Hydrocarbyl-Modified Methylaluminoxane Cocatalyst for Bis-Phenylphenoxy Metal-Ligand Complexes

Abstract

A process for polymerizing olefin monomers, comprising reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system, the catalyst system comprising less than 25 mole percent of a trihydrocarbyl aluminum compound, AlR, based on the total moles of aluminum. A1 R B1 R C1 wherein 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).

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims priority to U.S. Provisional Patent Application No. 63 / 053,342, filed Jul. 17, 2020, the entire disclosure of which is incorporated herein by reference.

[0002] (Field of the Invention) Embodiments of the present disclosure generally relate to hydrocarbyl - modified methylaluminoxane activators for catalyst systems comprising bis - phenylphenoxy metal - ligand complexes.

Background Art

[0003] Since the discovery of Ziegler and Natta regarding heterogeneous olefin polymerization, the world's polyolefin production has reached approximately 150 million tons per year in 2015, which has been increasing due to the increasing market demand. This success is partially based on a series of important elucidations in cocatalyst technology. The discovered cocatalysts include aluminoxanes, boranes, and boronic acids, including triphenylcarbenium or ammonium cations. These cocatalysts activate homogeneous single - site olefin polymerization procatalysts, and polyolefins are manufactured in the industry using these cocatalysts.

[0004] As part of the catalyst composition in α - olefin polymerization reactions, the activator can have beneficial characteristics for the production of α - olefin polymers and the final polymer compositions containing α - olefin polymers. Characteristics of activators that increase the production of α - olefin polymers include, but are not limited to, rapid activation of the procatalyst, high catalyst efficiency, high - temperature performance, consistent polymer composition, and selective deactivation.

[0005] In particular, borate cocatalysts have significantly contributed to the fundamental understanding of olefin polymerization mechanisms and have improved 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 has spurred the development of new homogeneous olefin polymerization catalyst systems capable of precisely controlling the microstructure and properties of polyolefins. However, when the cation of an activator or cocatalyst activates the precatalyst, the counterion of the activator may remain in the polymer composition. As a result, borate anions may affect the polymer composition. Specifically, the size and charge of the borate anion, the interaction of the borate anion with the surrounding medium, and the dissociation energy of the borate anion with the available counterions will likely affect the ability of ions to diffuse through the surrounding medium such as a solvent, gel, or polymer material.

[0006] Modified methylaluminoxane (MMAO) can be described as a mixture of an aluminoxane structure and trihydrocarbyl aluminum species. Trihydrocarbyl aluminum species such as trimethylaluminum are used as scavengers to remove impurities in the polymerization process that can contribute to the deactivation of olefin polymerization catalysts. However, trihydrocarbyl aluminum species are thought to be active in some polymerization systems. Catalyst inhibition 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 obfuscate the differences between MAO activation and borate activation and only have the potential to capture differences between some trimethylaluminum and none in direct comparisons. Furthermore, it is not clear whether such observations extend to other catalyst systems, ethylene polymerization, or polymerizations carried out at higher temperatures. Nevertheless, the preference for soluble MAO requires the use of MMAO and thus the presence of trihydrocarbyl aluminum species.

[0007] Modified methylaluminoxane (MMAO) is used as an activator in some PE processes instead of a boric acid-based activator. However, MMAO has been found to have an adverse effect on the performance of some catalysts, such as some bis-phenylphenoxypro catalysts, and has an adverse effect on the production of polymer resins. The adverse effects on the polymerization process include a decrease in catalyst activity, an expansion of the composition distribution of the produced polymer, and an adverse effect on the handling of pellets.

Summary of the Invention

[0008] There is a continuing need to create catalyst systems while maintaining catalyst efficiency, reactivity, and the ability to produce polymers with good physical properties.

[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 hydrocarbyl-modified methylaluminoxane and a metal-ligand complex. Based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane, less than 25 mole percent of a trihydrocarbyl aluminum compound AlR A R B R C having a hydrocarbyl-modified methylaluminoxane, wherein in the formula, R A , R B , and R C are independently (C1-C 40 ) alkyl, a hydrocarbyl-modified methylaluminoxane, and one or more metal-ligand complexes according to formula (I).

Chemical formula

[0010] In formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 are independently -H, a (C1 - C 40 ) hydrocarbyl, a (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 CC(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, and are selected from the group consisting of halogen.

[0011] In formula (I), R 1 and R 16 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 )2NC(O)-, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV).

Chemical formula

[0012] 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

[0013]

Figure 1

Figure 2

Figure 3

Figure 4

Modes for Carrying Out the Invention

[0014] Here, specific embodiments of the catalyst system are described. It should be understood that the catalyst system of the present disclosure may be implemented in different forms and should not be construed as being 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.

[0015] General abbreviations are listed below.

[0016] 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: Trifluoromethanesulfonic acid, 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: n-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: Mole, min or mins: Minute; h or hrs: Hour, d: Day.

[0017] 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.

[0018] The term "procatalyst" refers to a transition metal compound that has olefin polymerization catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with the procatalyst to convert the procatalyst into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms.

[0019] When used to describe a particular carbon atom-containing chemical group, the parenthetical expression in the form of "(C x ~C y )" means that the unsubstituted form of the chemical group has from x to y carbon atoms. For example, (C1~C 50 )alkyl is an alkyl group having from 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, a particular chemical group may be substituted by one or more substituents such as R S . A chemical group substituted by R x ~C y defined using the parenthetical "(C S )" may contain more than y carbon atoms depending on the identity of any group R S . For example, "(C1~C S )alkyl substituted by exactly one R 50 group (R S is phenyl (-C6H5))" may contain from 7 to 56 carbon atoms. Thus, generally, when a chemical group defined using the parenthetical "(C x ~C y )" is substituted by a substituent R S containing one or more carbon atoms, the minimum and maximum total number of carbon atoms of the chemical group is determined by adding to both x and y the total number of carbon atoms from all carbon atom-containing substituents R S .

[0020] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R SIt means being replaced by . The term "-H" means hydrogen or a hydrogen radical that is covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0021] "(C1-C 50 ) alkyl" means a saturated straight-chain or branched hydrocarbon radical containing 1 to 50 carbon atoms, and the term "(C1-C 30 ) alkyl" means a saturated straight-chain or branched hydrocarbon radical of 1 to 30 carbon atoms. Each (C1-C 50 ) alkyl and (C1-C 30 ) alkyl can be unsubstituted or substituted with one or more R S . In some examples, each hydrogen atom in the hydrocarbon radical can be substituted with an R S such as trifluoromethyl. Examples of unsubstituted (C1-C 50 ) alkyl are unsubstituted (C1-C 20 ) alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. Examples of substituted (C1-C 40 ) alkyl are substituted (C1-C 20 ) alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 alkyl. The term "[C 45 alkyl" means that there are up to 45 carbon atoms (including substituents) in the radical, for example, (C1-C5) alkyl such as methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl, substituted by one R S , for example, (C 27 ~C 40 ) alkyl.

[0022] (C3-C 50) The term "alkenyl" means a branched or unbranched, cyclic or acyclic monovalent hydrocarbon radical containing 3 to 50 carbon atoms, at least one double bond, and being unsubstituted or substituted by one or more R S s. Unsubstituted (C3-C 50 ) alkenyl examples: n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, and cyclohexadienyl. Substituted (C3-C 50 ) alkenyl examples: (2-trifluoromethyl)pent-1-enyl, (3-methyl)hex-1-enyl, (3-methyl)hexa-1,4-dienyl, and (Z)-1-(6-methylhept-3-en-1-yl)cyclohex-1-enyl.

[0023] The term "(C3-C 50 ) cycloalkyl" means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms that is unsubstituted or substituted by one or more R S s. Other cycloalkyl groups (e.g., (C x -C y ) cycloalkyl) are defined in a similar manner as having x to y carbon atoms and being either unsubstituted or substituted by one or more R S s. Examples of unsubstituted (C3-C 40 ) cycloalkyl are unsubstituted (C3-C 20 ) cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3-C 40 ) cycloalkyl are substituted (C3-C 20 ) cycloalkyl, substituted (C3-C 10 ) cycloalkyl, and 1-fluorocyclohexyl.

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

[0025] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. When a saturated chemical group is substituted by one or more substituents R S , one or more double or triple bonds may optionally be present in the substituent R S . The term "unsaturated" means 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, and does not include double bonds that may be present in the substituent R S (if present), or in an aromatic or heteroaromatic ring (if present).

[0026] The term "hydrocarbyl-modified methylaluminoxane" refers to a methylaluminoxane (MMAO) structure that contains an amount of trihydrocarbylaluminum. Hydrocarbyl-modified methylaluminoxane comprises a combination of a hydrocarbyl-modified methylaluminoxane matrix and trihydrocarbylaluminum. The total molar amount of aluminum in the hydrocarbyl-modified methylaluminoxane is composed 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 the trihydrocarbylaluminum. Hydrocarbyl-modified methylaluminoxane contains more than 2.5 mole percent of trihydrocarbylaluminum based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane. These additional hydrocarbyl substituents can affect the subsequent aluminoxane structure and can result in differences in the distribution and size of the aluminoxane clusters (Bryliakov, K.P et.al. Macromol.Chem.Phys. 2006, 207, 327-335). The additional hydrocarbyl substituents can also increase the solubility of the aluminoxane in hydrocarbon solvents such as, but not limited to, hexane, heptane, methylcyclohexane, and ISOPAR E (trademark) as demonstrated in U.S. Patent No. 5,777,143. Modified methylaluminoxane compositions are generally disclosed and can be prepared as described in U.S. Patent No. 5,066,631 and U.S. Patent No. 5,728,855, both of which are incorporated herein by reference.

[0027] Embodiments of the disclosure include a process for polymerizing an olefin monomer. In one or more embodiments, the process includes reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system.

[0028] In some embodiments, the olefin monomer is a (C3-C 20 ) α-olefin. In other embodiments, the olefin monomer is a (C3-C 20)It is not an α-olefin. In various embodiments, the olefin monomer is a cyclic olefin.

[0029] In one or more embodiments, the catalyst system includes a hydrocarbyl-modified methylaluminoxane and a metal-ligand complex. The hydrocarbyl-modified methylaluminoxane has less than 25 mole percent of trihydrocarbylaluminum based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane. The trihydrocarbylaluminum has the formula AlR A1 R B1 R C1 wherein R A1 , R B1 , and R C1 are independently (C1-C 40 ) alkyl.

[0030] In embodiments, the hydrocarbyl-modified methylaluminoxane in the polymerization process has less than 20 mole percent and more than 5 mole percent of trihydrocarbylaluminum based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane. In some embodiments, the hydrocarbyl-modified methylaluminoxane has less than 15 mole percent of trihydrocarbylaluminum based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane. In one or more embodiments, the hydrocarbyl-modified methylaluminoxane has less than 10 mole percent of trihydrocarbylaluminum based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane. In various embodiments, the hydrocarbyl-modified methylaluminoxane is a modified methylaluminoxane.

[0031] In some embodiments, the trihydrocarbylaluminum has the formula AlR A1 R B1 R C1 wherein R A1 , R B1 , and R C1 are independently (C1-C 10 ) alkyl. In one or more embodiments, RA1 , R B1 , and R C1 is independently methyl, ethyl, propyl, 2-propyl, butyl, tert-butyl, or octyl. In some embodiments, R A1 , R B1 , and R C1 are the same. In other embodiments, at least one of R A1 , R B1 , and R C1 is different from the other R A1 , R B1 , and R C1 .

[0032] In embodiments, the catalyst system comprises a hydrocarbyl-modified methylaluminoxane and a metal-ligand complex. In some embodiments, the catalyst system comprises one or more metal-ligand complexes according to formula (I). [Chemical formula] In formula (I), M is titanium, zirconium, hafnium, scandium, yttrium, or an element of the lanthanide series of the periodic table having an oxidation number in the form of +2, +3, or +4. In some embodiments, M is Zr or Sc.

[0033] (X) n The subscript n of is 1, 2, or 3. Each X is an unsaturated (C2-C 50 ) hydrocarbon, an unsaturated (C2-C 50 ) heterohydrocarbon, a saturated (C2-C 50 ) heterohydrocarbon, a (C1-C 50 ) hydrocarbyl, a (C6-C 50 ) aryl, a (C6-C 50 ) heteroaryl, a cyclopentadienyl, a substituted cyclopentadienyl, a (C4-C 12 ) diene, a halogen, -N(R N )2, and -N(R N )COR CIt is a monodentate ligand independently selected therefrom. The metal-ligand complex is overall charge-neutral. Each Z is independently selected from -O-, -S-, -N(R N )-, or -P(R P )-. L is a (C1-C 40 ) hydrocarbylene or a (C2-C 40 ) heterohydrocarbylene.

[0034] In formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 are independently -H, a (C1-C 40 ) hydrocarbyl, a (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 )2NC(O)-, and halogen.

[0035] In formula (I), R 1 and R 16 are independently -H, a (C1-C 40 ) hydrocarbyl, a (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(RN ) 2. -OR C . -SR C . -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, -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).

Chemical formula

[0036] In formulas (I), (II), (III), and (IV), each R C , R P , and R N is independently (C1-C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or -H.

[0037] In one or more embodiments, the metal-ligand complex of formula (I) is a precatalyst.

[0038] In some embodiments, the groups R 1 and R 16 in the metal-ligand complex of formula (I) are independently selected from each other. For example, R 1 may be selected from radicals having formula (II), (III), or (IV), and R 16 may be (C1-C 40 ) hydrocarbyl, or R 1 may be selected from radicals having formula (II), (III), or (IV), and R 16 may be selected from radicals having formula (II), (III), or (IV), and may be the same as or different from that of R 1 . Both R 1 and R 16 may be radicals having formula (II), in which case the group R 31-35 is the same as or different from that in R 1 and R 16 . In other examples, both R 1 and R 16 may be radicals having formula (III), in which case the group R 41-48 is the same as or different from that in R 1 and R 16 , or both R 1 and R 16 may be radicals having formula (IV), in which case the group R 51-59 is the same as or different from that in R 1 and R 16 .

[0039] In some embodiments, R 1 and R 16 at least one of which is a radical having formula (II), where R 32 and R 34 are tert-butyl. In one or more embodiments, R 32 and R 34 are (C1-C 12 ) hydrocarbyl or -Si[(C1-C 10 ) alkyl]3.

[0040] In some embodiments, when at least one of R 1 or R 16 is a radical having formula (III), one or both of R 43 and R 46 are tert-butyl, and R 41~42 , R 44~45 and R 47~48 are -H. In other embodiments, one or both of R 42 and R 47 are tert-butyl, and R 41 , R 43~46 and R 47~48 are -H. In some embodiments both R 42 and R 47 are -H. In various embodiments, R 42 and R 47 are (C1-C 20 ) hydrocarbyl or -Si[(C1-C 10 ) alkyl]3. In other embodiments, R 43 and R 46 are (C1-C 20 ) hydrocarbyl or -Si[(C1-C 10 ) alkyl]3.

[0041] In an embodiment, when at least one of R 1 or R 16 is a radical having formula (IV), each R 52 , R 53 , R 55 , R 57 and R58 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 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 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 are (C3-C 10 ) alkyl, -Si[(C3-C 10 ) alkyl]3, or -Ge[(C3-C 10 ) alkyl]3.

[0042] In some embodiments, when at least one of R 1 or R 16 is a radical having formula (IV), at least two of R 52 , R 53 , R 55 , R 57 , and R 58 are (C1-C 20 ) hydrocarbyl or -Si[(C1-C 20 ) hydrocarbyl]3.

[0043] (C3-C10 ) Examples of alkyl include, but are not limited to, 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.

[0044] In formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 are independently selected from -H, (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 )2NC(O)-, and halogen.

[0045] In one or more embodiments, R 2 , R 4 , R 5 , R 12 , R 13 , and R 15 are hydrogen, and each Z is oxygen.

[0046] In various embodiments, R 5 , R 6 , R 7 , and R 8 of at least one of them is a halogen atom, and R 9 , R 10 , R 11 , and R 12 of at least one of them is a halogen atom. In some embodiments, R 8 and R 9 are independently (C1-C4) alkyl.

[0047] In some embodiments, R 3 and R 14 are (C1-C 20 ) alkyl. In one or more embodiments, R 3 and R 14 are methyl, and R 6 and R 11 are halogen. In an embodiment, R 6 and R 11 are tert-butyl. In other embodiments, R 3 and R 14 are tert-octyl or n-octyl.

[0048] In various embodiments, R 3 and R 14 are (C1-C 24 ) alkyl. In one or more embodiments, R 3 and R 14 are (C4-C 24 ) alkyl. In some embodiments, R 3 and R 14 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 an embodiment, R 3and R 14 is -OR C and R C is (C1-C 20 ) hydrocarbon, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), or 1,1-dimethylethyl.

[0049] In one or more embodiments, one of R 8 and R 9 is not -H. In various embodiments, at least one of R 8 and R 9 is (C1-C 24 ) alkyl. In some embodiments, both R 8 and R 9 are (C1-C 24 ) alkyl. In some embodiments, R 8 and R 9 are methyl. In other embodiments, R 8 and R 9 are halogen.

[0050] In some embodiments, R 3 and R 14 are methyl. In one or more embodiments, R 3 and R 14 are (C4-C 24 ) alkyl. In some embodiments, R 3 and R 14 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.

[0051] In various embodiments, in the metal-ligand complex of formula (I), R 6 and R 11is a halogen. In some embodiments, R 6 and R 11 are (C1-C 24 ) alkyl. In various embodiments, R 6 and R 11 are independently selected from methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, n-pentyl, 3-methylbutyl, n-hexyl, 4-methylpentyl, n-heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. In some embodiments, R 6 and R 11 are tert-butyl. In an embodiment, R 6 and R 11 are -OR C , and R C is (C1-C 20 ) hydrocarbon, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), or 1,1-dimethylethyl. In other embodiments, R 6 and R 11 are -SiR C 3, wherein each R C is independently (C1-C 20 ) hydrocarbyl, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), or 1,1-dimethylethyl.

[0052] In some embodiments, any or all of the chemical groups (e.g., X and R 1-59 ) of the metal-ligand complex of formula (I) may be unsubstituted. In other embodiments, either none or one or more of the chemical groups X and R 1-59 of the metal-ligand complex of formula (I) may be unsubstituted with one or more RS, or any or all of them may be substituted with one or more RS. Two or three or more RS When it is bonded to the same chemical group of the metal-ligand complex of formula (I), the individual R of the chemical group S may be bonded to the same carbon atom or heteroatom, or to different carbon atoms or heteroatoms. In some embodiments, neither of the chemical groups X and R 1-59 is oversubstituted with R S , or any or all of them may be oversubstituted with R S . In a chemical group oversubstituted with R S , the individual R S may all be the same or may be independently selected. In one or more embodiments, R S is selected from (C1-C 20 ) hydrocarbyl, (C1-C 20 ) alkyl, (C1-C 20 ) heterohydrocarbyl, or (C1-C 20 ) heteroalkyl.

[0053] In formula (I), L is (C1-C 40 ) hydrocarbylene or (C1-C 40 ) heterohydrocarbylene, and each Z is independently selected from -O-, -S-, -N(R N )-, or -P(R P )-. In one or more embodiments, L contains 1 to 10 atoms.

[0054] 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.

[0055] In some embodiments of formula (I), L is, for example, -CH2CH2CH2-, -CH(CH3)CH2C * H(CH3), -CH(CH3)CH(CH3)C *It may be selected from (C3-C7) alkyl 1,3-diradicals such as H(CH3), -CH2C(CH3)2CH2-, cyclopentane-1,3-diyl, or cyclohexane-1,3-diyl. In some embodiments, L is, for example, -CH2CH2CH2CH2-, -CH2C(CH3)2C(CH3)2CH2-, cyclohexane-1,2-diyldimethyl, and bicyclo[2.2.2]octane-2,3-diyldimethyl, etc. (C4-C 10 ) alkyl 1,4-diradicals. In some embodiments, L is (C5-C 12 ) alkyl 1,5-diradicals, for example, -CH2CH2CH2CH2CH2-, and 1,3-bis(methylene)cyclohexane. In some embodiments, L is, for example, (C6-C 14 ) alkyl 1,6-diradicals, for example, -CH2CH2CH2CH2CH2CH2-, or 1,2-bis(ethylene)cyclohexane.

[0056] In one or more embodiments, L is a (C2-C 40 ) heterohydrocarbylene. In some embodiments, L is -CH2Ge(R C )2CH2-, wherein each R C is a (C1-C 30 ) hydrocarbyl. In some embodiments, L is -CH2Ge(CH3)2CH2-, -CH2Ge(ethyl)2CH2-, -CH2Ge(2-propyl)2CH2-, -CH2Ge(t-butyl)2CH2-, -CH2Ge(cyclopentyl)2CH2-, or -CH2Ge(cyclohexyl)2CH2-.

[0057] In one or more embodiments, L is -CH2-, -CH2CH2-, -CH2(CH2) m CH2-, CH2(C(H)R C ) m CH2-, and -CH2(CR C ) m CH2- (where the subscript m is 1-3), ~CH2Si(R C )2CH2-, -CH2Ge(RC ) 2CH2-, -CH(CH3)CH2CH * (CH3), and -CH2(phen-1,2-di-yl)CH2- selected from, each R in L C is, (C1~C 20 ) hydrocarbyl.

[0058] Such (C1~C 12 ) alkyl examples include methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl, cyclopentyl, or cyclohexyl, butyl, tert-butyl, pentyl, hexyl, heptyl, n-octyl, tert-octyl (2,4,4-trimethylpent-2-yl), nonyl, decyl, undecyl, and dodecyl, but are not limited thereto.

[0059] In some embodiments, in the metal-ligand complex according to formula (I), R 8 and R 9 both are methyl. In other embodiments, one of R 8 and R 9 is methyl, and the other of R 8 and R 9 is -H.

[0060] In the metal-ligand complex according to formula (I), X is bonded to M through a covalent bond or an ionic bond. In some embodiments, X can be a monoanionic ligand having a net formal oxidation number of -1. Each monoanionic ligand is independently hydride, (C1~C 40 ) hydrocarbyl carbanion, (C1~C 40 ) hetero hydrocarbyl 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 - and may be, wherein each R K , R L , and R M is independently hydrogen, (C1-C 40 ) hydrocarbyl, or (C1-C 40 ) heterohydrocarbyl, or R K and R L together form a (C2-C 40 ) hydrocarbylene or a (C1-C 20 ) heterohydrocarbylene, and R M is as defined above.

[0061] In some embodiments, X is halogen, unsubstituted (C1-C 20 ) hydrocarbyl, unsubstituted (C1-C 20 ) hydrocarbyl C(O)O-, or R K R L N-, wherein each of R K and R L is independently unsubstituted (C1-C 20 ) hydrocarbyl. In some embodiments, each monodentate ligand X is a chlorine atom, a (C1-C 10 ) hydrocarbyl (e.g., (C1-C6) alkyl or benzyl), an unsubstituted (C1-C 10 ) hydrocarbyl C(O)O-, or R K R L N-, wherein each of R K and R L is independently unsubstituted (C1-C10 ) is hydrocarbyl.

[0062] In a further embodiment, X is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, or chloro. X may be different ones of 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 Xs are independently monoanionic monodentate ligands. In a particular embodiment, n is 2 and the two X groups together form a bidentate ligand. In a further embodiment, the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

[0063] In one or more embodiments, each X is independently -(CH2)SiR X 3, where each R X is independently (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl, and at least one R X is (C1-C 30 ) alkyl. In some embodiments, when one of the Rs X is (C1-C 30 ) heteroalkyl, the heteroatom is a silica or oxygen atom. In some embodiments, R X is methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or, tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl.

[0064] 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 that are covalently bonded or exactly three R X that are covalently bonded.

[0065] 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 , where the subscript Q is 0, 1, 2, or 3, and each R C is independently a substituted or unsubstituted (C1-C 30 ) hydrocarbyl or a substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl.

[0066] Co-catalyst component The catalyst system comprising the metal-ligand complex of formula (I) can be catalytically activated by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, the precatalyst by the metal-ligand complex of formula (I) can be catalytically activated by contacting the complex with an activating cocatalyst or by combining the complex with an activating cocatalyst. Further, the metal-ligand complex according to formula (I) includes both a neutral precatalyst type and a catalyst type that can be positively charged due to the loss of a monoanionic ligand such as methyl, benzyl or phenyl. Suitable activating cocatalysts for use herein include oligomeric aluminoxane or hydrocarbyl-modified methylaluminoxane.

[0067] In embodiments, the catalyst system does not contain a borate activator. In one or more embodiments, the borate activator is the tetrakis(pentafluorophenyl)borate(1-) anion and a counter cation. In some embodiments, the borate activator is bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate.

[0068] Polyolefin The catalyst systems described in the preceding paragraphs are utilized in 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, producing a homopolymer. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin comonomers typically have 20 or fewer carbon atoms. For example, the 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.

[0069] Ethylene-based polymers, such as homopolymers and / or interpolymers (including copolymers) of ethylene, and optionally 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 subsumed within "at least 50 mole percent" are disclosed herein as separate embodiments. For example, ethylene-based polymers, homopolymers and / or interpolymers (including copolymers) of ethylene, and optionally one or more comonomers such as α-olefins, may contain at least 60 mole percent, at least 70 mole percent, at least 80 mole percent, or 50 to 100 mole percent, or 80 to 100 mole percent of monomer units derived from ethylene.

[0070] In some embodiments, the ethylene-based polymer may contain at least 90 mole percent of units derived from ethylene. All individual values and subranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer may contain at least 93 mole percent of units, at least 96 mole percent of units, at least 97 mole percent of units derived from ethylene, or alternatively, 90 to 100 mole percent of units derived from ethylene, 90 to 99.5 mole percent of units derived from ethylene, or 97 to 99.5 mole percent of units derived from ethylene.

[0071] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50%, in other embodiments, it includes at least 1 mole percent (mol%) to 25 mol%, and in further embodiments, the amount of additional α-olefin includes at least 5 mol% to 100 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0072] Any conventional polymerization process may be used to produce the ethylene-based polymer. Such conventional polymerization processes include, for example, solution polymerization processes, slurry-phase polymerization processes, and combinations thereof that use one or more conventional reactors such as loop reactors, isothermal reactors, stirred tank reactors, batch reactors, etc. in parallel, series, or any combination thereof, but are not limited thereto.

[0073] In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, such as a dual loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized in the presence of the catalyst system described herein and optionally one or more cocatalysts. In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, such as a dual loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized in the presence of the catalyst systems disclosed and described herein and optionally one or more other catalysts. The catalyst systems described herein can be used, optionally in combination with one or more other catalysts, in the first reactor or the second reactor. In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, such as a dual loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized in both reactors in the presence of the catalyst system described herein.

[0074] In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single reactor system, such as a single loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized in the presence of the catalyst systems described within the disclosure and optionally one or more cocatalysts described in the previous paragraph.

[0075] The ethylene-based polymer may further contain one or more additives. Such additives include, but are not limited to, antistatic agents, color intensifiers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, ultraviolet stabilizers, and combinations thereof. The ethylene-based polymer may contain any amount of additives. The ethylene-based polymer may contain such additives in a total amount of about 0 to about 10 weight percent, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further contain a filler, and examples of such fillers include, but are not limited to, organic or inorganic fillers. The ethylene-based polymer may contain a filler in an amount of about 0 to about 20 weight percent, such as calcium carbonate, talc, or Mg(OH)2, based on the total weight of the ethylene-based polymer and all additives or fillers. The ethylene-based polymer may be further blended with one or more polymers to form a blend.

[0076] In some embodiments, the polymerization process for producing the ethylene-based polymer may include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system according to the present disclosure. The polymer obtained from such a catalyst system incorporating the metal-ligand complex of formula (I) has, according to ASTM D792 (incorporated herein by reference in its entirety), for example, a density of 0.850 g / cm 3 to 0.970 g / cm 3 , 0.880 g / cm 3 to 0.920 g / cm 3 , 0.880 g / cm 3 to 0.910 g / cm 3 , or 0.880 g / cm 3 to 0.900 g / cm 3 , 0.950 g / cm 3 to 0.965 g / cm 3 .

[0077] In another embodiment, the polymer obtained from the catalyst system according to the present disclosure has a melt flow ratio (I 10has an Melt Index I2, and the Melt Index I2 is measured at 190 °C and a load of 2.16 kg according to ASTM D1238 (incorporated herein by reference in its entirety), and the Melt Index I 10 is measured at 190 °C and a load of 10 kg according to ASTM D1238. In other embodiments, the Melt Flow Ratio (I 10 / I2) is from 5 to 10, and in other embodiments, the Melt Flow Ratio is from 5 to 9.

[0078] In some embodiments, the polymer obtained from the catalyst system according to the present disclosure has a molecular weight distribution (MWD) of from 1 to 25, and the MWD is defined as M w / M n where M w is the weight average molecular weight and M n is the number average molecular weight. In other embodiments, the polymer obtained from the catalyst system has an MWD of from 1 to 6. Another embodiment includes an MWD of from 1 to 3, and other embodiments include an MWD of from 1.5 to 2.5.

[0079] The embodiments of the catalyst system described in the present disclosure result in a catalyst system having high efficiency as compared to a catalyst system lacking a hydrocarbyl-modified methylaluminoxane.

[0080] One or more features of the present disclosure are illustrated in view of the following examples.

Examples

[0081] Procedure for continuous process reactor polymerization: The raw materials (ethylene, 1-octene) and the process solvent (a narrow-boiling-range high-purity isoparaffin solvent commercially available under the trademark ISOPAR E from ExxonMobil Corporation) were purified with molecular sieves before being introduced into the reaction environment. Hydrogen was supplied in a pressurized cylinder as a high-purity grade and not further purified. The reactor monomer feed (ethylene) stream was pressurized until it exceeded the reaction pressure. The solvent and comonomer feeds were pressurized until they exceeded the reaction pressure. The individual catalyst components (metal ligand complex and cocatalyst) were manually batch-diluted to the specified component concentrations using the purified solvent and pressurized until they exceeded the reaction pressure. All reaction feed streams were measured using mass flow meters and independently controlled by a valve control system automated by a computer.

[0082] Continuous solution polymerization is carried out in a continuously stirred-tank reactor (CSTR). The combined feed of solvent, monomer, comonomer, and hydrogen to the reactor is temperature-controlled between 5°C and 50°C, typically 15 - 25°C. All of the components are fed to the polymerization reactor together with the solvent feed. The catalyst is fed to the reactor to reach a specific conversion of ethylene. The cocatalyst component is fed separately based on the calculated specified molar ratio or ppm ratio. The effluent from the polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and polymer) exits the reactor and contacts water. Additionally, various additives such as antioxidants can be added at this point. The stream is then passed through a static mixer to uniformly disperse the mixture.

[0083] Following the addition of the additive, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the temperature of the stream in preparation for the separation of the polymer from other low-boiling components. The stream is then passed through a reactor pressure control valve where the pressure is significantly reduced overall. 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, monomer, comonomer, and water are removed from the polymer. At the exit of the extruder, the strands of the formed 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.

[0084] Procedure for batch reactor polymerization. The raw materials (ethylene, 1-octene) and the process solvent (ISOPAR E) are purified with molecular sieves before being introduced into the reaction environment. The stirred autoclave reactor was charged with ISOPAR E and 1-octene. The reactor was then heated to a certain temperature and filled with ethylene to reach a desired pressure. Optionally, hydrogen was also added. The catalyst system was prepared in a dry box under an inert atmosphere by mixing a metal-ligand complex and optionally one or more additives with an additional solvent. The catalyst system was then injected into the reactor. The pressure and temperature of the reactor were kept constant by supplying ethylene during the polymerization and cooling the reactor as necessary. After 10 minutes, the supply of ethylene was stopped and the solution was transferred to a resin kettle purged with nitrogen. The polymer was thoroughly dried in a vacuum oven and the reactor was thoroughly rinsed with hot ISOPAR E during the polymerization experiment.

[0085] Test Methods Unless otherwise specifically indicated herein, the following analytical methods are used in the description of the embodiments of the present disclosure.

[0086] Melt Index The melt index I2 (or I2) and I of the polymer sample 10(Or I10) was measured according to ASTM D-1238 (Method B) at 190 °C and loads of 2.16 kg and 10 kg, respectively. Report those values in g / 10 min.

[0087] Density Samples for density measurement were prepared according to ASTM D4703. The measurement was carried out according to ASTM D792, Method B within 1 hour of sample pressurization.

[0088] Gel Permeation Chromatography (GPC) The chromatography system consisted of a high-temperature GPC chromatograph of PolymerChar GPC-IR (Valencia, Spain) equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set at 160 °C and the column compartment was set at 150 °C. Four Agilent "Mixed A" 30 cm 20 micron linear mixed-bed columns and a 20 um precolumn were used for the columns. The chromatography solvent used was 1,2,4-trichlorobenzene and contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen-sparged. The injection volume used was 200 microliters and the flow rate was 1.0 milliliter / minute.

[0089] The calibration of the GPC column set was performed using 21 narrow molecular weight distribution polystyrene standards having molecular weights in the range of 580 to 8,400,000 and placed in six “cocktail” mixtures having at least a 10-fold interval between individual molecular weights. The standards were purchased from Agilent Technologies. For molecular weights above 1,000,000, the polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent, and for molecular weights below 1,000,000, at 0.05 grams in 50 milliliters of solvent. 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 Equation 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) Where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0090] A fifth-degree polynomial was used to fit to each polyethylene equivalent calibration point. A slight adjustment (about 0.375 - 0.445) was made to A to correct for column resolution and band broadening effects such that a linear homopolymer polyethylene standard gave 120,000 Mw.

[0091] The total plate count of the GPC column set was performed using decane (prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20 minutes with gentle stirring). The plate count (Equation 2) and symmetry (Equation 3) were measured with a 200 microliter injection according to the following equations.

[0092]

Number

[0093]

Number

[0094] Wherein, RV is the retention volume (in milliliters), the peak width is in milliliters, the peak maximum is the maximum position of the peak, the one-tenth height is the height that is one-tenth of the peak maximum, the trailing peak refers to the peak tail at the retention volume after the peak maximum, and the leading peak refers to the peak front at the retention volume earlier than the peak maximum. The plate count of the chromatography system should be more than 18,000, and the symmetry should be between 0.98 and 1.22.

[0095] The sample was prepared in a semi-automatic mode using PolymerChar "Instrument Control" software, with 2 mg / mL as the target weight of the sample. Through the PolymerChar high-temperature autosampler, a solvent (containing 200 ppm of BHT) was added to a vial with a septum cap that had been pre-nitrogen sparged. The sample was dissolved at 160 degrees Celsius for 2 hours under "low-speed" shaking.

[0096] Mn (GPC) , Mw (GPC) and Mz (GPC) The calculations of were based on the GPC results using PolymerChar GPCOne (trademark) software, the IR chromatogram with the baseline subtracted at each equally spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) of Equation 1, and using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph in accordance with Equations 4 to 6.

[0097]

Number

[0098] To monitor the deviation over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. Using this flow rate marker (FM), the pump flow rate (apparent flow rate) of each sample was linearly corrected by RV-aligning each decane peak in the sample (RV(FM sample)) with that of the decane peak within the narrow standard calibration (RV(FM calibrated)). Subsequently, any change in the time of the decane marker peak is presumed to be related to a linear shift in the flow rate (effective flow rate) over the course of the run. To facilitate the highest accuracy in RV measurement of the flow rate marker peak, a least-squares fitting routine that fits the peak of the flow rate marker concentration chromatogram to a quadratic equation is used. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on the peak of the flow rate marker, the effective flow rate (relative to the narrow standard calibration) is calculated as shown in Equation 7. The processing of the flow rate marker peak was performed via PolymerChar GPCOne (trademark) software. The acceptable flow rate correction should be such that the effective flow rate should be within + / - 0.5% of the apparent flow rate. Effective flow rate = Apparent flow rate * (RV(FM calibrated) / RV(FM sample)) (Equation 7)

[0099] Analysis of Hydrocarbyl-Modified Methylaluminoxane Example 1 is an analytical procedure for determining the aluminum concentration in a solution.

[0100] In a nitrogen atmosphere glove box, of the formula AlR A1 R B1 R C1The aluminum-based analyte having [was transferred to a tared flask, and the mass of the sample was recorded. The sample was diluted with methylcyclohexane and then quenched with methanol. The mixture was rotated and reacted for 15 minutes before removing the sample from the glove box. The sample was further hydrolyzed by the addition of H2SO4. The flask was capped and shaken for 5 minutes. Periodic venting of the flask may be necessary depending on the aluminum concentration. The solution was transferred to a separatory funnel. The flask 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 further rinsed with water, and each rinse was added to the volumetric flask. The flask was diluted to a known volume, mixed well, and analyzed by complex formation with excess EDTA and subsequent back-titration with ZnCl2 using xylenol orange as an indicator.

[0101] AlR in hydrocarbyl-modified methylaluminoxane A1 R B1 R C1 Calculation of compounds

[0102]

Number

[0103] AlR A1 R B1 R C1 The compound content is analyzed using the methods described previously (Macromol.Chem.Phys. 1996, 197, 1537, WO2009029857A1, Analytical Chemistry 1968, 40(14), 2150 - 2153, and Organometallics 2013, 32(11), 3354 - 3362).

[0104] The metal-complex is conveniently prepared by standard metallation and ligand exchange procedures involving a transition metal source and a neutral polyfunctional ligand source. Further, the complex can also be prepared by an amide removal and hydrocarbylation process starting from corresponding transition metal tetraamides and hydrocarbylating agents such as trimethylaluminum. The techniques used are the same as or similar to those disclosed in U.S. Patent Nos. 6,320,005, 6,103,657, International Patent Application Publication Nos. 02 / 38628, 03 / 40195, and U.S. Patent Application Publication No. A-2004 / 0220050.

[0105] Synthetic procedures for synthesizing metal-ligand complexes 1-12 can be found in the following procedures and, if previously disclosed, in the following publications: U.S. Patent Application Publication No. 2004 / 0010103(A1), International Patent Application Publication Nos. 2007 / 136494(A2), 2012 / 027448(A1), 2016 / 003878(A1), 2016014749(A1), 2017 / 058981(A1), 2018 / 022975(A1).

[0106] The bis-phenylphenoxy (BPP) complexes BPP-1 to BPP-13 have the structure according to formula (I) and are as follows. [Table 1-1] [Table 1-2] [Table 1-3]

[0107] Preparation of BPP3 (ligand disclosed in International Patent Application Publication No. 2018 / 022975(A1))

[0108] [Chemical formula]

[0109] Synthesis of 6’,6’’’-(((Diisopropylsilanediyl)bis(methylene))bis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1’-biphenyl]-2-ol)dimethyl-zirconium (BPP-3): 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, the solid ligand (5.00 g, 3.77 mmol) was added portionwise. The mixture was stirred for 8 hours and then the solvent was removed under reduced pressure overnight to give a dark residue. Hexane / toluene (10:1 70 mL) was added to the residue, the solution was shaken at room temperature for a few minutes, and then the material was passed through a frit funnel 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 yellowish-brown solid and the heterogeneous mixture was placed in the freezer (-35 °C) for 18 hours. The brown pentane layer was removed using a pipette. The remaining material was dried under vacuum to give BPP-3 (4.50 g, yield: 83%) as a white powder.

[0110] 11H NMR (400 MHz, C6D6) δ 8.65 - 8.56 (m, 2H), 8.40 (dd, J = 2.0, 0.7 Hz, 2H), 7.66 - 7.55 (m, 8H), 7.45 (d, J = 1.9 Hz, 1H), 7.43 (d, J = 1.9 Hz, 1H), 7.27 (d, J = 2.5 Hz, 2H), 7.10 (d, J = 3.2 Hz, 1H), 7.08 (d, J = 3.1 Hz, 1H), 6.80 (ddd, J = 9.0, 7.4, 3.2 Hz, 2H), 5.21 (dd, J = 9.1, 4.7 Hz, 2H), 4.25 (d, J = 13.9 Hz, 2H), 3.23 (d, J = 14.0 Hz, 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 = 7.3 Hz, 12H), 0.31 (hept, J = 7.5 Hz, 2H), -0.84 (s, 6H); 19 19F NMR (376 MHz, C6D6) δ -116.71.

[0111] Synthesis of BPP-9:

[0112]

Chem.

[0113] Into an oven-dried 100 mL glass bottle, ZrCl4 (798 mg, 3.43 mmol), toluene (30 mL), and a stir bar were placed. The solution was placed in the freezer and cooled to -30 °C for 20 minutes. The solution was taken out of the freezer and treated with MeMgBr (4.35 mL, 13.1 mmol, 3 M in Et2O) and stirred for 15 minutes. To the cold suspension, the BPP-9 ligand (5.00 g, 3.26 mmol) was added as a solid. The reaction 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 BPP-9 as an off-white powder (3.31 g, 62%).

[0114] 11H NMR (400 MHz, benzene-d6) δ 8.19 (d, J = 8.2 Hz, 2H), 8.03 - 7.96 (m, 4H), 7.87 (d, J = 2.5 Hz, 2H), 7.81 - 7.76 (m, 2H), 7.64 (d, J = 2.5 Hz, 2H), 7.56 (d, J = 1.7 Hz, 2H), 7.51 (dd, J = 8.2, 1.7 Hz, 2H), 7.30 (dd, J = 8.3, 1.7 Hz, 2H), 7.06 - 7.01 (m, 2H), 3.57 (dt, J = 9.9, 4.9 Hz, 2H), 3.42 (dt, J = 10.3, 5.2 Hz, 2H), 1.79 (d, J = 14.5 Hz, 2H), 1.66 (d, J = 14.4 Hz, 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).

[0115] Preparation of BPP-10

[0116]

Chemical formula

[0117] Synthesis of 2-bromo-4-fluoro-6-methyl-phenol: A 1-liter glass bottle was filled with acetonitrile (400 mL), 4-fluoro-6-methyl-phenol (50 g, 396.4 mmol), and p-toluenesulfonic acid (monohydrate) (75.6 g, 396 mmol), and it was confirmed that all were in solution. The solution was cooled to 0 °C with 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 while stirring overnight. The reaction was 19Analysis by 19F NMR spectroscopy and GC / MS confirmed complete conversion. Volatiles were removed under vacuum, and the resulting solid was treated with dichloromethane (600 mL), cooled in a freezer (0 °C), and filtered through a large plug of silica gel. The silica gel was washed several times with cold CH2Cl2. Volatiles were removed under vacuum (first fraction yield: 46 g, 56%). 1 1H 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). 19 19F NMR (376 MHz, chloroform-d) δ -122.84.

[0118] [Chemical formula]

[0119] Synthesis of bis((2-bromo-4-fluoro-6-methylphenoxy)methyl)diisopropylgermane: In a 250 mL flask equipped with a magnetic stir bar in a glove box, 95% NaH (1.76 g) (note H2 gas is generated) was slowly added to a solution of 2-bromo-4-fluoro-6-methyl-phenol (15 g, 73.2 mmol) in N,N-dimethylformamide (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 was removed from the glove box and quenched with saturated aqueous NH4Cl (20 mL) and H2O (8 mL). Et2O (30 mL) was added, the phases were transferred to a separatory funnel and separated. The aqueous phase was further extracted with Et2O (20 mL), and the combined organic extracts were 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 containing ethyl acetate rising to 10% over 20 minutes) to obtain a pale yellow oil as the product. All clean fractions (some fractions contained less than 10% starting phenol) were combined and the final product was left under vacuum overnight (yield: 9 g, 62%).

[0120] 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); 19 F NMR (376 MHz, chloroform-d) δ -118.03.

[0121] Synthesis of BPP-10 ligand

[0122]

Chemical Structure

[0123] A 500 mL glass bottle equipped with a stir bar was charged with 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (disclosed in International Patent Application Publication No. 2014 / 105411 (A1)) (29.0 g, 41.9 mmol), bis((2-bromo-4-fluoro-6-methylphenoxy)methyl)diisopropylgermanium (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%) with stirring. An 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 reaction mixture was stirred at 55 °C overnight. 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 plug of silica gel. The filtrate was dried on a rotary evaporator, dissolved in THF / methanol (40 mL / 40 mL), treated with HCl (2 mL), and stirred at 70 °C overnight. The solution was dried under vacuum and purified by C18 reverse-phase column chromatography to obtain the BPP-10 ligand as an off-white solid (yield: 6.5 g, 54%).

[0124] 11H NMR (400 MHz, chloroform-d) δ 8.01 (d, J = 8.2 Hz, 4H), 7.42 (dd, J = 25.5, 2.4 Hz, 4H), 7.32 (dd, J = 8.2, 1.6 Hz, 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 19F NMR (376 MHz, chloroform-d) δ -119.02.

[0125] Synthesis of BPP10:

[0126]

Chemical formula

[0127] ZrCl4 (402 mg, 1.72 mmol), toluene (83 mL), and a stir bar were placed in an oven-dried 100 mL glass bottle. The solution was placed in a freezer and cooled to -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, the BPP-10 ligand (2.3 g, 1.64 mmol) was added as a solid, and the residual powder was dissolved in cold toluene (3 mL) and added to the reaction. The reaction 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 plug of CELITE, and dried again under vacuum. The resulting solid was washed with pentane (ca. 5 mL) and dried under vacuum to give BPP-10 as an off-white powder (2.1 g, 84%).

[0128] 11H NMR (400 MHz, benzene-d6) δ 8.20 (dd, J = 8.2, 0.5 Hz, 2H), 8.11 (dd, J = 8.2, 0.6 Hz, 2H), 7.88 - 7.82 (m, 4H), 7.77 (d, J = 2.6 Hz, 2H), 7.50 (dd, J = 8.3, 1.7 Hz, 2H), 7.42 - 7.37 (m, 4H), 6.99 (dd, J = 8.7, 3.1 Hz, 2H), 6.20 - 6.10 (m, 2H), 4.29 (d, J = 12.2 Hz, 2H), 3.90 (d, J = 12.2 Hz, 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 = 7.4 Hz, 6H), 0.80 (s, 18H), 0.74 (d, J = 7.4 Hz, 6H), -0.47 (s, 6H); 19 19F NMR (376 MHz, benzene-d6) δ -116.24.

[0129] Synthesis of BPP-12 Preparation of bis((2-bromo-4-t-butylphenoxy)methyl)diisopropylsilane

[0130]

Chemical formula

[0131] In a glove box, diisopropyldichlorosilane (3.703 g, 20 mmol, 1.0 equiv) was dissolved in anhydrous THF (120 mL) in a 250 mL one-neck 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 mmol, 3.0 equiv) was added. Using a syringe pump, a solution of n-BuLi in hexane (18.4 mL, 46 mmol, 2.3 equiv) was added to the cooled wall of the flask over 3 hours. The mixture was warmed to room temperature overnight (16 hours), and saturated NH4Cl (30 mL) was added. Two layers separated. The aqueous layer was extracted with ether (2 × 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.

[0132] In a glove box, a 40 mL vial was charged with bis(chloromethyl)diisopropylsilane (2.14 g, 10 mmol, 1.0 equiv), 4-t-butyl-2-bromophenol (6.21 g, 27 mmol, 2.7 equiv), K3PO4 (7.46 g, 35 mmol, 3.5 equiv), and DMF (10 mL). The reaction mixture was stirred at 80 °C overnight. 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 oil was recovered, and the overall yield after two steps was 73%.

[0133] 1 H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 2.4 Hz, 2H), 7.26 (dd, J = 8.6, 2.4 Hz, 2H), 6.98 (d, J = 8.6 Hz, 2H), 3.93 (s, 4H), 1.45 - 1.33 (m, 2H), 1.28 (s, 18H), 1.20 (d, J = 7.3 Hz, 12H).

[0134] 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)

[0135] [Chemical Formula]

[0136] In a glove box, a 40 mL vial equipped with a stir bar was charged with bis((2-bromo-4-t-butylphenoxy)methyl)diisopropylsilane (1.20 g, 2.0 mmol, 1.0 equiv), 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 equiv), tBu3P Pd G2 (0.031 g, 0.06 mmol, 0.03 equiv), THF (3 mL), and 4 M NaOH solution (3.0 mL, 12.0 mmol, 6.0 equiv). The vial was heated at 55 °C for 2 h under nitrogen. Upon completion, the upper organic layer was extracted with ether and filtered through a short plug of silica gel. 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 h and cooled to room temperature. The solvent was removed under reduced pressure. The residue was purified by reverse-phase column chromatography using THF / MeCN (0 / 100 → 100 / 0) as the eluent. 1.62 g of a white solid was recovered in 78% yield.

[0137] 11H NMR (400 MHz, CDCl3) δ 7.39 (t, J = 1.8 Hz, 2H), 7.36 (d, J = 1.8 Hz, 4H), 7.29 (d, J = 2.5 Hz, 2H), 7.22 (dd, J = 8.6, 2.6 Hz, 2H), 7.10 (d, J = 2.2 Hz, 2H), 6.94 (d, J = 2.3, 2H), 6.75 (d, J = 8.6 Hz, 2H), 5.37 (s, 2H), 3.61 (s, 4H), 2.32 (d, J = 0.9 Hz, 6H), 1.33 (s, 36H), 1.29 (s, 18H), 0.90 - 0.81 (m, 2H), 0.73 (d, J = 7.1 Hz, 12H).

[0138] Preparation of BPP-12

[0139]

Chem.

[0140] In a glove box, an oven-dried 40 mL vial equipped with a stir bar was charged with ZrCl4 (47 mg, 0.2 mmol, 1.0 equiv) and anhydrous toluene (6.0 mL). 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 equiv) 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 equiv) was added as a solid. The resulting mixture was stirred at room temperature overnight. The solvent was removed under vacuum to give 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, in 74% yield.

[0141] 11H NMR (400 MHz, C6D6) δ 8.20 - 7.67 (m, 4H), 7.79 (t, J = 1.8 Hz, 2H), 7.56 (d, J = 2.5 Hz, 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 = 8.6 Hz, 2H), 4.61 (d, J = 13.5 Hz, 2H), 3.46 (d, J = 13.5 Hz, 2H), 2.26 (s, 6H), 1.47 (s, 36H), 1.25 (s, 18H), 0.52 (dd, J = 17.0, 7.5 Hz, 12H), 0.30 - 0.18 (m, 2H), -0.05 (s, 6H).

[0142] Synthesis of BPP-13

[0143] [Chemical formula]

[0144] In a nitrogen glove box, an oven-dried vial was charged with ScCl3 (0.016 g, 0.106 mmol), THF (ca. 50 mL), and a magnetic stir bar. The mixture was cooled to -30 °C, then LiCH2TMS (1.0 M in pentane, 0.35 mL, 0.35 mmol) was added dropwise, and then the mixture was stirred at room temperature for 1.5 h. To this mixture, 1 equivalent of ligand formula i (0.168 g, 0.106 mmol) in THF (ca. 10 mL) was slowly added, and the reaction mixture was stirred at room temperature for 18 h. The solvent was then removed in vacuo to afford BPP-19 as a white solid (0.154 g, 83%).

[0145] Example 2 - Polymerization reaction using a hydrocarbyl-modified methylaluminoxane having less than 25 mol% of the compound AlR based on the total moles of the metal-ligand complex, the comparative activator, and aluminum A1 R B1 R C1

[0146] The metal-ligand complexes 2, 4, and 11 were tested in a batch reactor using MMAO-A2 or MMAO-Comparison 2 as the activator, and the data are summarized in Tables 1-2. The dry weight efficiency is higher when the catalyst is activated with MMAO-A2, in contrast to MMAO-Comparison 2.

[0147]

Table 2

[0148]

Table 3

[0149] Polymerization conditions: 150 °C, 1342 g of ISOPAR E, 177 g of 1-octene, 52 g of ethylene, total pressure of 230 psi, total MMAO in a ratio of 100 of Al: catalyst metal. [A] The catalyst efficiency (Eff.) is measured as 10 6 g polymer / g of metal in the catalyst. [B] AlR A1 R B1 R C1 aluminum species as

[0150]

Table 4

[0151] Polymerization conditions: 165 °C, 1345 g of ISOPAR E, 175 g of 1-octene, 50 g of ethylene, total pressure of 237 psi, total MMAO in a ratio of 100 of Al: catalyst metal. [A] The catalyst efficiency (Eff.) is measured as 10 6 g polymer / g of metal in the catalyst. [B] AlRA1 R B1 R C1 Aluminum species as

[0152]

Table 5

[0153] Polymerization at a reactor temperature of 160 °C, an ethylene feed flow rate of 3.4 kg / hour, a 1-octene feed flow rate of 3.3 kg / hour, and 21 kg / hour of ISOPAR E, [A] The % solids is the concentration of the polymer in the reactor. [B] H2 (mol%) is defined as the molar fraction of hydrogen with respect to the ethylene fed to the reactor. [C] Efficiency (Eff.) is 10 6 Measured as g polymer / g of metal in the catalyst component. The ethylene conversion is measured as the difference between the ethylene fed to the reactor and the amount leaving the reactor and is expressed as a percentage. 1 Reactor temperature = 153 °C, 2.5 kg / hour of ethylene, 3.3 kg / hour of 1-octene, 21 kg / hour of ISOPAR E. 2 Reactor temperature of 160 °C, 3.4 kg / hour of ethylene, 2.4 kg / hour of 1-octene, 22 kg / hour of ISOPAR E. N / D = Not determined. [D] AlR A1 R B1 R C1 Aluminum species as. N / A = A steady-state reaction cannot be achieved under these reactor conditions.

[0154]

Table 6

[0155] Polymerization at a reactor temperature of 190 °C, an ethylene feed flow rate of 4.6 kg / hour, a 1-octene feed flow rate of 2.0 kg / hour, and 21 kg / hour of ISOPAR E, [A] The % solids is the concentration of the polymer in the reactor. [B]H2 (mol%) is defined as the molar fraction of hydrogen with respect to ethylene supplied to the reactor. The ethylene conversion rate is measured as the difference between the ethylene supplied to the reactor and the amount exiting the reactor, and is expressed as a percentage. [C] Efficiency (Eff.) is measured as 10 6 g polymer / g metal in the catalyst. [D] AlR A1 R B1 R C1 aluminum species as

[0156]

Table 7

[0157] Polymerization conditions: 190 °C, 1250 g of ISOPAR E, 65 g of octene, 85 g of ethylene, total pressure = 415 psi, reaction time = 10 minutes. [A] Efficiency (Eff) is calculated based on the ethylene uptake and is expressed as 10 6 g ethylene uptake / g metal in the catalyst.

[0158] Equipment specifications 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, Q-5 reactant. Solvents used in experiments conducted in a nitrogen-filled glove box were further dried by storage over activated 4 Å molecular sieves. Glassware for moisture-sensitive reactions was dried in an oven overnight before use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. 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 was carried out on an XBridge C18 3.5 μm 2.1×50 mm column using a gradient of 5:95 to 100:0 acetonitrile and water (containing 0.1% formic acid as the ionizing agent). HRMS analysis was performed using an Agilent 1290 Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm 2.1×50 mm column combined with an Agilent 6230 TOF mass spectrometer equipped with electrospray ionization. 1 1H NMR data are reported as follows: chemical shift (multiplicity (br = broad line, s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sex = sextet, sept = septet, and m = multiplet), integration value, and assignment). 1 Chemical shifts for 1H NMR data are reported as low field (ppm) from internal tetramethylsilane (TMS, δ scale) using the residual proton in the deuterated solvent as a reference. 13 13C NMR data are 1 determined using 1H decoupling, and chemical shifts are reported as low field (ppm) from tetramethylsilane (TMS, δ scale) using the residual carbon in the deuterated solvent as a reference.

Claims

1. A process for polymerizing an olefin monomer, said process comprising reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system, said catalyst system being A hydrocarbyl-modified methylaluminoxane having less than 25 mole percent of a trihydrocarbyl aluminum compound AlR Ａ１ R Ｂ１ R Ｃ１ R based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane, wherein R Ａ１ R Ｂ１ and R Ｃ１ are independently linear (C １ -C ４０ ) alkyl, branched (C １ -C ４０ ) alkyl, or (C ６ -C ４０ ) aryl, and a hydrocarbyl-modified methylaluminoxane, one or more metal-ligand complexes according to formula (I), 【Chemical 1】 wherein M is titanium, zirconium and hafnium, n is 1, 2, or 3, Each X is a monodentate ligand independently selected from unsaturated (C ２ ~C ５０ ) hydrocarbons, unsaturated (C ２ ~C ５０ ) heterohydrocarbons, saturated (C ２ ~C ５０ ) heterohydrocarbons, (C １ ~C ５０ ) hydrocarbyls, (C ６ ~C ５０ ) aryls, (C ６ ~C ５０ ) heteroaryls, cyclopentadienyl, substituted cyclopentadienyl, and (C ４ ~C １２ ) dienes, and halogens, the metal-ligand complex is overall charge-neutral, each Z is -O-, R １ and R １６ are independently selected from the group consisting of -H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV). 【Chemical 2】 In the formula, R ３１～３５ , R ４１～４８ , and R ５１～５９ each independently represents -H, (C １ - C ４０ ) hydrocarbyl, (C １ - C ４０ ) heterohydrocarbyl, -Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , or is 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 are independently selected from -H, (C １ ~C ４０ ), hydrocarbyl, (C １ ~C ４０ ), heterohydrocarbyl, -Si(R Ｃ ３ ), and halogen;​ L is (C １ ~C ４０ ) hydrocarbylene or (C ２ ~C ４０ ) heterohydrocarbylene, and Each R in formula (I) Ｃ , R Ｐ , and R Ｎ are independently, (C １ ~C ３０ ) hydrocarbyl, (C １ ~C ３０ ) heterohydrocarbyl, or -H, one or more metal-ligand complexes, comprising a polymerization process in which the catalyst system does not contain a boric acid activator.

2. The polymerization process according to claim 1, wherein the hydrocarbyl-modified methylaluminoxane has less than 20 mole percent of trihydrocarbylaluminum based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane.

3. The polymerization process according to claim 1, wherein the hydrocarbyl-modified methylaluminoxane has less than 15 mole percent of trihydrocarbylaluminum based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane, or the hydrocarbyl-modified methylaluminoxane has less than 10 mole percent of trihydrocarbylaluminum based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane.

4. The polymerization process according to claim 1, wherein the hydrocarbyl-modified methylaluminoxane is a modified methylaluminoxane.

5. R １ and R １６ The polymerization process according to claim 1, wherein at least one of them is a radical having the formula (III).

6. R ４２ and R ４７ are (C １ ~C ２０ ) hydrocarbyl or -Si[(C １ ~C ２０ ) hydrocarbyl], ３ The polymerization process according to claim 5.

7. R １ and R １６ The polymerization process according to claim 1, wherein at least one of them is a radical having the formula (II).

8. R ３２ and R ３４ are (C １ ~C １２ ) hydrocarbyl or -Si[(C １ -C ２０ ) hydrocarbyl], ３ The polymerization process according to claim 7

9. R １ and R １６ The polymerization process according to claim 1, wherein at least one of them is a radical having the formula (IV).

10. R ５２ 、 R ５３ 、 R ５５ 、 R ５７ 、 and R ５８ in which at least two of them are (C １ ~C ２０ ) hydrocarbyl or -Si[(C １ ~C ２０ ) hydrocarbyl] ３ The polymerization process according to claim 9

11. R ８ and R ９ are independently (C １ ~C ４ ) alkyl, the polymerization process according to claim 1.

12. R ３ and R １４ are (C １ to C ２０ ) alkyl, the polymerization process according to claim 1.

13. R ６ and R １１ The polymerization process according to claim 1, wherein R is tert-butyl.

14. R ３ and R １４ The polymerization process according to claim 1, wherein R and R are tert-octyl or n-octyl.

15. L is -CH ２ (CH ２ ) ｍ CH ２ -(wherein m is 1 to 3), -CH ２ Si(R Ｃ )(R Ｄ )CH ２ -, -CH ２ Ge(R Ｃ )(R Ｄ )CH ２ -, -CH(CH ３ )CH ２ CH(CH ３ )-, bis(methylene)cyclohexane-1,2-diyl; -CH ２ CH(R Ｃ )CH ２ -, -CH ２ C(R Ｃ ) ２ CH ２ -(wherein each R Ｃ in L is (C １ to C ２０ )hydrocarbyl, and R Ｄ in L is (C １ to C ２０ )hydrocarbyl), the polymerization process according to claim 1.

16. The olefin monomer is (C ３ ~C ２０ ) α-olefin, and the polymerization process according to claim 1.

17. The olefin monomer is not a (C ３ -C ２０ ) α-olefin, and the polymerization process according to claim 1.

18. The polymerization process according to claim 1, wherein the olefin monomer is a cyclic olefin.

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