Catalyst system and method for producing polyethylene using the same

Abstract

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

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

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

[0003] Embodiments of the present disclosure are generally directed to processes for producing polyethylene, and in particular to the polymerization of ethylene and optionally one or more (C3-C 12 ) an alpha-olefin comonomer is contacted with a germanium-bridged bisphenylphenoxy catalyst system. Background Art

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

[0005] However, when used in some polymerization processes such as gas phase polymerization, catalyst systems comprising BPP metal-ligand complexes often exhibit: 1) operability problems associated with rapid light-off; and / or 2) poor productivity. In other terms, catalyst systems comprising BPP metal-ligand complexes often may cause reactor fouling and / or produce less polymer relative to the amount of catalyst system used. Therefore, the use of catalyst systems comprising BPP metal-ligand complexes in gas phase polymerization processes may not be commercially viable. Summary of the invention

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

[0007] Embodiments of the present disclosure include processes for producing polyethylene. The process comprises reacting ethylene and optionally one or more (C3-C 12 ) α-olefin comonomer is contacted with a catalyst system, the reactor temperature is 70°C to less than or equal to 150°C, wherein the ethylene partial pressure is greater than or equal to 150 psi, and one or more (C3-C 12 ) a molar feed ratio of alpha-olefin comonomer to ethylene is less than or equal to 0.030, wherein the catalyst system comprises an activated metal-ligand complex disposed on one or more support materials. The metal-ligand complex has a structure according to formula (Ia):

[0008]

[0009] In formula (Ia), A - is an anion; M is titanium, zirconium or hafnium; and n is 1, 2 or 3. Each X is independently selected from (1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, (C6-C 50 ) aryl, (C4-C 50 ) a monodentate ligand of the group consisting of a heteroaryl group and a halogen;

[0010] In formula (Ia), R 1 and R 8 are independently selected from the group consisting of a group having formula (II) and a group having formula (III):

[0011]

[0012] In formula (II), R 9 – 13 are independently selected from -H, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C or halogen. In formula (III), R 14 – 21 are independently selected from -H, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-ORC 、-SR C or halogen.

[0013] In formula (Ia), R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from -H, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C and halogens.

[0014] The process of the present disclosure comprises consuming less ethylene during the first 5 minutes after the catalyst system is injected into the gas phase polymerization reactor after the initial addition of the catalyst system than the entire average residence time t R 25% of the total ethylene consumed in the time period, of which 25% of the total ethylene uptake time (t 25％ ) is calculated by the equation according to formula (IV):

[0015] And t 25％ >5min(IV).

[0016] These and additional features provided by embodiments of the present disclosure will be more fully understood from the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 are the ethylene uptake curves for Examples 4 and 7 from Table 1.

[0018] Figure 2 is a graphical depiction of the reactor temperature profiles for Examples 1 to 3.

[0019] Figure 3 is a graphical depiction of the reactor temperature profiles for Examples 4 to 6, wherein the polymerization reactions were run under Condition 2b.

[0020] Figure 4 is a graphical depiction of the reactor temperature profiles for Examples 7 to 9, wherein the polymerization reactions were run under Condition 3.

[0021] Figure 5 ] are the ethylene uptake curves of Example 7 and Example 9, wherein the polymerization reactions were run under Condition 3.

[0022] Figure 6 is a graphical depiction of the ethylene and total ethylene uptake curves for Catalyst System 2 in Example 14.

[0023] Figure 7 These are the ethylene uptake curve and internal reactor curve for catalyst system 2 in Example 16.

[0024] Figure 8 is a graphical depiction of the ethylene and total ethylene uptake curves for Catalyst System 2 in Example 19. DETAILED DESCRIPTION

[0025] The specific embodiments of the primary catalyst, catalyst system, method for producing the catalyst system and the process for producing polyethylene will now be described. However, it should be understood that the system, method and process of the present disclosure can be embodied in different forms and should not be construed as being limited to the specific embodiments set forth in the present disclosure. On the contrary, embodiments are provided so that the present disclosure will be thorough and complete, and the embodiments will fully convey the scope of the subject matter to those skilled in the art.

[0026] The following is a list of common abbreviations used in this disclosure:

[0027] Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl; i-Pr: isopropyl; t-Bu: tert-butyl; t-Oct: tert-octyl (2,4,4-trimethylpentan-2-yl); Tf: trifluoromethanesulfonate; THF: tetrahydrofuran; Et2O: ether; CH2Cl2: dichloromethane; CV: column volume (used in column chromatography); EtOAc: ethyl acetate; C6D6: deuterated benzene or benzene-d6; CDCl3: deuterated Chloroform; Na2SO4: sodium sulfate; MgSO4: magnesium sulfate; HCl: hydrogen chloride; n-BuLi: butyl lithium; t-BuLi: tert-butyl lithium; MAO: methylaluminoxane; MMAO: modified methylaluminoxane; GC: gas chromatography; LC: liquid chromatography; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimole; mL: milliliter; M: mole; min or mins: minutes; h or hrs: hours; d: day.

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

[0029] The term "independently selected" means that R groups such as R 1 , R2 and R 3 Can be the same or different (e.g. R 1 , R 2 and R 3 may be substituted alkyl; or R 1 and R 2 may be a substituted alkyl group, and R 3 The chemical names associated with the R groups are intended to convey chemical structures that are recognized in the art to correspond to the chemical structures of the chemical names. Thus, the chemical names are intended to supplement and illustrate rather than exclude structural definitions known to those skilled in the art.

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

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

[0032] When used to describe certain chemical groups containing carbon atoms, the group having the form "(C x -C y )" means that the unsubstituted form of the chemical group has from x to y carbon atoms, including x and y. For example, (C1-C 50 ) alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be replaced by, for example, R S etc. is substituted with one or more substituents. x -C y )" insert the defined R S The substituted chemical group may contain more than y carbon atoms, depending on the number of any group R S For example, "with exactly one group R S Substituted (C1-C 50 ) alkyl, wherein R S is phenyl (-C6H5)" can contain 7 to 56 carbon atoms. Therefore, when using "(C x -C y)" is inserted into the chemical group defined by one or more carbon-containing substituents R S When substituted, both x and y are added to the substituent R from all carbon atoms. S The combined sum of the number of carbon atoms is used to determine the minimum and maximum total number of carbon atoms in a chemical group.

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

[0034] The term "C1-C 50 "Alkyl" means a saturated straight or branched hydrocarbon group containing 1 to 50 carbon atoms. Each (C1-C 50 ) The alkyl group may be unsubstituted or substituted with one or more R S In some embodiments, each hydrogen atom in the hydrocarbon group may be replaced by R S substituted, such as, for example, trifluoromethyl. 50 Examples of alkyl groups 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. Substituted (C1-C5)alkyl 50 Examples of alkyl groups 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 a maximum of 45 carbon atoms in the group including the substituents, and for example one R is (C1-C5)alkyl (such as for example methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl or 1,1-dimethylethyl) S Replaced (C 27 -C 40 )alkyl.

[0035] The term "(C3-C 50 "Cycloalkyl" means a saturated cyclic hydrocarbon group having 3 to 50 carbon atoms, which is unsubstituted or substituted by one or more R S Other cycloalkyl groups (e.g., (C x -C y )cycloalkyl) is defined in a similar manner as having x to y carbon atoms and being unsubstituted or substituted with one or more R S Substituted. Unsubstituted (C3-C 50 Examples of cycloalkyl groups are unsubstituted (C3-C 20 )cycloalkyl, unsubstituted (C3-C 10 )cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. 50 Examples of cycloalkyl groups are substituted (C3-C 20 )cycloalkyl, substituted (C3-C 10 )cycloalkyl and 1-fluorocyclohexyl.

[0036] The term "(C6C 50 ) aryl" means an unsubstituted or substituted (one or more R S ) substituted monocyclic, bicyclic or tricyclic aromatic hydrocarbon groups, wherein at least 6 to 14 carbon atoms are aromatic ring carbon atoms. Monocyclic aromatic hydrocarbon groups include one aromatic ring; bicyclic aromatic hydrocarbon groups have two rings; and tricyclic aromatic hydrocarbon groups have three rings. When bicyclic or tricyclic aromatic hydrocarbon groups are present, at least one of the rings of the group is aromatic. The other one or more rings of the aromatic group may independently be fused or non-fused and be aromatic or non-aromatic. Unsubstituted (C6-C 50 Examples of aryl groups include: unsubstituted (C6-C 20 )aryl, unsubstituted (C6-C 18 )aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; dicyclopentadienylphenyl; hexahydrodicyclopentadienylphenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C6-C 50Examples of aryl groups include: substituted (C1-C 20 ) aryl; substituted (C6-C 18 ) aryl; 2,4-bis([C 20 ] alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-on-1-yl.

[0037] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include O, S, S(O), S(O)2, Si(R C )2. P(R P )、N(R N )、-N=C(R C )2、-Ge(R C )2- or -Si(R C )-, where each R C and each RP is unsubstituted (C1-C 18 )alkyl or -H, and each R N is unsubstituted (C1-C 18 ) hydrocarbon group. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by a heteroatom. 50 )heteroalkyl" means a heteroalkyl group having 1 to 50 carbon atoms, and the term "(C1-C 50 ) heteroalkylene" means a heteroalkylene group having 1 to 50 carbon atoms. 50 )heteroalkyl or (C1-C 50 The heteroalkylene of the heteroalkylene has one or more heteroatoms. The radical of the heteroalkylene can be on a carbon atom or a heteroatom. The two radicals of the heteroalkylene can be on a single carbon atom or on a single heteroatom. In addition, one of the two radicals of the diradical can be on a carbon atom and the other can be on a different carbon atom; one of the two radicals can be on a carbon atom and the other can be on a heteroatom; or one of the two radicals can be on a heteroatom and the other can be on a different heteroatom. Each (C1-C 50 ) heteroalkyl and (C1-C 50 ) heteroalkylene may be unsubstituted or substituted with (one or more R S ) substituted, aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0038] The term "(C2-C 50 ) heteroaryl" means an unsubstituted or substituted (one or more R S) substituted monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon groups. Monocyclic heteroaromatic hydrocarbon groups include one heteroaromatic ring; bicyclic heteroaromatic hydrocarbon groups have two rings; and tricyclic heteroaromatic hydrocarbon groups have three rings. When a bicyclic heteroaromatic hydrocarbon group or a tricyclic heteroaromatic hydrocarbon group is present, at least one of the rings in the group is heteroaromatic. The other one or more rings of the heteroaromatic group may independently be fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., typically (C x -C y ) heteroaryl, such as (C4-C 12 ) heteroaryl) is defined in a similar manner as having x to y carbon atoms (such as 4 to 12 carbon atoms) and being unsubstituted or substituted by one or more than one R S Substituted. The monocyclic heteroaromatic hydrocarbon group is a 5-membered ring or a 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2 or 3, and each heteroatom can be O, S, N or P. Examples of 5-membered heteroaromatic hydrocarbon groups include: pyrrol-1-yl; piperidin-2-yl; furan-3-yl; thien-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazole-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazole-1-yl; 1,3,4-oxadiazole-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatoms can be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon groups include pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. Bicyclic heteroaromatic hydrocarbon groups can be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring system bicyclic heteroaromatic hydrocarbon groups are indol-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-ring system bicyclic heteroaromatic hydrocarbon groups are quinolin-2-yl; and isoquinolin-1-yl. Bicyclic heteroaromatic hydrocarbon groups can be fused 5,6,5-ring systems; 5,6,6-ring systems; 6,5,6-ring systems; or 6,6,6-ring systems. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridin-9-yl.

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

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

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

[0042] The terms "polyethylene" and "ethylene polymer" refer to polyolefins containing more than 50 mole percent (%) of ethylene monomer derived units, including polyethylene homopolymers and copolymers. Common forms of polyethylene known in the art include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (ULDPE), very low-density polyethylene (VLDPE), medium-density polyethylene (MDPE) and high-density polyethylene (HDPE).

[0043] The term "molecular weight distribution" refers to the ratio of two different molecular weights of a polymer. The general term molecular weight distribution includes the weight average molecular weight (M) of a polymer. w ) and the number average molecular weight (M n ) ratio, which can also be called "molecular weight distribution (M w / M n )”, and the z-average molecular weight (M z ) and the weight average molecular weight (M w ) ratio, which can also be called "molecular weight distribution (M z / M w )”.

[0044] The term "composition" is intended to refer to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0045] The terms "comprising," "including," "having," and derivatives thereof are not intended to exclude the presence of any additional components, steps, or procedures, whether or not specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of excludes from the scope of any subsequently recited component, step, or procedure, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically recited or listed.

[0046] In an embodiment, the catalyst system includes a procatalyst. The procatalyst includes a metal-ligand complex. The metal-ligand complex may have a structure according to formula (I):

[0047]

[0048] 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.

[0049] In formula (I), (X) n The subscript n is 1, 2 or 3, and each X is independently selected from unsaturated (C2-C 50 ) hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, (C6-C 50 ) aryl, (C2-C 50 )heteroaryl, halogen, –N(R N )2 and –N(R N )COR C In some embodiments, each X is independently selected from methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chlorine. In some embodiments, (X) n The subscript n is 2, and each X is the same. In other embodiments, at least two X are different. For example, (X) nThe subscript n of may be 2, and each X may be a different group from the following: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chloro. In an embodiment, (X) n The subscript n is 1 or 2, and at least two X are independently monoanionic monodentate ligands, and if present, the third X is a neutral monodentate ligand. In one or more embodiments, (X) n The subscript n of is 2. In formula (I), the metal-ligand complex is electrically neutral as a whole.

[0050] In formula (I), R 1 and R 8 are independently selected from the group consisting of a group having formula (II) and a group having formula (III):

[0051]

[0052] In formula (II), R 9 , R 10 , R 11 , R 12 , R 13 are independently selected from -H, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)- or halogen.

[0053] In formula (III), R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21 are independently selected from -H, (C1-C 50 ) hydrocarbon group, (C1-C50 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)- or halogen.

[0054] The group R in the metal-ligand complex of formula (I) 1 and R 8 are chosen independently of each other. For example, R 1 can be selected from groups having formula (II) or (III), and R 8 It can be (C2-C 50 ) heteroaryl; or R 1 can be selected from groups having formula (II), (III) or (IV), and R 16 Can be selected from R 1 The same or different groups have formula (II) or (IV). In an embodiment, R 1 and R 8 Both are radicals of formula (II) in which the radical R 9-13 In R 1 and R 8 In some embodiments, R 1 and R 8 Both are groups of formula (III) in which the group R 14-21 In R 1 and R 8 The same or different.

[0055] In some embodiments, R 1 and R 8 At least one of them is a group having formula (II), wherein R 10 and R 12 In some embodiments, when R 1 or R 8 When at least one of them is a group having formula (III), R 16 and R 19One or both of them are tert-butyl, and R 14-15 , R 17-18 and R 20-21 is -H. In some embodiments, R 15 and R 20 One or both of them are tert-butyl, and R 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 Yes – H.

[0056] In formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently selected from -H, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)- and halogen.

[0057] In some embodiments, R 3 or R 4 At least one of is a halogen atom; and R 5 or R 6 At least one of is a halogen atom. 3 and R 4 Both are halogen atoms; and both or R 5 or R 6 It is a halogen atom.

[0058] In an embodiment, R 2 and R 7 Yes (C1-C 24) alkyl. In various embodiments, R 2 and R 7 Yes (C1-C 20 In some embodiments, R 2 and R 7 Yes (C4-C 24 ) alkyl. In one or more embodiments, R 2 and R 7 Yes (C8-C 12 In some embodiments, R 2 and R 7 is 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl. In an embodiment, R 2 and R 7 Yes-OR C , where R C Yes (C1-C 20 ) hydrocarbon, and in some embodiments, R C It is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl) or 1,1-dimethylethyl.

[0059] In some embodiments, R 4 and R 5 Yes (C1-C 20 In some embodiments, R 4 and R 5 is 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl. In an embodiment, R 4 and R 5 It's methyl.

[0060] In some embodiments, R 3 and R 6 is halogen. In other embodiments, R 3 and R 6 Yes (C1-C 24 In some embodiments, R 3 and R 6R is independently selected from methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. In some embodiments, R 6 and R 11 In the embodiment, R 3 and R 6 Yes-OR C , where R C Yes (C1-C 20 ) alkyl, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl) or 1,1-dimethylethyl. In other embodiments, R 3 and R 6 Yes-SiR C 3, where each R C Independently (C1-C 20 ) alkyl, and in some embodiments, R C It is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl) or 1,1-dimethylethyl.

[0061] In some embodiments, R 2 and R 7 is a methyl group, and R 3 and R 6 is halogen. In other embodiments, R 3 and R 6 In other embodiments, R 2 and R 7 It is tert-octyl or n-octyl.

[0062] In formula (I), (Ia), (II) and (III), each R C , R P and R N are independently selected from -H, (C1-C 50 ) alkyl and (C1-C 50 ) heteroalkyl.

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

[0064] Aluminoxane activators can be used as activators for one or more of the catalyst compositions. Aluminoxanes or alkylaluminums are typically oligomeric compounds containing --Al(R)--O--subunits, wherein R is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, particularly when the extractable ligand is a halide. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. For further description, see U.S. Patent Nos. 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP 0 561 476, EP 0 279586, EP 0 516 476, EP 0 594218, and WO 94 / 10180.

[0065] When the activator is an aluminoxane (modified or unmodified), the maximum amount of the activator may be selected to be a 10,000-fold molar excess of Al / M relative to the catalyst precursor (per metal catalytic site). Alternatively or additionally, the minimum amount of activator to catalyst precursor may be set to a 1:1 molar ratio. In embodiments, the amount of activator to catalyst precursor may be selected from 10,000:1Al / M, 5,000:1Al / M, 1,000:1Al / M, 500:1Al / M, 250:1Al / M, 150:1Al / M, 120:1Al / M, 100:1Al / M, 50:1Al / M, 20:Al / M, 10:1Al / M, 5:1Al / M, 1:1Al / M.

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

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

[0068]

[0069] In formula (Ia), A - is an anion, and M, (X) n The subscript n, each X, each Z and R 1 -R 8 As previously described for the metal-ligand complex of formula (I).

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

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

[0072] Suitable support materials, such as inorganic oxides, include metal oxides of Groups 2, 3, 4, 5, 13 or 14 of the IUPAC Periodic Table. In embodiments, the support material includes dehydrated or non-dehydrated silica, fumed silica, alumina (e.g., as described in International Patent Application No. 1999 / 060033), silica-alumina, and mixtures of these. The fumed silica may be hydrophilic (untreated), alternatively hydrophobic (treated). In embodiments, the support material is hydrophobic fumed silica, which may be prepared by treating untreated fumed silica with a treating agent such as dimethyldichlorosilane, polydimethylsiloxane fluid, or hexamethyldisilazane. In some embodiments, the support material includes magnesium oxide, titanium dioxide, zirconium oxide, magnesium chloride (e.g., as described in U.S. Patent No. 5,965,477), montmorillonite (e.g., as described in European Patent No. 0 511 665), phyllosilicates, zeolites, talc, clays (e.g., as described in U.S. Patent No. 6,034,187), and mixtures of these. In other embodiments, combinations of these support materials may be used, such as, for example, silica-chromium, silica-alumina, silica-titania, and combinations of these. Additional support materials may also include those porous acrylic polymers described in European Patent No. 0 767184. Other support materials may also include nanocomposites described in International Patent Application No. 1999 / 047598; aerogels described in International Patent Application No. 1999 / 048605; spherulites described in U.S. Patent No. 5,972,510; and polymer beads described in International Patent Application No. 1999 / 050311.

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

[0074] There are various suitable methods to produce the catalyst system of the present disclosure. In one or more embodiments, the method for producing the catalyst system includes contacting one or more support materials, one or more activators and a metal-ligand complex in an inert hydrocarbon solvent to produce the catalyst system. In some embodiments, the method for producing the catalyst system may include disposing the one or more activators on the one or more support materials to produce a supported activator, and contacting the supported activator with a solution of the metal-ligand complex in an inert hydrocarbon solvent (commonly referred to as "fine-tuning the catalyst" or "fine-tuning the feed"). For example, in some embodiments, the method for producing the catalyst system includes contacting a spray-dried supported activator (i.e., a supported activator produced via spray drying) with a solution of the metal-ligand complex in an inert hydrocarbon solvent. In some embodiments, the supported activator may be included in a slurry, such as, for example, a mineral oil slurry.

[0075] In some embodiments, the method for producing a catalyst system may include mixing one or more support materials, one or more activators and a metal-ligand complex to produce a catalyst system precursor. These methods may further include drying a catalyst system precursor to produce a catalyst system. More specifically, these methods may include preparing a mixture of a metal-ligand complex, one or more support materials, one or more activators, or a combination of these and an inert hydrocarbon solvent. The inert hydrocarbon solvent may then be removed from the mixture to produce a metal-ligand complex, one or more activators, or a combination of these disposed on the one or more support materials. In an embodiment, the removal step may be achieved by conventionally evaporating the inert hydrocarbon solvent from the mixture (i.e., conventional concentration methods), which produces an evaporation / supported catalyst system. In other embodiments, the removal step may be achieved by spray-drying the mixture, which produces spray-dried particles. It should be understood that the drying and / or removal steps may not result in the complete removal of liquid from the resulting catalyst system. That is, the catalyst system may include a residual amount (i.e., 1 wt % to 3 wt %) of an inert hydrocarbon solvent.

[0076] As previously described, the catalyst systems of the present disclosure can be used in methods for producing polymers (such as polyethylene) via the polymerization of olefins (such as ethylene). When used in some polymerization processes such as gas phase polymerization, catalyst systems including BPP metal-ligand complexes often exhibit: 1) operability problems associated with rapid ignition; and / or 2) poor productivity. For example, catalyst systems including BPP metal-ligand complexes may ignite too quickly in a gas phase polymerization reactor, that is, consume ethylene too quickly after injection, resulting in particle overheating, melting and aggregation, resulting in catalyst ball formation, agglomeration and other "debris" that may contaminate the gas phase polymerization reactor.

[0077] In an embodiment, one or more olefins may be contacted with the catalyst system of the present disclosure in a gas phase polymerization reactor, such as a gas phase fluidized bed polymerization reactor. Exemplary gas phase systems are described in U.S. Pat. Nos. 5,665,818; 5,677,375; and 6,472,484; and European Patent Nos. 0 517 868 and 0 794 200. For example, in some embodiments, ethylene and optionally one or more (C3-C4) hydrocarbons may be contacted with the catalyst system of the present disclosure in a gas phase polymerization reactor. 12 ) α-olefin comonomer is contacted with the catalyst system of the present disclosure. The catalyst system can be fed into the gas phase polymerization reactor in pure form (i.e., as a dry solid), as a solution, or as a slurry. For example, in some embodiments, spray-dried particles of the catalyst system can be fed directly into the gas phase polymerization reactor. In other embodiments, a solution or slurry of the catalyst system in a solvent (such as an inert hydrocarbon or mineral oil) can be fed into the reactor. For example, the primary catalyst can be fed into the reactor in an inert hydrocarbon solution, and the activator can be fed into the reactor in a mineral oil slurry.

[0078] In an embodiment, the gas phase polymerization reactor includes a fluidized bed reactor. The fluidized bed reactor may include a "reaction zone" and a "speed reduction zone". The reaction zone may include a bed of growing polymer particles, forming polymer particles and a small amount of a catalyst system, which is fluidized by a continuous flow of gaseous monomers and diluents to remove the polymerization heat passing through the reaction zone. Optionally, some recycle gases may be cooled and compressed to form liquids, which increase the heat removal capacity of the circulating gas stream when reentering the reaction zone. Suitable gas flow rates can be easily determined by simple experiments. The replenishment rate of gaseous monomers to the circulating gas stream may be equal to the rate at which the particle polymer product and the monomers associated therewith can be taken out of the reactor, and the composition of the gas passing through the reactor may be adjusted to maintain a substantially stable gaseous composition in the reaction zone. The gas leaving the reaction zone may be transferred to a speed reduction zone for removing entrained particles. Finer entrained particles and dust may be removed in a cyclone dust collector and / or a fine filter. The gas may pass through a heat exchanger, where the polymerization heat may be removed, compressed in a compressor, and then returned to the reaction zone. Additional reactor details and means for operating the reactor are described, for example, in U.S. Patent Nos. 3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,882,400; 5,352,749; and 5,541,270; European Patent No. 0 802 202; and Belgian Patent No. 839,380.

[0079] Catalyst systems with rapid light-off can contaminate gas phase polymerization reactors by forming "catalyst balls" or lumps, which can impede catalyst injection, polymer particle removal, or create other problems that are detrimental to operability. Agglomeration and "catalyst ball" formation are believed to be phenomena exacerbated by the rapid light-off catalyst causing overheating and fusion of polymer particles. The light-off of a catalyst system can be conveniently expressed in terms of ethylene uptake or ethylene consumption and the ethylene uptake ratio Ut, which is represented by formula (IV)

[0080]

[0081] wherein the total ethylene uptake of the catalyst system within the average residence time tR of the polymerization process is represented by formula (V), and the ethylene uptake at a given time after the catalyst system is injected into the polymerization reactor is represented by formula (VI):

[0082]

[0083] The ignition of this process can be controlled by increasing or decreasing the catalyst feed rate or increasing or decreasing the ethylene partial pressure in the reactor. However, it is usually impractical to alleviate the severity of catalyst ignition and the associated reactor operability problems by reducing the catalyst feed rate or reducing the ethylene partial pressure, because this reduces the reactor productivity and the amount of polymer produced per unit time, which is ultimately uneconomical in a production-scale polymerization reactor. In addition, the major component of the ignition of the catalyst system is the activated metal-ligand complex inherent to the catalyst system. In this article, the structural features of the active organometallic component of the catalyst system are described as improving the operability of the catalyst by changing the inherent ignition of the catalyst system.

[0084] In the present disclosure, a catalyst system having favorable light-off is quantified by formula (VII) wherein the amount of ethylene consumed during the first 5 minutes of catalyst life after initial addition of the catalyst system is less than the total average residence time t R 25% of the total ethylene consumed during the time period, including 25% of the total ethylene uptake during the time period (t 25％ ) is calculated by the equation according to formula (IV):

[0085] And t 25％ >5min(VII)

[0086] Alternatively, after the catalyst system is delivered to the polymerization reactor, the uptake ratio (U t ) or the percentage of ethylene consumed at a specific time t vs. catalyst life or average residence time t R The total ethylene consumed during the entire period (whichever is shorter) can be quantitatively ignited and can be calculated according to formula (IV). For example, at the time point 0.5 minutes (30 seconds) after the catalyst system is fed into the reactor, the U of the catalyst system is t Less than or equal to 0.02 (2%), as represented by formula (X) and (XI):

[0087] Taken at 30 seconds (0.5min),

[0088] Taken at 30 seconds (0.5min),

[0089] The ethylene uptake and ethylene uptake ratio of the catalyst system can be measured by the Light-off Batch Reactor Test Method.

[0090] In an embodiment, the reactor temperature of the gas phase polymerization reactor is 70°C to 150°C. For example, the reactor temperature of the gas phase polymerization reactor can 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. Typically, the 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 make polyethylene, the reactor temperature should be lower than the melting temperature or "sintering" temperature of the polymer product. Therefore, the upper temperature limit can be the melting temperature of the polymer product.

[0091] In some embodiments, the process of the present disclosure further comprises an internal reactor temperature, wherein the internal reactor temperature is approximately reactor temperature ± 5 degrees Celsius. In various embodiments, the internal reactor temperature is reactor temperature ± 3°C or reactor temperature ± 2°C; and in one or more embodiments, the internal reactor temperature is reactor temperature ± 1°C.

[0092] Rapid ignition leads to operability problems due to overheating of the particles due to rapid consumption of ethylene and / or comonomer, and may be better controlled based on the internal reactor temperature (T int ), which is a measure of the heat of polymerization and an indirect measure of the catalyst particle temperature. int It is a convenient way to quantify and compare the severity of light-off of different catalysts in a semi-batch gas phase polymerization process.

[0093] 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 can 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).

[0094] In one or more embodiments, the reactor pressure of the gas phase polymerization reactor is greater than or equal to 150 psi (1035 kPa). In various embodiments, the reactor pressure of the gas phase polymerization reactor is greater than or equal to 180 psi (1241 kPa), greater than or equal to 190 psi (1310 kPa), greater than or equal to 200 psi (1379 kPa), or greater than or equal to 230 psi (1586 kPa).

[0095] In some embodiments, the amount of ethylene consumed during the first 5 minutes after the catalyst system is injected into the gas phase polymerization reactor after the initial addition of the catalyst system is less than the total average residence time t R 25% of the total ethylene consumed in the time period, of which 25% of the total ethylene uptake time (t 25％ ) is calculated by the equation according to formula (IV):

[0096] And t 25％ >5min(IV).

[0097] In one or more embodiments, the amount of ethylene consumed during the first 25 minutes after the catalyst system is injected into the gas phase polymerization reactor after the initial addition of the catalyst system is less than the total average residence time t R 50% of the total ethylene consumed in the time period, of which 50% of the total ethylene uptake time (t 50％ ) is calculated by the equation according to formula (IV):

[0098] And t 50％ >25min(IV).

[0099] In an embodiment, hydrogen may be used during polymerization to control the final properties of the polyethylene. The amount of hydrogen in the polymerization may be expressed as a molar ratio relative to the total polymerizable monomers (such as, for example, ethylene or a blend of ethylene and 1-hexene). The amount of hydrogen used in the polymerization process may be the amount required to achieve the desired properties of the polyethylene, such as, for example, the melt flow rate (MFR). In an embodiment, the molar ratio of hydrogen to total polymerizable monomers (H2:monomers) is greater than 0.0001. For example, the molar ratio of hydrogen to total polymerizable monomers (H2:monomers) can be 0.0001 to 10, 0.0001 to 5, 0.0001 to 3, 0.0001 to 0.10, 0.0001 to 0.001, 0.0001 to 0.0005, 0.0005 to 10, 0.0005 to 5, 0.0005 to 3, 0.0005 to 0.10, 0.0005 to 0.001, 0.001 to 10, 0.001 to 5, 0.001 to 3, 0.001 to 0.10, 0.10 to 10, 0.10 to 5, 0.10 to 3, 3 to 10, 3 to 5, or 5 to 10.

[0100] In embodiments, the catalyst system of the present disclosure can be used to polymerize a single type of olefin to produce a homopolymer. However, in other embodiments, additional α-olefins can be incorporated into the polymerization process. Such additional α-olefin comonomers typically have no more than 20 carbon atoms. For example, the catalyst system of the present disclosure can be used to polymerize ethylene and one or more (C3-C 12) α-olefin comonomer polymerization. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, the one or more α-olefin comonomers can be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or alternatively, selected from the group consisting of 1-hexene and 1-octene.

[0101] In an embodiment, the one or more (C3-C 12 )α-olefin comonomers may not be derived from propylene. That is, the one or more (C3-C 12 )α-olefin comonomers may be substantially free of propylene. The term "substantially free" of a compound means that the material or mixture contains less than 1.0 wt. % of the compound. For example, the one or more (C3-C 12 ) The α-olefin comonomer may include less than 1.0 wt% propylene, such as less than 0.8 wt% propylene, less than 0.6 wt% propylene, less than 0.4 wt% propylene, or less than 0.2 wt% propylene.

[0102] In embodiments, the polyethylene produced, such as homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers, may include at least 50 mole % (mol.%) of monomer units derived from ethylene. For example, the polyethylene may include at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, or at least 90 mol% of monomer units derived from ethylene. In embodiments, the polyethylene includes 50 mol.% to 100 mol.% of monomer units derived from ethylene. For example, the polyethylene may include 50 mol.% to 90 mol.%, 50 mol.% to 80 mol.%, 50 mol.% to 70 mol.%, 50 mol.% to 60 mol.%, 60 mol.% to 100 mol.%, 60 mol.% to 90 mol.%, 60 mol% to 80 mol.%, 60 mol% to 70 mol%, 70 mol% to 100 mol%, 70 mol% to 90 mol%, 70 mol% to 80 mol%, 80 mol% to 100 mol%, 80 mol% to 90 mol.%, or 90 mol% to 100 mol% of monomer units derived from ethylene.

[0103] In embodiments, the polyethylene produced includes at least 90 mol.% of monomer units derived from ethylene. For example, the polyethylene may include at least 93 mol.%, at least 96 mol.%, at least 97 mol.%, or at least 99 mol.% of monomer units derived from ethylene. In embodiments, the polyethylene includes 90 mol.% to 100 mol.% of monomer units derived from ethylene. For example, the polyethylene may include 90 mol.% to 99.5 mol.%, 90 mol.% to 99 mol.%, 90 mol.% to 97 mol.%, 90 mol.% to 96 mol.%, 90 mol.% to 93 mol.%, 93 mol.% to 100 mol.%, 93 mol.% to 99.5 mol.%, 93 mol.% to 99 mol.%, 93 mol.% to 97 mol.%, 93 mol.% to 96 mol.%, 96 mol.% to 98 mol.%, 99 mol.% to 99 mol.%, 9 ... % to 100 mol.%, 96 mol.% to 99.5 mol.%, 96 mol.% to 99 mol.%, 96 mol.% to 97 mol.%, 97 mol.% to 100 mol.%, 97 mol.% to 99.5 mol.%, 97 mol.% to 99 mol.%, 99 mol.% to 100 mol.%, 99 mol.% to 99.5 mol.%, or 99.5 mol.% to 100 mol.% of monomer units derived from ethylene.

[0104] In embodiments, the polyethylene produced includes less than 50 mol.% of monomer units derived from additional α-olefins. For example, the polyethylene may include less than 40 mol.%, less than 30 mol.%, less than 20 mol.%, or less than 10 mol.% of monomer units derived from additional α-olefins. In embodiments, the polyethylene includes 0 mol.% to 50 mol.% of monomer units derived from additional α-olefins. For example, polyethylene may include 0 mol.% to 40 mol.%, 0 mol.% to 30 mol.%, 0 mol.% to 20 mol.%, 0 mol.% to 10 mol.%, 0 mol.% to 5 mol.%, 0 mol.% to 1 mol.%, 1 mol.% to 50 mol.%, 1 mol.% to 40 mol.%, 1 mol.% to 30 mol.%, 1 mol.% to 20 mol.%, 1 mol.% to 10 mol.%, 1 mol.% to 5 mol.%, 5 mol.% to 50 mol.%, 5 mol.% to 40 mol.%, 5m % to 30 mol.%, 5 mol.% to 20 mol.%, 5 mol.% to 10 mol.%, 10 mol.% to 50 mol.%, 10 mol.% to 40 mol.%, 10 mol.% to 30 mol.%, 10 mol.% to 20 mol.%, 20 mol.% to 50 mol.%, 20 mol.% to 40 mol.%, 20 mol.% to 30 mol.%, 30 mol.% to 50 mol.%, 30 mol.% to 40 mol.%, or 40 mol.% to 50 mol.% of monomer units derived from additional α-olefins.

[0105] In embodiments, the polyethylene produced further includes one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, ultraviolet (UV) stabilizers, and combinations of these. Polyethylene may include any amount of additives. In embodiments, the polyethylene produced further includes fillers, which may include, but are not limited to, organic or inorganic fillers, such as, for example, calcium carbonate, talc, or Mg(OH)2.

[0106] The polyethylene produced can be used in various products and end-use applications. The polyethylene produced can also be blended and / or coextruded with any other polymer. Non-limiting examples of other polymers include linear low-density polyethylene, elastomers, plastomers, high-pressure low-density polyethylene, high-density polyethylene, polypropylene, etc. In various other end uses, the polyethylene produced and blends including the polyethylene produced can be used to produce blow molding components or products. The polyethylene produced and blends including the polyethylene produced can be used to form operations such as film, sheet and fiber extrusion and coextrusion and blow molding, injection molding and rotational molding. The film includes a blown or cast film formed by coextrusion or lamination, which can be used as shrink film, cling film, stretch film, sealing film, oriented film, snack packaging, heavy-duty bags, grocery store sacks, baked and frozen food packaging, medical packaging, industrial pads and films in food contact and non-food contact applications. Fibers can include melt spinning, solution spinning and melt-blown fiber operations, which are used to make filter paper, diaper fabrics, medical clothing and geotextiles in woven or non-woven forms. Extruded articles may include medical catheters, wire and cable coatings, pipes, geomembranes, and pond liners. Molded articles may include single and multilayer constructions in the form of bottles, cans, large hollow articles, rigid food containers, and toys.

[0107] Test Method

[0108] Polymerization activity

[0109] Unless otherwise stated, all polymerization activities (also referred to as productivity) disclosed herein are determined as the ratio of polymer produced to the amount of catalyst charged to the reactor and are reported as grams polymer per gram catalyst per hour (gPE / gcat / hr).

[0110] Comonomer content

[0111] Unless otherwise stated, all comonomer contents disclosed herein (i.e., the amount of comonomer incorporated into a polymer) are determined by rapid FT-IR spectroscopy of dissolved polymers in gel permeation chromatography (GPC) measurements and are reported as weight percent (wt%). In GPC measurements, the comonomer content of a polymer can be determined relative to the polymer molecular weight by using an infrared detector such as an IR5 detector, as described by Lee et al. in Toward absolute chemical composition distribution measurement of polyolefins by high-temperature liquid chromatography hyphenated with infrared absorbance and light scattering detectors, Vol. 86, A NAL .C HEM .Page 8649, 2014.

[0112] High load melt index (I 21 )

[0113] Unless otherwise stated, all high load melt indexes (I 21 ) are measured according to ASTM D1238-10 Method B at 190°C and 21.6 kg load and are reported in decigrams per minute (dg / min).

[0114] Melting temperature (T m )

[0115] Unless otherwise stated, all melting temperatures (T m ) are measured according to ASTM D3418-08 and are reported in degrees Celsius (°C). Unless otherwise stated, a scan rate of 10 degrees Celsius / minute (°C / min) is used for 10 milligrams (mg) of sample, and the second heating cycle is used to determine the melting temperature (T m ).

[0116] Intake ratio

[0117] Unless otherwise stated, all uptake ratios disclosed herein are based on the ratio of the monomers derived from the comonomers (e.g., (C3-C 12 )α-olefin comonomer) to the amount of monomer units derived from ethylene.

[0118] Molecular weight

[0119] Unless otherwise indicated, all molecular weights disclosed herein, including weight average molecular weight (M)w ), number average molecular weight (M n ) and z-average molecular weight (M z ), are measured using conventional GPC and are reported in grams per mole (g / mol).

[0120] The chromatographic system consisted of a high temperature gel permeation chromatography (Polymer Laboratories) equipped with a differential refractive index detector (DRI). Three Polymer Laboratories PLgel 10μm Mixed-B columns were used. The nominal flow rate was 1.0mL / min, and the nominal injection volume was 300μL. Various transfer lines, columns, and differential refractometers (DRI detectors) were placed in an oven maintained at 160°C. The solvent for the experiment was prepared by dissolving 6 grams of butylated hydroxytoluene in 4 liters of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.1μm Teflon filter. The TCB was then degassed with an online degasser before entering the GPC instrument.

[0121] The polymer solution was prepared by placing the dried polymer in a glass bottle, adding the required amount of TCB, and then heating the mixture at 160°C and continuously shaking for about 2 hours. All quantities were measured gravimetrically. The injection concentration was 0.5 mg / ml to 2.0 mg / ml, with lower concentrations used for higher molecular weight samples. Before running each sample, the DRI detector was purged. The flow rate in the device was then increased to 1.0 mL / molecule, and the DRI was stabilized for 8 hours before injecting the first sample. The molecular weight was determined by combining a universal calibration relationship with a column calibration, which was performed with a series of monodisperse polystyrene (PS) standards. The MW of each elution volume was calculated using the following equation:

[0122]

[0123] The variables with the subscript "X" support the test sample, while the variables with the subscript "PS" support the PS. PS =0.67 and K PS =0.000175, and a X and K X is obtained from publicly published literature. Specifically, for (PE), a / K=0.695 / 0.000579, and for PP, it is 0.705 / 0.0002288.

[0124] The concentration c at each point in the chromatogram was calculated from the baseline-subtracted DRI signal IDRI using the following equation:

[0125]

[0126] Where KDRI is a constant determined by calibrating the DRI, and (dn / dc) is the refractive index increment of the system. Specifically, for polyethylene, dn / dc=0.109.

[0127] The mass recovery was calculated from the ratio of the integrated area of ​​the concentration chromatogram to the elution volume and the injected mass, which was equal to the predetermined concentration multiplied by the injected loop volume.

[0128] Light-off batch reactor test method .

[0129] Overview. The ethylene uptake or ethylene consumption of the catalyst system was observed in separate polymerization runs, each run being conducted in a 2 liter (L) semi-batch autoclave polymerization reactor equipped with a mechanical stirrer. In the batch reactor, ethylene was copolymerized with 1-hexene in the presence of hydrogen (H2) in the gas phase. The concentrations of ethylene ("C2"), 1-hexene ("C6"), and H2 in the gas phase were analyzed by mass spectrometry and gas chromatography. The C6 and H2 components were added continuously throughout the 3 hour polymerization run to maintain their concentrations at steady state, but no more C2 was added. The ethylene uptake was measured versus time to obtain a relative representation of the catalyst kinetic curve.

[0130] The batch reactor is dried and loaded. Before each operation, the batch reactor was dried for 1 hour. Then 200g NaCl was loaded into the dry batch reactor. By heating the batch reactor and its contents under 100 ℃ N2 atmosphere for 30 minutes to further dry the batch reactor. Then add 3g spray-dried methylaluminoxane (SDMAO) of loaded silica to remove residue, seal the batch reactor, and stir the contents. Then 3.04 liters (L) of H2 and 1-hexene were loaded into the dry batch reactor of gained, so that 1-hexene and ethylene (C6 / C2) mol ratio is 0.004. With ethylene, the batch reactor is pressurized to 1.52 MPa (MPa). The system of gained is allowed to reach steady state.

[0131] Then add catalyst system to batch reactor to initiate polymerization.Record the time of adding catalyst as time zero (Time0).Make reactor temperature consistent with target temperature (usually 80 ℃ to 100 ℃), and keep 1 hour to 5 hours at this temperature.Reactor is cooled, vented, opened, and the polyolefin product obtained by water, methanol washing, and dried to obtain dry polyolefin product.

[0132] For each batch reactor run, catalyst activity / polymerization productivity is calculated as grams of dry polyolefin product prepared / grams of catalyst added to the reactor per hour (gPE / gcat-hr). The higher the number of gPE / gcat-hr, the higher the catalyst activity / polymerization productivity. Ethylene uptake is measured throughout the run, and the total ethylene uptake at any time during the reaction can be determined by formula (VI):

[0133]

[0134] And the total ethylene uptake during the run is represented by formula (V):

[0135]

[0136] Comparing two catalyst systems, all things being equal, the uptake ratio Ut of the catalyst that ignites faster will have a Ut of 0.0001 in a given time than the catalyst system that ignites slower. t Large value.

[0137] Example

[0138] Synthesis of Metal-Ligand Complex 1 (MLC-1)

[0139]

[0140] A glass bottle (1 liter (L)) was charged with acetonitrile (400 mL), 4-fluoro-6-methylphenol (50 g, 396.4 mmol) and p-toluenesulfonic acid (monohydrate; 75.6 g, 396 mmol). The resulting solution was cooled to 0° for 25 minutes, treated slowly with N-bromosuccinimide (70.55 g, 396.4 mmol) over approximately 5 minutes, and allowed to reach room temperature while stirring overnight. The volatiles were removed under vacuum, and the resulting precipitate was treated with dichloromethane (600 mL), cooled to 0°, and filtered through a large block of silica gel, followed by washing several times with cold dichloromethane (CH2Cl2). The volatiles were removed under vacuum to give 2-bromo-4-fluoro-6-methyl-phenol (46 g, yield: 56%).

[0141] 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.05 (ddd, J = 7.7, 3.0, 0.7 Hz, 1H), 6.83 (ddt, J = 8.7, 3.0, 0.8 Hz, 1H), 5.35 (s, 1H), 2.29 (d, J = 0.7 Hz, 3H).

[0142] 19 F NMR (376 MHz, chloroform-d) δ -122.84.

[0143]

[0144] In a glove box, NaH (95%; 1.76 g) was slowly added to a solution of 2-bromo-4-fluoro-6-methyl-phenol (15 g, 73.2 mmol) in N,N-dimethylformamide (DMF; 35 mL) in a flask (250 mL) equipped with a magnetic stirring bar until the evolution of hydrogen ceased. The resulting mixture was stirred at room temperature for 30 minutes. Thereafter, diisopropylgermane dichloride (6.29 g, 24.4 mmol) was added. The mixture was heated to 55°C and maintained at this temperature for 18 hours, then removed from the glove box and quenched with saturated aqueous ammonium chloride solution (NH4Cl20 mL) and water (H2O; 8 mL). Diethyl ether (Et2O; 30 mL) was added to the mixture, which was transferred to a separatory funnel to separate the resulting phases. The aqueous phase was further extracted with Et2O (20 mL), and the combined organic extracts were washed with brine (10 mL). The organic layer is then dried (MgSO ), filtered and concentrated to dryness. The thick residue is dried and loaded on silica gel, then rapid column chromatography (100mL / min, pure hexane, add ethyl acetate and rise to 10% in 20 minutes) is used to purify, and the product in the form of light yellow oil is obtained. All clean fractions (some fractions contain <10% starting phenol) are merged, and the final product is dried overnight under vacuum, and obtains two ((the fluoro-6-methylphenoxy group of 2-bromo-4-) methyl) diisopropylgermane (9g, productive rate: 62%).

[0145] 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.10 (dd, J = 7.7, 3.0 Hz, 2H), 6.84 (ddd, J = 8.8, 3.1, 0.8 Hz, 2H), 4.14 (s, 4H), 2.33 (s, 6H), 1.74 (hept, J = 7.4 Hz, 2H), 1.35 (d, J = 7.4 Hz, 12H).

[0146] 19 F NMR (376 MHz, chloroform-d) δ -118.03.

[0147]

[0148] A glass bottle (500 mL) equipped with a stir bar was charged with 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (as described in International Patent No. WO 2014 / 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-methyl-phenol) 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 aqueous NaOH solution (17.3 mL, 51.9 mmol, 3 M) was purged with nitrogen for 20 minutes and then added to the THF solution. The reactants were stirred overnight at 55 ° C. The aqueous phase was separated and discarded, and the remaining organic phase was diluted with ether and washed twice with brine. The solution was passed through a short silica gel plug. The filtrate was dried on a rotary evaporator, dissolved in THF / methanol (40 mL / 40 mL), treated with HCl (2 mL), and stirred overnight at 70 ° C. The solution was dried under vacuum and purified by C18 reverse phase column chromatography to obtain the ligand (6.5 g, yield: 54%) as an off-white solid.

[0149] 1 H NMR (400MHz, chloroform-d) δ8.01(d,J=8.2Hz,4H),7.42(dd,J=25.5,2.4Hz,4H),7.32(dd,J=8.2,1.6Hz,4H),7.17(s,4H),6.87(ddd,J=16.4 ,8.8,3.0Hz,4H),6.18(s,2H),3.79(s,4H),2.12(s,6H),1.71(s,6H),1.56(s,4H),1.38(s,12H),1.31(s,36H),0.83–0.73(m,30H).

[0150] 19 F NMR (376 MHz, chloroform-d) δ -119.02.

[0151]

[0152] In a glove box, an ether solution of MeMgBr (3M, 2.4 mL, 7.1 mmol) was added to a -30°C suspension of an anhydrous toluene (83 mL) solution of ZrCl4 (402 mg, 1.72 mmol). After stirring the resulting mixture for 3 minutes, ligand (2.3 g, 1.64 mmol) was added in batches. The reactant was stirred at room temperature overnight and then filtered through a sintered plastic funnel. The filtrate was dried under vacuum, redissolved in toluene (40 mL), filtered through a plug of CELITE again, and dried again under vacuum. The resulting solid was washed with pentane (approximately 5 mL) and dried under vacuum to obtain a metal-ligand complex (2.1 g, yield: 84%) in the form of an off-white powder.

[0153] 1 H NMR (400MHz, benzene-d6) δ8.20(dd,J=8.2,0.5Hz,2H),8.11(dd,J=8.2,0.6Hz,2H),7.88–7.82(m,4H),7.77(d, J=2.6Hz,2H),7.50(dd,J=8.3,1.7Hz,2H),7.42–7.37(m,4H),6.99(dd,J=8.7,3.1Hz,2H),6.20–6.10(m,2 H),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).

[0154] 19 F NMR (376 MHz, benzene-d6) δ -116.24.

[0155] Synthesis of Metal-Ligand Complex 2 (MLC-2)

[0156]

[0157] The metal-ligand complex was synthesized in the manner described in International Publication No. WO 2018 / 183056 A1.

[0158] 1H NMR (400MHz, C6D6) δ8.04 (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),3.6 9(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).

[0159] Preparation of Catalyst System 1

[0160] In a nitrogen-purged glove box, 0.80 g of hydrophobic fumed silica (available from Cabot Corporation as TS-610 is commercially available) was added to 20.0 grams of toluene and mixed until fully dispersed to produce a slurry. Next, 6.60 grams of methylaluminoxane (10 wt % in toluene solution) was added to the slurry, stirred for 15 minutes, and 0.043 grams of MLC-1 was added to the resulting mixture, which was then stirred for an additional 30 to 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).

[0161] Preparation of Catalyst System 2

[0162] In a nitrogen-purged glove box, 0.68 g of hydrophobic fumed silica (available from Cabot Corporation as TS-610 is commercially available) was added to 20.0 grams of toluene and mixed until fully dispersed to produce a slurry. Next, 9.05 grams of methylaluminoxane (10 wt % in toluene solution) was added to the slurry, stirred for 15 minutes, and 0.046 grams of MLC-1 was added to the resulting mixture, which was then stirred for an additional 30 to 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 2 (Catalyst System 2).

[0163] Preparation of Catalyst System 3

[0164] In a nitrogen-purged glove box, 0.80 g of hydrophobic fumed silica (available from Cabot Corporation as TS-610 is commercially available) was added to 20.0 grams of toluene and mixed until fully dispersed to produce a slurry. Next, 6.98 grams of methylaluminoxane (10 wt % in toluene solution) was added to the slurry, stirred for 15 minutes, and 0.091 grams of MLC-1 was added to the resulting mixture, which was then stirred for an additional 30 to 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 3).

[0165] Preparation of Catalyst System 4

[0166] In a nitrogen-purged glove box, 0.66 g of hydrophobic fumed silica (available from Cabot Corporation as TS-610 is commercially available) was added to 37.5 grams of toluene and mixed until well dispersed to produce a slurry. Next, 5.90 grams of methylaluminoxane (10 wt % in toluene solution) was added to the slurry, stirred for 15 minutes, and 0.074 grams of MLC-2 was added to the resulting mixture, which was then stirred for an additional 30 to 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.

[0167] Preparation of comparative catalyst system C1

[0168] In a nitrogen-purged glove box, 1.33 g of hydrophobic fumed silica (available from Cabot Corporation as TS-610 is commercially available) was added to 37.5 grams of toluene and mixed until well dispersed to produce a slurry. Next, 11.00 grams of methylaluminoxane (10 wt % in toluene solution) was added to the slurry, which was stirred for 15 minutes, and then 0.189 grams of a metal-ligand complex having the following structure was added:

[0169]

[0170] The mixture was then stirred for an additional 30 to 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 comparative catalyst system C1 (Comparative Catalyst C1).

[0171] Preparation of comparative catalyst system C2

[0172] In a nitrogen-purged glove box, 2.65 g of hydrophobic fumed silica (available from Cabot Corporation as TS-610 commercially available) was added to 75.0 grams of toluene and mixed until well dispersed to produce a slurry. Next, 22.00 grams of methylaluminoxane (10 wt % in toluene solution) was added to the slurry, which was stirred for 15 minutes, and then 0.155 grams of a metal-ligand complex having the following structure was added:

[0173]

[0174] The mixture was then stirred for an additional 30 to 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 Comparative Catalyst System 2 (Comparative Catalyst C2).

[0175] Gas Phase Batch Reactor Testing :

[0176] The spray-dried catalyst prepared above was used for ethylene / 1-hexene copolymerization in a 2L semi-batch autoclave polymerization reactor in the gas phase. The individual run conditions and the characteristics of the polymers produced in these runs are listed in Tables 1 to 5.

[0177] Gas phase batch reactor catalyst testing 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, 200 g of NaCl was added, and dried by heating at 100° C. for 30 minutes under nitrogen. After the reactor was baked, 3 g of SDMAO (spray-dried supported methylaluminoxane) was introduced as a scavenger under nitrogen pressure. After the addition of SDMAO, the reactor was sealed and the components were stirred. Hydrogen and 1-hexene pressurized with ethylene were then added to the reactor. Once the system reached a steady state, the catalyst was loaded into the reactor at 80° C. to start polymerization. The reactor temperature was brought to the desired reaction temperature and maintained at that temperature, and the feed ratio of ethylene, 1-hexene and hydrogen was maintained throughout the 1 hour run. At the end of the run, the reactor was cooled, vented and opened. The resulting product mixture was washed with water and methanol and then dried. The polymerization activity (grams of polymer / grams of catalyst-hour) was determined as the ratio of the amount of polymer produced to the amount of catalyst added to the reactor.

[0178] Table 1. Batch Reactor Run Data for Catalyst Systems 1 to 3 and Comparative Examples .

[0179]

[0180] Condition 1a: Injection T = 80°C, Run T = 90°C, 0.003C6 / C2, 0.004H2 / C2, 100psi C2, 1 hour run time. Condition 2a: Injection T = 80°C, Run T = 100°C, 0.004C6 / C2, 0.0068H2 / C2, 230psi C2, 1 hour run time. Condition 3: Injection T = 80°C, Run T = 93°C, 0.0043C6 / C2, 0.004H2 / C2, 220psi C2, 1 hour run time. Condition 1b: Injection T = 80°C, Run T = 90°C, 0.004C6 / C2, 0.0011H2 / C2, 115psi C2, 1 hour run time. Condition 2b: injection T = 80°C, run T = 90°C, 0.004C6 / C2, 0.0011H2 / C2, 230psi C2, 1 hour run time.

[0181] *Run time increased to 3 hours.

[0182] Rapid ignition leads to operability problems due to overheating of the particles due to rapid consumption of ethylene and / or comonomer, and may be better controlled based on the internal reactor temperature (Tint ), which is a measure of the heat of polymerization and an indirect measure of the catalyst particle temperature. int It is a convenient way to quantify and compare the severity of light-off of different catalysts in a semi-batch gas phase polymerization process.

[0183] exist Figure 2 , the internal temperature profiles of Examples 1 to 3 (catalyst systems 1 to 3) under Condition 1a and Comparative Example 10 (Comparative Catalyst System C1) under Condition 1b. In each example, the catalyst was injected at 80°C and then the temperature was rapidly increased to a target temperature of 90°C. Figure 2 In the three runs of catalyst systems 1 to 3 in , the maximum temperature did not exceed the target temperature (Table 1). In the comparative example with comparative catalyst system C1, T int The target temperature of 90°C was exceeded by about 10°C to 99.9°C. Similarly, under condition 2b, comparative catalyst system C1 also exceeded the target temperature of 90°C by about 43°C to 132.5°C. Under condition 3*, comparative catalyst system C2 also exceeded the target temperature of 93°C by about 26°C to 118.5°C. The productivity of germanium-bridged catalyst systems 1 to 3 was also significantly higher (Table 1).

[0184] exist Figure 1 The ethylene uptake curves for catalyst system 1 are shown in Table 1. These are Examples 4 and 7 in Table 1. The productivity values ​​for Example 4 are 283,771 gPE / gcat / h, and Example 7 is 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 agglomeration, which, as described above, is caused by overheating and fusing of particles together and is exacerbated by rapid catalyst ignition. The productivity of this catalyst is much higher than any previous CARL batch reactor run, and despite this, the ethylene uptake curves show that the catalyst has a relatively mild ignition and slow decay, which is more typical of metallocene catalysts than spray-dried bis-phenylphenoxy (i.e., MCL-1, MCL-2, and MCL-C1) catalysts.

[0185] Table 2. Batch Reactor Operation Data for Catalyst System 4 (Catalyst System 4)

[0186]

[0187] Conditions: injection T = 80°C, 0C6 / C2, 1 hour running time.

[0188] The internal temperature curves of Examples 4 to 6 (catalyst systems 1 to 3) under Condition 2a and Comparative Example 11 (Comparative Catalyst C1) under Condition 2b are as follows: Figure 3As shown. Despite the high productivity (as recorded in Table 1), Catalyst System 1 does not exceed the target temperature of 100°C. The catalyst system exceeds the target temperature by about 8°C. However, the temperature does require about 6 minutes to reach the maximum temperature of the run of 108.1°C. Because Comparative Catalyst C1 often suffers from severe agglomeration problems caused by overheating at economically favorable operating ethylene partial pressures (approximately 200psi C2PP), the target temperature of the conditions of Comparative Example 11 for Comparative Catalyst C1 is 90°C. In Example 11 of Table 1, Comparative Catalyst C1 exceeds the target temperature by 42.5°C (maximum T = 132.5°C).

[0189] In each example in Table 1, the catalyst system was injected at 80°C and the temperature was rapidly increased to a target temperature of 90°C. Figure 3 In the three runs of catalyst system 1 in , the maximum temperature did not exceed the target temperature (Table 1). In the comparative example with comparative catalyst C1, T int The target temperature of 90°C was exceeded by about 10°C to 99.9°C. The productivity of the germanium bridged catalyst systems 1 to 3 is also significantly higher in Table 2. The productivity (and efficiency of the germanium bridged catalyst systems 1 to 3 examples) is much higher than the comparative catalyst system with three carbon bridges.

[0190] Catalyst Systems 1 to 3 were also tested under Condition 3 and compared to Comparative Catalyst 2, which was used in several different commercial catalyst systems. Figure 4 The internal temperature profiles for runs 7 to 9 with catalyst system 1A and comparative run 12 with comparative catalyst C2 are shown in . Despite the high C2PP conditions of 230 psi ethylene, none of the examples of MLC-1 showed reactor overtreatment, with the maximum temperature recorded being only 3°C above the target temperature of 93°C (as recorded in Table 1). In contrast, comparative catalyst C2 did show rapid light-off, with a maximum temperature of 118.5°C. Catalyst systems 1 to 3 were two orders of magnitude more productive in the runs than comparative catalyst C2, despite the more controlled light-off. Additionally, the ethylene uptake curves ( Figure 5 ) show that catalyst systems 1 to 3 will have much higher productivity at three hour residence time, which is standard for gas phase polymerization processes.

[0191] Examples 13 to 20 in Table 2 using this catalyst all show very high productivity, about 45,000 gPE / gcat / h to 60,000 gPE / gcat / h at high C2PP (230 psiC2). Even at lower C2PP, the productivity is relatively high. Although not as high as the examples using catalyst systems 1 to 3, these are unprecedentedly high productivity for any type of well-doped catalyst (metallocene, post-metallocene). Figures 6 to 8 The ethylene uptake curve in shows a gradual light-off and long catalyst life, which is more generally associated with metallocene catalysts that perform well at low C2PP. Figure 7 The internal temperature curves in are representative of all runs in Table 2. The decay of the ethylene uptake curve is very slow, but Figure 8 In Example 19, the decay rate of the catalyst increased significantly at 115° C. Catalysts with high productivity accompanied by gradual light-off and accelerated temperature decay are very promising candidates for good operation in gas phase polyethylene processes.

[0192] Table 3. Batch Reactivity Run Data for Catalyst System 4 .

[0193]

[0194] Conditions: injection T = 80°C, 0C6 / C2, 1 hour running time.

[0195] The light-off or initial exotherm and total ethylene uptake within the first 5% or first 3 minutes of a 1 hour run can also be quantified to assess the operability of the catalyst. For Catalyst Systems 1 to 4, as well as Comparative Catalyst C1 and Comparative Catalyst C2, the exotherms measured at various time points within the first 3 minutes of several batch experiments as well as the percentage of total ethylene uptake are presented in Table 5. The exotherm was calculated using Equation 1 below, where T int is the internal temperature measured on the thermocouple in the reactor, and Set T rx is the set reactor temperature for the experiment. The percentage of total ethylene uptake was calculated using Equation 2 below; where C2 uptake time is the total ethylene consumed at a particular time in the experiment, and C2 uptake is always the total ethylene consumed for the entire run (1 hour or 3 hours).

[0196] Heat release = maximum T int – Set T rx Equation 1

[0197] % C2 uptake time = (C2 uptake time / total C2 uptake total) * 100% Equation 2

[0198] The light-off or ethylene uptake curve of the catalyst system can be expressed as the percent exotherm (%) Exo ), the percent heat release can be conveniently measured by batch reactor test method and is quantified as the maximum reactor temperature (T max ) and the target reactor temperature (T rx ) and T rx The difference, expressed as a percentage, is represented by formula (XII):

[0199]

[0200] The percent exotherms are best compared over similar ethylene partial pressure ranges. At ethylene partial pressures less than 150 psi, a catalyst system with mild light-off without evidence of operability problems can be characterized as having a percent exotherm (% exo ). For example, Examples 1 to 3 and 18 all have a % of <2.0% exo , while the comparative example has 11.0%% exo For reactors operating at ethylene partial pressures above 150 psi, a mild light-off catalyst system with no evidence of operability problems can be characterized as the percent exotherm (% exo ) is less than 10%. For example, % of Examples 4 to 9, 13 to 17 and 19 to 20 exo Less than 4%, while the % of Comparative Examples 11 and 12 exo 47.2% and 27.4% respectively.

[0201] Consistently lower exotherms were observed for Catalyst Systems 1 to 4 (≤8°C) compared to the Comparative Examples, which had significantly higher exotherms (≥17°C) at initial catalyst injection under conditions with high ethylene partial pressures (Table 4). Catalyst Systems 1 to 4 also showed significantly lower total ethylene uptake at various time points within the first 3 minutes under various conditions of both low and high C2PP compared to Comparative Catalyst C1 and Comparative Catalyst C2 (Table 4, Nos. 1 to 17 vs. Nos. 18 to 24). The significantly lower exotherms and initial ethylene uptake or light-off of Catalyst Systems 1 to 4 compared to the Comparative Examples, Comparative Catalyst C1 and Comparative Catalyst C2 indicate that these catalysts have improved light-off, and therefore improved operability.

[0202] Table 4. Total ethylene uptake percentage for catalyst systems 1 to 4 and comparative examples at time points within the initial 3 minutes. Percentage .

[0203]

[0204]

[0205] Condition 1a: injection T = 80 ° C, run T = 90 ° C, 0.003C6 / C2, 0.004H2 / C2, 100psi C2, 1 hour run time. Condition 1b: injection T = 80 ° C, run T = 90 ° C, 0.004C6 / C2, 0.0011H2 / C2, 115psi C2, 1 hour. Condition 1c: injection T = 80 ° C, run T = 90 ° C, 0.004C6 / C2, 0.0011H2 / C2, 230psi C2, 1 hour. Condition 2a: injection T = 80 ° C, run T = 100 ° C, 0.004C6 / C2, 0.0068H2 / C2, 230psi C2, 1 hour. Condition 2b: Injection T = 80 ° C, operation T = 100 ° C, 0.004C6 / C2, 0.0016H2 / C2, 230psi C2, 1 hour. Condition 3: Injection T = 80 ° C, operation T = 93 ° C, 0.0043C6 / C2, 0.004H2 / C2, 220psi C2, 1 hour. *3 hours. Condition 4: Injection T = 80 ° C, operation T = 90 ° C, 0C6 / C2, 0.018H2 / C2, 230psi C2, 1 hour. Condition 5: Injection T = 80 ° C, operation T = 90 ° C, 0C6 / C2, 0.01H2 / C2, 230psi C2, 1 hour. Condition 6: Injection T = 80 ° C, operation T = 90 ° C, 0C6 / C2, 0.007H2 / C2, 230psi C2, 1 hour. Condition 7: injection T = 80 ° C, operation T = 90 ° C, 0C6 / C2, 0.004H2 / C2, 230psi C2, 1 hour. Condition 8: injection T = 80 ° C, operation T = 90 ° C, 0C6 / C2, 0.01H2 / C2, 165psi C2, 1 hour. Condition 9: injection T = 80 ° C, operation T = 90 ° C, 0C6 / C2, 0.01H2 / C2, 100psi C2, 1 hour. Condition 10: injection T = 80 ° C, operation T = 105 ° C, 0C6 / C2, 0.01H2 / C2, 230psi C2, 1 hour. Condition 11: injection T = 80 ° C, operation T = 80 ° C, 0C6 / C2, 0.01H2 / C2, 230psi C2, 1 hour.

[0206] Another method of evaluating the light-off and controlled ethylene consumption of a catalyst is to measure the time at which the catalyst has consumed a specific amount of the total ethylene consumed during the experiment. Catalysts with rapid, uncontrollable light-off and ethylene consumption that result in inoperable behavior tend to rapidly consume ethylene in a manner in which most of their total ethylene uptake occurs within the initial stage of operation (i.e., 10% of the first 6 minutes or 60 minutes of operation). This behavior also tends to result in agglomeration and / or aggregation in the reactor. Table 5 shows the specific time points at which the catalyst consumes 25%, 50%, 75% and 90% of the total ethylene consumed during operation of each of the various conditions. Under reactor conditions at higher ethylene partial pressures (C2PP≥165psi), the time at which catalyst systems 1 to 4 consume 25%, 50%, 75% and 90% of the total ethylene consumed during 1 hour of operation is significantly slower than the comparative examples, comparative catalyst systems C1 and C2 (Table 5, Nos. 4-13 and 15-16 vs. 18, 19 and 21). Combined with the data in Table 4, the data in Table 5 indicate that under conditions with high ethylene partial pressures, the slower initial ethylene consumption and controlled ethylene consumption during operation of each of the inventive catalyst systems 1 to 4 is in sharp contrast to the rapid, uncontrollable ethylene consumption during operation of the comparative example, comparative catalyst system 1.

[0207] Table 5. For Catalyst System 1C and Catalyst System 2 and the Comparative Examples, 25%, 50%, 75% and Time to 90% total ethylene uptake .

[0208]

[0209] Condition 1a: injection T = 80 ° C, run T = 90 ° C, 0.003C6 / C2, 0.004H2 / C2, 100psi C2, 1 hour run time. Condition 1b: injection T = 80 ° C, run T = 90 ° C, 0.004C6 / C2, 0.0011H2 / C2, 115psi C2, 1 hour. Condition 2a: injection T = 80 ° C, run T = 100 ° C, 0.004C6 / C2, 0.0068H2 / C2, 230psi C2, 1 hour. Condition 2b: injection T = 80 ° C, run T = 90 ° C, 0.004C6 / C2, 0.0011H2 / C2, 230psi C2, 1 hour. Condition 2c: Injection T = 80 ° C, operation T = 100 ° C, 0.004C6 / C2, 0.0016H2 / C2, 230psi C2, 1 hour. Condition 3: Injection T = 80 ° C, operation T = 93 ° C, 0.0043C6 / C2, 0.004H2 / C2, 220psi C2, 1 hour. *3 hours. Condition 4: Injection T = 80 ° C, operation T = 90 ° C, 0C6 / C2, 0.018H2 / C2, 230psi C2, 1 hour. Condition 5: Injection T = 80 ° C, operation T = 90 ° C, 0C6 / C2, 0.01H2 / C2, 230psi C2, 1 hour. Condition 6: Injection T = 80 ° C, operation T = 90 ° C, 0C6 / C2, 0.007H2 / C2, 230psi C2, 1 hour. Condition 7: injection T = 80 ° C, operation T = 90 ° C, 0C6 / C2, 0.004H2 / C2, 230psi C2, 1 hour. Condition 8: injection T = 80 ° C, operation T = 90 ° C, 0C6 / C2, 0.01H2 / C2, 165psi C2, 1 hour. Condition 9: injection T = 80 ° C, operation T = 90 ° C, 0C6 / C2, 0.01H2 / C2, 100psi C2, 1 hour. Condition 10: injection T = 80 ° C, operation T = 105 ° C, 0C6 / C2, 0.01H2 / C2, 230psi C2, 1 hour. Condition 11: injection T = 80 ° C, operation T = 80 ° C, 0C6 / C2, 0.01H2 / C2, 230psi C2, 1 hour.

[0210] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Indeed, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a value disclosed as "40 g / cm 3 " is intended to mean "approximately 40g / cm 3 ”.

[0211] Notations used in equations included herein have their standard meanings, as understood in the mathematical arts. For example, "="

[0212] means equal to, "×" means multiplication, "+" means addition, and "-" means subtraction.

[0213] ">" is the "greater than" symbol, "<" is the "less than" symbol, and " / " represents a division operation.

[0214] Unless expressly excluded or otherwise limited, each document cited herein, if any, including any cross-referenced or related patent or patent application to which this application claims priority or rights, and any patent or patent application in its entirety, is incorporated by reference. The citation of any document does not admit that it is prior art with respect to any embodiment disclosed or claimed, or that it alone or in combination with any other reference document or multiple reference documents teaches, suggests or discloses any such embodiment. In addition, in the event of any meaning or definition of a term in this document that conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to the term in this document shall prevail.

Claims

1. A process for producing polyethylene, comprising reacting ethylene and optionally one or more C3-C 12 The α-olefin comonomer is contacted with the catalyst system at a reactor temperature of 70°C to less than or equal to 150°C, wherein the ethylene partial pressure is greater than or equal to 150 psi, and one or more C3-C 12 A molar feed ratio of alpha-olefin comonomer to ethylene is less than or equal to 0.030, using the catalyst system comprising a metal-ligand complex disposed on one or more support materials, wherein the metal-ligand complex has a structure according to formula (Ia): in: A - It is an anion; M is titanium, zirconium or hafnium; n is 1, 2, or 3; Each X is independently selected from C1-C 50 Hydrocarbon, C1-C 50 Heteroalkyl, C6-C 50 Aryl, C2-C 50 Monodentate ligands from the group consisting of heteroaryl and halogen; R 1 and R 8 are independently selected from the group consisting of a group having formula (II) and a group having formula (III): Where R 9–13 and R 14–21 are independently selected from -H, C1-C 50 Hydrocarbon, C1-C 50 Heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2. -OR C 、-SR C or halogen; R 2 , R 3 , R 4 , R 5 , R 6 and R 7 Independently selected from -H, C1-C 50 Hydrocarbon, C1-C 50 Heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C , -SR C and halogens; and Where R C , R P and R N Each independently selected from -H, C1-C 50 Hydrocarbon, and C1-C 50 heteroalkyl; The amount of ethylene consumed during the first 5 minutes after the catalyst system is injected into the gas phase polymerization reactor after the initial addition of the catalyst system is less than the total average residence time t R 25% of the total ethylene uptake during the time period (t 25％ ) is calculated by the equation according to formula (IV): And t 25％ >5min(IV).

2. The method according to claim 1, wherein the method further comprises calculating the average residence time t in the whole according to formula (V) R The uptake ratio (U t ): And at the time point of 0.5 minutes (30 seconds) after the catalyst system is fed into the reactor, the U of the catalyst system is t Less than or equal to 0.02 (2%), as represented by formula (X) and (XI): Taken at 30 seconds (0.5min), Taken at 30 seconds (0.5min), 3. The process according to claim 2, wherein at a time point of 1.5 minutes (90 seconds) after the catalyst system is fed into the reactor, the U of the catalyst system is t Less than or equal to 0.05 (5%), as expressed by the following formula:

4. The process according to claim 2, wherein at a time point of 3.0 minutes (180 seconds) after the catalyst system is fed into the reactor, the U of the catalyst system is t Less than or equal to 0.15 (15%), as expressed by the following formula:

5. The process according to claim 3, wherein at a time point of 3.0 minutes (180 seconds) after the catalyst system is fed into the reactor, the U of the catalyst system is t Less than or equal to 0.15 (15%), as expressed by the following formula:

6. The process according to any one of claims 2 to 5, wherein at a time point of 3.0 minutes (180 seconds) after the catalyst system is fed into the reactor, the U of the catalyst system is t Less than or equal to 0.10 (10%), as expressed by the following formula:

7. The process according to any one of claims 1 to 5, wherein the amount of ethylene consumed during the first 18 minutes after the initial addition of the catalyst system after the catalyst system is injected into the gas phase polymerization reactor is less than the entire average residence time t R 50% of the total ethylene consumed within a certain period of time, wherein the time of 50% of the total ethylene uptake (t 50％ ) is calculated by the equation according to the following formula: And t 50％ >20min.

8. The method according to any one of claims 1 to 5, wherein the heat release percentage (% Exo ) is less than 10%, wherein the light-off or ethylene uptake curve of the catalyst system is expressed as a percentage of heat release (% Exo ) is characterized by the heat release percentage measured by the batch reactor test method and quantified as the maximum reactor temperature (T max ) and the target reactor temperature (T rx ) and T rx The difference, expressed as a percentage, is given by: Heat release percentage 9. The method according to any one of claims 1 to 5, Where R 1 and R 8 are the same; or Where R 1 and R 8 At least one of is a group having formula (II), and R 10 and R 12 At least one of is tert-butyl; or Where R 1 and R 8 At least one of is a group having formula (III); or Where R 15 , R 16 , R 19 and R 20 At least one of is tert-butyl; or Where R 14-21 Yes – H.

10. The process of any one of claims 1 to 5, wherein the one or more support materials comprises fumed silica.

11. The method of any one of claims 1 to 5, wherein the anion is aluminate.

12. The process of any one of claims 1 to 5, wherein the ethylene partial pressure in the reactor is greater than or equal to 150 psi.

13. The process of any one of claims 1 to 5, wherein the reactor temperature is less than or equal to 120°C.

14. The method according to claim 8, wherein the heat release percentage (% Exo ) is less than 5%.

15. The process of any one of claims 1 to 5, wherein the ethylene partial pressure is greater than or equal to 170 psi.

16. The process of any one of claims 1 to 5, wherein the ethylene partial pressure is greater than or equal to 200 psi.

17. The process of any one of claims 1 to 5, wherein the reactor temperature is 75°C to 110°C.

18. The process of any one of claims 1 to 5, wherein the reactor temperature is 80°C to 105°C.

19. The process according to any one of claims 1 to 5, wherein the reactor temperature is 85°C to 100°C.

20. A process for producing polyethylene, the process comprising reacting ethylene and optionally one or more C3-C 12 The α-olefin comonomer is contacted with the catalyst system at a reactor temperature of 70°C to less than or equal to 150°C, wherein the ethylene partial pressure is 50 psi to 150 psi, and one or more C3-C 12 A molar feed ratio of alpha-olefin comonomer to ethylene is less than or equal to 0.030, using the catalyst system comprising a metal-ligand complex disposed on one or more support materials, wherein the metal-ligand complex has a structure according to formula (Ia): in: A - It is an anion; M is titanium, zirconium or hafnium; n is 1, 2, or 3; Each X is independently selected from C1-C 50 Hydrocarbon, C1-C 50 Heteroalkyl, C6-C 50 Aryl, C4-C 50 Monodentate ligands from the group consisting of heteroaryl and halogen; R 1 and R 8 are independently selected from the group consisting of a group having formula (II) and a group having formula (III): Where R 9–13 and R 14–21 are independently selected from -H, C1-C 50 Hydrocarbon, C1-C 50 Heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2. -OR C 、-SR C or halogen; R 2 , R 3 , R 4 , R 5 , R 6 and R 7 Independently selected from -H, C1-C 50 Hydrocarbon, C1-C 50 Heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C , -SR C and halogens; and Where R C , R P and R N Each independently selected from -H, C1-C 50 Hydrocarbon, and C1-C 50 heteroalkyl; The amount of ethylene consumed during the first 25 minutes after the catalyst system is injected into the gas phase polymerization reactor after the initial addition of the catalyst system is less than the total average residence time t R 50% of the total ethylene uptake within a certain period of time (t 50％ ) is calculated by the equation according to the following formula: And t 50％ >25min.

21. The method of claim 20, wherein the ethylene partial pressure is from 80 psi to 115 psi.

22. The process of claim 20, wherein the amount of ethylene consumed during the first 30 minutes after initial injection of the catalyst system into the gas phase polymerization reactor is less than 50% of the total ethylene consumed during the entire average residence time.

23. The method according to any one of claims 20 to 22, wherein the percent heat release (% Exo ) is less than 5%, wherein the light-off or ethylene uptake curve of the catalyst system is expressed as a percentage of heat release (% Exo ) is characterized by the heat release percentage measured by the batch reactor test method and quantified as the maximum reactor temperature (T max ) and the target reactor temperature (T rx ) and T rx The difference, expressed as a percentage, is expressed by the following formula: Heat release percentage 24. The method of claim 23, wherein the heat release percentage (% Exo ) is less than 2%.

25. The method of claim 20, wherein the ethylene partial pressure is from 90 psi to 130 psi.

26. The method of claim 20, wherein the ethylene partial pressure is 100 psi to 150 psi.

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