[0102] The chromatography system consisted of a high-temperature gel permeation chromatograph (Polymer Laboratories) equipped with a differential refractive index detector (DRI). Three Polymer Laboratories PLgel 10 μm Mixed-B columns were used. The nominal flow rate was 1.0 mL / min, and the nominal injection volume was 300 μL. Various transfer lines, columns, and the differential refractometer (DRI detector) were placed in an oven maintained at 160°C. The experimental solvent was prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.1 μm Teflon filter. The TCB was then degassed using an online degasser before entering the GPC instrument.

[0103] A polymer solution was prepared by placing the dry polymer in a glass vial, adding the desired amount of TCB, and then heating the mixture at 160°C with continuous shaking for approximately 2 hours. All volumes were measured by gravimetric method. The injection concentrations ranged from 0.5 to 2.0 mg / mL, with lower concentrations used for higher molecular weight samples. The DRI detector was purged before each sample was run. The flow rate in the instrument was increased to 1.0 mL / min, and the DRI detector was stabilized for 8 hours before injecting the first sample. Molecular weight was determined by combining column calibration performed using a series of monodisperse polystyrene (PS) standards with a universal calibration relationship. The MW at each elution volume was calculated using the following formula:

[0104]

number

[0105] The concentration c at each point in the chromatogram was calculated from the DRI signal, IDRI, after subtracting the baseline, using the following formula:

[0106]

number

[0107] The mass recovery rate was calculated from the ratio of the integral area of ​​concentration chromatography over the elution volume to the injected mass, which is equal to the value obtained by multiplying the predetermined concentration by the injection loop volume.

[0108] Light-off batch reactor test method. Overview. The ethylene uptake or consumption and catalyst system are observed in each polymerization run conducted in a 2-liter (L) semi-batch autoclave polymerization reactor equipped with a mechanical stirrer. In the batch reactor, ethylene and 1-hexene are copolymerized in the gas phase in the presence of hydrogen (H2). The concentrations of ethylene ("C2"), 1-hexene ("C6"), and H2 in the gas phase are analyzed by mass spectrometry and gas chromatography. To maintain these concentrations in a steady state, C6 and H2 components are continuously added throughout the entire 3-hour polymerization run, but no further C2 is added. Ethylene uptake over time is measured to obtain a relative representation of the catalyst dynamics profile.

[0109] Drying and filling of the batch reactor. Before each run, the batch reactor is dried for 1 hour. Then, 200 g of NaCl is packed into the dried batch reactor. The batch reactor is further dried by heating the reactor and its contents at 100°C in an N2 atmosphere for 30 minutes. Then, 3 g of spray-dried silica-supported methylaluminoxane (SDMAO) is added to capture the residue, the batch reactor is sealed, and the contents are stirred. Then, 3.04 liters (L) of H2 and 1-hexene are packed into the resulting dried batch reactor so that the molar ratio of 1-hexene to ethylene (C6 / C2) is 0.004. The batch reactor is pressurized with ethylene to 1.52 megapascals (MPa). The resulting system is allowed to reach a steady state.

[0110] Next, the batch reactor is filled with the catalyst system to initiate polymerization. The addition time of the catalyst is recorded as time zero (time 0). The temperature of the reactor is set to the target temperature (typically 80 - 100 °C) and maintained at that temperature for 1 - 5 hours. The reactor is cooled, vented, opened, and the obtained polyolefin product is washed with water and methanol and dried to obtain the dry polyolefin product.

[0111] For each run of the batch reactor, the catalyst activity / polymerization productivity is calculated as the grams of dry polyolefin product produced per gram of catalyst added to the reactor - hour (gPE / gcat - hr). The larger the number of gPE / gcat - hr, the higher the catalyst activity / polymerization productivity. Ethylene uptake is measured throughout the course of the run, and the total ethylene uptake at any time during the reaction can be determined by Equation (VI):

[0112]

Number

[0113]

Number

Example

[0114] Synthesis of Metal - Ligand Complex 1 (MLC - 1)

[0115]

Chemical formula

[0116]

[0112] A glass bottle (1 liter (L)) was filled with acetonitrile (400 mL), 4-fluoro-6-methylphenol (50 g, 396.4 mmol), and p-toluenesulfonic acid (monohydrate, 75.6 g, 396 mmol). The resulting solution was cooled to 0°C over 25 minutes, slowly treated with N-bromosuccinimide (70.55 g, 396.4 mmol) for about 5 minutes, and allowed to reach room temperature overnight with stirring. Volatile substances were removed under vacuum, and the resulting precipitate was treated with dichloromethane (600 mL), cooled to 0°C, filtered through a large silica gel plug, and subsequently washed several times with cold dichloromethane (CH2Cl2). Volatile substances were removed under vacuum to obtain 2-bromo-4-fluoro-6-methylphenol (46 g, yield: 56%).

[0117] 1 ¹H NMR (400MHz, chloroform-d)δ 7.05 (ddd, J = 7.7, 3.0, 0.7Hz, 1H), 6.83 (ddt, J = 8.7, 3.0, 0.8Hz, 1H), 5.35 (s, 1H), 2.29 (d, J = 0.7Hz, 3H).

[0118] 19 F NMR (376 MHz, chloroform-d) δ -122.84.

[0119] [ka]

[0120] In a glove box, in a 250 mL flask equipped with a magnetic stirring bar, NaH (95%, 1.76 g) was slowly added to a solution of 2-bromo-4-fluoro-6-methylphenol (15 g, 73.2 mmol) in N,N-dimethylformamide (DMF; 35 mL) until hydrogen generation ceased. The reaction mixture was stirred at room temperature for 30 minutes. After this time, diisopropyl gelmyl dichloride (6.29 g, 24.4 mmol) was added. The mixture was heated to 55 °C and held at this temperature for 18 hours. After being removed from the glove box, it was quenched with saturated ammonium chloride aqueous solution (NH₄Cl; 20 mL) and water (H₂O; 8 mL). Diethyl ether (Et₂O; 30 mL) was added to the mixture, and the resulting phase was separated by transferring it to a separatory funnel. The aqueous phase was further extracted with Et2O (20 mL), and the combined organic extract was washed with brine (10 mL). The organic layer was then dried with (MgSO4), filtered, and concentrated to dryness. The crude residue was dry-loaded onto silica gel and then purified using flash chromatography (100 mL / min, pure hexane with ethyl acetate increasing to 10% over 20 minutes) to obtain a pale yellow oily product. All clean fractions (some fractions contained <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%).

[0121] 1 H NMR (400MHz,chloroform-d)δ 7.10 (dd, J = 7.7, 3.0Hz, 2H), 6.84 (ddd, J = 8.8, 3.1, 0.8Hz, 2H), 4.14 (s, 4H), 2.33 (s, 6H), 1.74 (hept, J = 7.4Hz, 2H), 1.35 (d, J = 7.4Hz, 12H).

[0122] 19 F NMR (376 MHz, chloroform-d) δ -118.03.

[0123] [ka]

[0124] A glass bottle (500 mL) equipped with a stirring bar was filled 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 Publication No. 2014 / 105411(A1); 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-methylphenol), and THF (80 mL). The solution was heated to 55°C and treated with chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) (tBu3P-PdG2; 199 mg, 0.346 mmol, 4 mol%) while stirring. The mixture was purged with NaOH aqueous solution (17.3 mL, 51.9 mmol, 3 M) with nitrogen for 20 minutes and then added to the THF solution. The reaction mixture was stirred overnight at 55°C. The aqueous phase was separated and discarded, and the remaining organic phase was diluted with diethyl ether and washed twice with brine. The solution was passed through a short silica gel plug. The filtrate was dried in a rotary evaporator, dissolved in THF / methanol (40 mL / 40 mL), treated with HCl (2 mL), and stirred overnight at 70°C. The solution was dried under vacuum and purified by C18 reversed-phase column chromatography to obtain the ligand (6.5 g, yield: 54%) as an off-white solid.

[0125] 1H NMR (400MHz,chloroform-d)δ 8.01 (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).

[0126] 19 F NMR (376 MHz, chloroform-d) δ -119.02.

[0127] [ka]

[0128] In a glove box, MeMgBr (3M, 2.4 mL, 7.1 mmol) in diethyl ether was added to a suspension of ZrCl4 (402 mg, 1.72 mmol) in anhydrous toluene (83 mL) at -30°C. The resulting mixture was stirred for 3 minutes, after which the ligand (2.3 g, 1.64 mmol) was added gradually. The reaction mixture was stirred overnight at room temperature and then filtered through a frit plastic funnel. The filtrate was dried under vacuum, redissolved in toluene (40 mL), filtered again through a Celite plug, and dried again under vacuum. The resulting solid was washed with pentane (approximately 5 mL) and dried under vacuum to provide the metal-ligand complex (2.1 g, yield: 84%) as an off-white powder.

[0129] 1H NMR (400MHz, ベンゼン-d6)δ 8.20 (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).

[0130] 19 F NMR (376MHz, ベンゼン-d6)δ -116.24.

[0131] Synthesis of metal-ligand complex 2 (MLC-2)

[0132]

change

[0133] International Publication No. 2018 / 183056(A1) describes the synthesis of metal-ligand complexes.

[0134] 1H NMR (400MHz, C6D6)δ 8.04 (br s, 2H), 7.76 (t, J = 1.9Hz, 2H), 7.61 (br s, 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 (376MHz, C6D6)δ -108.63 (m, 2F).

[0135] Preparation of catalyst system 1 In a nitrogen-purged glove box, 0.80 grams of hydrophobic fumed silica (commercially available from Cabot Corporation as CAB-O-SIL® TS-610) was added to 20.0 grams of toluene and mixed until well dispersed to produce a slurry. Next, 6.60 grams of methylaluminoxane (10% by weight in toluene) was added to the slurry and stirred for 15 minutes. To the resulting mixture, 0.043 grams of MLC-1 was added and then stirred for a further 30-60 minutes. The mixture 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 to produce catalyst system 1 (catalyst system 1).

[0136] Preparation of catalyst system 2 In a nitrogen-purged glove box, 0.68 grams of hydrophobic fumed silica (commercially available from Cabot Corporation as CAB-O-SIL® TS-610) was added to 20.0 grams of toluene and mixed until well dispersed to produce a slurry. Next, 9.05 grams of methylaluminoxane (10% by weight in toluene) was added to the slurry and stirred for 15 minutes. To the resulting mixture, 0.046 grams of MLC-1 was added and then stirred for a further 30-60 minutes. The mixture 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 / min (rpm), and a pump speed of 150 rpm to produce catalyst system 2 (catalyst system 2).

[0137] Preparation of catalyst system 3 In a nitrogen-purged glove box, 0.80 grams of hydrophobic fumed silica (commercially available from Cabot Corporation as CAB-O-SIL® TS-610) was added to 20.0 grams of toluene and mixed until well dispersed to produce a slurry. Next, 6.98 grams of methylaluminoxane (10% by weight in toluene) was added to the slurry and stirred for 15 minutes. To the resulting mixture, 0.091 grams of MLC-1 was added and then stirred for a further 30-60 minutes. The mixture 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 / min (rpm), and a pump speed of 150 rpm to produce catalyst system 1 (catalyst system 3).

[0138] Preparation of catalyst system 4 In a nitrogen-purged glove box, 0.66 grams of hydrophobic fumed silica (commercially available from Cabot Corporation as CAB-O-SIL® TS-610) was added to 37.5 grams of toluene and mixed until well dispersed to produce a slurry. Next, 5.90 grams of methylaluminoxane (10% by weight in toluene) was added to the slurry and stirred for 15 minutes. To the resulting mixture, 0.074 grams of MLC-2 was added and then stirred for a further 30-60 minutes. The mixture 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 to produce catalyst system 4.

[0139] Preparation of comparative catalyst system C1 In a nitrogen-purged glove box, 1.33 grams of hydrophobic fumed silica (commercially available from Cabot Corporation as CAB-O-SIL® TS-610) was added to 37.5 grams of toluene and mixed until well dispersed to produce a slurry. Next, 11.00 grams of methylaluminoxane (10% by weight in toluene) was added to the slurry and stirred for 15 minutes, after which 0.189 grams of a metal-ligand complex having the following structure was added:

[0140] [ka]

[0141] Next, the mixture was stirred for a further 30-60 minutes. The mixture 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 / min (rpm), and a pump speed of 150 rpm to produce comparative catalyst system C1 (comparative catalyst C1).

[0142] Preparation of comparative catalyst system C2 In a nitrogen-purged glove box, 2.65 grams of hydrophobic fumed silica (commercially available from Cabot Corporation as CAB-O-SIL® TS-610) was added to 75.0 grams of toluene and mixed until well dispersed to produce a slurry. Next, 22.00 grams of methylaluminoxane (10% by weight in toluene) was added to the slurry and stirred for 15 minutes, after which 0.155 grams of a metal-ligand complex having the following structure was added:

[0143] [ka]

[0144] Next, the mixture was stirred for a further 30-60 minutes. The mixture 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 / min (rpm), and a pump speed of 150 rpm to produce comparative catalyst system 2 (comparative catalyst C2).

[0145] Gas-phase batch reactor testing: The spray-dried catalyst prepared above was used in the copolymerization of ethylene / 1-hexene in the gas phase in a 2 L half-batch autoclave polymerization reactor. The individual run conditions and the properties of the polymers produced in these runs are shown in Tables 1-5.

[0146] Gas-phase batch reactor catalyst test procedure: The gas-phase reactor used was a 2-liter stainless steel autoclave equipped with a mechanical stirrer. For the experimental run, the reactor was first dried for 1 hour, then filled with 200 g of NaCl and dried by heating at 100°C for 30 minutes under nitrogen. After heating the reactor, 3 g of SDMAO (spray-dried supported methylaluminoxane) was introduced as a scavenger under nitrogen pressure. After adding the SDMAO, the reactor was sealed and the components were stirred. Next, hydrogen and 1-hexene were packed into the reactor and pressurized with ethylene. Once the system reached a steady state, the catalyst was packed into the reactor at 80°C to initiate polymerization. The reactor temperature was set to the desired reaction temperature and maintained at this temperature, ethylene, 1-hexene, and hydrogen supply ratio throughout the entire 1-hour run. At the end of the run, the reactor was cooled, evacuated, and opened. The resulting product mixture was washed with water and methanol and then dried. Polymerization activity (polymer (grams) / catalyst-time (grams)) was determined as the ratio of the generated polymer to the amount of catalyst added to the reactor.

[0147] [Table 1]

[0148] Condition 1a: Injection T=80℃, Run T=90℃, 0.003 C6 / C2, 0.004 H2 / C2, 100psi C2, Runtime 1 hour. Condition 2a: Injection T=80℃, Run T=100℃, 0.004 C6 / C2, 0.0068 H2 / C2, 230psi C2, Runtime 1 hour. Condition 3: Injection T=80℃, Run T=93℃, 0.0043 C6 / C2, 0.004 H2 / C2, 220psi C2, Runtime 1 hour. Condition 1b: Injection T=80℃, Run T=90℃, 0.004 C6 / C2, 0.0011 H2 / C2, 115psi C2, Runtime 1 hour. Condition 2b: Injection T=80°C, Run T=90°C, 0.004 C6 / C2, 0.0011 H2 / C2, 230 psi C2, Runtime 1 hour.

[0149] * The runtime has been extended to 3 hours.

[0150]

[0137] Rapid light-off causes operability problems due to the rapid consumption of ethylene and / or comonomers, which leads to overheating of the particles, and presumably the internal reactor temperature (T), which is a measure of the heat of polymerization and an indirect measure of the catalyst particle temperature. int It can be quantified more effectively from the perspective of T. int This is a convenient method for quantifying and comparing the severity of light-off of different catalysts in a semi-batch gas-phase polymerization process.

[0151]

[0138] Figure 2 shows the internal temperature profiles of Examples 1-3 (catalyst systems 1-3) under condition 1a and Comparative Example 10 (comparative catalyst system C1) under condition 1b. In each example, the catalyst is injected at 80°C, and then the temperature is rapidly increased to a target temperature of 90°C. In the three runs of catalyst systems 1-3 in Figure 2, the maximum temperature does not exceed the target temperature (Table 1). In the comparative example including comparative catalyst system C1, T int The target temperature of 90°C is exceeded by approximately 10°C to reach 99.9°C. Similarly, under condition 2b, the comparative catalyst system C1 also exceeds the target temperature of 90°C by approximately 43°C to reach 132.5°C. The comparative catalyst system C2 also under condition 3 * The target temperature of 93°C was exceeded by approximately 26°C to reach 118.5°C. Furthermore, the productivity of germanium-bridged catalyst systems 1-3 was remarkably high (Table 1).

[0152]

[0139] The ethylene uptake curves for catalyst system 1 are shown in Figure 1. These are Examples 4 and 7 from Table 1. The productivity values ​​for Example 4 were 283,771 gPE / gcat / h and for Example 7, 259,108 gPE / gcat / h (or 155.7 MM gPE / gZr and 142.2 MM gPE / gZr, respectively, in terms of efficiency). These runs did not experience operability problems such as chunking, which are caused by the overheating and fusion of particles as described above and are worsened by catalysts with rapid light-off. The productivity of this catalyst is much higher than any previous CARL batch reactor runs. Nevertheless, the ethylene uptake curves show that the catalyst light-off is relatively mild and decay is slow, which is more typical of metallocene catalysts than spray-dried bis-phenylphenoxy (i.e., MCL-1, MCL-2, and MCL-C1) catalysts.

[0153] [Table 2]

[0154] Conditions: Injection time = 80°C, 0°C / C2, runtime 1 hour.

[0155] Figure 3 shows the internal temperature profiles of Examples 4-6 (catalyst systems 1-3) under condition 2a and Comparative Example 11 (comparative catalyst C1) under condition 2b. Catalyst system 1 does not exceed the target temperature of 100°C, despite both exhibiting extremely high productivity (as recorded in Table 1). The catalyst system exceeds the target temperature by approximately 8°C. However, the temperature takes approximately 6 minutes per run to reach a maximum of 108.1°C. Comparative catalyst C1 often suffers from serious chunking problems caused by overheating at the economically advantageous operating ethylene partial pressure (approximately 200 psi C2PP); therefore, the conditions for Comparative Example 11 of comparative catalyst C1 targeted a temperature of 90°C. In Example 11 in Table 1, comparative catalyst C1 exceeds the target temperature by 42.5°C (maximum T=132.5°C).

[0156] In each of the examples in Table 1, the catalyst system was injected at 80°C and the temperature was rapidly increased to a target temperature of 90°C. In the three runs of catalyst system 1 in Figure 3, the maximum temperature did not exceed the target temperature (Table 1). In the comparative example including comparative catalyst C1, T int The temperature exceeded the target temperature of 90°C by approximately 10°C, reaching 99.9°C. Furthermore, Table 2 shows that the productivity of germanium-bridged catalyst systems 1-3 was remarkably high. The productivity (and the efficiency of the germanium-bridged catalyst systems 1-3 in the examples) is far higher than that of the comparative catalyst system having a three-carbon bridge.

[0157] Catalyst systems 1-3 were also tested under condition 3 and compared with comparative catalyst 2, which is used in several different commercially available catalyst systems. The internal temperature profiles of runs 7-9 using catalyst system 1A and comparative run 12 using comparative catalyst C2 are shown in Figure 4. Despite the high C2PP conditions with 230 psi of ethylene, none of the examples with MLC-1 showed reactor overheating, and the maximum temperature recorded (as recorded in Table 1) was only 3°C above the target temperature of 93°C. In contrast, comparative catalyst C2 showed rapid light-off, with a maximum temperature of 118.5°C. The productivity of catalyst systems 1-3 in the runs was up to two orders of magnitude higher than comparative catalyst C2, despite the more controlled light-off. Furthermore, the ethylene uptake curves (Figure 5) show that catalyst systems 1-3 have much higher productivity over a residence time of 3 hours, which is standard for gas-phase polymerization processes.

[0158] Examples 13–20 in Table 2, using this catalyst, all exhibit very high productivity of approximately 45,000–60,000 gPE / gcat / h at high C2PP (230 psi C2). Even at lower C2PP, productivity remains relatively high. While not as high as the examples using catalyst systems 1–3, these are the most productive to date for any type of good integrated catalyst (metallocene, post-metallocene). The ethylene uptake curves in Figures 6–8 show gradual light-off and long catalyst lifetime, which are more generally associated with metallocene catalysts that behave well at low C2PP. For example, the internal temperature profile in Figure 7 for Example 16 is representative of all runs in Table 2. The decay of the ethylene uptake profile is very gradual, but in Example 19 in Figure 8, the catalyst decay rate increases significantly at 115°C. Highly productive catalysts with gradual light-off and temperature-accelerated decay are very promising candidates for operations that behave well in gas-phase polyethylene processes.

[0159] [Table 3]

[0160] Conditions: Injection time = 80°C, 0°C / C2, runtime 1 hour.

[0161] Initial exothermic reactions and total ethylene uptake within the first 5% of a 1-hour run or within the first 3 minutes, with the lights off, can also be quantified to evaluate the operability of the catalyst. Table 5 shows the measured exothermic reactions and total ethylene uptake rates at various time points within the first 3 minutes of several batch experiments for catalyst systems 1-4, as well as comparative catalysts C1 and C2. Exothermic reactions were calculated using the following equation 1, where T int This is the internal temperature measured by a thermocouple inside the reactor, and the setting T rx is the reactor temperature set for the experiment. The total ethylene uptake rate is calculated using the following equation 2, where C2 uptake is expressed as . 時間 This is the total ethylene consumed during the specified time of the experiment, and the C2 incorporation. 全体This represents the total ethylene consumed during the entire run (1 hour or 3 hours). Fever = Highest T int -Setting T rx formula 1 %C2 import 時間 =(Import from C2) 時間 / Import all C2 全体 )×100% Formula 2

[0162] The light-off or ethylene uptake profile of the catalyst system is the exothermic rate (%). Exo Characterized by ), conveniently measured by conventional batch reactor testing methods, and represented by formula (XII), T rx The maximum reactor temperature (T max ) and target reactor temperature (T rx ) This can be quantified as a percentage difference from the temperature:

[0163]

number

[0164] Compared to comparative examples that exhibit significantly high exothermic reaction (≧17°C) at initial catalyst injection under conditions with high ethylene partial pressure, catalyst systems 1-4 consistently show lower exothermic reaction (≦8°C) (Table 4). Catalyst systems 1-4 also show significantly lower total ethylene uptake at various time points within the first 3 minutes under various conditions including both low and high C2PP, compared to comparative catalysts C1 and C2 (Table 4, 1-17 vs. 18-24). The significantly lower exothermic reaction and initial ethylene uptake, or light-off, of catalyst systems 1-4 provide evidence that these catalysts have improved light-off and, therefore, improved operability, compared to comparative examples C1 and C2.

[0165] [Table 4]

[0166] Condition 1a: Injection T=80°C, Run T=90°C, 0.003 C6 / C2, 0.004 H2 / C2, 100psi C2, 1 hour run time. Condition 1b: Injection T=80°C, Run T=90°C, 0.004 C6 / C2, 0.0011 H2 / C2, 115psi C2, 1 hour. Condition 1c: Injection T=80°C, Run T=90°C, 0.004 C6 / C2, 0.0011 H2 / C2, 230psi C2, 1 hour. Condition 2a: Injection T=80°C, Run T=100°C, 0.004 C6 / C2, 0.0068 H2 / C2, 230psi C2, 1 hour. Condition 2b: Injection T=80°C, Run T=100°C, 0.004 C6 / C2, 0.0016 H2 / C2, 230psi C2, 1 hour. Condition 3: Injection T=80℃, Run T=93℃, 0.0043 C6 / C2, 0.004 H2 / C2, 220psi C2, 1 hour. *3. Time. Condition 4: Injection T=80℃, Ran T=90℃, 0 C6 / C2, 0.018 H2 / C2, 230psi C2, 1 time. Condition 5: Injection T=80℃, Ran T=90℃, 0 C6 / C2, 0.01 H2 / C2, 230psi C2, 1 time. Condition 6: Injection T=80℃, Ran T=90℃, 0 C6 / C2, 0.007 H2 / C2, 230psi C2, 1 time. Condition 7: Injection T=80℃, Ran T=90℃, 0 C6 / C2, 0.004 H2 / C2, 230psi C2, 1 time. Condition 8: Injection T=80℃, Ran T=90℃, 0 C6 / C2, 0.01 H2 / C2, 165psi C2, 1 time. Condition 9: Injection T=80℃, Ran T=90℃, 0 C6 / C2, 0.01 H2 / C2, 100psi C2, 1 time. Condition 10: Injection T=80℃, Ran T=105℃, 0 C6 / C2, 0.01 H2 / C2, 230psi C2, 1 time. Condition 11: Injection T=80℃, Ran T=80℃, 0 C6 / C2, 0.01 H2 / C2, 230psi C2, 1 time.

[0167] Another method for evaluating catalyst light-off and controlled ethylene consumption is to measure the time it takes for the catalyst to consume a specified amount of total ethylene during the experiment. Catalysts with rapid and uncontrollable light-off and ethylene consumption that lead to uncontrollable behavior tend to consume ethylene rapidly, with the majority of their total ethylene uptake occurring within the initial stages of the run (i.e., the first 6 minutes, or 10%, of a 60-minute run). This behavior also tends to lead to chunking and / or aggregation in the reactor. Table 5 shows the specified time points at which the catalyst consumed 25%, 50%, 75%, and 90% of the total ethylene consumed during the run, for each of the various conditions. Under reactor conditions with higher ethylene partial pressure (C2PP ≥ 165 psi), the time it took for catalyst systems 1-4 to consume 25%, 50%, 75%, and 90% of the total ethylene consumed during a 1-hour run was significantly slower than that of comparative catalyst systems C1 and C2 (Table 5, items 4-13 and 15-16 vs. 18, 19, and 21). Combined with the data in Table 4, the data in Table 5 shows slower initial ethylene consumption and controlled ethylene consumption throughout the entire run for each of the catalyst systems 1-4 of the present invention, in stark contrast to the rapid and uncontrollable ethylene consumption throughout the entire run of comparative catalyst system 1 under conditions with high ethylene partial pressure.

[0168] [Table 5]

[0169] Condition 1a: Injection T=80°C, Run T=90°C, 0.003 C6 / C2, 0.004 H2 / C2, 100psi C2, 1 hour run time. Condition 1b: Injection T=80°C, Run T=90°C, 0.004 C6 / C2, 0.0011 H2 / C2, 115psi C2, 1 hour. Condition 2a: Injection T=80°C, Run T=100°C, 0.004 C6 / C2, 0.0068 H2 / C2, 230psi C2, 1 hour. Condition 2b: Injection T=80°C, Run T=90°C, 0.004 C6 / C2, 0.0011 H2 / C2, 230psi C2, 1 hour. Condition 2c: Injection T=80°C, Run T=100°C, 0.004 C6 / C2, 0.0016 H2 / C2, 230psi C2, 1 hour. Condition 3: Injection T=80℃, Run T=93℃, 0.0043 C6 / C2, 0.004 H2 / C2, 220psi C2, 1 hour. * 3 hours. Condition 4: Injection T=80℃, Run T=90℃, 0 C6 / C2, 0.018 H2 / C2, 230psi C2, 1 hour. Condition 5: Injection T=80℃, Run T=90℃, 0 C6 / C2, 0.01 H2 / C2, 230psi C2, 1 hour. Condition 6: Injection T=80℃, Run T=90℃, 0 C6 / C2, 0.007 H2 / C2, 230psi C2, 1 hour. Condition 7: Injection T=80℃, Run T=90℃, 0 C6 / C2, 0.004 H2 / C2, 230psi C2, 1 hour. Condition 8: Injection T=80°C, Run T=90°C, 0 C6 / C2, 0.01 H2 / C2, 165psi C2, 1 hour. Condition 9: Injection T=80℃, Run T=90℃, 0 C6 / C2, 0.01 H2 / C2, 100psi C2, 1 hour. Condition 10: Injection T=80°C, Run T=105°C, 0 C6 / C2, 0.01 H2 / C2, 230psi C2, 1 hour. Condition 11: Injection T=80°C, Run T=80°C, 0 C6 / C2, 0.01 H2 / C2, 230psi C2, 1 hour.

[0170] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​listed. Instead, unless otherwise specified, each such dimension is intended to mean both the listed value and the functionally equivalent range surrounding that value. For example, "40 g / cm²". 3The dimensions disclosed as "approximately 40g / cm²" are "approximately 40g / cm²". 3 This is intended to mean "...".

[0171] The symbols used in the formulas contained herein refer to their standard meanings as understood in the field of mathematics. For example, "=" means equal, "×" means multiplication, "+" means addition, "-" means subtraction, ">" is the sign for "greater than", "<" is the sign for "less than", and " / " means division.

[0172] All documents referenced herein, including any cross-referenced or related patents or patent applications, and any patents or patent applications to which this application claims priority or interest, are incorporated in their entirety by reference unless expressly excluded or otherwise limited. No reference to any document constitutes prior art with respect to any embodiment disclosed or claimed, nor does it imply, suggest, or disclose any such embodiment, either alone or in combination with any other single or multiple references. Furthermore, if any meaning or definition of any term in this document conflicts with any meaning or definition of the same term in any document incorporated by reference, the meaning or definition assigned to the term in this document shall prevail. The present specification includes the following embodiments. Section 1: A process for producing polyethylene, comprising a catalyst system containing a metal-ligand complex disposed on one or more carrier materials, wherein the ethylene partial pressure is 150 psi or higher and one or more (C3~C3) 12 ) In a gas-phase polymerization reactor at a reactor temperature of 70°C to 150°C, with a molar supply ratio of α-olefin comonomer to ethylene of 0.030 or less, ethylene and one or more optionally (C3-C3) are polymerized. 12 ) comprising contacting an α-olefin comonomer with the catalyst system, wherein the metal-ligand complex has the structure of formula (Ia): [ka] (In the formula, A - is an anion, M is titanium, zirconium, or hafnium. n is 1, 2, or 3. Each X is (C1~C 50 ) Hydrocarbyl, (C1~C 50 ) Heterohydrocarbyl, (C6~C 50 )aryl, (C2~C 50 ) A monodentate ligand independently selected from the group consisting of heteroaryls and halogens, R 1 and R 8 This is independently selected from the group consisting of radicals having formula (II) and radicals having formula (III), [ka] (In the formula, R 9~13 and R 14~21 is -H, (C1~C 50 ) Hydrocarbyl, (C1~C 50 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C (or selected independently of halogens) R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 is -H, (C1~C 50 ) Hydrocarbyl, (C1~C 50 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C (and selected independently from halogens), The amount of ethylene consumed in the first 5 minutes when the catalyst system is injected into the gas-phase polymerization reactor is equal to the average residence time t at the time of initial addition of the catalyst system. R This is less than 25% of the total ethylene consumed over the entire time, and the time during which 25% of the total ethylene is taken in (t 25% The process is as follows: ) is calculated by the equation (IV):

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Claims

1. A process for producing polyethylene, comprising a catalyst system containing a metal-ligand complex disposed on one or more carrier materials, wherein the ethylene partial pressure is 150 psi or more and one or more (C ３ ~C １２ ) In a gas-phase polymerization reactor at a reactor temperature of 70°C to 150°C, with a molar supply ratio of α-olefin comonomer to ethylene of 0.030 or less, ethylene and one or more optionally (C ３ ~C １２ ) comprising contacting an α-olefin comonomer with the catalyst system, wherein the metal-ligand complex has the structure of formula (Ia): 【number】 (In the formula, A － is an anion, M is titanium, zirconium, or hafnium. n is 1, 2, or 3. Each X is a monodentate ligand independently selected from the group consisting of (C １ ~C ５０ ) hydrocarbyl, (C １ ~C ５０ ) heterohydrocarbyl, (C ６ ~C ５０ ) aryl, (C ２ ~C ５０ ) heteroaryl, and halogen, R １ and R ８ This is independently selected from the group consisting of radicals having formula (II) and radicals having formula (III), 【number】 (In the formula, R ９～１３ and R １４～２１ is -H, (C １ ~C ５０ ) Hydrocarbyl, (C １ ~C ５０ ) Heterohydrocarbyl, -Si(R Ｃ ) ３ ,-Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , or selected independently of halogen, each R Ｃ , R Ｐ , and R Ｎ is -H, (C １ ~C ５０ ) hydrocarbyl, and (C １ ~C ５０ (Selected independently from heterohydrocarbils) R ２ , R ３ , R ４ , R ５ , R ６ , and R ７ is -H, (C １ ~C ５０ ) Hydrocarbyl, (C １ ~C ５０ ) Heterohydrocarbyl, -Si(R Ｃ ) ３ ,-Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , and selected independently from halogen, each R Ｃ , R Ｐ , and R Ｎ is -H, (C １ ~C ５０ ) hydrocarbyl, and (C １ ~C ５０ (Selected independently from heterohydrocarbils), The amount of ethylene consumed in the first 5 minutes when the catalyst system is injected into the gas-phase polymerization reactor is equal to the average residence time t at the time of initial addition of the catalyst system. Ｒ This is less than 25% of the total ethylene consumed over the entire time, and the time (t) during which 25% of the total ethylene is taken in is less than 25% of the total ethylene. ２５％ The process is as follows: ) is calculated by the formula (IV): [Math 1]

2. The process, the average residence time t Ｒ The capture ratio (U) at a specified time t over the entire period. ｔ This further includes the fact that ) can be calculated according to formula (V), [Math 2] U of the catalyst system ｔ The process according to claim 1, wherein the concentration is 0.02 (2 percent) or less at 0.5 minutes (30 seconds) after the catalyst system has been supplied to the reactor, as shown by formulas (X) and (XI): Data acquisition in 30 seconds (0.5 minutes), [Math 3] Data acquisition in 30 seconds (0.5 minutes), [Math 4]

3. Heat generation rate (%) ｅｘｏ The process according to claim 1 or 2, wherein ) is less than 10%.

4. R １ and R ８ However, they are the same, or R １ and R ８ At least one of them is a radical having formula (II), and R １０ and R １２ At least one of them is tert-butyl, R １ and R ８ At least one of them is a radical having formula (III), or R １５ , R １６ , R １９ , and R ２０ At least one of them is tert-butyl, R １４～２１ The process according to any one of claims 1 to 3, wherein the result is -H.

5. The process according to any one of claims 1 to 4, wherein one or more carrier materials include fumed silica.

6. The process according to any one of claims 1 to 5, wherein the anion is aluminate.

7. The process according to any one of claims 1 to 6, wherein the catalyst system is supplied to the gas-phase polymerization reactor in its original form, either as a solution or as a slurry.

8. The process according to any one of claims 1 to 7, wherein the catalyst system includes spray-dried particles.

9. The process according to any one of claims 1 to 8, wherein the ethylene partial pressure in the reactor is 170 psi or more.

10. The process according to any one of claims 1 to 9, wherein the reactor temperature is 120°C or lower.

11. A method for preparing the catalyst system described in claim 1, A supported activator is produced by placing one or more activators on the one or more carrier materials, The supported activator is brought into contact with a solution or slurry of a neutral metal-ligand complex in an inert hydrocarbon solvent. Methods that include...

12. The method according to claim 11, wherein the activator comprises methylarmoxane (MAO).

13. A process for producing polyethylene, comprising a catalyst system containing a metal-ligand complex disposed on one or more carrier materials, wherein the ethylene partial pressure is 50 psi to 150 psi and one or more (C ３ ~C １２ ) In a gas-phase polymerization reactor at a reactor temperature of 70°C to 150°C, with a molar supply ratio of α-olefin comonomer to ethylene of 0.030 or less, ethylene and one or more optionally (C ３ ~C １２ ) comprising contacting an α-olefin comonomer with the catalyst system, wherein the metal-ligand complex has the structure of formula (Ia): 【number】 (In the formula, A － is an anion, M is titanium, zirconium, or hafnium. n is 1, 2, or 3. Each X is a monodentate ligand independently selected from the group consisting of (C １ ~C ５０ ), (C １ ~C ５０ ), (C ６ ~C ５０ ), (C ４ ~C ５０ ), and halogen, R １ and R ８ This is independently selected from the group consisting of radicals having formula (II) and radicals having formula (III), 【number】 (In the formula, R ９～１３ and R １４～２１ is -H, (C １ ~C ５０ ) Hydrocarbyl, (C １ ~C ５０ ) Heterohydrocarbyl, -Si(R Ｃ ) ３ ,-Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , or selected independently of halogen, each R Ｃ , R Ｐ , and R Ｎ is -H, (C １ ~C ５０ ) hydrocarbyl, and (C １ ~C ５０ (Selected independently from heterohydrocarbils) R ２ , R ３ , R ４ , R ５ , R ６ , and R ７ is -H, (C １ ~C ５０ ) Hydrocarbyl, (C １ ~C ５０ ) Heterohydrocarbyl, -Si(R Ｃ ) ３ ,-Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , and selected independently from halogen, each R Ｃ , R Ｐ , and R Ｎ is -H, (C １ ~C ５０ ) hydrocarbyl, and (C １ ~C ５０ (Selected independently from heterohydrocarbils), The amount of ethylene consumed in the first 25 minutes when the catalyst system is injected into the gas-phase polymerization reactor is equal to the average residence time t at the time of initial addition of the catalyst system. Ｒ Less than 50% of the total ethylene consumed over the entire time, and the time (t) during which 25% of the total ethylene is taken in. ２５％ The process is as follows: ) is calculated by the formula (IV): [Number 9]

14. The process according to claim 13, wherein the ethylene partial pressure is 80 psi to 150 psi.

15. The process according to claim 13, wherein the amount of ethylene consumed in the first 30 minutes during the initial injection of the catalyst system into the gas-phase polymerization reactor is less than 50% of the total ethylene consumed over the entire average residence time.

16. Heat generation rate (%) ｅｘｏ The process according to any one of claims 13 to 15, wherein the percentage is less than 5%.

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