Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-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 comprising an activator and less than 25 mole percent, based on the total moles of aluminum, of a trihydrocarbyl aluminum compound, AlR A1 R B1 R C1 wherein R A1 , R B1 , and R C1 However, independently, linear chain (C1 to C 40 ) Alkyl, branched (C1-C 40 ) alkyl, or (C6-C 40 ) aryl, and one or more metal-ligand complexes according to formula (I). [Case 1] JPEG2023537217000029.jpg60170

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 053,350, filed July 17, 2020, the entire disclosure of which is incorporated herein by reference.

[0002] FIELD OF THE INVENTION SUMMARY OF THE DISCLOSURE Embodiments of the present disclosure generally relate to catalyst systems comprising a hydrocarbyl-modified methylaluminoxane, an activator, and a bis-phenylphenoxy metal-ligand complex. [Background technology]

[0003] Since Ziegler and Natta's discovery of heterogeneous olefin polymerization, global polyolefin production reached approximately 150 million tons per year in 2015, rising due to increasing market demand. This success is based in part on a series of important breakthroughs in cocatalyst technology. The cocatalysts discovered include aluminoxanes, boranes, and borates containing triphenylcarbenium or ammonium cations. These cocatalysts activate homogeneous single-site olefin polymerization catalysts, and polyolefins are produced using these cocatalysts in industry.

[0004] Modified methylaluminoxane (MMAO), in combination with borate-based activators, can be used as an impurity scavenger in some PE processes. However, increasing the amount of MMAO has been shown to adversely affect the performance of some catalysts, such as bis-phenylphenoxy metal-ligand complexes, and to adversely affect the production of polyvinyl resins. Adverse effects on the polymerization process include reduced catalyst activity, a broader compositional distribution of the resulting polymer, and adverse effects on pellet handling. Summary of the Invention

[0005] There is a continuing need to create catalyst systems that maintain catalytic efficiency, reactivity, and the ability to produce polymers with good physical properties.

[0006] Embodiments of the present disclosure include a process for polymerizing olefin monomers. In one or more embodiments, the process comprises reacting ethylene and, optionally, one or more olefin monomers in the presence of a catalyst system. The catalyst system comprises a hydrocarbyl-modified methylaluminoxane, an activator, and a metal-ligand complex. The catalyst system comprises less than 25 mole percent of the trialkylaluminum compound AlR, based on the total moles of aluminum. A1 R B1 R C1 a hydrocarbyl-modified methylaluminoxane having R A1 , R B1 , and R C1 However, independently, linear chain (C1 to C 40 ) Alkyl, branched (C1-C 40 ) alkyl, (C1-C 40 ) aryl, or combinations thereof, and one or more metal-ligand complexes comprising a hydrocarbyl-modified methylaluminoxane and a metal-ligand complex according to formula (I):

[0007] [ka]

[0008] In formula (I), M is titanium, zirconium, hafnium, scandium, yttrium, or an element of the lanthanide series of the periodic table having a formal oxidation state of +2, +3, or +4. (X) n The subscript n is 1, 2, or 3. Each X is an unsaturated (C2-C 50 ) Hydrocarbons, unsaturated (C2-C 50 ) Heterohydrocarbons, saturated (C2-C 50 ) Heterohydrocarbons, (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 )C(O)R C and each Z is a monodentate ligand independently selected from: Optionally, two X groups may be linked together. The metal-ligand complex is overall charge neutral. Each Z is selected from: -O-, -S-, -N(R N )-, or -P(R P )-. L is independently selected from (C1 to C 40 ) hydrocarbylene or (C2-C 40 ) heterohydrocarbylene.

[0009] 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, (C1 to 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.

[0010] In formula (I), R 1and R 16 are independently -H, (C1 to 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).

[0011] [ka]

[0012] In formulas (II), (III), and (IV), R 31~35 , R 41~48 , and R 51~59 Each of the groups independently represents -H, (C1 to 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)2NC(O)-, or halogen.

[0013] In formulas (I), (II), (III), and (IV), each R in formula (I) C , R P , and R N are independently (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H. DETAILED DESCRIPTION OF THE INVENTION

[0014] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments described in this disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0015] Common abbreviations are listed below. Me: methyl, Et: ethyl, Ph: phenyl, Bn: benzyl; i-Pr: isopropyl, t-Bu: tert-butyl, t-Oct: tert-octyl (2,4,4-trimethylpentan-2-yl), Tf: trifluoromethane sulfonate, 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: mole, min or mins: minute; h or hrs: hour, d: day.

[0016] The term "independently selected" refers to 1 , R 2 , R 3 , R 4 , and R 5 and the R groups 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, R 3 The R group is used herein to indicate that the R group may be an aryl group, etc. Chemical names associated with R groups are intended to convey chemical structures recognized in the art as corresponding to the chemical structure of the chemical name. Thus, the chemical names are intended to supplement and illustrate, not preclude, structural definitions known to those of skill in the art.

[0017] 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 it into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms.

[0018] When used to describe certain carbon atom-containing chemical groups, "(C x ~C y A parenthesized expression having the form "(C1-C)" means that the unsubstituted form of the chemical group has at least x, and at most y, carbon atoms. For example, (C1-C 50 ) Alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups are S The parenthesized "(C x ~C y )" S The chemical group substituted with any group R Smay contain more than y carbon atoms depending on the identity of R. For example, "exactly one R S Substituted with groups (C1-C 50 ) alkyl(R S The "(C is phenyl (-C H))" can contain 7 to 56 carbon atoms. x ~C y )" is a substituent R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group are the substituents R containing all carbon atoms in both x and y. S It is determined by adding the total number of carbon atoms from

[0019] 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 S ) The term "-H" means a hydrogen or hydrogen radical that is covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0020] "(C1~C 50 The term "(C1-C) alkyl" means a saturated straight-chain or branched hydrocarbon radical containing 1 to 50 carbon atoms. 30 The term "alkyl" means a saturated straight or branched hydrocarbon radical of 1 to 30 carbon atoms. 50 ) alkyl and (C1-C 30 ) Alkyl may be unsubstituted or may contain one or more R S In some instances, each hydrogen atom in a hydrocarbon radical may be substituted with R, such as trifluoromethyl. S may be substituted with unsubstituted (C1-C 50 Examples of 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. 40 Examples of substituted (C1-C 20 ) Alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "alkyl" means that there are up to 45 carbon atoms in the radical (including substituents), e.g., one R which is (C1-C5) alkyl, such as methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl. S replaced by, for example, (C 27 ~C 40 ) alkyl.

[0021] (C3~C 50 The term alkenyl refers to alkyl groups containing 3 to 50 carbon atoms, at least one double bond, and which are unsubstituted or have one or more R S means a branched or unbranched, cyclic or acyclic monovalent hydrocarbon radical substituted with unsubstituted (C3-C 50 Examples of alkenyl are n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, and cyclohexadienyl. 50 Examples of alkenyl are (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.

[0022] "(C3~C 50 The term "cycloalkyl" refers to a group that is unsubstituted or has one or more R S means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms substituted by other cycloalkyl groups, such as (Cx ~C y )cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S Unsubstituted (C3-C 40 Examples of cycloalkyl are unsubstituted (C-C 20 ) Cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C3-C 20 ) Cycloalkyl, substituted (C3-C 10 ) cycloalkyl, and 1-fluorocyclohexyl.

[0023] The term "halogen atom" or "halogen" refers to a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to the anionic form of a halogen atom, fluoride (F - ), chloride (Cl - ), bromide (Br - ), or iodide (I - ) means

[0024] 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. A saturated chemical group is one or more substituents R S When one or more double or triple bonds are substituted by a substituent R S 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, and the substituent R SThis means that the aromatic ring or heteroaromatic ring does not contain any double bonds that may be present in the ring (if present), or in the aromatic or heteroaromatic ring (if present).

[0025] The term "hydrocarbyl-modified methylaluminoxane" refers to a methylaluminoxane (MMAO) structure containing a certain amount of trihydrocarbylaluminum. The 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 aluminum contributions from the moles of aluminum from the hydrocarbyl-modified methylaluminoxane matrix and the moles of aluminum from the trihydrocarbylaluminum. The hydrocarbyl-modified methylaluminoxane contains more than 2.5 mole percent trihydrocarbylaluminum based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane. These additional hydrocarbyl substituents can affect the subsequent aluminoxane structure, resulting in differences in the distribution and size of the aluminoxane clusters (Bryliakov, KP 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™, as disclosed in U.S. Patent No. 5,777,143. Modified methylaluminoxane compositions are generally disclosed and can be prepared as described in U.S. Patent Nos. 5,066,631 and 5,728,855, both of which are incorporated herein by reference.

[0026] Modified methylaluminoxane (MMAO) can be described as a mixture of aluminoxane structures and trihydrocarbylaluminum species. Trihydrocarbylaluminum 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, it is believed that trihydrocarbylaluminum species may be active in some polymerization systems. Catalyst inhibition has been observed in the presence of trimethylaluminum during hafnocene-catalyzed propylene homopolymerization at 60°C (Busico, V. et al. Macromolecules 2009, 42, 1789-1791). However, these observations convolute differences in MAO activation versus borate activation and may only capture differences between the presence and absence of some trimethylaluminum, even in direct comparisons. Additionally, it is unclear whether such observations extend to other catalyst systems, ethylene polymerizations, or polymerizations conducted at higher temperatures. In any event, the preference for soluble MAO requires the use of MMAO and therefore the presence of trihydrocarbylaluminum species.

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

[0028] In various embodiments, the catalyst system does not contain a borate activator.

[0029] In some embodiments, the olefin monomer is (C3-C 20 In other embodiments, the olefin monomer is a (C3-C 20 ) is not an α-olefin. In various embodiments, the olefin monomer is a cyclic olein.

[0030] In one or more embodiments, the catalyst system comprises a hydrocarbyl-modified methylaluminoxane and a metal-ligand complex. The hydrocarbyl-modified methylaluminoxane has less than 25 mole percent trialkylaluminum, based on the total moles of aluminum. The trialkylaluminum is AlR A1 R B1 R C1 wherein R A1 , R B1 , and R C1 are independently linear (C1 to C 40 ) Alkyl, branched (C1-C 40 ) alkyl, or (C6-C 40 ) aryl. The catalyst system comprises one or more metal-ligand complexes according to formula (I).

[0031] [ka]

[0032] In formula (I), M is titanium, zirconium, hafnium, scandium, yttrium, or an element of the lanthanide series of the periodic table having a formal oxidation state of +2, +3, or +4. (X) n The subscript n is 1, 2, or 3. Each X is an unsaturated (C2-C 50 ) Hydrocarbons, unsaturated (C2-C 50 ) Heterohydrocarbons, saturated (C2-C 50 ) Heterohydrocarbons, (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 metal-ligand complex is overall charge neutral. Each Z is independently selected from -O-, -S-, -N(R N )-, or -P(R P )-. L is independently selected from (C1 to C40 ) hydrocarbylene or (C2-C 40 ) heterohydrocarbylene.

[0033] 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, (C1 to 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.

[0034] In formula (I), R 1 and R 16 are independently -H, (C1 to 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(RC )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).

[0035] [ka]

[0036] When present in a metal-ligand complex of formula (I) as part of a radical having formula (II), formula (III), or formula (IV), the group R of the metal-ligand complex of formula (I) 31~35 , R 41~48 , and R 51~59 are each independently (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(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 N )NC(O)-, halogen, hydrogen (-H), or a combination thereof. C , R P , and R N is unsubstituted (C1 to C 18 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H.

[0037] In formulas (I), (II), (III), and (IV), each R C , RP , and R N are independently (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H.

[0038] In embodiments, the hydrocarbyl-modified methylaluminoxane in the polymerization process has less than 20 mole percent trialkylaluminum based on the total moles of aluminum. In some embodiments, the hydrocarbyl-modified methylaluminoxane has less than 15 mole percent trialkylaluminum based on the total moles of hydrocarbyl-modified methylaluminoxane. In one or more embodiments, the hydrocarbyl-modified methylaluminoxane has less than 10 mole percent trialkylaluminum based on the total moles of hydrocarbyl-modified methylaluminoxane. In various embodiments, the hydrocarbyl-modified methylaluminoxane is a modified methylaluminoxane.

[0039] In some embodiments, the trialkylaluminum is 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, R A1 , R B1 , and R C1 is independently methyl, ethyl, propyl, 2-propyl, butyl, tert-butyl, or octyl. A1 , R B1 , and R C1 are the same. In another embodiment, R A1 , R B1 , and R C1 At least one of the other R A1 , R B1 , and R C1 is different.

[0040] In various embodiments, the ratio of moles of aluminum in the hydrocarbyl-modified methylaluminoxane to moles of metal in the metal-ligand complex is greater than 10. In some embodiments, the ratio of moles of aluminum in the hydrocarbyl-modified methylaluminoxane to moles of metal in the metal-ligand complex is less than 500. In a further embodiment, the ratio of moles of aluminum in the hydrocarbyl-modified methylaluminoxane to moles of metal in the metal-ligand complex is greater than 20 and less than 300.

[0041] The group R in the metal-ligand complex of formula (I) 1 and R 16 are selected independently of each other. For example, R 1 may be selected from radicals having formula (II), (III), or (IV), and R 16 is (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 R 1 R 1 and R 16 may both be radicals having the formula (II), in which case the group R 31~35 is R 1 and R 16 In another embodiment, R 1 and R 16 may both be radicals having the formula (III), in which case the group R 41~48 is R 1 and R 16 are the same or different in R 1 and R 16 may both be radicals having the formula (IV), in which case the group R 51~59 is R 1 and R 16 are the same or different in

[0042] In some embodiments, R 1and R 16 at least one of which is a radical having formula (II), where R 32 and R 34 is tert-butyl. In one or more embodiments, R 32 and R 34 is (C1~C 12 ) hydrocarbyl or -Si[(C 10 ) alkyl]3.

[0043] In some embodiments, R 1 or R 16 is a radical having the formula (III), then R 43 and R 46 one or both of R 41~42 , R 44~45 , and R 47~48 is —H. In other embodiments, R 42 and R 47 one or both of R 41 , R 43~46 , and R 48 is —H. In some embodiments, R 42 and R 47 and R are —H. In various embodiments, R 42 and R 47 is (C1~C 20 ) hydrocarbyl or -Si[(C 10 ) alkyl]3. In other embodiments, R 43 and R 46 is (C1~C 20 ) hydrocarbyl or -Si[(C 10 ) alkyl]3.

[0044] In embodiments, R 1 or R 16 at least one of R is a radical having formula (IV) 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 (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 the 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 the 10 ) alkyl, -Si[(C3~C 10 ) alkyl]3, or -Ge[(C3-C 10 ) alkyl]3.

[0045] In some embodiments, R 1 or R 16 at least one of R is a radical having formula (IV) 52 , R 53 , R 55 , R 57 , and R 58 At least two of the 20 ) hydrocarbyl or -C(H)2Si[(C1-C 20 ) hydrocarbyl]3.

[0046] (C3~C 10Examples of alkyl 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.

[0047] 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, (C1 to 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.

[0048] In one or more embodiments, R 2 , R 4 , R 5 , R 12 , R 13 , and R 15 is hydrogen and each Z is oxygen.

[0049] In various embodiments, R 5 , R 6 , R 7 , and R 8 At least one of R is a halogen atom, 9 , R 10 , R 11 , and R 12 At least one of R is a halogen atom. 8 and R 9 is independently (C1-C4) alkyl.

[0050] In some embodiments, R 3 and R 14 is (C1~C 20 ) alkyl. In one or more embodiments, R 3 and R 14 is benzyl and R 6 and R 11 is halogen. In another embodiment, R 6 and R 11 is tert-butyl. In other embodiments, R 3 and R 14 is tert-octyl or n-octyl.

[0051] In various embodiments, R 3 and R 14 is (C1~C 24 ) alkyl. In one or more embodiments, R 3 and R 14 (C4~C 24 ) alkyl. In some embodiments, R 3 and R 14 is 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.3 and R 14 -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.

[0052] In one or more embodiments, R 8 and R 9 In various embodiments, one of R 8 and R 9 At least one of (C1~C 24 ) alkyl. In some embodiments, R 8 and R 9 Both of (C1~C 24 ) alkyl. In some embodiments, R 8 and R 9 is methyl. In another embodiment, R 8 and R 9 is a halogen.

[0053] In some embodiments, R 3 and R 14 is methyl. In one or more embodiments, R 3 and R 14 (C4~C 24 ) alkyl. In some embodiments, R 8 and R 9 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.

[0054] In various embodiments, in the metal-ligand complex of formula (I), R 6 and R11 is halogen. In some embodiments, R 6 and R 11 is (C1~C 24 ) alkyl. In various embodiments, R 6 and R 11 is 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. 6 and R 11 is tert-butyl. In embodiments, R 6 and R 11 -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 isopropyl), or 1,1-dimethylethyl. 6 and R 11 -SiR C 3, wherein each R C are 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.

[0055] In some embodiments, the chemical groups (e.g., X and R) of the metal-ligand complex of formula (I) 1~59 In another embodiment, the chemical groups X and R of the metal-ligand complex of formula (I) may be unsubstituted. 1~59 Any of the following may contain one or more R S Even if they are not substituted with one or more R SIt may be substituted with two or more R S are attached to the same chemical group of the metal-ligand complex of formula (I), the individual R S may be attached to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, the chemical groups X and R 1~59 Any of the above is R S Even if they are not over-substituted with R, any or all of them may be S It may also be oversubstituted with R S In chemical groups that are over-substituted with S may all be the same or may be independently selected. In one or more embodiments, R S is (C1~C 20 ) hydrocarbyl, (C1-C 20 ) alkyl, (C1-C 20 ) heterohydrocarbyl, or (C1-C 20 ) heteroalkyl.

[0056] In formula (I), L is (C1 to C 40 ) hydrocarbylene or (C1-C 40 ) heterohydrocarbylene, and each Z is independently —O—, —S—, —N(R N )-, or -P(R P )- In one or more embodiments, L contains 1 to 10 atoms.

[0057] In formulas (I), (II), (III), and (IV), each R C , R P , and R N are independently (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H.

[0058] In some embodiments of Formula (I), L is a (C-C) alkyl 1,3-diradical, such as, for example, —CHCHCH—, —CH(CH)CHC *H(CH3), -CH(CH3)CH(CH3)C * In some embodiments, L may be selected from (C4-C 10 ) alkyl 1,4-diradicals, such as -CH2CH2CH2CH2-, -CH2C(CH3)2C(CH3)2CH2-, cyclohexane-1,2-diyldimethyl, and bicyclo[2.2.2]octane-2,3-diyldimethyl. In some embodiments, L is selected from (C5-C 12 ) alkyl 1,5-diradicals, such as —CH2CH2CH2CH2CH2—, and 1,3-bis(methylene)cyclohexane. In some embodiments, L is (C6-C 14 ) alkyl 1,6-diradicals, such as -CH2CH2CH2CH2CH2CH2-, or 1,2-bis(ethylene)cyclohexane.

[0059] In one or more embodiments, L is (C2-C 40 ) heterohydrocarbylene, where at least one of the 2 to 10 atoms comprises a heteroatom. In some embodiments, L is —CHGe(R C )2CH2-, and each R C is (C1~C 30 ) hydrocarbyl. In some embodiments, L is —CHGe(CH3)2CH2—, —CH2Ge(ethyl)2CH2—, —CH2Ge(2-propyl)2CH2—, —CH2Ge(t-butyl)2CH2—, —CH2Ge(cyclopentyl)2CH2—, or —CH2Ge(cyclohexyl)2CH2—.

[0060] In one or more embodiments, L is -CH2-; -CH2CH2-; -CH2(CH2) where m is 1 to 3. m CH2-, -CH2(CHR C ) m CH2-, -CH2(CR C 2) m CH2-;-CH2Si(RC )2CH2-;-CH2Ge(R C )2CH2-;-CH(CH3)CH2CH * (CH); and —CH(phen-1,2-diyl)CH—, and each R in L is selected from C is (C1~C 20 ) hydrocarbyl.

[0061] It takes (C1~C 12 Examples of alkyl include, but are not limited to, 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.

[0062] In some embodiments, in the metal-ligand complex according to formula (I), R 8 and R 9 and R are both methyl. 8 and R 9 one of R 8 and R 9 The other is -H.

[0063] In the metal-ligand complex according to formula (I), X is bonded to M through a covalent or ionic bond. In some embodiments, X may be a monoanionic ligand having a net formal oxidation number of -1. Each monoanionic ligand may independently be a hydride, (C1-C 40 ) hydrocarbyl carbanions, (C1-C 40 ) Heterohydrocarbyl carbanions, halides, nitrates, carbonates, phosphates, sulfates, HC(O)O - , HC(O)N(H) - , (C1~C 40 ) Hydrocarbyl C(O)O - , (C1~C 40 ) Hydrocarbyl C(O)N((C1-C20 )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 - Each R may be K , R L , and R M are independently hydrogen, (C1 to C 40 ) hydrocarbyl, or (C1-C 40 ) heterohydrocarbyl, or R K and R L Together, (C2~C 40 ) hydrocarbylene or (C1-C 20 ) form a heterohydrocarbylene, and R M is as defined above.

[0064] 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- and R K and R L each of which is independently unsubstituted (C1 to C 20 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-, where R K and RL each independently is unsubstituted (C1 to C 10 ) hydrocarbyl.

[0065] 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 groups are independently monoanionic monodentate ligands. In certain embodiments, n is 2, and two X groups join to form a bidentate ligand. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

[0066] In one or more embodiments, each X is independently —(CH)SiR X 3, wherein each R X are independently (C1~C 30 ) alkyl or (C1-C 30 ) heteroalkyl, and at least one R X is (C1~C 30 ) alkyl. In some embodiments, R X One of them 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.

[0067] In one or more embodiments, X is —(CH)Si(CH), —(CH)Si(CH)(CHCH), —(CH)Si(CH)(CHCH), —(CH)Si(CHCH), —(CH)Si(CH)(n-butyl), —(CH)Si(CH)(n-hexyl), —(CH)Si(CH)(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) contains exactly two R X are covalently bonded or exactly three R X are covalently bonded.

[0068] In some embodiments, X is —CHSi(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 are independently substituted or unsubstituted (C1 to C 30 ) hydrocarbyl, or substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl.

[0069] Co-catalyst component Catalyst systems containing metal-ligand complexes 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, procatalysts based on metal-ligand complexes of formula (I) can be made catalytically active by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. Furthermore, metal-ligand complexes based on formula (I) include both neutral procatalyst forms and catalyst forms that can be positively charged by loss of a monoanionic ligand, such as benzyl, methyl, or phenyl. Activating cocatalysts suitable for use herein include alkylaluminums; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the aforementioned activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means a monoalkylaluminum dihydride or dihalide, a dialkylaluminum hydride or halide, or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0070] The Lewis acid activating cocatalyst may be any of the compounds described herein (C1-C 20 In some embodiments, the Group 13 metal compounds include tri((C1-C) hydrocarbyl substituents. 20 )hydrocarbyl)-substituted-aluminum or tri((C1-C 20 In other embodiments, the Group 13 metal compound is a tri(hydrocarbyl)-substituted aluminum, tri((C1-C 20 )hydrocarbyl)-boron compounds, tri((C1-C 10 ) alkyl) aluminum, tri((C6-C 18)aryl)boron compounds and their halogenated (including perhalogenated) derivatives. In further embodiments, the Group 13 metal compound is tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tris((C1-C 20 ) hydrocarbyl borate (e.g., trityl tetrafluoroborate) or tri((C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)borane (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to a ((C1-C 20 ) Hydrocarbyl) 4N + , ((C1~C 20 )hydrocarbyl)3N(H) + , ((C1~C 20 )hydrocarbyl)2N(H)2 + , (C1~C 20 ) Hydrocarbyl N(H)3 + , or N(H)4 + Each of the nitrogen cations (C1 to C 20 ) When two or more hydrocarbyls are present, they may be the same or different.

[0071] The combination of neutral Lewis acid activating cocatalysts is tri((C1-C4) alkyl)aluminum and tri((C6-C 18)aryl)boron compounds, particularly tris(pentafluorophenyl)borane. Other embodiments include mixtures of such neutral Lewis acid mixtures with polymeric or oligomeric alumoxanes, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymeric or oligomeric alumoxanes. The molar ratio of (metal-ligand complex):(tris(pentafluorophenyl)borane):(alumoxane) [e.g., Group 4 metal-ligand complex):(tris(pentafluorophenyl)borane):(alumoxane)] is from 1:1:1 to 1:10:30, and in other embodiments, from 1:1:1.5 to 1:5:10.

[0072] A catalyst system comprising a metal-ligand complex of formula (I) can be activated to form an active catalyst composition by combining it with one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, as well as inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate, and combinations thereof.

[0073] In some embodiments, two or more of the aforementioned activating cocatalysts may be used in combination with one another. A specific example of a cocatalyst combination is a mixture of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of the total number of moles of the one or more metal-ligand complexes of Formula (I) to the total number of moles of the one or more activating cocatalysts is 1:10,000 to 100:1. In some embodiments, this ratio is at least 1:5000; in some other embodiments, it is at least 1:1000 and not more than 10:1; and in some other embodiments, it is not more than 1:1. When alumoxane is used alone as the activating cocatalyst, it is preferred that the number of moles of alumoxane used be at least 100 times the number of moles of the metal-ligand complex of Formula (I). When tris(pentafluorophenyl)borane is used alone as the activating cocatalyst, in some other embodiments, the ratio of moles of tris(pentafluorophenyl)borane in the reaction to the total moles of the one or more metal-ligand complexes of Formula (I) is 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1. The remaining activating cocatalyst is generally used in a molar amount approximately equal to the total molar amount of the one or more metal-ligand complexes of Formula (I).

[0074] Polyolefin The catalyst systems described in the preceding paragraphs are utilized in the polymerization of olefins, primarily ethylene and propylene, to form ethylene-based 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 comonomer typically has 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.

[0075] An ethylene-based polymer, e.g., a homopolymer and / or interpolymer (including copolymer) of ethylene, and optionally one or more comonomers such as an α-olefin, can comprise 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, an ethylene-based polymer, a homopolymer and / or interpolymer (including copolymer) of ethylene, and optionally one or more comonomers such as an α-olefin can comprise 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 from 50 to 100 mole percent of monomer units derived from ethylene, or from 80 to 100 mole percent of monomer units derived from ethylene.

[0076] In some embodiments, the ethylene-based polymer can comprise at least 90 mole percent ethylene-derived units. 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 can comprise at least 93 mole percent ethylene-derived units, at least 96 mole percent units, at least 97 mole percent ethylene-derived units, or alternatively, 90 to 100 mole percent ethylene-derived units, 90 to 99.5 mole percent ethylene-derived units, or 97 to 99.5 mole percent ethylene-derived units.

[0077] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50 mol %, in other embodiments from at least 1 mole percent (mol %) to 25 mol %, and in further embodiments, the amount of additional α-olefin is from at least 5 mol % to 103 mol %, hi some embodiments, the additional α-olefin is 1-octene.

[0078] Any conventional polymerization process may be used to produce the ethylene-based polymers, including, but 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, batch reactors, and the like, in parallel, series, or any combination thereof.

[0079] In one embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of a catalyst system described herein and, optionally, one or more cocatalysts. In another embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of a catalyst system described herein and herein and, optionally, one or more other catalysts. The catalyst system described herein, optionally in combination with one or more other catalysts, can be used in the first reactor or the second reactor. In one embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in both reactors in the presence of a catalyst system described herein.

[0080] 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 within this disclosure, and optionally one or more cocatalysts described in the previous paragraph.

[0081] The ethylene-based polymer may further comprise 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. The ethylene-based polymer may comprise any amount of additives. The ethylene-based polymer may comprise from about 0 to about 10 weight percent of such additives, based on the weight of the ethylene-based polymer and one or more additives. The ethylene-based polymer may further comprise a filler, which may include, but is not limited to, organic or inorganic fillers. The ethylene-based polymer may comprise from about 0 to about 20 weight percent of a filler, 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.

[0082] In some embodiments, a polymerization process for producing an ethylene-based polymer can 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 a metal-ligand complex of formula (I) can have a molecular weight of, for example, 0.850 g / cm or more according to ASTM D792 (which is incorporated herein by reference in its entirety). 3 ~0.970g / cm 3 , 0.880g / cm 3 ~0.920g / cm 3 , 0.880g / cm 3 ~0.910g / cm 3 , or 0.880 g / cm 3 ~0.900g / cm 3 The density may be

[0083] In another embodiment, the polymer resulting from the catalyst system according to the present disclosure has a melt flow ratio (I) of 5 to 15. 10 / I2), where the melt index I2 is measured at 190°C and a load of 2.16 kg according to ASTM D1238 (which is incorporated herein by reference in its entirety), and the melt index I 10 is measured according to ASTM D1238 at 190°C and a load of 10 kg. In other embodiments, the melt flow ratio (I 10 / I2) is 5-10, and in another embodiment the melt flow ratio is 5-9.

[0084] In some embodiments, the polymers obtained from the catalyst systems according to the present disclosure have a molecular weight distribution (MWD) of 1 to 25, w / M n is defined as M w is the weight average molecular weight, and M n is the number average molecular weight. In another embodiment, the polymer resulting from the catalyst system has an MWD of 1 to 6. Another embodiment includes an MWD of 1 to 3, and another embodiment includes an MWD of 1.5 to 2.5.

[0085] Embodiments of the catalyst systems described in this disclosure result in unique polymer properties as a result of the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer.

[0086] Procedure for continuous process reactor polymerization: Feedstocks (ethylene, 1-octene) and process solvent (high-purity narrow-boiling isoparaffin solvent commercially available from ExxonMobil Corporation under the trademark ISOPAR E) were purified with molecular sieves. Hydrogen was supplied as a high-purity grade in a pressurized cylinder without further purification. The reactor monomer feed (ethylene) was pressurized above the reaction pressure. The solvent and comonomer feeds were pressurized above the reaction pressure. The individual catalyst components (metal-ligand complex and cocatalyst) were manually batch diluted with purified solvent to the specified component concentrations and pressurized to a pressure above the reaction pressure. All reaction feeds were metered using mass flow meters and independently controlled by computer-automated valve control systems.

[0087] Continuous solution polymerization is carried out in a continuously stirred-tank reactor (CSTR). The combined reactor feed of solvent, monomer, comonomer, and hydrogen is temperature-controlled between 5°C and 50°C, typically 15°C and 25°C. All of the components are fed to the polymerization reactor along with the solvent feed. Catalyst is fed to the reactor to achieve a specific ethylene conversion. Cocatalyst components are fed separately based on a calculated, specified molar ratio or ppm amount. The effluent from the polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and polymer) exits the reactor and is contacted with water. Additionally, various additives, such as antioxidants, can be added at this point. The stream then passes through a static mixer to homogeneously disperse the mixture.

[0088] Following the addition of additives, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the stream's temperature in preparation for separation of the polymer from other low-boiling components. The stream 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, monomer, comonomer, and water, are removed from the polymer. At the extruder exit, the resulting strands of molten polymer pass through a cold water bath, where they solidify. The strands then pass through a strand chopper, where the polymer is air-dried and then chopped into pellets.

[0089] Procedure for batch reactor polymerization. The raw materials (ethylene, 1-octene) and process solvent (ISOPAR E) were purified with molecular sieves before being introduced into the reaction environment. A stirred autoclave reactor was charged with ISOPAR E and 1-octene. The reactor was then heated to a certain temperature and charged with ethylene to reach a certain pressure. Optionally, hydrogen was also added. The catalyst system was prepared in an inert atmosphere dry box by mixing the metal-ligand complex and, optionally, one or more additives with additional solvent. The catalyst system was then injected into the reactor. The reactor pressure and temperature were kept constant during the polymerization by feeding ethylene and cooling the reactor as needed. After 10 minutes, the ethylene feed was stopped, and the solution was transferred to a nitrogen-purged resin kettle. The polymer was thoroughly dried in a vacuum oven, and the reactor was thoroughly rinsed with hot ISOPAR E between polymerization runs.

[0090] Test Method Unless otherwise indicated herein, the following analytical methods are used in describing aspects of the present disclosure.

[0091] Melt Index The melt index I2 (or I2) and I of the polymer sample 10 (or I10) were measured according to ASTM D-1238 (Method B) at 190° C. and 2.16 kg and 10 kg loads, respectively, and the values ​​are reported in g / 10 min.

[0092] density Samples for density measurements were prepared according to ASTM D4703. Measurements were performed according to ASTM D792, Method B, within 1 hour of sample pressing.

[0093] 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°C, and the column compartment was set to 150°C. The columns used were four Agilent "Mixed A" 30 cm 20-micron linear mixed-bed columns and a 20-um precolumn. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters / minute.

[0094] The GPC column set was calibrated using 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000, arranged in six "cocktail" mixtures with at least a 10-fold separation between individual molecular weights. The standards were purchased from Agilent Technologies. Polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards were dissolved at 80°C for 30 minutes with gentle agitation. 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_polyethylene = A × (M_polystyrene)^B (Equation 1) where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0095] A fifth-order polynomial was used to fit each polyethylene-equivalent calibration point. A small adjustment (approximately 0.375 to 0.445) was made to A to correct for column resolution and band-broadening effects for a linear homopolymer polyethylene standard obtained at 120,000 MW.

[0096] Total plate counts for the GPC column set were performed using decane (prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20 minutes with gentle agitation). Plate counts (Equation 2) and symmetry (Equation 3) were measured with a 200 microliter injection according to the following equations: Plate count = 5.54 * (((RV _ (peak maximum) / (peak width at half height)^2 (Equation 2) where RV is the retention volume in milliliters, Peak Width is in milliliters, Peak Max is the maximum height of the peak, and Half Height is half the height of the Peak Max.

[0097]

number

[0098] Samples were prepared in a semi-automated fashion using PolymerChar "Instrument Control" software, with a target sample weight of 2 mg / ml, and solvent (containing 200 ppm BHT) was added via the PolymerChar high-temperature autosampler to a pre-nitrogen-sparged septa-capped vial. Samples were dissolved at 160°C for 2 hours under "slow" shaking.

[0099] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculation was based on GPC results using PolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram at each equally spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from a narrow standard calibration curve at point (i) of Equation 1, according to Equations 4-6, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph.

[0100]

number

[0101] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (Flow Rate (Nominal)) for each sample by matching the RV of each decane peak in the sample (RV (FM Sample)) to the RV of the decane peak in the narrow standard calibration (RV (FM Calibrated)). Any change in the time of the decane marker peak is thus assumed to be related to a linear shift in flow rate (Flow Rate (Effective)) throughout the run. To facilitate the highest accuracy in measuring the RV of the flow rate marker peak, a least-squares fitting routine was used to fit the peaks in the flow rate marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation was then used to solve for the true peak position. After calibrating the system based on the flow rate marker peaks, the effective flow rate (relative to the narrow standard calibration) was calculated as per Equation 7. Processing of the flow rate marker peaks was performed via PolymerChar GPCOne™ software. An acceptable flow correction is one where the effective flow rate should be within + / - 0.5% of the nominal flow rate. Flow rate (effective) = Flow rate (nominal) * (RV(FM calibrated) / RV(FM sample)) (Equation 7)

[0102] Short chain branches per 1000 total carbons (SCB / 1000C) are measured according to the method described in the "Molecular Weighted Comonomer Distribution Index (MWCDI)" section of WO 2015 / 200743(A1). The present specification includes the following aspects. Section 1. 1. A process for polymerizing olefin monomers, comprising reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system, said catalyst system comprising an activator and a hydrocarbyl-modified methylaluminoxane having less than 25 mole percent trialkylaluminum, based on the total moles of aluminum, wherein the trialkylaluminum is AlR A1 RB1 R C1 wherein R A1 , R B1 , and R C1 However, independently, linear chain (C1 to C 40 ) Alkyl, branched (C1-C 40 ) alkyl, or (C1-C 40 ) aryl, and one or more metal-ligand complexes comprising a hydrocarbyl-modified methylaluminoxane and a metal-ligand complex according to formula (I): [ka] During the ceremony, M is titanium, zirconium, hafnium, scandium, yttrium, or an element from the lanthanide series of the periodic table; n is 1, 2, or 3; Each X is unsaturated (C2 to C 50 ) Hydrocarbons, unsaturated (C2-C 50 ) Heterohydrocarbons, (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 and optionally two X's may be linked together; the metal-ligand complex is overall charge neutral; Each Z is -O-, -S-, -N(R N )-, or -P(R P )- are independently selected from R 1 and R 16 But -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, -ORC , -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 N )-, (R C )NC(O)—, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV); [ka] In the formula, R 31~35 , R 41~48 , and R 51~59 Each of the following is -H, (C1 to 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 )NC(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 15Independently, -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 )NC(O)—, and halogen; L is (C1~C 40 ) hydrocarbylene or (C2-C 40 ) heterohydrocarbylene, Each R in formula (I) C , R P , and R N However, independently, (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H; and A polymerization process wherein the ratio of moles of aluminum in said hydrocarbyl-modified methylaluminoxane to moles of metal in said metal-ligand complex is less than 500. Section 2. Item 1. The polymerization process according to item 1, wherein the ratio of the moles of aluminum in the hydrocarbyl-modified methylaluminoxane to the moles of metal in the metal-ligand complex is greater than 20 and less than 300. Section 3. 3. The polymerization process of claim 1 or 2, wherein the hydrocarbyl-modified methylaluminoxane has less than 20 mole percent trialkylaluminum, based on the total moles of aluminum. Section 4. 3. The polymerization process of claim 1 or 2, wherein the hydrocarbyl-modified methylaluminoxane has less than 15 mole percent trialkylaluminum, based on the total moles of aluminum. Section 5. 3. The polymerization process of claim 1 or 2, wherein the hydrocarbyl-modified methylaluminoxane has less than 10 mole percent trialkylaluminum based on the total moles of aluminum. Section 6. Item 6. The polymerization process according to any one of items 1 to 5, wherein the hydrocarbyl-modified methylaluminoxane is a modified methylaluminoxane. Section 7. R 1 and R 16 and (c) are the same as each other. Section 8. R 1 and R 16 8. The polymerization process according to any one of items 1 to 7, wherein at least one of the radicals is a radical having formula (III). Section 9. R 42 and R 47 However, (C1~C 20 ) hydrocarbyl or -Si[(C 20 Item 9. The polymerization process according to item 8, wherein the aryl group is a methyl group, ... Section 10. R 43 and R 46 However, (C1~C 20 ) hydrocarbyl or -Si[(C 20 Item 9. The polymerization process according to item 8, wherein the aryl group is a methyl group, ... Section 11. R 1 and R 16 Item 7. The polymerization process according to any one of Items 1 to 6, wherein at least one of the following is a radical having formula (II): Section 12. R 32 and R 34 However, (C1~C 12 ) hydrocarbyl or -Si[(C 20Item 12. The polymerization process according to item 11, wherein the aryl group is a methyl group, ... Section 13. R 1 and R 16 7. The polymerization process according to any one of items 1 to 6, wherein at least one of the radicals is a radical having formula (IV). Section 14. R 52 , R 53 , R 55 , R 57 , and R 58 At least two of the 20 ) hydrocarbyl or -Si[(C 20 Item 14. The polymerization process of item 13, wherein the aryl group is methyl)hydrocarbyl]3. Section 15. R 5 , R 6 , R 7 , and R 8 at least one of is a halogen atom, R 9 , R 10 , R 11 , and R 12 Item 15. The polymerization process according to any one of items 1 to 14, wherein at least one of the groups is a halogen atom. Section 16. R 8 and R 9 However, (C1~C 20 Item 15. The polymerization process according to any one of items 1 to 14, wherein the alkyl is independently selected from the group consisting of alkyl, aryl, aryl, aryls ... Section 17. R 8 and R 9 Item 15. The polymerization process according to any one of items 1 to 14, wherein is independently selected from methyl, ethyl, 1-propyl, or 2-propyl. Section 18. R 3 and R 14 However, (C1~C 10 Item 18. The polymerization process according to any one of items 1 to 17, wherein the alkyl is alkyl. Section 19. R 3 and R 14 is methyl, and R6 and R 11 Item 19. The polymerization process according to any one of items 1 to 18, wherein is a halogen. Section 20. R 7 and R 10 Item 16. The polymerization process according to any one of items 1 to 15, wherein is a halogen. Section 21. R 6 and R 11 Item 16. The polymerization process according to any one of items 1 to 15, wherein is tert-butyl. Section 22. R 3 and R 14 Item 16. The polymerization process according to any one of items 1 to 15, wherein is tert-octyl or n-octyl. Section 23. L is -CH2(CH2) where m is 1 to 3. m CH2-, -CH2Si(R C )(R D )CH2-, -CH2Ge(R C )(R D )CH2-, -CH2(CH3)CH2CH * (CH3), bis(methylene)cyclohexane-1,2-diyl; -CH2CH(R C )CH2-, -CH2C(R C )2CH2-, and each R in L is selected from C (C1~C 20 ) hydrocarbyl, and R in L D (C1~C 20 23. The polymerization process according to any one of items 1 to 22, wherein the alkyl group is a methyl group. Section 24. Item 24. The polymerization process according to any one of items 1 to 23, wherein M is zirconium or hafnium. Section 25. The olefin monomer is (C3 to C 20 25. The polymerization process according to any one of items 1 to 24, wherein the olefin is an α-olefin. Section 26. Item 26. The polymerization process according to any one of items 1 to 25, wherein the olefin monomer is a cyclic olefin. Section 27. The olefin monomer is (C3 to C 20 27. The polymerization process according to any one of items 1 to 26, wherein the olefin is not an α-olefin. Section 28. Item 28. The polymerization process according to any one of items 1 to 27, wherein the polymerization process is a solution polymerization process.

[0103] One or more features of the present disclosure will be illustrated in light of the following examples. [Example]

[0104] Analysis of hydrocarbyl-modified methylaluminoxanes Example 1 is an analytical procedure for determining the aluminum concentration in a solution.

[0105] In a nitrogen atmosphere glove box, A1 R B1 R C1 The aluminum-based analyte, having a pH of 1.0, was transferred to a weighed bottle and the sample mass was recorded. The sample was diluted with methylcyclohexane and then quenched with methanol. The mixture was swirled and allowed to react for 15 minutes before removing the sample from the glovebox. Further hydrolysis was performed by adding H2SO4. The bottle was capped and shaken for 5 minutes. Depending on the aluminum concentration, periodic venting of the bottle may be necessary. The solution was transferred to a separatory funnel. The bottle was repeatedly rinsed with water, with each rinse from this process being 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, with each rinse being added to the volumetric flask. The flask was diluted to a known volume, mixed thoroughly, and analyzed by complexation with excess EDTA, followed by back-titration with ZnCl2 using xylenol orange as the indicator.

[0106] AlR in hydrocarbyl-modified methylaluminoxane A1 R B1 R C1 Compound calculations.

[0107]

number

[0108] AlR A1 R B1 R C1 The compound content is analyzed using methods previously described (Macromol. Chem. Phys. 1996, 197, 1537; WO 2009029857(A1); Analytical Chemistry 1968, 40(14), 2150-2153; and Organometallics 2013, 32(11), 3354-3362).

[0109] Examples 1-3 are synthetic procedures for intermediates and isolated cocatalysts.

[0110] Synthetic procedures for synthesizing metal-ligand complexes 1-12 can be found in the following procedures and, where previously disclosed, in the following published patent applications: U.S. Patent Application Publication No. 2004 / 0010103(A1), WO 2007 / 136494(A2), WO 2012 / 027448(A1), WO 2016 / 003878(A1), WO 2016 / 014749(A1), WO 2017 / 058981(A1), WO 2018 / 022975(A1), WO 2012 / 027448(A1), WO 2018 / 022975(A1).

[0111] Metal-ligand complexes 1-15 have a structure according to formula (I) and are as follows:

[0112] [ka]

[0113] [ka]

[0114] Preparation of BPP-3 (ligand disclosed in WO 2018 / 022975(A1))

[0115] [ka] 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 −30 °C solution of ZrCl (0.895 g, 3.84 mmol) in toluene (60 mL). After stirring for 3 min, solid ligand (5.00 g, 3.77 mmol) was added portionwise. The mixture was stirred for 8 h, and then the solvent was removed in vacuo to give 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 before the material was passed through a fritted 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 tan 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 give BPP-3 (4.50 g, 83% yield) as a white powder. 1H 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); 19 F NMR(376MHz,C6D6)δ-116.71.

[0116] Synthesis of BPP-9

[0117] [ka] An oven-dried 100 mL glass bottle was charged with ZrCl4 (798 mg, 3.43 mmol), toluene (30 mL), and a stir bar. The solution was placed in a freezer and cooled to −30 °C for 20 min. 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 min. To the cooled suspension, BPP-9 ligand (5.00 g, 3.26 mmol) was added as a solid. The reaction was stirred at room temperature for 3 h and then filtered through a fritted plastic funnel. The filtrate was evaporated to dryness. The resulting solid was washed with hexane and dried in vacuo to give BPP-9 as an off-white powder (3.31 g, 62%). 1H NMR(400 MHz,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).

[0118] Preparation of BPP-10

[0119] [ka] Synthesis of 2-bromo-4-fluoro-6-methyl-phenol: A 1 L glass bottle was charged with acetonitrile (400 mL), 4-fluoro-6-methyl-phenol (50 g, 396.4 mmol), and p-toluenesulfonic acid (monohydrate) (75.6 g, 396 mmol), ensuring everything was in solution. The solution was cooled to 0° C. in ice for 25 minutes (a precipitate formed). The cooled solution was slowly treated (over approximately 5 minutes) with N-bromosuccinimide (70.55 g, 396.4 mmol) and allowed to reach room temperature with stirring overnight. The reaction was then cooled to 0° C. for 25 minutes (a precipitate formed). The reaction mixture ... 19 Analysis by F NMR spectroscopy and GC / MS confirmed complete conversion. Volatiles were removed in vacuo, 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 CHCl. ​​Volatiles were removed in vacuo (yield of the first fraction: 46 g, 56%). 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 F NMR (376 MHz, chloroform-d) δ −122.84.

[0120] [ka]

[0121] Bis((2-bromo-4-fluoro-6- Methylphenoxy)methyl)diisopropylgermane: In a glovebox, in a 250 mL flask equipped with a magnetic stir bar, 95% NaH (1.76 g) (Caution, H2 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 (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 glovebox and quenched with saturated aqueous NH4Cl (20 mL) and HO (8 mL). Et2O (30 mL) was added, and the phases were transferred to a separatory funnel and separated. The aqueous phase was further extracted with EtO (20 mL), and the combined organic extracts were washed with brine (10 mL). The organic layer was then dried (MgSO), 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 hexanes with ethyl acetate increasing to 10% over 20 min) to give a pale yellow oil as the product. All clean fractions (some fractions contained less than 10% of the starting phenol) were combined, and the final product was left under vacuum overnight (yield: 9 g, 62%). 1H NMR(400MHz,クロロホルム-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 (376MHz, クロロホルム-d) δ-118.03.

[0122] Synthesis of BPP-10 ligand

[0123]

change

[0124] Synthesis of BPP-10

[0125] [ka] An oven-dried 100 mL glass bottle was charged with ZrCl4 (402 mg, 1.72 mmol), toluene (83 mL), and a stir bar. The solution was placed in a freezer and cooled to −30 °C for 20 min. 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 min. To the cold suspension, 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 fritted 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 (approximately 5 mL) and dried under vacuum to give BPP-10 as an off-white powder (2.1 g, 84%). 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.

[0126] Synthesis of BPP-12 Preparation of bis((2-bromo-4-t-butylphenoxy)methyl)diisopropylsilane

[0127] [ka] In a glovebox, diisopropyldichlorosilane (3.703 g, 20 mmol, 1.0 equiv.) was dissolved in anhydrous THF (120 mL) in a 250 mL single-neck round-bottom flask. The flask was capped with a septum, sealed, removed from the glovebox, 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 hexanes (18.4 mL, 46 mmol, 2.3 equiv.) was added to the cold wall of the flask over 3 hours. The mixture was allowed to warm to room temperature overnight (16 hours), and saturated NH4Cl (30 mL) was added. The two layers were 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.

[0128] In a glovebox, 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.), K-3PO4 (7.46 g, 35 mmol, 3.5 equiv.), and DMF (10 mL). The reaction mixture was stirred at 80 °C overnight. After cooling back 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, representing an overall yield of 73% after two steps.

[0129] 1H NMR(400 MHz,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).

[0130] 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)

[0131] [ka] 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 a 4 M solution of NaOH (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). Concentrated HCl (0.5 mL) was then added. The resulting reaction 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 reverse-phase column chromatography using THF / MeCN (0 / 100→100 / 0) as the eluent. 1.62 g of a white solid was recovered (78% yield).

[0132] 1H 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).

[0133] Preparation of BPP-12

[0134] [ka] In a glovebox, an oven-dried 40 mL vial 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 min. The vial was removed from the freezer. MeMgBr (3 M, 0.29 mL, 0.86 mmol, 4.3 equiv.) was added to the stirring suspension. After 2 min, 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 in vacuo 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 in vacuo. 170 mg of a white solid was recovered (74% yield).

[0135] 1H 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).

[0136] Preparation of BPP-15

[0137] [ka] In a nitrogen glovebox, an oven-dried vial was charged with ScCl (0.016 g, 0.106 mmol), THF (approximately 50 mL), and a magnetic stir bar. After the mixture was cooled to -30 °C, LiCH TMS (1.0 M in pentane, 0.35 mL, 0.35 mmol) was added dropwise, and the mixture was then 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 (approximately 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 give BPP-19 as a white solid (0.154 g, 83%).

[0138] Preparation of the ligand as detailed in WO 2017 / 058981 A1. Example 1—Metal-Ligand Complexes 7, 8, 12, 13, 14, Borate Activator, and Less than 25 Mole Percent AlR Based on Total Moles of Aluminum A1 R B1 R C1 Batch reactor polymerization reaction using hydrocarbyl-modified methylaluminoxane having

[0139] Metal-ligand complexes 7, 8, 12, 13, and 14 were tested in a batch reactor using MMAO-A1, MMAO-A2, or MMAO-comp1 with a borate activator, and the data are summarized in Tables 1–6. Dry weight efficiencies are higher when the catalyst is activated with borate in the presence of MMAO-A1 or MMAO-A2, as opposed to MMAO-comp1.

[0140] [Table 1]

[0141] Polymerization conditions: 1.47 kg ISOPAR E; 100 g 1-octene; 100 g ethylene; total pressure = 410 psi at 160 °C; metal-ligand complex:activator = 1:1.2; activator = [HNMe(C 18 H 37 )2][B(C6F5)4]; reaction time = 10 min.

[0142] [Table 2]

[0143] Polymerization conditions: 1.25 kg ISOPAR E; 60 g 1-octene; 100 g ethylene; 40 mmol H2, total pressure = 320 psi at 160 °C; metal-ligand complex:activator = 1:1.2; activator = [HNMe(C 18 H 37 )2][B(C6F5)4]; reaction time = 10 min.

[0144] [Table 3]

[0145] Polymerization conditions: 1.25 kg ISOPAR E; 60 g 1-octene; 100 g ethylene; 40 mmol H2, total pressure = 320 psi at 160 °C; metal-ligand complex:activator = 1:1.2; activator = [HNMe(C 18 H 37 )2][B(C6F5)4]; reaction time = 10 min.

[0146] [Table 4]

[0147] Polymerization conditions: 1.25 kg ISOPAR E; 60 g 1-octene; 100 g ethylene; 40 mmol H2, total pressure = 320 psi at 160 °C; metal-ligand complex:activator = 1:1.2; activator = [HNMe(C 18 H 37 )2][B(C6F5)4]; reaction time = 10 min.

[0148] [Table 5]

[0149] Polymerization conditions: 1.25 kg ISOPAR E; 60 g 1-octene; 100 g ethylene; 40 mmol H2, total pressure = 320 psi at 160 °C; metal-ligand complex:activator = 1:1.2; activator = [HNMe(C 18 H 37 )2][B(C6F5)4]; reaction time = 10 min.

[0150] Example 2—BPP-8, borate activator, and less than 25 mole percent AlR based on total moles of aluminum A1 R B1 R C1 Continuous process polymerization reaction data using hydrocarbyl-modified methylaluminoxane having the formula:

[0151] [Table 6]

[0152] Polymerization conditions: 175°C, feed rate 191 lb / h ethylene, 69 lb / h 1-octene, 648 lb / h ISOPAR E, 650 psi, metal-ligand complex:activator=1:1.0; activator=[HNMe(C 18 H 37)2][B(C6F5)4]; [A] The % solids is the polymer concentration in the reactor. [B] H2 (mol %) is defined as the mole fraction of hydrogen relative to the ethylene fed to the reactor. [C] Efficiency (Eff.) is 10 6 It is measured as g polymer / g metal.

[0153] 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 passage through activated alumina and, in some cases, Q-5 reactants. Solvents used in experiments conducted in a nitrogen-filled glovebox were further dried by storage over activated 4 Å molecular sieves. Moisture-sensitive reaction glassware was dried overnight in an oven before use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analysis was performed using a Waters e2695 separations module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separation is performed on an XBridge C18 3.5 μm 2.1 × 50 mm column using a 5:95 to 100:0 gradient of acetonitrile and water (containing 0.1% formic acid as the ionizing agent). HRMS analysis is performed using an Agilent 1290 Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm 2.1 × 50 mm column coupled to an Agilent 6230 TOF mass spectrometer equipped with electrospray ionization. 1 H NMR data are reported as follows: chemical shifts (multiplicities (br = broad line, s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, sex = sextet, sept = septet, and m = multiplet), integrals, and assignments). 1Chemical shifts for H NMR data are reported as ppm downfield from internal tetramethylsilane (TMS, δ scale) using residual protons in the deuterated solvent as the reference. 13 C NMR data is 1 Determined with 1 H decoupling, chemical shifts are reported as ppm downfield from tetramethylsilane (TMS, δ scale) using residual carbon in the deuterated solvent as the reference.

Claims

1. 1. A process for polymerizing olefin monomers, comprising reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system, said catalyst system comprising an activator and a hydrocarbyl-modified methylaluminoxane having less than 25 mole percent trialkylaluminum, based on the total moles of aluminum, wherein the trialkylaluminum is AlR Ａ１ R Ｂ１ R Ｃ１ wherein R Ａ１ , R Ｂ１ , and R Ｃ１ are independently linear (C １ ~C ４０ ) alkyl, branched (C １ ~C ４０ ) alkyl, or (C １ ~C ４０ ) aryl, and one or more metal-ligand complexes comprising a hydrocarbyl-modified methylaluminoxane and a metal-ligand complex according to formula (I): 【Chemical 1】 During the ceremony, M is titanium, zirconium, hafnium, scandium, yttrium, or an element from the lanthanide series of the periodic table; n is 1, 2, or 3; Each X is an unsaturated (C ２ ~C ５０ ) hydrocarbons, unsaturated (C ２ ~C ５０ ) heterohydrocarbons, (C １ ~C ５０ ) hydrocarbyl, (C ６ ~C ５０ ) aryl, (C ６ ~C ５０ ) heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C ４ ~C １２ ) diene, halogen, -N(R Ｎ ) ２ , and −N(R Ｎ ) COR Ｃ and optionally two X may be linked together; the metal-ligand complex is overall charge neutral; Each Z is -O-, -S-, -N(R Ｎ ) - or -P(R Ｐ )—independently selected from R １ and R １６ But -H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, -N=C(R Ｃ ) ２ , R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ ) -, (R Ｃ ) ２ independently selected from the group consisting of NC(O)—, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV); 【Chemistry 2】 In the formula, R ３１～３５ , R ４１～４８ , and R ５１～５９ Each of １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ ) -, (R Ｃ ) ２ independently selected from NC(O)—, or halogen; R 2 , R 3 , R 4 , R 13 , R 14 , and R 15 are —H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ independently selected from NC(O)— and halogen; (1) R 5 to R 12 are —H, or (2) R 5 , R 7 , R 8 , R 9 , R 10 , and R 12 are —H, and R 6 and R 11 are (C 1 to C 40 )hydrocarbyl, (C 1 to C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C independently selected from C(O)N(R)—, (R C ) 2 NC(O)—, and halogen; L is (C １ ~C ４０ ) hydrocarbylene or (C ２ ~C ４０ ) heterohydrocarbylene; Each R in formula (I) Ｃ , R Ｐ , and R Ｎ But independently, (C １ ~C ３０ ) hydrocarbyl, (C １ ~C ３０ ) heterohydrocarbyl, or —H; and wherein the ratio of moles of aluminum in said hydrocarbyl-modified methylaluminoxane to moles of metal in said metal-ligand complex is 100 or greater.

2. 2. The polymerization process of claim 1, wherein the ratio of moles of aluminum in said hydrocarbyl-modified methylaluminoxane to moles of metal in said metal-ligand complex is less than 500.

3. 10. The polymerization process of claim 1, wherein the hydrocarbyl-modified methylaluminoxane has less than 20 mole percent trialkylaluminum, based on the total moles of aluminum.

4. 2. The polymerization process of claim 1, wherein the hydrocarbyl-modified methylaluminoxane has less than 15 mole percent trialkylaluminum based on the total moles of aluminum, or wherein the hydrocarbyl-modified methylaluminoxane has less than 10 mole percent trialkylaluminum based on the total moles of aluminum.

5. 2. The polymerization process of claim 1, wherein the hydrocarbyl-modified methylaluminoxane is a modified methylaluminoxane.

6. R １ and R １６ is a radical having the formula (III).

7. R ４２ and R ４７ However, (C １ ~C ２０ ) hydrocarbyl or —Si[(C １ ~C ２０ ) hydrocarbyl] ３ or R ４３ and R ４６ However, (C １ ~C ２０ ) hydrocarbyl or —Si[(C １ ~C ２０ ) hydrocarbyl] ３ 7. The polymerization process of claim 6, wherein

8. R １ and R １６ is a radical having the formula (II).

9. R ３２ and R ３４ However, (C １ ~C １２ ) hydrocarbyl or —Si[(C １ ~C ２０ ) hydrocarbyl] ３ 9. The polymerization process of claim 8, wherein

10. R １ and R １６ 2. The polymerization process of claim 1, wherein at least one of: is a radical having formula (IV):

11. R ５２ , R ５３ , R ５５ , R ５７ , and R ５８ At least two of (C １ ~C ２０ ) hydrocarbyl or —Si[(C １ ~C ２０ ) hydrocarbyl] ３ 11. The polymerization process of claim 10, wherein

12. R ３ and R １４ However, (C １ ~C １０ 2. The polymerization process of claim 1 wherein:

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

14. L is —CH where m is 1 to 3. ２ (CH ２ ) ｍ CH ２ -, -CH ２ Si(R Ｃ ) (R Ｄ ) CH ２ -, -CH ２ Ge(R Ｃ ) (R Ｄ ) CH ２ -, -CH ２ (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 -, and each R in L is selected from Ｃ But (C １ ~C ２０ ) hydrocarbyl, and R in L Ｄ But (C １ ~C ２０ 2. The polymerization process of claim 1 wherein the alkyl group is a methyl group.

15. The olefin monomer (C ３ ~C ２０ 2. The polymerization process of claim 1, wherein the olefin is an α-olefin.

16. 10. The polymerization process of claim 1, wherein the olefin monomer is a cyclic olefin.

17. The olefin monomer (C ３ ~C ２０ 2. The polymerization process of claim 1, wherein the olefin is not an α-olefin.

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