Hydrocarbyl-modified methylaluminoxane cocatalyst for bis-phenylphenoxymetal-ligand complexes

Abstract

A process for polymerizing olefin monomers, the process comprising reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system, the catalyst system comprising less than 50 mole percent AlR, based on the total moles of aluminum. A1 R B1 R C1 a modified hydrocarbyl methylaluminoxane having R A1 , R B1 , and R C1 are independently linear (C1 to C 40 ) Alkyl, branched chain (C1-C 40 ) alkyl, or (C6-C 40 ) aryl, and one or more metal-ligand complexes according to formula (I). [Formula 1] JPEG2023534663000034.jpg60170

Description

[Technical Field] 【0001】 (Cross-reference of related applications) This application claims priority to U.S. Provisional Patent Application No. 63 / 053,354, filed on 17 July 2020, the entire disclosure of which is incorporated herein by reference. 【0002】 (Field of invention) Embodiments of the present disclosure generally relate to modified hydrocarbylmethylaluminoxane activators for catalytic systems comprising bis-phenylphenoxymetal-ligand complexes having a triatomic ether linker. [Background technology] 【0003】 Since the discovery of heterogeneous olefin polymerization by Ziegler and Natta, global polyolefin production reached approximately 150 million tons per year in 2015, and this is on the rise due to increasing market demand. This success is partly based on a series of important discoveries in co-catalysis technology. The discovered co-catalysts include aluminoxanes, boranes, and borates containing triphenylcarbenium or ammonium cations. These co-catalysts activate homogeneous single-site olefin polymerization catalysts, and polyolefins are now produced in industry using these co-catalysts. 【0004】 As part of the catalyst composition in α-olefin polymerization reactions, activators may possess characteristics beneficial to the formation of α-olefin polymers and to the final polymer composition containing α-olefin polymers. Characteristics of activators that increase the formation of α-olefin polymers include, but are not limited to, rapid activation of the procatalyst, high catalytic efficiency, high-temperature performance, consistent polymer composition, and selective deactivation. 【0005】 In particular, borate cocatalysts have significantly contributed to a fundamental understanding of olefin polymerization mechanisms, improving the ability to precisely control the microstructure of polyolefins by intentionally tuning the catalyst structure and process. This has led to increased interest in reaction mechanism studies and the development of novel homogeneous olefin polymerization catalyst systems that precisely control the microstructure and performance of polyolefins. However, when activator or cocatalyst cations activate the procatalyst, activator ions may remain in the polymer composition. As a result, borate anions may affect the polymer composition. Specifically, the size and charge of borate anions, the interaction between borate anions and the surrounding medium, and the dissociation energy between borate anions and available counterions will affect the ability of ions to diffuse through the surrounding medium, such as solvents, gels, or polymer materials. 【0006】 Modified methylaluminoxane (MMAO) can be described as a mixture of an aluminoxane structure and a trihydrocarbyl aluminum species. Trihydrocarbyl aluminum species, such as trimethylaluminum, are used as scavengers to remove impurities in polymerization processes that may contribute to the deactivation of olefin polymerization catalysts. However, trihydrocarbyl aluminum species are thought to be active in some polymerization systems. Catalyst suppression has been noted when trimethylaluminum is present in propylene homopolymerization using a hafnocene catalyst at 60°C (Busico, V. et al. Macromolecules 2009, 42, 1789-1791). However, these observations complicate the differences between MAO activation and borate activation, and even in direct comparisons, they may only capture some difference between the presence and absence of trimethylaluminum. Furthermore, it is unclear whether such observations extend to other catalytic systems, ethylene polymerization, or polymerization carried out at higher temperatures. In any case, the use of MMAO is necessary to favor soluble MAO, and consequently, trihydrocarbyl aluminum species are present. 【0007】 Modified methylaluminoxane (MMAO) is used as an activator in place of borate activators in some PE processes. However, MMAO has been found to have an adverse effect on the performance of some catalysts, such as bis-biphenylphenoxy metal-ligand complexes, and an adverse effect on the production of vinyl resins. The adverse effects in the polymerization process include a decrease in catalyst activity, an increase in the composition distribution of the produced polymer, and an adverse effect on pellet handling. SUMMARY OF THE INVENTION 【0008】 There is a continuing need to create catalyst systems while maintaining the ability to produce polymers with high catalytic efficiency, reactivity, and good physical properties. Further, there is a need to produce a uniform polymer composition. 【0009】 Embodiments of the present disclosure include a process for polymerizing olefin monomers. In one or more embodiments, the process includes reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system. The catalyst system includes a modified hydrocarbyl methylaluminoxane and a procatalyst. The modified hydrocarbyl methylaluminoxane has less than 50 moles of AlR A R B R C based on the total moles of aluminum [where R A , R B and R C are independently linear (C1-C 40 ) alkyl, branched (C1-C 40 ) alkyl, or (C6-C 40 ) aryl], and one or more metal-ligand complexes according to formula (I): 【0010】 【Chemical formula】 In formula (I), M is titanium, zirconium, or hafnium. (X) 【0011】 式(I)において、Mは、チタン、ジルコニウム、又はハフニウムである。(X)n The subscript n is 1, 2, or 3. Each X is independently unsaturated (C2~C 50 ) hydrocarbons, unsaturated (C2~C 50 ) Heterocarbons, (C1~C 50 ) Hydrocarbyl, (C6~C 50 )aryl, (C6~C 50 )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4~C 12 ) Diene, halogen, -N(R N )2, and -N(R N )COR C The selected monodentate ligand is one of several components, and the metal-ligand complex is charge-neutral overall. 【0012】 In equation (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 These are independently -H, (C1~C 40 ) Hydrocarbyl, (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2-OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C ) Selected from 2NC(O)- and halogens. 【0013】 In equation (I), R1 and R 16 These are independently -H, (C1~C 40 ) Hydrocarbyl, (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, R C S(O)²⁻, -N=C(R) C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C ) Selected from the group consisting of 2NC(O)-, halogens, radicals having formula (II), radicals having formula (III), and radicals having formula (IV). 【0014】 [ka] 【0015】 In equations (II), (III), and (IV), R 31~35 , R 41~48 , and R 51~59 Each of these is independent of -H, (C1~C 40 ) Hydrocarbyl, (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C)It is selected from 2NC(O)- or halogen. 【0016】 In formula (I), Y is CH2, CHR 21 , CR 21 R 22 , SiR 21 R 22 , or GeR 21 R 22 and R 21 and R 22 are (C1-C 20 ) alkyl; provided that when Y is CH2, at least one of R 8 and R 9 is not -H. 【0017】 In formula (I), (II), (III), and formula (IV), each R C , R P , and R N is independently (C1-C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or -H. 【Brief Description of the Drawings】 【0018】 [Figure 1] Graph of the catalytic efficiency of metal-ligand complexes I1, I3, and I7 as functions of the MMAO cocatalyst. 【Modes for Carrying Out the Invention】 【0019】 Here, specific embodiments of the catalyst system are described. It should be understood that the catalyst system of the present disclosure can be embodied in different forms and should not be construed as limited to the specific embodiments described in the present disclosure. Rather, the embodiments are provided so that the present disclosure will be thorough and complete and will fully convey the scope of the subject matter to those skilled in the art. 【0020】 List common abbreviations below. Me: Methyl, Et: Ethyl, Ph: Phenyl, Bn: Benzyl, i-Pr: iso-Propyl, t-Bu: tert-Butyl, t-Oct: tert-Octyl (2,4,4-Trimethylpentan-2-yl), Tf: Trifluoromethanesulfonate, THF: Tetrahydrofuran, Et2O: Diethyl ether, CH2Cl2: Dichloromethane, CV: Column volume (used in column chromatography), EtOAc: Ethyl acetate, C6D6: Deuterated benzene or benzene-d6, CDCl3: Deuterated chloroform, Na2SO4: Sodium sulfate, MgSO4: Magnesium sulfate, HCl: Hydrogen chloride, n-BuLi: Butyllithium, t-BuLi: tert-Butyllithium, MAO: Methylaluminoxane, MMAO: Modified methylaluminoxane, GC: Gas chromatography, LC: Liquid chromatography, NMR: Nuclear magnetic resonance, MS: Mass spectrometry, mmol: Millimole, mL: Milliliter, M: Molar concentration, min or mins: Minute, h or hrs: Hour, d: Day. 【0021】 The term "independently selected" means that the R 1 , R 2 , R 3 , R 4 , and R 5 groups such as may be the same or different (e.g., R 1 , R 2 , R 3 , R 4 , and R 5 may all be substituted alkyl, or R 1 and R 2 may be substituted alkyl, and R 3 may be aryl, etc.) is used herein to indicate. The chemical names associated with the R groups are intended to convey the chemical structures recognized in the art as corresponding to the chemical structures of the chemical names. Thus, the chemical names are intended to supplement and exemplify the structural definitions known to those skilled in the art and are not intended to exclude. 【0022】 The term "procatalyst" refers to a transition metal compound that exhibits olefin polymerization catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with a procatalyst to convert it into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable. 【0023】 When used to describe a chemical group containing a specific carbon atom, use "(C x ~C y The parenthetical expression in the form of ")" means that the unsubstituted form of the chemical group has x carbon atoms to y carbon atoms, including x and y. For example, (C1~C 50 ) Alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, a particular chemical group is R S It can be replaced by one or more substituents such as (C x ~C y R defined using ")" S Substituting chemical groups are any group R S It can contain more than y carbon atoms depending on its identity. For example, "R S Strictly speaking, one group R is phenyl (-C6H5). S Replaced with (C1~C 50 )alkyl can contain 7 to 56 carbon atoms. Therefore, generally, the parenthetical "(C x ~C y A substituent R, defined using ")", contains one or more carbon atoms in the chemical group. S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group is such that both x and y contain all carbon atoms of substituent R. S It is determined by adding up the total number of carbon atoms from each origin. 【0024】 The term "substitution" means that at least one hydrogen atom (-H) bonded to the carbon atom of the corresponding unsubstituted compound or functional group is a substituent (e.g., R SThis means that it is substituted by ). The term "-H" means hydrogen or hydrogen radical that is covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified. 【0025】 (C1~C 50 The term "(C1~C)alkyl" refers to a saturated linear or branched hydrocarbon radical containing 1 to 50 carbon atoms. 30 The term "alkyl" refers to a saturated linear or branched hydrocarbon radical consisting of 1 to 30 carbon atoms. Each (C1-C) 50 ) Alkyl and (C1~C 30 ) Alkyl may be unsubstituted or one or more R S It can be substituted with R. In some examples, each hydrogen atom in a hydrocarbon radical is R, such as trifluoromethyl. S It can be replaced by (C1~C 50 Examples of alkyl groups include 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~C 40 Examples of alkyl groups include substitutions (C1~C 20 ) alkyl, substituted (C1~C 10 ) alkyl, trifluoromethyl, and [C 45 It is alkyl. [C 45 The term "alkyl" means that there are up to 45 carbon atoms in the substituent radical, such as (C1-C5) alkyls like methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl, with one R S (C 27 ~C 40 It is alkyl. 【0026】 (C3~C 50The term alkenyl refers to a compound containing 3 to 50 carbon atoms, at least one double bond, and being unsubstituted or having one or more R atoms. S This refers to branched or unbranched cyclic or acyclic monovalent hydrocarbon radicals that are substituted with (C3~C). 50 Examples of alkenyls: n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, and cyclohexadienyl. Substitution (C3~C 50 Examples of alkenyls: (2-trifluoromethyl)penta-1-enyl, (3-methyl)hexa-1-enyl, (3-methyl)hexa-1,4-dienyl, and (Z)-1-(6-methylhepta-3-en-1-yl)cyclohexa-1-enyl. 【0027】 (C3~C 50 The term "cycloalkyl" means unsubstituted or one or more R S This refers to saturated cyclic hydrocarbon radicals of 3 to 50 carbon atoms that are substituted with other cycloalkyl groups (e.g., (C) x ~C y A cycloalkyl group has x to y carbon atoms and is either unsubstituted or has one or more R atoms. S It is defined in a similar format as either being replaced by (C3~C). 40 Examples of cycloalkyl groups include unsubstituted (C3~C) 20 ) Cycloalkyl, unsubstituted (C3~C 10 These are cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substitutions (C3~C 40 Examples of cycloalkyl groups include substitutions (C3~C 20 )Cycloalkyl, substituted (C3~C 10 These are cycloalkyl and 1-fluorocyclohexyl compounds. 【0028】 The terms "halogen atom" or "halogen" refer to the group of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I). The term "halide" refers to the anionic form of a halogen atom, fluoride (F - ), chloride (Cl - ), bromide (Br - ), or yogurt (I - ) means. 【0029】 The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. A saturated chemical group has one or more substituents R S If substituted by, one or more double or triple bonds are optionally substituted with R S It may be present in. The term "unsaturated" refers to a group containing one or more carbon-carbon double bonds or carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds, or carbon-silicon double bonds, with substituent R S This means that it does not contain any double bonds (if present) or any double bonds that may be present in an aromatic ring or heteroaromatic ring (if present). 【0030】 Embodiments of this disclosure include processes for polymerizing olefin monomers. In one or more embodiments, the process includes reacting ethylene with one or more olefin monomers optionally in the presence of a catalyst system. 【0031】 In various embodiments, the catalyst system does not contain a borate activator. 【0032】 In some embodiments, the olefin monomer is (C3~C 20 )α-olefin. In other embodiments, the olefin monomer is (C3~C 20 ) It is not an α-olefin. In various embodiments, the olefin monomer is a cyclic olefin. 【0033】 In one or more embodiments, the catalyst system comprises hydrocarbyl-modified methylaluminoxane and a procatalyst. The hydrocarbyl-modified methylaluminoxane is less than 50 mole percent AlR based on the total number of moles of aluminum. A1 R B1 R C1 It has the formula AlR A1 R B1 R C1 In R A1 , R B1 , and R C1 These are, independently, linear (C1~C 40 ) alkyl, branched chain (C1~C 40 ) Alkyl, (C1~C 40 ) Aryl, or a combination thereof. 【0034】 The term "hydrocarbyl-modified methylaluminoxane" refers to a methylaluminoxane (MMAO) structure containing a certain amount of trihydrocarbyl aluminum. Hydrocarbyl-modified methylaluminoxane includes a combination of a hydrocarbyl-modified methylaluminoxane matrix and trihydrocarbyl aluminum. The total molar amount of aluminum in hydrocarbyl-modified methylaluminoxane consists of the aluminum contribution from the number of moles of aluminum from the hydrocarbyl-modified methylaluminoxane matrix and the number of moles of aluminum from trihydrocarbyl aluminum. Hydrocarbyl-modified methylaluminoxane contains more than 2.5 mole percent of trihydrocarbyl aluminum based on the total number of moles of aluminum in hydrocarbyl-modified methylaluminoxane. These additional hydrocarbyl substituents can affect the subsequent aluminoxane structure, resulting in differences in the distribution and size of aluminoxane clusters (Bryliakov, KP et al. Macromol. Chem. Phys. 2006, 207, 327-335). Additional hydrocarbyl substituents can also increase the solubility of aluminoxane in hydrocarbon solvents, including but not limited to hexane, heptane, methylcyclohexane, and ISOPAR E(trademark), as shown in U.S. Patent No. 5,777,143. Modified methylaluminoxane compositions are generally disclosed and can be prepared as described in U.S. Patents No. 5,066,631 and No. 5,728,855, both of which are incorporated herein by reference. 【0035】 In embodiments of this disclosure, the catalyst system comprises a metal-ligand complex according to formula (I). 【0036】 [ka] 【0037】 In formula (I), M is titanium, zirconium, or hafnium having a formal oxidation state of +2, +3, or +4. (X) nThe subscript n is 1, 2, or 3. Each X is independently unsaturated (C2~C 50 ) hydrocarbons, unsaturated (C2~C 50 ) Heterocarbons, (C1~C 50 ) Hydrocarbyl, (C6~C 50 )aryl, (C6~C 50 )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4~C 12 ) Diene, halogen, -N(R N )2, and -N(R N )COR C The selected monodentate ligand is one of several components, and the metal-ligand complex is charge-neutral overall. 【0038】 In equation (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 These are independently -H, (C1~C 40 ) Hydrocarbyl, (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C ) Selected from 2NC(O)- and halogens. 【0039】 In equation (I), R 1 and R16 is, independently, -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, -N=C(R C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV), and is selected from the group consisting of. 【0040】 【Chemical formula】 【0041】 In formulas (II), (III), and (IV), each of R 31~35 , R 41~48 , and R 51~59 is, independently, -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C) Selected from 2NC(O)- or halogen. 【0042】 In equation (I), Y is CH2, CHR 21 , CR 21 R 22 , SiR 21 R 22 , or GeR 21 R 22 And R 21 and R 22 (C1~C 20 ) is alkyl, however, when Y is CH2, R 8 and R 9 At least one of them is not -H. 【0043】 While not bound by theory, these preferred substitution patterns, including 3-atom bridges (-CH2YCH2-), are within the scope of this disclosure. 8 and R 9 Combined with substitution patterns at the base, this is thought to primarily result in single-site behavior. Second polymerization sites, often observed in MMAO activation, are not formed with these catalytic systems of the present invention. Second polymerization sites can unduly introduce additional properties into the resulting polymer. These properties may then manifest as broadening of the molecular weight distribution curve or through heterogeneous comonomer distribution. 【0044】 In equations (I), (II), (III), and (IV), each R in equation (I) C , R P , and R N (C1~C 30 ) Hydrocarbyl, (C1~C 30 ) Heterohydrocarbyl, or -H. 【0045】 In some embodiments, the modified hydrocarbylmethylaluminoxane in the polymerization process has less than 20 mole percent and more than 5 mole percent of trihydrocarbylaluminooxane, based on the total number of moles of aluminum in the hydrocarbyl-modified methylaluminoxane. In some embodiments, the modified hydrocarbylmethylaluminoxane has less than 15 mole percent of trihydrocarbylaluminooxane, based on the total number of moles of aluminum in the hydrocarbyl-modified methylaluminoxane. In one or more embodiments, the modified hydrocarbylmethylaluminoxane has less than 10 mole percent of trihydrocarbylaluminooxane, based on the total number of moles of aluminum in the hydrocarbyl-modified methylaluminoxane. In various embodiments, the modified hydrocarbylmethylaluminoxane is modified methylaluminoxane. 【0046】 In some embodiments, trihydrocarbyl aluminum is AlR A1 R B1 R C1 The formula has the following, where R A1 , R B1 , and R C1 These are, independently, linear (C1~C 40 ) alkyl, branched chain (C1~C 40 ) alkyl, or (C6~C 40 ) is an aryl. In one or more embodiments, R A1 , R B1 , and R C1 R is independently methyl, ethyl, propyl, 2-propyl, butyl, tert-butyl, or octyl. In some embodiments, R A1 , R B1 , and R C1 They are the same. In other embodiments, R A1 , R B1 , and R C1 At least one of them is another R A1 , R B1 , and R C1 It is different. 【0047】 R in the metal-ligand complex of formula (I) 1 Base and R 16 The elements are selected independently of each other. For example, R 1 R may be selected from radicals having formula (II), (III), or (IV), 16 (C1~C 40 ) may be hydrocarbyl, or R 1 R may be selected from radicals having formula (II), (III), or (IV), 16 R may be selected from radicals having formula (II), (III), or (IV), 1 It is the same as or different from that of R. 1 and R 16 Both can be radicals having formula (II), in which case R 31~35 The base is R 1 and R 16 In other embodiments, R 1 and R 16 Both can be radicals having formula (III), in which case R 41~48 The base is R 1 and R 16 In R, they are the same or different, or R 1 and R 16 Both can be radicals having formula (IV), in which case R 51~59 The base is R 1 and R 16 They are the same or different in that respect. 【0048】 In some embodiments, R 1 and R 16 At least one of them is a radical having formula (II), and R 32 and R 34 is tert-butyl. In one or more embodiments, R 32 and R 34 (C1~C 12 ) Hydrocarbyl or -Si[(C1~C 10 )alkyl]3. 【0049】 In some embodiments, R1 or R 16 When at least one of them is a radical having formula (III), R 43 and R 46 One or both of these are tert-butyl, and R 41~42 , R 44~45 , and R 47~48 In other embodiments, R 42 and R 47 One or both of these are tert-butyl, and R 41 , R 43~46 , and R 48 is -H. In some embodiments, R 42 and R 47 Both are -H. In various embodiments, R 42 and R 47 (C1~C 20 ) Hydrocarbyl or -Si[(C1~C 10 )alkyl]3. In other embodiments, R 43 and R 46 (C1~C 20 ) Hydrocarbyl or -Si[(C1~C 10 )alkyl]3. 【0050】 In one embodiment, R 1 or R 16 When at least one of them is a radical having formula (IV), each R 52 , R 53 , R 55 , R 57 , and R 58 is -H, (C1~C 20 ) Hydrocarbyl, -Si[(C1~C 20 ) Hydrocarbyl]3, or -Ge[(C1~C 20 ) Hydrocarbyl 3. In some embodiments, R 52 , R 53 , R 55 , R 57 , and R 58 At least one of them is (C3~C 10 ) Alkyl, -Si[(C3~C 10)alkyl]3, or -Ge[(C3~C 10 )alkyl]3. In one or more embodiments, R 52 , R 53 , R 55 , R 57 , and R 58 At least two of them are (C3~C 10 ) Alkyl, -Si[(C3~C 10 )alkyl]3, or -Ge[(C3~C 10 )alkyl]3. In various embodiments, R 52 , R 53 , R 55 , R 57 , and R 58 At least three of them are (C3~C 10 ) Alkyl, -Si[(C3~C 10 )alkyl]3, or -Ge[(C3~C 10 )alkyl]3. 【0051】 In some embodiments, R 1 or R 16 When at least one of them is a radical having formula (IV), R 52 , R 53 , R 55 , R 57 , and R 58 At least two of them are (C1~C 20 ) Hydrocarbyl or -C(H)2Si[(C1~C 20 ) Hydrocarbyl-3. 【0052】 (C3~C 10 Examples of alkyl groups include, but are not limited to, propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. 【0053】 In equation (I), R2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 These are independently -H, (C1~C 40 ) Hydrocarbyl, (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C ) Selected from 2NC(O)- and halogens. 【0054】 In one or more embodiments, R 2 , R 4 , R 5 , R 12 , R 13 , and R 15 It is hydrogen. 【0055】 In various embodiments, R 5 , R 6 , R 7 , and R 8 At least one of them is a halogen atom, R 9 , R 10 , R 11 , and R 12 At least one of them is a halogen atom. In some embodiments, R 8 and R 9These are independently (C1-C4) alkyl groups. 【0056】 In some embodiments, R 3 and R 14 (C1~C 20 ) is alkyl. In one or more embodiments, R 3 and R 14 It is methyl, and R 6 and R 11 is a halogen. In the embodiment, R 6 and R 11 In other embodiments, R 3 and R 14 It is either tert-octyl or n-octyl. 【0057】 In various embodiments, R 3 and R 14 (C1~C 24 ) is alkyl. In one or more embodiments, R 3 and R 14 (C4~C 24 ) is alkyl. In some embodiments, R 3 and R 14 These are 1-propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. In embodiments, R 3 and R 14 is -OR C And R C (C1~C 20 ) is a hydrocarbon, and in some embodiments, R C These are methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), or 1,1-dimethylethyl. 【0058】 In one or more embodiments, R8 and R 9 One of them is not -H. In various embodiments, R 8 and R 9 At least one of them is (C1~C 24 ) is alkyl. In some embodiments, R 8 and R 9 Both are (C1~C 24 ) is alkyl. In some embodiments, R 8 and R 9 is methyl. In other embodiments, R 8 and R 9 It is a halogen. 【0059】 In some embodiments, R 3 and R 14 R is methyl. In one or more embodiments, R 3 and R 14 (C4~C 24 ) is alkyl. In some embodiments, R 8 and R 9 These include 1-propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. 【0060】 In various embodiments, in the metal-ligand complex of formula (I), R 6 and R 11 is a halogen. In some embodiments, R 6 and R 11 (C1~C 24 ) is alkyl. In various embodiments, R 6 and R 11R is independently selected from 1-propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. In some embodiments, R 6 and R 11 is tert-butyl. In the embodiment, R 6 and R 11 is -OR C And R C (C1~C 20 ) Hydrocarbyl, and in some embodiments, R C R is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), or 1,1-dimethylethyl. In other embodiments, R 6 and R 11 -SiR C 3, and each R C (C1~C 20 ) Hydrocarbyl, and in some embodiments, R C These are methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), or 1,1-dimethylethyl. 【0061】 In some embodiments, the chemical groups of the metal-ligand complex of formula (I) (e.g., X and R) 1~59 ) any or all of these may be unsubstituted. In other embodiments, the chemical groups X and R of the metal-ligand complex of formula (I) 1~59 One or more of the following R S Even if they are not replaced by R, one or all of them may be one or more R S It may also be replaced by two or more R S If the R groups are bonded to the same chemical group in the metal-ligand complex of formula (I), then the individual R groups of the chemical group SThese may be bonded to the same carbon atom or heteroatom, or to different carbon atoms or heteroatoms. In some embodiments, chemical groups X and R 1~59 All of the above are R S Even if they are not oversubstituted, one or all of them are R S In some cases, it may be oversubstituted. S In chemical groups that are oversubstituted with R, each R S These may all be the same or may be independently selected. In one or more embodiments, R S (C1~C 20 ) Hydrocarbyl, (C1~C 20 ) Alkyl, (C1~C 20 ) Heterohydrocarbyl, or (C1~C 20 ) Selected from heteroalkyl groups. 【0062】 In equations (I), (II), (III), and (IV), each R C , R P , and R N (C1~C 30 ) Hydrocarbyl, (C1~C 30 ) Heterohydrocarbyl, or -H. 【0063】 In some embodiments, in the metal-ligand complex according to formula (I), R 8 and R 9 Both are methyl. In other embodiments, R 8 and R 9 One of them is methyl, and R 8 and R 9 The other side is -H. 【0064】 In the metal-ligand complex of formula (I), X is bonded to M through covalent or ionic bonds. In some embodiments, X may be a monoanionic ligand having a net formal oxidation state of -1. Each monoanionic ligand is independently a hydride ion, (C1~C 40 ) Hydrocarbyl carbanion, (C1~C 40) Heterohydrocarbyl carbanion, halide, nitrate, carbonate, phosphate, sulfate, HC(O)O - , HC(O)N(H) - , (C1~C 40 ) Hydrocarbyl C(O)O - , (C1~C 40 ) Hydrocarbyl C(O)N((C1~C 20 (Hydrocarbyl) - , (C1~C 40 ) Hydrocarbyl C(O)N(H) - , R K R L B - , R K R L N - , R K O - , R K S - , R K R L P - , or R M R K R L Si - This may also be the case, and each R K , R L , and R M Independently, hydrogen, (C1~C 40 ) Hydrocarbyl, or (C1~C 40 ) Heterohydrocarbyl or R K and R L These come together, (C2~C 40 ) Hydrocarbylene or (C1~C 20 ) Forms heterohydrocarbylene, R M This is as defined above. 【0065】 In some embodiments, X is a halogen, unsubstituted (C1~C 20 ) Hydrocarbyl, unsubstituted (C1~C 20 ) Hydrocarbyl C(O)O-, or R K R L N- and R K and R L Each of these is independent of the non-substitutable (C1~C 20) is hydrocarbyl. In some embodiments, each monodentate ligand X is a chlorine atom, (C1~C 10 ) Hydrocarbyl (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C 10 ) Hydrocarbyl C(O)O-, or R K R L N- and R K and R L Each of these is independent of the non-substitutable (C1~C 10 ) It is hydrocarbyl. 【0066】 In further embodiments, X is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, or chloro. X is methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, and chloro. In one embodiment, n is 2, and at least two X are independently monoanionic monodentate ligands. In a particular embodiment, n is 2, and the two X groups together form a bidentate ligand. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene. 【0067】 In one or more embodiments, each X is independently -(CH2)SiR X 3, and each R X (C1~C 30 ) Alkyl or (C1~C 30 ) is heteroalkyl and has at least one R X (C1~C 30 ) is alkyl. In some embodiments, R X One of them is (C1~C 30 ) When it is a heteroalkyl, the heteroatom is silica or oxygen. In some embodiments, R XThese are methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl. 【0068】 In one or more embodiments, X is -(CH2)Si(CH3)3, -(CH2)Si(CH3)2(CH2CH3), -(CH2)Si(CH3)(CH2CH3)2, -(CH2)Si(CH2CH3)3, -(CH2)Si(CH3)2(n-butyl), -(CH2)Si(CH3)2(n-hexyl), -(CH2)Si(CH3)(n-Oct)R X -(CH2)Si(n-Oct)R X 2, -(CH2)Si(CH3)2(2-ethylhexyl), -(CH2)Si(CH3)2(dodecyl), -CH2Si(CH3)2CH2Si(CH3)3 (referred to herein as -CH2Si(CH3)2CH2TMS). Optionally, in some embodiments, the metal-ligand complex according to formula (I) has exactly two R X They are covalently bonded, or exactly three R X They are covalently bonded. 【0069】 In some embodiments, X is -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q The subscript Q is 0, 1, 2, or 3, and each R C These can be substituted or not substituted independently (C1~C 30 ) Hydrocarbyl, or substituted or unsubstituted (C1~C 30 ) It is a heterohydrocarbyl. 【0070】 cocatalyst component A catalyst system comprising the metal-ligand complex of formula (I) can be catalytically activated by any technique known in the art for activating metal catalysts in olefin polymerization reactions. For example, a procatalyst of the metal-ligand complex of formula (I) can be catalytically activated by contacting the complex with an activated cocatalyst or by combining the complex with an activated cocatalyst. In addition, the metal-ligand complex of formula (I) includes both a neutral procatalyst form and a catalytic form that can be positively charged by the loss of a monoanionic ligand such as benzyl or phenyl. Suitable activated cocatalysts for use herein include oligomeric alumoxanes or modified alkylaluminoxanes. 【0071】 Polyolefins The catalyst systems described in the preceding paragraphs are used for the polymerization of olefins, mainly ethylene and propylene, to form ethylene-based polymers or propylene-based polymers. In some embodiments, only a single type of olefin or α-olefin is present in the polymerization scheme to produce homopolymers. However, additional α-olefins may be incorporated into the polymerization procedure. Additional α-olefin comonomers typically have 20 or fewer carbon atoms. For example, an α-olefin comonomer may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, one or more α-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-hexene and 1-octene. 【0072】 Ethylene-based polymers, such as homopolymers of ethylene and / or interpolymers (including copolymers) of ethylene with one or more comonomers, such as α-olefins, may contain at least 50 mole percent (mol%) of monomer units derived from ethylene. All individual values ​​and subranges encompassed by "at least 50 mole percent" are disclosed herein as separate embodiments, for example, ethylene-based polymers, homopolymers of ethylene and / or interpolymers (including copolymers) of ethylene with one or more comonomers, such as α-olefins, may contain at least 60 mole percent of monomer units derived from ethylene, at least 70 mole percent of monomer units derived from ethylene, at least 80 mole percent of monomer units derived from ethylene, or 50 to 100 mole percent of monomer units derived from ethylene, or 80 to 100 mole percent of monomer units derived from ethylene. 【0073】 In some embodiments, the ethylene-based polymer may contain at least 90 mole percent units derived from ethylene. All individual values ​​and sub-ranges from at least 90 mole percent are incorporated herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer may contain at least 93 mole percent units, at least 96 mole percent units, at least 97 mole percent units derived from ethylene, or alternatively, 90 to 100 mole percent units derived from ethylene, 90 to 99.5 mole percent units derived from ethylene, or 97 to 99.5 mole percent units derived from ethylene. 【0074】 In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50 mol%, in other embodiments it contains at least 1 mol% to 25 mol%, and in further embodiments the amount of additional α-olefin contains at least 5 mol% to 103 mol%. In some embodiments, the additional α-olefin is 1-octene. 【0075】 Ethylene-based polymers may be produced using any conventional polymerization process. Such conventional polymerization processes include, but are not limited to, solution polymerization processes, slurry phase polymerization processes, and combinations thereof, using one or more conventional reactors, such as loop reactors, isothermal reactors, stirred tank reactors, and batch reactors, in parallel, in series, or in any combination thereof. 【0076】 In one embodiment, the ethylene polymer can be produced by solution polymerization in a double reactor system, for example, a double-loop reactor system, and ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein and optionally one or more co-catalysts. In another embodiment, the ethylene polymer can be produced by solution polymerization in a double reactor system, for example, a double-loop reactor system, and ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein and optionally one or more other catalysts. The catalyst system described herein can be used in combination with optionally one or more other catalysts in a first reactor or a second reactor. In one embodiment, the ethylene polymer can be produced by solution polymerization in a double reactor system, for example, a double-loop reactor system, and ethylene and optionally one or more α-olefins are polymerized in both reactors in the presence of the catalyst system described herein. 【0077】 In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single reactor system, for example, a single-loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system described in this disclosure and optionally one or more co-catalysts described in the preceding paragraph. 【0078】 Ethylene polymers may further contain 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, UV stabilizers, and combinations thereof. Ethylene polymers may contain any amount of additives. Based on the weight of the ethylene polymer and one or more additives, such additives may constitute about 0 to about 10 percent of the total weight. Ethylene polymers may further contain fillers, which may include, but are not limited to, organic or inorganic fillers. Based on the total weight of the ethylene polymer and all additives or fillers, such fillers may constitute about 0 to about 20 percent by weight, for example, calcium carbonate, talc, or Mg(OH)2. Ethylene polymers may be further compounded with one or more polymers to form blends. 【0079】 In some embodiments, a polymerization process for producing an ethylene-based polymer may involve polymerizing ethylene and at least one additional α-olefin in the presence of a catalytic system according to the present disclosure. The polymer obtained from such a catalytic system incorporating a metal-ligand complex of formula (I) may be polymerized, for example, 0.850 g / cm³ according to ASTM D792 (which is incorporated herein by reference in its entirety). 3 ~0.970g / cm 3 , 0.880 g / cm³ 3 ~0.920g / cm 3 , 0.880 g / cm³ 3 ~0.910 g / cm³ 3 , or 0.880 g / cm³ 3 ~0.900g / cm 3 It may have a density of . 【0080】 In another embodiment, the polymer obtained from the catalyst system according to this disclosure has a melt flow ratio of 5 to 15 (I 10The melt index I2 is measured at 190°C and a 2.16 kg load according to ASTM D1238 (which is incorporated herein by reference in its entirety). 10 This is measured at 190°C and a 10kg load according to ASTM D1238. In other embodiments, the melt flow ratio (I 10 In other embodiments, the melt flow ratio is 5 to 9. 【0081】 In some embodiments, the polymer obtained from the catalyst system according to this disclosure has a molecular weight distribution (MWD) of 1 to 25, where MWD is M w / M n Defined as, M w This is the weight-average molecular weight, M n This is the number-average molecular weight. In other embodiments, the polymer obtained from the catalyst system has MWD 1 to 6. Another embodiment includes 1 to 3 MWD, and yet another embodiment includes 1.5 to 2.5 MWD. 【0082】 Gel Permeation Chromatography (GPC) The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 160 degrees Celsius, and the column compartment to 150 degrees Celsius. The columns used were four Agilent "Mixed A" 30 cm, 20 micrometer linear mixed-bed columns. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was spurged with nitrogen. The injection volume used was 200 microliters, and the flow rate was 1.0 ml / min. 【0083】 Calibration of the GPC column set was performed using polystyrene standards with a narrow molecular weight distribution of at least 20, ranging from 580 to 8,400,000, arranged in six “cocktail” mixtures with at least 10 intervals between individual molecular weights. The standards were purchased from Agilent Technologies. Polystyrene standards were prepared using 0.025 grams in 50 ml of solvent for molecular weights greater than 1,000,000, and 0.05 grams in 50 ml of solvent for molecular weights less than 1,000,000. The polystyrene standards were dissolved at 80 degrees Celsius for 30 minutes with gentle stirring. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Formula 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)). M ポリエチレン =A × (M ポリスチレン ) B (Equation 1) In the formula, M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0. 【0084】 A fifth-order polynomial was used to fit the equivalent calibration points for each polyethylene column. A slight adjustment (approximately 0.40-0.44) was made to A to compensate for column resolution and band broadening effects so that the NIST standard NBS 1475 could be obtained at 52,000 Mw. 【0085】 High-temperature gradient interaction chromatography (HT-TGIC or TGIC) High-temperature thermal gradient interaction chromatography (HT-TGIC or TGIC) measurements were performed using a commercially available crystallization elution fractionation instrument (CEF) (Polymer Char, Spain) (Cong, et al., Macromolecules, 2011, 44(8), 3062-3072). The CEF instrument is equipped with an IR-5 detector. Graphite was used as the stationary phase for the HT-TGIC column (Freddy, A. Van Damme et al., U.S. Patent No. 8,476,076; Winniford et al., U.S. Patent No. 8,318,896). A single graphite column (250 × 4.6 mm) was used for separation. Graphite was packed into the column using a dry packing technique followed by a slurry packing technique (Cong et al., European Patent No. 2714226(B1) and references). The experimental parameters were as follows: top oven / transfer line / needle temperature 150°C, dissolution temperature 150°C, dissolution stirring setting 2, pump stabilization time 15 seconds, pump flow rate for column washing 0.500 mL / min, pump flow rate for column packing 0.300 mL / min, stabilization temperature 150°C, stabilization time (before column packing) 2.0 minutes, stabilization time (after column packing) 1.0 minute, SF (soluble fraction) time 5.0 minutes, cooling rate from 150°C to 30°C 3.00°C / min, flow rate during the cooling process 0.04 mL / min, heating rate from 30°C to 160°C 2.00°C / min, isothermal time at 160°C for 10 minutes, elution flow rate 0.500 mL / min, and injection loop size 200 microliters. 【0086】 The flow rate during the cooling process is adjusted according to the length of the graphite column to ensure that all polymer fractions remain on the column at the end of the cooling cycle. 【0087】 Samples were prepared using a PolymerChar autosampler at 150°C for 120 minutes at a concentration of 4.0 mg / mL in ODCB (defined below). Silica gel 40 (particle size 0.2-0.5 mm, catalog number 10181-3, EMD) was dried in a vacuum oven at 160°C for approximately 2 hours before use. For CEF instruments equipped with an autosampler with N2 purging capability, silica gel 40 was packed into three 300 × 7.5 mm GPC-sized stainless steel columns, and the silica gel 40 columns were attached to the pump inlet of the CEF instrument to purify the ODCB. No BHT was added to the mobile phase. The ODCB dried with silica gel 40 is referred to here as "ODCB". TGIC data were processed using PolymerChar (Spain)'s "GPC One" software platform. Temperature calibration was performed using a mixture of approximately 4-6 mg of eicosane and 14.0 mg of isotactic homopolymer polypropylene (iPP) (polydispersibility of 3.6-4.0, molecular weight Mw reported as polyethylene equivalent of 150,000-190,000, and polydispersity (Mw / Mn) of 3.6-4.0; the DSC melting temperature of iPP was measured at 158-159°C (DSC method described below in this specification). 14.0 mg of homopolymer polyethylene HDPE (comonomer content zero, weight-average molecular weight (Mw) reported as polyethylene equivalent of 115,000-125,000, and polydispersity of 2.5-2.8) was dissolved in a 10 mL vial filled with 7.0 mL of ODCB. The dissolution time was 2 hours at 160°C. 【0088】 Data processing for HT-TGIC polymer samples Solvent blanks (pure solvent injection) were performed under the same experimental conditions as the polymer samples. Data processing for the polymer samples included subtracting the solvent blank for each detector channel calculated from the calibration heating rate, temperature extrapolation as described in the calibration process, temperature correction due to the delay amount measured in the calibration process, and adjustment of the elution temperature axis to the range of 30°C to 160°C. 【0089】 The chromatogram (measurement channel of the IR-5 detector) was integrated with PolymerChar "GPC One" software. A linear baseline was subtracted from the visible difference when the peak fell to a flat baseline (approximately zero in the blank subtraction chromatogram) at high elution temperatures, and to the minimum or flat region of the detector signal on the high-temperature side of the soluble fraction (SF). 【0090】 Broadness index (B index) of the TGIC profile The TGIC chromatogram is related to comonomer content and its distribution. It may be related to the number of catalytically active sites. The TGIC profile can be influenced to some extent by experimental factors related to chromatography (Stregel, et al., "Modern size-exclusion liquid chromatography," Wiley, 2nd edition, Chapter 3). The TGIC broadness index (B index) can be used to quantitatively compare the broadness of TGIC chromatograms of samples with different compositions and distributions. The B index can be calculated at any ratio of the maximum profile height. For example, the "N" B index can be obtained by measuring the profile width at 1 / N of the maximum profile height and using the following formula. 【0091】 【number】 In the formula, Tp is the temperature at which the maximum height is observed in the profile, and N is an integer of 2, 3, 4, 5, 6, or 7. If the TGIC chromatogram has multiple peaks with similar peak heights, the peak at the highest elution temperature is defined as the profile temperature (Tp). 【0092】 TGIC Profile U Index (U Index) The polymer composition distribution was measured using TGIC. To evaluate the uniformity of the composition distribution, the obtained chromatograms were fitted to a Gaussian distribution according to the following formula. 【0093】 【number】 【0094】 The above function was used to fit the data using the least squares method. (Data and function f(x)) i The residuals between β and β were squared and then summed. In the formula, xi is the elution temperature above 35°C, i=0, and n is the final elution temperature of the TGIC profile. 【0095】 【number】 【0096】 The fitting function was adjusted to provide the minimum sum. In addition to the least squares method, the fitting equation was further combined with a weighting function to prevent overestimation of the peak shape. 【0097】 【number】 【0098】 During the ceremony, w i is, (y i -f(x i For all positive cases of ,β)) it is equal to 1, and (y i -f(x i For all negative values ​​of β), it is equal to 11. Using this method, the fitting function prevents overestimation of peak shape and provides a better approximation of the area covered by the single-site catalyst. Once the curve is fitted, the total area of ​​the distribution covered by the fitting can be compared to the total area of ​​the sample chromatogram excluding the fraction remaining at 30°C at the end of the cooling step in the TGIC experiment. Multiplying this value by 100 gives the uniformity index (U index). 【0099】 【number】 【0100】 As mentioned in the previous paragraph, low-density polymers generally have a broader molecular weight distribution (MWD) than high-density polymers, due to their elution temperature. The TGIC profile can be influenced by the polymer MWD (Abdulaal, et al., Macromolecular Chem Phy, 2017, 218, 1600332). Therefore, when analyzing the breadth of the MWD curve using TGIC, the width of the curve is not an accurate indicator of the polymer's chemical composition. 【0101】 The embodiments of the catalyst systems described herein result in unique polymer properties as a result of the high molecular weight of the formed polymer and the amount of comonomers incorporated into the polymer. The present specification includes the following embodiments. Section 1. A process for polymerizing olefin monomers, the process comprising reacting ethylene with one or more olefin monomers in the presence of a catalyst system, the catalyst system is Modified hydrocarbylmethylaluminoxane, wherein the AlR is less than 50 mole percent based on the total number of moles of aluminum in the hydrocarbyl-modified methylaluminoxane. A1 R B1 R C1 It has R A1 , R B1 , and R C1 These are, independently, linear (C1~C 40 ) alkyl, branched chain (C1~C 40 ) Alkyl or (C6~C 40 ) Modified hydrocarbylmethylaluminoxane, which is an aryl compound, One or more metal-ligand complexes according to formula (I): [ka] [In the formula, M is titanium, zirconium, or hafnium. n is 1, 2, or 3. Each X is independently unsaturated (C2~C 50 ) hydrocarbons, unsaturated (C2~C 50 ) Heterocarbons, (C1~C 50 ) Hydrocarbyl, (C6~C 50 )aryl, (C6~C 50 )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4~C 12 ) Diene, halogen, -N(R N )2, and -N(R N )COR C A monodentate ligand selected from, The aforementioned metal-ligand complex is charge-neutral overall. R 1 and R 16 These are independently -H, (C6~C 40 )Aaryl, (C5~C 40 ) Selected from the group consisting of heteroaryls, radicals having formula (II), radicals having formula (III), and radicals having formula (IV), [ka] In the formula, R 31~35 , R 41~48 and R 51~59 Each of these is independent of -H, (C1~C 40 ) Hydrocarbyl, (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C ) Selected from 2NC(O)-, or halogen, R 2, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 These are independently -H, (C1~C 40 ) Hydrocarbyl, (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2-OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C ) Selected from 2NC(O)- and halogen, Y is CH2, CHR 21 , CR 21 R 22 , SiR 21 R 22 , or GeR 21 R 22 And R 21 and R 22 (C1~C 20 ) is alkyl, However, (1) when Y is CH2, R 8 and R 9 At least one of them is not -H, Each R in equation (I) C , R P , and R N (C1~C 30 ) Hydrocarbyl, (C1~C 30 ) containing heterohydrocarbyl, or -H, The catalyst system is a polymerization process that does not contain a borate activator. Section 2. The modified hydrocarbylmethylaluminoxane is less than 25 mole percent AlR based on the total number of moles of aluminum in the hydrocarbyl-modified methylaluminoxane. A1 R B1 R C1 The polymerization process described in item 1, comprising the following: Section 3. The modified hydrocarbyl methylaluminoxane is less than 15 mole percent AlR based on the total number of moles of aluminum in the hydrocarbyl modified methylaluminoxane. A1 R B1 R C1 A polymerization process according to item 1 or 2, comprising: Section 4. The modified hydrocarbyl methylaluminoxane is less than 10 mole percent AlR based on the total number of moles of aluminum in the hydrocarbyl modified methylaluminoxane. A1 R B1 R C1 A polymerization process according to item 1 or 2, comprising: Section 5. The polymerization process according to any one of claims 1 to 4, wherein the modified hydrocarbylmethylaluminoxane is a modified methylaluminoxane. Section 6. The polymerization process according to any one of claims 1 to 5, wherein the aluminum to catalyst metal ratio is less than 500:1. Section 7. The polymerization process according to any one of claims 1 to 6, wherein the aluminum to catalyst metal ratio is less than 200:1 or less than 50:1. Section 8. R 8 and R 9 At least one of them is (C1~C 40 ) Hydrocarbyl, (C1~C 40 ) A polymerization process according to any one of items 1 to 7, wherein the atom is a heterohydrocarbyl or a halogen atom. Section 9. R 8and R 9 The polymerization process according to any one of items 1 to 8, wherein at least one of the members is a (C1-C5) alkyl group. Section 10. R 1 and R 16 The polymerization process described in any one of items 1 to 9 is identical to the polymerization process described in item 1 to 9. Section 11. R 1 and R 16 A polymerization process according to any one of items 1 to 10, wherein at least one of the is a radical having formula (III). Section 12. R 42 and R 47 (C1~C 20 ) Hydrocarbyl or -Si[(C1~C 20 The polymerization process described in item 7, wherein the polymer is hydrocarbyl-3. Section 13. R 43 and R 46 (C1~C 20 ) Hydrocarbyl or -Si[(C1~C 20 The polymerization process described in item 7, wherein the polymer is hydrocarbyl-3. Section 14. R 1 and R 16 A polymerization process according to any one of items 1 to 5, wherein at least one of the is a radical having formula (II). Section 15. R 32 and R 34 (C1~C 12 ) Hydrocarbyl or -Si[(C1~C 20 The polymerization process described in item 10, wherein the polymer is hydrocarbyl-3. Section 16. R 1 and R 16 A polymerization process according to any one of items 1 to 5, wherein at least one of the is a radical having formula (IV). Section 17. R 52 , R 53 , R 55 , R 57, and R 58 At least two of them are (C1~C 20 ) Hydrocarbyl or -Si[(C1~C 20 The polymerization process described in item 12, wherein the polymerization process is )hydrocarbyl-3. Section 18. R 8 and R 9 The polymerization process according to any one of claims 1 to 13, independently selected from methyl, ethyl, 1-propyl, or 2-propyl. Section 19. R 3 and R 14 (C1~C 20 A polymerization process according to any one of items 1 to 18, wherein the alkyl group is alkyl. Section 20. R 3 and R 14 It is methyl, and R 6 and R 11 The polymerization process described in any one of items 1 to 19, wherein the halogen is a halogen. Section 21. R 6 and R 11 The polymerization process according to any one of items 1 to 20, wherein tert-butyl is used. Section 22. R 3 and R 14 The polymerization process according to any one of items 1 to 20, wherein is tert-octyl or n-octyl. Section 23. A polymerization process according to any one of items 1 to 22, wherein M is zirconium. Section 24. The aforementioned olefin monomers are (C3~C 20 A polymerization process according to any one of items 1 to 23, wherein the material is an α-olefin. Section 25. The polymerization process according to any one of claims 1 to 24, wherein the olefin monomer is a cyclic olefin. Section 26. The polymerization process is a solution polymerization reaction, as described in any one of items 1 to 25. 【0102】 One or more features of this disclosure are illustrated by considering the following embodiments. [Examples] 【0103】 Procedure for continuous process reactor polymerization: The raw materials (ethylene, 1-octene) and process solvent (high-purity isoparaffin solvent with a narrow boiling point range, commercially available from ExxonMobil Corporation under the trademark ISOPAR E) are purified using molecular sieves and then introduced into the reaction environment. Hydrogen is supplied into the pressurized cylinder as high-purity grade and is not further purified. The reactor monomer feed stream (ethylene) is pressurized to exceed the reaction pressure. The solvent and comonomer feed streams are pressurized to exceed the reaction pressure. Individual catalyst components (metal-ligand complexes and cocatalysts) are manually batch diluted to the specified component concentrations using the purified solvent and pressurized to a pressure higher than the reaction pressure. All reaction feed streams are measured using mass flow meters and independently controlled by a computer-automated valve control system. 【0104】 Continuous solution polymerization is carried out in a continuously stirred-tank reactor (CSTR). The feed to the reactor, a combination of solvent, monomer, comonomer, and hydrogen, is temperature-controlled between 5°C and 50°C, typically 15°C to 25°C. All components are fed into the polymerization reactor along with the solvent feed. The catalyst is fed into the reactor to reach a specific conversion rate of ethylene. Cocatalyst components(s) are fed separately based on a calculated specific molar ratio or ppm amount. The effluent from the polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and polymer) exits the reactor and comes into contact with water. In addition, various additives such as antioxidants can be added at this point. The flow is then passed through a static mixer to uniformly disperse the mixture. 【0105】 Following the addition of additives, the effluent (containing solvent, monomers, comonomers, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the flow temperature in preparation for the separation of the polymer from other low-boiling-point components. The flow then passes through a reactor pressure control valve, where the pressure is significantly reduced throughout. From there, the effluent enters a two-stage separation system consisting of a devolatizer and a vacuum extruder, where the solvent, as well as unreacted hydrogen, monomers, comonomers, and water, are removed from the polymer. At the extruder outlet, the formed strands of molten polymer pass through a cold water bath where they solidify. The strands are then fed through a strand chopper, and after air drying, the polymer is cut into pellets. 【0106】 Procedure for batch reactor polymerization. The raw materials (ethylene, 1-octene) and process solvent (ISOPAR E) were purified using molecular sieves and then introduced into the reaction environment. ISOPAR E and 1-octene were placed in a stirred autoclave reactor. The reactor was then heated to a certain temperature, ethylene was added, and the desired pressure was reached. Hydrogen was also added optionally. The catalyst system was prepared in a dry box under an inert atmosphere by mixing a metal-ligand complex and one or more additives optionally with an additional solvent. The catalyst system was then injected into the reactor. The reactor pressure and temperature were kept constant by supplying ethylene during polymerization and cooling the reactor as needed. After 10 minutes, the supply of ethylene was stopped, and the solution was transferred to a nitrogen-purged plastic kettle. The polymer was thoroughly dried in a vacuum oven, and the reactor was thoroughly rinsed with hot ISOPAR E between polymerization experiments. 【0107】 Test method Unless otherwise specified herein, the following analytical methods are used in describing aspects of this disclosure. 【0108】 Melt Index Melt index I2 (or I2) and I 10(or I10) were measured according to ASTM D-1238 (Method B) at 190°C and loads of 2.16 kg and 10 kg, respectively. The values ​​were reported in g / 10 min. 【0109】 density Samples for density measurement were prepared according to ASTM D4703. Measurements were performed within one hour of sample pressurization, according to ASTM D792, Method B. 【0110】 Analysis of hydrocarbyl-modified methylaluminoxane Example 1 is an analytical procedure for determining the aluminum concentration in a solution. 【0111】 In a nitrogen atmosphere glove box, formula AlR A1 R B1 R C1 The aluminum-based analytes were transferred to tare-weighed bottles, and the mass of the samples was recorded. The samples were diluted with methylcyclohexane and then quenched with methanol. The mixture was stirred in the bottle and allowed to react for 15 minutes, after which the samples were removed from the glove box. The samples were further hydrolyzed by the addition of H2SO4. The bottle was capped and shaken for 5 minutes. Depending on the aluminum concentration, periodic aeration of the bottle may be necessary. The solution was transferred to a separatory funnel. The bottle was rinsed repeatedly with water, and each rinse from this process was added to the separatory funnel. The organic layer was discarded, and the remaining aqueous solution was transferred to a volumetric flask. The separatory funnel was rinsed further with water, and each rinse was added to the volumetric flask. The flasks were diluted to known volumes, thoroughly mixed, and analyzed by complex formation with excess EDTA and subsequent back titration with ZnCl2 using xylenol orange as an indicator. 【0112】 AlR in hydrocarbyl-modified alkylaluminoxanes A1 R B1 R C1 Compound calculations. 【0113】 【number】 【0114】 AlR A1 R B1 R C1 Compound content is analyzed using previously described methods (Macromol.Chem.Phys.1996,197,1537, International Publication No. 2009029857(A1), Analytical Chemistry 1968,40(14),2150-2153 and Organometallics 2013,32(11),3354-3362). 【0115】 Metal complexes can be conveniently prepared by standard metallation and ligand exchange procedures involving a transition metal source and a neutral polyfunctional ligand source. Furthermore, complexes can also be prepared by amide removal and hydrocarbylation processes starting from the corresponding transition metal tetraamide and a hydrocarbylating agent such as trimethylaluminum. The techniques used are similar to those disclosed in U.S. Patent Nos. 6,320,005 and 6,103,657, International Publication Nos. 02 / 38628 and 03 / 40195, and U.S. Patent No. A2004 / 0220050. 【0116】 The synthesis procedures for synthesizing metal-ligand complexes I1-18 and C1-C3 can be found in the following procedure and, if previously disclosed, in the following publications: U.S. Publication No. 20040010103(A1), International Publication No. 2007136494(A2), U.S. Publication No. 2012027448(A1), U.S. Publication No. 2016003878(A1), U.S. Publication No. 2016014749(A1), U.S. Publication No. 2017058981(A1), and U.S. Publication No. 2018022975(A1). 【0117】 Preparation I1 (Ligand disclosed in International Publication No. 2018022975(A1)) 【0118】 [ka] 【0119】 Synthesis of 6',6'''-(((diisopropylsilanediyl)bis(methylene))bis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol)dimethyl-zirconium(I1): MeMgBr (3.00 M, 5.33 mL, 16.0 mmol) in diethyl ether was added to a solution of ZrCl4 (0.895 g, 3.84 mmol) in toluene (60 mL) at -30°C. After stirring for 3 minutes, a solid ligand (5.00 g, 3.77 mmol) was added in small amounts. The mixture was stirred for 8 hours, and then the solvent was removed overnight under reduced pressure to obtain a dark residue. Hexane / toluene (10:1 70 mL) was added to the residue, and the solution was shaken at room temperature for several minutes. The material was then passed through a frit funnel with a CELITE plug. The frit was extracted with hexane (2 × 15 mL). The combined extracts were concentrated to dryness under reduced pressure. Pentane (20 mL) was added to the light brown solid, and the heterogeneous mixture was placed in a freezer (-35°C) for 18 hours. The brown pentane layer was removed using a pipette. The remaining material was dried under vacuum to obtain I1 (4.50 g, yield: 83%) as a white powder. 【0120】 1 H NMR(400MHz,C6D6)δ 8.65-8.56(m,2H),8.40(dd,J=2.0,0.7Hz,2H),7.66-7.55(m,8H),7.45(d,J=1.9Hz,1H),7.43(d,J=1.9Hz, 1H),7.27(d,J=2.5Hz,2H),7.10(d,J=3.2Hz,1H),7.08(d,J=3.1Hz,1H),6.80(ddd,J=9.0,7.4,3.2Hz,2H), 5.21(dd,J=9.1,4.7Hz,2H),4.25(d,J=13.9Hz,2H),3.23(d,J=14.0Hz,2H),1.64-1.52(m,4H),1.48(s,18H) ),1.31(s,24H),1.27(s,6H),0.81(s,18H),0.55(t,J=7.3Hz,12H),0.31(hept,J=7.5Hz,2H),-0.84(s,6H); 19F NMR(376MHz,C6D6)δ-116.71. 【0121】 Synthesis of I5: 【0122】 [ka] 【0123】 In a 100 mL glass bottle dried in an oven, ZrCl4 (798 mg, 3.43 mmol), toluene (30 mL), and a stirring rod were placed. The solution was placed in a freezer and cooled at -30°C for 20 minutes. The solution was removed from the freezer and treated with MeMgBr (4.35 mL, 13.1 mmol, 3 M in Et2O), and stirred for 15 minutes. I5 ligand (5.00 g, 3.26 mmol) was added as a solid to the cold suspension. The reaction mixture was stirred at room temperature for 3 hours, and then filtered through a frit plastic funnel. The filtrate was dried under vacuum. The resulting solid was washed with hexane and dried under vacuum to obtain I5 as an off-white powder (3.31 g, 62%). 【0124】 1 H NMR(400MHz,benzene-d6)δ 8.19(d,J=8.2Hz,2H),8.03-7.96(m,4H),7.87(d,J=2.5Hz,2H),7.81-7.76(m,2H),7.64(d,J=2.5Hz,2H),7.56( d,J=1.7Hz,2H),7.51(dd,J=8.2,1.7Hz,2H),7.30(dd,J=8.3,1.7Hz,2H),7.06-7.01(m,2H),3.57(dt,J=9.9,4.9 Hz,2H),3.42(dt,J=10.3,5.2Hz,2H),1.79(d,J=14.5Hz,2H),1.66(d,J=14.4Hz,2H),1.60(s,18H),1.46(s,6H), 1.42(s,6H),1.37-1.22(m,50H),0.94-0.91(m,24H),0.62-0.56(m,4H),0.11(s,6H),0.08(s,6H),-0.64(s,6H). 【0125】 I6 synthesis scheme 【0126】 [ka] 【0127】 Synthesis of 2-bromo-4-fluoro-6-methylphenol: In a 1 L glass bottle, acetonitrile (400 mL), 4-fluoro-6-methylphenol (50 g, 396.4 mmol), and p-toluenesulfonic acid (monohydrate) (75.6 g, 396 mmol) were added, and it was confirmed that all were dissolved. The solution was cooled to 0°C on ice for 25 minutes (a precipitate formed). The cooled solution was slowly treated with N-bromosuccinimide (70.55 g, 396.4 mmol) (over approximately 5 minutes) and allowed to reach room temperature overnight with stirring. 19 Complete conversion was confirmed by analysis using 1F NMR spectroscopy and GC / MS. Volatile substances were removed under vacuum, the resulting solid was treated with dichloromethane (600 mL), cooled in a freezer (0°C), and filtered through a large silica gel plug. The silica gel was washed several times with cold CH2Cl2. Volatile substances were removed under vacuum (yield of the first fraction: 46 g, 56%). 1 ¹H NMR (400MHz, chloroform-d) δ 7.05 (ddd, J=7.7, 3.0, 0.7Hz, 1H), 6.83 (ddt, J=8.7, 3.0, 0.8Hz, 1H), 5.35 (s, 1H), 2.29 (d, J=0.7Hz, 3H). 19 F NMR (376MHz, Chloroform-d) δ-122.84. 【0128】 [ka] 【0129】 Synthesis of bis((2-bromo-4-fluoro-6-methylphenoxy)methyl)diisopropylgermane: In a 250 mL flask equipped with a magnetic stirring rod in a glove box, 95% NaH (1.76 g) (note: H2 will be produced) was slowly added to a solution of 2-bromo-4-fluoro-6-methylphenol (15 g, 73.2 mmol) in N,N-dimethylformamide (DMF) (35 mL) until hydrogen evolution ceased. The mixture was stirred at room temperature for 30 minutes. After this time, diisopropylgermyl dichloride (6.29 g, 24.4 mmol) was added. The mixture was warmed to 55 °C and held at this temperature for 18 hours. The reaction product was removed from the glove box and quenched with saturated aqueous NH4Cl (20 mL) and H2O (8 mL). Et2O (30 mL) was added, and the phase was transferred to a separatory funnel and separated. The aqueous phase was further extracted with Et2O (20 mL), and the combined organic extract was washed with brine (10 mL). The organic layer was then dried (MgSO4), filtered, and concentrated to dryness. The crude residue was dry-loaded onto silica gel and then purified using flash column chromatography (100 mL / min, pure hexane with ethyl acetate increasing to 10% over 20 minutes) to obtain a pale yellow oily product. All clean fractions (some fractions contained less than 10% of the starting phenol) were combined, and the final product was left overnight under vacuum (yield: 9 g, 62%). 【0130】 1 H NMR(400MHz,chloroform-d)δ 7.10(dd,J=7.7,3.0Hz,2H),6.84(ddd,J=8.8,3.1,0.8Hz,2H),4.14(s,4H),2.33(s,6H),1.74(hept,J=7.4Hz,2H),1.35(d,J=7.4Hz,12H); 19 F NMR (376 MHz, chloroform-d) δ-118.03. 【0131】 Synthesis of I6 ligands 【0132】 [ka] 【0133】 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 (disclosed in International Publication No. 2014105411(A1)) (29.0 g, 41.9 mmol), bis((2-bromo-4-fluoro-6-methylphenoxy)methyl)diisopropylgermane (6.00 g, 8.65 mmol, containing 10% 2-bromo-4-fluoro-2-methylphenol), and THF (80 mL) were placed in a 500 mL glass bottle equipped with a stirring rod. The solution was heated to 55°C and treated with chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) (tBu3P-PdG2) (199 mg, 0.346 mmol, 4 mol%) while stirring. The mixture was purged with NaOH aqueous solution (17.3 mL, 51.9 mmol, 3 M) with nitrogen for 20 minutes and then added to the THF solution. The reaction mixture was stirred overnight at 55°C. The aqueous phase was separated and discarded, and the remaining organic phase was diluted with diethyl ether and washed twice with brine. The solution was passed through a short silica gel plug. The filtrate was dried in a rotary evaporator, dissolved in THF / MeOH (40 mL / 40 mL), treated with HCl (2 mL), and stirred overnight at 70°C. The solution was dried under vacuum and purified by C18 reversed-phase column chromatography to obtain the I6 ligand as an off-white solid (yield: 6.5 g, 54%). 【0134】 1 H NMR(400MHz,chloroform-d)δ 8.01(d,J=8.2Hz,4H),7.42(dd,J=25.5,2.4Hz,4H),7.32(dd,J=8.2,1.6Hz,4H),7.17(s,4H),6.87(ddd,J=16.4,8.8,3.0 Hz,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);19 F NMR (376 MHz, chloroform-d) δ-119.02. 【0135】 Synthesis of I6: 【0136】 [ka] 【0137】 In a 100 mL glass bottle dried in an oven, ZrCl4 (402 mg, 1.72 mmol), toluene (83 mL), and a stirring rod were placed. The solution was placed in a freezer and cooled at -30°C for 20 minutes. The solution was removed from the freezer and treated with MeMgBr (2.4 mL, 7.1 mmol, 3 M in Et2O), and stirred for 3 minutes. To the cold suspension, I6 ligand (2.3 g, 1.64 mmol) was added as a solid, the residual powder was dissolved in cold toluene (3 mL), and added to the reaction mixture. The reaction mixture was stirred overnight at room temperature, and then filtered through a frit plastic funnel. The filtrate was dried under vacuum, redissolved in toluene (40 mL), filtered again through a Celite plug, and dried again under vacuum. The resulting solid was washed with pentane (approximately 5 mL) and dried under vacuum to obtain I10 as an off-white powder (2.1 g, 84%). 【0138】 1 H NMR(400MHz,benzene-d6)δ 8.20(dd,J=8.2,0.5Hz,2H),8.11(dd,J=8.2,0.6Hz,2H),7.88-7.82(m,4H),7.77(d,J=2.6Hz,2H),7 .50(dd,J=8.3,1.7Hz,2H),7.42-7.37(m,4H),6.99(dd,J=8.7,3.1Hz,2H),6.20-6.10(m,2H),4.29(d ,J=12.2Hz,2H),3.90(d,J=12.2Hz,2H),1.56(s,4H),1.53(s,18H),1.29(s,24H),1.27(s,6H),1.18 (s,6H),1.04-0.94(m,2H),0.81(d,J=7.4Hz,6H),0.80(s,18H),0.74(d,J=7.4Hz,6H),-0.47(s,6H);19 F NMR (376 MHz, benzene-d6) δ-116.24. 【0139】 I7 synthesis scheme Preparation of bis((2-bromo-4-t-butylphenoxy)methyl)diisopropylsilane 【0140】 [ka] 【0141】 In a glove box, diisopropyldichlorosilane (3.703 g, 20 mmol, 1.0 equivalent) was dissolved in anhydrous THF (120 mL) in a 250 mL round-bottom flask. The flask was capped with a septum, sealed, removed from the glove box, and cooled to -78°C in a dry ice-acetone bath. Bromochloromethane (3.9 mL, 60.0 mmol, 3.0 equivalent) was added. Using a syringe pump, a hexane solution of n-BuLi (18.4 mL, 46 mmol, 2.3 equivalents) was added to the cooling wall of the flask over 3 hours. The mixture was heated to room temperature overnight (16 hours), and saturated NH4Cl (30 mL) was added. Two layers were separated. The aqueous layer was extracted with ether (2 x 50 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under reduced pressure. The crude product was used in the next step without further purification. 【0142】 In a glove box, bis(chloromethyl)diisopropylsilane (2.14 g, 10 mmol, 1.0 equivalent), 4-t-butyl-2-bromophenol (6.21 g, 27 mmol, 2.7 equivalents), K3PO4 (7.46 g, 35 mmol, 3.5 equivalents), and DMF (10 mL) were placed in a 40 mL vial. The reaction mixture was stirred overnight at 80°C. After cooling to room temperature, the reaction mixture was purified by column chromatography using ether / hexane (0 / 100 → 30 / 70) as the eluent. 4.4 g of a colorless oily substance was recovered, and the total yield after two steps was 73%. 【0143】 1H NMR(400MHz,CDCl3)δ 7.51(d,J=2.4Hz,2H),7.26(dd,J=8.6,2.4Hz,2H),6.98(d,J=8.6Hz,2H),3.93(s,4H),1.45-1.33(m,2H),1.28(s,18H),1.20(d,J=7.3Hz,12H). 【0144】 Preparation of 6'',6''''-(((diisopropylsilanediyl)bis(methylene))bis(oxy))bis(3,3'',5-tri-tert-butyl-5'-methyl-[1,1':3',1''-terphenyl]-2'-ol) 【0145】 [ka] 【0146】 In a glove box, a 40 mL vial equipped with a stirring rod contained bis((2-bromo-4-t-butylphenoxy)methyl)diisopropylsilane (1.20 g, 2.0 mmol, 1.0 equivalent), 2-(3',5'-di-tert-butyl-5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.54 g, 5.0 mmol, 2.5 equivalents), tBu3P Pd G2 (0.031 g, 0.06 mmol, 0.03 equivalents), THF (3 mL), and NaOH 4M solution (3.0 mL, 12.0 mmol, 6.0 equivalents). The vial was heated under nitrogen at 55°C for 2 hours. Upon completion, the upper organic layer was extracted with ether and filtered through a short silica gel plug. The solvent was removed under reduced pressure. The residue was dissolved in THF (10 mL) and MeOH (10 mL). Then concentrated HCl (0.5 mL) was added. The resulting mixture was heated at 75°C for 2 hours and then cooled to room temperature. The solvent was removed under reduced pressure. The residue was purified by reversed-phase column chromatography using THF / MeCN (0 / 100 → 100 / 0) as the eluent. 1.62 g of white solid was recovered (yield 78%). 【0147】 1 H NMR(400MHz,CDCl3)δ 7.39(t,J=1.8Hz,2H),7.36(d,J=1.8Hz,4H),7.29(d,J=2.5Hz,2H),7.22(dd,J=8.6,2.6Hz,2H),7.10(d,J=2.2Hz,2H),6.94(d,J=2.3,2H),6 .75(d,J=8.6Hz,2H),5.37(s,2H),3.61(s,4H),2.32(d,J=0.9Hz,6H), 1.33(s,36H),1.29(s,18H),0.90-0.81(m,2H),0.73(d,J=7.1Hz,12H). 【0148】 Preparation of I7 【0149】 [ka] 【0150】 In a glove box, ZrCl4 (47 mg, 0.2 mmol, 1.0 equivalent) and anhydrous toluene (6.0 mL) were placed in an oven-dried 40 mL vial equipped with a stirring rod. The vial was cooled to -30°C in a freezer for at least 30 minutes. The vial was removed from the freezer. MeMgBr (3 M, 0.29 mL, 0.86 mmol, 4.3 equivalents) was added to the stirred suspension. After 2 minutes, 6'',6''''-(((diisopropylsilanediyl)bis(methylene))bis(oxy))bis(3,3'',5-tri-tert-butyl-5'-methyl-[1,1':3',1''-terphenyl]-2'-ol (206 mg, 0.2 mmol, 1.0 equivalent) was added as a solid. The resulting mixture was stirred overnight at room temperature. The solvent was removed under vacuum to obtain a dark solid, which was washed with hexane (10 mL) and then extracted with toluene (12 mL). After filtration, the toluene extract was dried under vacuum. 170 mg of a white solid was recovered (yield 74%). 【0151】 11H NMR (400MHz, C6D6)δ 8.20-7.67(m,4H),7.79(t,J=1.8Hz,2H),7.56(d,J=2.5Hz,2H),7.26(d,J= 2.4,2H),7.21(d,J=2.4,2H),7.18(d,J=2.4,2H),5.67(d,J=8.6Hz,2H),4. 61(d,J=13.5Hz,2H),3.46(d,J=13.5Hz,2H),2.26(s,6H),1.47(s,36H),1. 25(s,18H),0.52(dd,J=17.0,7.5Hz,12H),0.30-0.18(m,2H),-0.05(s,6H). 【0152】 The metal-ligand complexes I1 to I8 have the structure shown in formula (I), and are as follows: 【0153】 [ka] 【0154】 [ka] 【0155】 Metal-ligand complexes C1 to C3 are comparative examples and are as follows. 【0156】 [ka] 【0157】 Example 2 - Polymerization Reaction Metal-ligand complexes (MLCs) I1-I8 were tested in a continuous polymerization process using MMAO-A1, MMAO-B, MMAO-C, MMAO-D1, MMAO-D2, MMAO-E, or MMAO-F as activators. The results were compared with comparative metal-ligand complexes C1-C3, and the data are summarized in Tables 2-9. 【0158】 [Table 1] * MMAO-A1 and A2 are modified with n-octyl substituents so that the methyl:n-octyl ratio is approximately 6:1. MMAO-B is modified with n-octyl substituents so that the methyl:n-octyl ratio is approximately 19:1. 【0159】 [Table 2] 【0160】 Polymerization was performed at a reactor temperature of 160°C with a continuous feed stream of ethylene at 3.4 kg / hour, 1-octene at 3.3 kg / hour, and ISOPAR E at 21 kg / hour. [A] The % solids content represents the concentration of the polymer in the reactor. [B] H2 (mol%) is defined as the mole fraction of hydrogen relative to the ethylene supplied to the reactor. Expressed as a percentage. [C] Eff. is polymer 10 6 It is measured as g / g of metal. 1 Reactor temperature = 153°C, continuous feed stream of ethylene at 2.5 kg / hour, 1-octene at 3.3 kg / hour, and ISOPAR E at 21 kg / hour. 2 [HNMe(C 18 H 37 )2][B(C6F5)4] was used at a molar ratio of 1.2 to the complex, and MMAO-D was used at the reported Al concentration in the reactor. 3 Reactor temperature = 190°C, continuous feed stream of ethylene at 4.6 kg / hour, 1-octene at 2.0 kg / hour, and ISOPAR E at 22 kg / hour. 【0161】 [Table 3] The entry numbers refer to Table 2. 【0162】 [Table 4] The entry numbers refer to Table 2. 【0163】 The data recorded in Tables 2 to 4 demonstrate that the catalyst of the present invention, when combined with an MMAO activator, produces polymers having a narrow MWD, as indicated by the U index, regardless of the MMAO activator. 【0164】 As the U index approaches 100, the fitting area and the sample area are similar, thus indicating a single-site catalyst. As previously mentioned, the substitution pattern of the catalyst system of the present invention is thought to prevent the formation of a second active site, thus resulting in a narrower compositional distribution. Furthermore, the narrower the compositional distribution, the smaller the expected B index. All examples of the present invention shown in Tables 3 and 4 exhibit a smaller B index than the comparative examples having unsubstituted crosslinks. 【0165】 To demonstrate the advantages of MMAO-A1, MMAO-B, and MMAO-C, continuous process data are shown in Tables 5 to 8. The density was varied by adjusting H2 to reach the desired polymer melt index. 【0166】 [Table 5] 【0167】 Polymerization at 160°C, continuous feed stream of 3.4 kg / hour of ethylene, 3.3 kg / hour of 1-octene, and 21 kg / hour of ISOPAR E, 14% solid, 81% ethylene conversion. Efficiency (Eff.) is 10% of polymer. 6 It is measured as g / g of metal. 【0168】 [Table 6] 【0169】 Polymerization at 160°C, continuous feed stream of 3.4 kg / hour of ethylene, 3.3 kg / hour of 1-octene, and 21 kg / hour of ISOPAR E, 14% solid, 81% ethylene conversion. Efficiency (Eff.) is 10% of polymer.6 It is measured as g / g of metal. 【0170】 [Table 7] 【0171】 Polymerization at 175°C, continuous feed stream of ethylene (3.3 kg / hour), 1.6 kg / hour, 1-octene (1.6 kg / hour), and ISOPAR E (22 kg / hour), 14% solid, 87% C2 conversion. Efficiency (Eff.) is 10% of polymer. 6 It is measured as g / g of metal. 【0172】 Figure 1 shows a graph of catalytic efficiency according to the type of cocatalyst. The efficiencies of metal-ligand complexes I1, I3, and I7 when used in combination with MMAO-A1, MMAO-B, and MMAO-C are greater than when used in combination with the comparative cocatalyst MMAO-D / borate. 【0173】 [Table 8] 【0174】 Polymerization at 175°C, continuous flow of ethylene at 140 lbs / hour, 1-octene at 30.7-35.0 lbs / hour, and ISOPAR E at 900 lbs / hour, 14% solid, 93.8% ethylene conversion rate. Eff. is 10⁻¹⁰ of polymer. 6 It is measured as g / g of metal. 【0175】 Equipment standards All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passing them through activated alumina and, in some cases, the Q-5 reactant. Solvents used in experiments conducted in nitrogen-filled glove boxes were further dried by storage on activated 4Å molecular sieves. Moisture-sensitive glassware for reactions was dried overnight in an oven before use. NMR spectra were recorded using a Varian 400-MR spectrometer and a VNMRS-500 spectrometer. LC-MS analysis was performed using a Waters e2695 separation module combined with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separation is performed using an XBridge C18 3.5 μm 2.1 × 50 mm column with a 5:95 to 100:0 acetonitrile and water gradient (containing 0.1% formic acid as an ionizing agent). HRMS analysis is performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8 μm 2.1 × 50 mm column in combination with an Agilent 6230 TOF mass spectrometer with electrospray ionization. 1 1H NMR data are reported as follows: chemical shift (multiplicity (br=broadline, s=monabyl, d=doubleline, t=triplet, q=quadlet, p=quintlet, sex=hexabyl, sept=heptlet, and m=multipleline), integral value, and assignment). 1 Chemical shifts in 1H NMR data are reported in ppm from internal tetramethylsilane (TMS, δ scale) to low field, using residual protons in the deuterated solvent as reference. 13 The 13C NMR data is 1 The determination is made using H decoupling, and the chemical shift is reported in ppm from tetramethylsilane (TMS, δ scale) to low magnetic field, using residual carbon in the deuterated solvent as the reference.

Claims

[Claim 1] A process for polymerizing olefin monomers, the process comprising reacting ethylene with one or more olefin monomers in the presence of a catalyst system, the catalyst system is A hydrocarbyl-modified methylaluminoxane having, based on the total number of moles of aluminum in the hydrocarbyl-modified methylaluminoxane, 11 mole percent or more and less than 50 mole percent of AlR Ａ１ R Ｂ１ R Ｃ１ where R Ａ１ R Ｂ１ and R Ｃ１ are each independently a linear (C １ -C ４０ ) alkyl, a branched (C ３ -C ４０ ) alkyl or a (C ６ -C ４０ ) aryl, and a hydrocarbyl-modified methylaluminoxane, One or more metal-ligand complexes according to formula (I): 【Chemistry 1】 [In the formula, M is titanium, zirconium, or hafnium. n is 1, 2, or 3. Each X is independent of (C １ ~C ２０ ) A monodentate ligand selected from hydrocarbyl, phenyl, benzyl, and halogens, The aforementioned metal-ligand complex is generally charge-neutral. R １ and R １６ These are independently selected from the group consisting of radicals having formula (II), radicals having formula (III), and radicals having formula (IV), 【Chemistry 2】 In the formula, R ３１～３５ , R ４１～４８ and R ５１～５９ Each of these independently is -H, (C １ ~C ２０ ) Hydrocarbyl, -Si(R Ｃ ) ３ , -Si[(C １ ~C ２０ ) Hydrocarbil] ３ , -OR Ｃ ,-SR Ｃ -CN, -CF ３ , or selected from halogen, R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , and R １５ These are independently -H, (C １ ~C ４０ ) Hydrocarbyl, (C １ ~C ４０ ) Heterohydrocarbyl, -Si(R Ｃ ) ３ , -OR Ｃ ,-SR Ｃ -CN, -CF ３ Selected from, and halogens, Y is CH ２ _CHR ２１ CR ２１ R ２２ , SiR ２１ R ２２ , or GeR ２１ R ２２ And R ２１ and R ２２ is, (C １ ~C ２０ ) is alkyl, However, (1) Y is CH ２ When R ８ and R ９ At least one of them is not -H, R Ｃ (C １ ~C ３０ ) Hydrocarbyl, (C １ ~C ３０ ) containing heterohydrocarbyl, or -H, The catalyst system is a polymerization process that does not contain a borate activator. [Claim 2] The hydrocarbyl-modified methylaluminoxane is less than 25 mole percent AlR based on the total number of moles of aluminum in the hydrocarbyl-modified methylaluminoxane. Ａ１ R Ｂ１ R Ｃ１ A polymerization process according to claim 1, comprising: [Claim 3] The polymerization process according to claim 1, wherein the hydrocarbyl-modified methylaluminoxane contains less than 15 mole percent of AlR A1 R B1 R C1 based on the total number of moles of aluminum in the hydrocarbyl-modified methylaluminoxane. [Claim 4] The polymerization process according to claim 1, wherein the hydrocarbyl-modified methylaluminoxane is a modified methylaluminoxane. [Claim 5] The polymerization process according to claim 1, wherein the aluminum to catalyst metal ratio is less than 500:

1. [Claim 6] The polymerization process according to claim 1, wherein the aluminum to catalyst metal ratio is less than 200:1 or less than 50:

1. [Claim 7] R ８ and R ９ At least one of them is (C １ ~C ４０ ) Hydrocarbyl, (C １ ~C ４０ The polymerization process according to claim 1, wherein the atom is a heterohydrocarbyl or halogen atom. [Claim 8] R ８ and R ９ At least one of them is (C １ ~C ５ The polymerization process according to claim 1, wherein the alkyl group is alkyl. [Claim 9] R １ and R １６ The polymerization process according to claim 1, wherein at least one of the is a radical having formula (III). [Claim 10] R ４２ and R ４７ is (C １ to C ２０ ) hydrocarbyl or -Si[(C １ to C ２０ ) hydrocarbyl] ３ or R ４３ and R ４６ is (C １ to C ２０ ) hydrocarbyl or -Si[(C １ to C ２０ ) hydrocarbyl] ３ The polymerization process according to claim 9, wherein [Claim 11] R １ and R １６ The polymerization process according to claim 1, wherein at least one of the is a radical having formula (II). [Claim 12] R ３２ and R ３４ is, (C １ ~C １２ ) Hydrocarbyl or -Si[(C １ ~C ２０ ) Hydrocarbil] ３ The polymerization process according to claim 11. [Claim 13] R １ and R １６ The polymerization process according to claim 1, wherein at least one of them is a radical having formula (IV). [Claim 14] R ５２ , R ５３ , R ５５ , R ５７ , and R ５８ At least two of them are (C １ ~C ２０ ) Hydrocarbyl or -Si[(C １ ~C ２０ ) Hydrocarbil] ３ The polymerization process according to claim 13. [Claim 15] R ３ and R １４ is, (C １ ~C ２０ The polymerization process according to claim 1, wherein the alkyl group is alkyl. [Claim 16] R ６ and R １１ The polymerization process according to claim 1, wherein is tert-butyl. [Claim 17] R ３ and R １４ The polymerization process according to claim 1, wherein is tert-octyl or n-octyl. [Claim 18] The olefin monomer is (C ３ ~C ２０ The polymerization process according to claim 1, wherein the material is an α-olefin. [Claim 19] The polymerization process according to claim 1, wherein the olefin monomer is a cyclic olefin. [Claim 20] The polymerization process according to claim 1, wherein the polymerization process is a solution polymerization reaction.

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