Hydrocarbyl-modified methylaluminoxane cocatalysts for constrained geometry procatalysts.

Abstract

A process for polymerizing olefin monomers, the process comprising reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system, the catalyst system comprising less than 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 However, independently, linear (C1-C 40 ) Alkyl, branched (C1-C 40 ) alkyl, or (C6-C 40 ) aryl, and one or more procatalysts comprising a metal-ligand complex according to formula (I). [Formula 1] JPEG2023534659000019.jpg28170

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 053,348, filed July 17, 2020, the entire disclosure of which is incorporated herein by reference.

[0002] (Summary of the Invention) FIELD OF THE DISCLOSURE Embodiments of the present disclosure generally relate to hydrocarbyl-modified methylaluminoxane activators for catalyst systems, including constrain geometry catalysts (CGCs). [Background technology]

[0003] Olefin-based polymers, such as polyethylene, are produced through a variety of catalyst systems and polymerization processes. The selection of such catalyst system used in the polymerization process of an olefin-based polymer is an important factor that contributes to the characteristics and properties of such an olefin-based polymer.

[0004] Polyolefin polymerization processes can be varied in many ways to produce a wide variety of resulting polyolefin resins with different physical properties suitable for use in different applications. It is generally known that polyolefins can be produced in solution phase, gas phase, and / or slurry phase polymerization processes in the presence of one or more catalyst systems, for example, in one or more reactors connected in series or parallel. The use of activating agents in polyolefin polymerization processes to activate pre-catalyst compositions is generally known.

[0005] Although methylaluminoxane (MAO) works well to activate constrained geometry catalysts (CGC), MAO is typically incompatible with solution processing due to its limited solubility in hydrocarbon solvents. To increase solubility, MAO is modified with longer alkyl chains, creating modified methylaluminoxane (MMAO) with a mixture of both methyl and longer alkyl groups present in the structure. Both the amount of modifier and the amount of trialkylaluminum (AlR3) are important to maintain the solubility and stability of MMAO in hydrocarbon solvents.

[0006] As part of the catalyst composition in an α-olefin polymerization reaction, the activator can have characteristics that are beneficial to the production of α-olefin polymers and to the final polymer composition comprising the α-olefin polymer. Activator characteristics 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.

[0007] In particular, borate-based cocatalysts have significantly contributed to our fundamental understanding of olefin polymerization mechanisms, improving our ability to precisely control polyolefin microstructure by deliberately tailoring catalyst structure and process. This has led to increased interest in mechanistic studies and the development of novel homogeneous olefin polymerization catalyst systems that precisely control polyolefin microstructure and performance. However, when the activator or cocatalyst cation activates the procatalyst, the activator ion may remain in the polymer composition. As a result, the borate anion may affect the polymer composition. Specifically, the size of the borate anion, the charge of the borate anion, the interaction of the borate anion with the surrounding medium, and the dissociation energy of the borate anion with available counterions will affect the ability of the ion to diffuse through surrounding media, such as solvents, gels, or polymeric materials.

[0008] Modified methylaluminoxane (MMAO) is used as an activator in some PE processes. However, MMAO has been found to adversely affect the performance of some catalysts, such as CGC catalysts, and the production of polyolefin or polyvinyl resins. The adverse effects on the polymerization process include reduced catalyst activity, broadened compositional distribution of the produced polymer, and adversely affected pellet handling. Summary of the Invention

[0009] There is a continuing need to engineer catalyst systems that maintain catalytic efficiency, reactivity, and the ability to produce polymers with good physical properties.

[0010] 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 and a procatalyst. Less than 25 mole percent of the trihydrocarbyl aluminum compound AlR, based on the total moles of aluminum, is present. A1 R B1 R C1 wherein R A1 , R B1 , and R C1 However, independently, linear (C1-C 40 ) Alkyl, branched (C1-C 40 ) alkyl, or (C6-C 40 ) aryl, and one or more procatalysts comprising a metal-ligand complex according to formula (I):

[0011] [ka]

[0012] In formula (I), Ti is titanium. (X) nThe subscript n is 1, 2, or 3. Each X is independently an unsaturated (C-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 -NCOR C The metal-ligand complex is generally charge neutral.

[0013] In formula (I), Cp is cyclopentadienyl and R S substituted cyclopentadienyl, wherein Cp is selected from the group consisting of η 5 bonded to Ti in a bonding mode and R S However, independently, (C1-C 20 ) alkyl, (C1-C 20 Heteroalkyl, (C1-C 20 ) aryl, or R S Substituent (C1-C 20 ) aryl, (C1-C 20 ) heteroaryl, or R S Substituent (C1-C 20 ) heteroaryl, wherein two adjacent R S The groups are optionally joined to form a ring.

[0014] In formula (I), N is nitrogen. Y is carbon or silicon, where Y is covalently bonded to Cp and R 1 and R 2 However, independently, -H, (C1-C 40 ) hydrocarbyl, and (C-C 40 ) heterohydrocarbyl, R 3 However, independently, (C1-C 40 ) hydrocarbyl, and (C-C 40) heterohydrocarbyl. DETAILED DESCRIPTION OF THE INVENTION

[0015] 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.

[0016] Common abbreviations are listed below.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] When used to describe certain carbon atom-containing chemical groups, "(C x -C y A parenthesized expression having the form "(C1-C2)" means that the unsubstituted form of the chemical group has at least x, and at most y, carbon atoms. For example, (C1-C2) 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 S may 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 is phenyl (-C6H5)) 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

[0021] 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.

[0022] "(C1-C 50 The term "(C1-C2) 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 can be unsubstituted or can contain one or more R S In some instances, each hydrogen atom in a hydrocarbon radical can be substituted with R, such as trifluoromethyl. S can be substituted with unsubstituted (C1-C 50 Examples of alkyl are unsubstituted (C-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 (C-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 that is (C-C) alkyl, such as methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl. S replaced by, for example, (C 27 -C 40 ) alkyl.

[0023] (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-eneyl, (3-methyl)hexa-1,4-dienyl, and (Z)-1-(6-methylhept-3-en-1-yl)cyclohex-1-enyl.

[0024] "(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 (C x -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 (C-C 20 ) cycloalkyl, substituted (C3-C 10 ) cycloalkyl, and 1-fluorocyclohexyl.

[0025] 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

[0026] 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 substituted by, one or more double or triple bonds may optionally be 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 S This 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).

[0027] The term "hydrocarbyl-modified methylaluminoxane" refers to a methylaluminoxane (MAO) 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 impart increased solubility of the aluminoxane in hydrocarbon solvents such as, but not limited to, hexane, heptane, methylcyclohexane, and ISOPAR E™, as shown in U.S. Pat. No. 5,777,143. Modified methylaluminoxane compositions are generally disclosed and can be prepared as described in U.S. Pat. No. 5,066,631 and U.S. Pat. No. 5,728,855, both of which are incorporated herein by reference.

[0028] 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 in hafnocene-catalyzed propylene homopolymerizations at 60°C (Busico, V. et al. Macromolecules 2009, 42, 1789-1791). However, these observations may complicate differences in MAO activation versus borate activation, and even in direct comparisons, may only capture differences between some trimethylaluminum and no trimethylaluminum. Additionally, it is unclear whether such observations extend to other catalyst systems, ethylene polymerizations, or polymerizations conducted at higher temperatures. In any case, the preference for soluble MAO necessitates the use of MMAO, and therefore the presence of trihydrocarbylaluminum species.

[0029] In one or more embodiments, the process comprises reacting ethylene and, optionally, one or more olefin monomers in the presence of a catalyst system comprising a hydrocarbyl-modified methylaluminoxane and a procatalyst, wherein the catalyst system comprises less than 25 mole percent of the trihydrocarbyl aluminum compound AlR, based on the total moles of aluminum. A1 R B1 R C1 wherein R A1 , R B1 , and R C1 However, independently, linear (C1-C 40 ) Alkyl, branched (C1-C 40 ) alkyl, or (C6-C 40 ) aryl, and one or more procatalysts comprising a metal-ligand complex according to formula (I):

[0030] [ka]

[0031] In formula (I), Ti is titanium having a formal oxidation state of +2, +3, or +4. (X) n The subscript n is 1, 2, or 3. Each X is independently an unsaturated (C-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 -NCOR C The metal-ligand complex is generally charge neutral.

[0032] In formula (I), Cp is cyclopentadienyl and R S substituted cyclopentadienyl, wherein Cp is selected from the group consisting of η 5 bonded to Ti in a bonding mode and R S However, independently, (C1-C 20 ) alkyl, (C1-C 20 Heteroalkyl, (C1-C 20 ) aryl, or R S Substituent (C1-C 20 ) aryl, (C1-C 20 ) heteroaryl, or R S Substituent (C1-C 20 ) heteroaryl, wherein two adjacent R S The groups are optionally joined to form a ring.

[0033] In formula (I), N is nitrogen. Y is carbon or silicon, where Y is covalently bonded to Cp and R 1and R 2 However, independently, -H, (C1-C 40 ) hydrocarbyl, and (C-C 40 ) heterohydrocarbyl, R 3 However, independently, (C1-C 40 ) hydrocarbyl, and (C-C 40 ) heterohydrocarbyl.

[0034] 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.

[0035] In some embodiments, the olefin monomer is (C3-C 20 In other embodiments, the olefin monomer is a (C-C 20 ) an α-olefin. In various embodiments, the olefin monomer is a cyclic olefin.

[0036] In various embodiments, the polymerization process of the present disclosure does not include a borate activator.

[0037] In embodiments, the hydrocarbyl-modified methylaluminoxane in the polymerization process has less than 20 mole percent trihydrocarbyl aluminum, based on the total moles of aluminum. In some embodiments, the hydrocarbyl-modified methylaluminoxane has less than 15 mole percent trihydrocarbyl aluminum, based on the total moles of hydrocarbyl-modified methylaluminoxane. In one or more embodiments, the hydrocarbyl-modified methylaluminoxane has less than 10 mole percent trihydrocarbyl aluminum, based on the total moles of hydrocarbyl-modified methylaluminoxane. In various embodiments, the hydrocarbyl-modified methylaluminoxane is a modified methylaluminoxane.

[0038] In some embodiments, the trihydrocarbyl aluminum is AlRA1 R B1 R C1 wherein R A1 , R B1 , and R C1 However, independently, linear (C1-C 20 ) Alkyl, Linear (C1-C 15 ) alkyl, or linear (C1-C 12 ) alkyl. In one or more embodiments, R A1 , R B1 , and R C1 is independently methyl, ethyl, propyl, 2-propyl, butyl, n-octyl, nonyl, decyl, undecyl, or dodecyl. A1 , R B1 , and R C1 are the same. In another embodiment, R A1 , R B1 , and R C1 At least one of the R A1 , R B1 , and R C1 is different from.

[0039] In one or more embodiments, R 1 and R 2 are independently (C1-C 12 ) alkyl or (C6-C 20 ) aryl. In some embodiments, R 1 and R 2 is methyl, ethyl, propyl, or phenyl.

[0040] In various embodiments, R 3 are independently (C1-C 12 ) alkyl. In some embodiments, R 3 is independently tert-butyl, tert-octyl, or n-octyl.

[0041] In some embodiments, Cp is tetramethylcyclopentadienyl.

[0042] In one or more embodiments, Cp is selected from the following:

[0043] [ka]

[0044] [ka]

[0045] In some embodiments, the chemical groups (e.g., X and R) of the metal-ligand complex of formula (I) 1-3 In other embodiments, any or all of the chemical groups X and R of the metal-ligand complex of formula (I) may be unsubstituted. 1-3 Any of the following may contain one or more R S Even if they are not substituted with one or more R S It 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 1-3 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 (C-C 20 ) heteroalkyl.

[0046] It takes (C1-C 12Examples 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.

[0047] In the metal-ligand complex according to formula (I), X is bonded to Ti through a covalent or ionic bond. In some embodiments, X can be a monoanionic ligand having a net formal oxidation number of -1. Each monoanionic ligand can independently be a hydride, (C1-C 40 ) hydrocarbyl carbanion, (C 1- C 40 ) Heterohydrocarbyl carbanions, halides, nitrates, carbonates, phosphates, sulfates, HC(O)O - , HC(O)N(H) - , (C1-C 40 ) Hydrocarbyl C(O)O - , (C 1- C 40 ) hydrocarbylC(O)N((C 1- C 20 )hydrocarbyl) - , (C 1- 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 Mare independently hydrogen, (C 1- C 40 ) hydrocarbyl, or (C 1- C 40 ) heterohydrocarbyl, or R K and R L Together, (C 2- C 40 ) hydrocarbylene or (C 1- C 20 ) form a heterohydrocarbylene, and R M is as defined above.

[0048] In some embodiments, X is halogen, unsubstituted (C-C 20 ) hydrocarbyl, unsubstituted (C1-C 20 ) hydrocarbyl C(O)O—, or R K R L N-, where R K and R L each independently is unsubstituted (C-C 20 In some embodiments, each monodentate ligand X is a chlorine atom, (C-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 R L each independently is unsubstituted (C-C 10 ) hydrocarbyl.

[0049] 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 together form a bidentate ligand. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

[0050] In some embodiments, X is substituted benzyl or heteroarylbenzyl.

[0051] In one or more embodiments, X is

[0052] [ka] wherein the heteroatom coordinates to the titanium metal via a dative covalent bond.

[0053] In one or more embodiments, each X is independently —(CH 2 )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 Xis methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl.

[0054] 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.

[0055] 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.

[0056] In some embodiments, X is an unsaturated (C2-C 50) Hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, or saturated (C2-C 50 ) heterohydrocarbons. In various embodiments, X is butadiene, cyclopentadiene, or penta-1,3-diene.

[0057] In one or more embodiments, the olefin polymerization process is a solution polymerization process.

[0058] In solution processes for olefin polymerization, catalyst and cocatalyst components, such as scavengers and activators, are generally added as a homogeneous solution. In many solution processes, the solvent is a non-aromatic hydrocarbon. The use of a homogeneous solution allows for greater flexibility in process configuration and allows for the use of delivery and storage vessels that do not require internal stirring, which is commonly used with heterogeneous solutions. Cocatalysts, such as methylaluminoxane, which can act as both activators and scavengers in olefin polymerization, are typically not soluble in non-aromatic hydrocarbons.

[0059] 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 procatalyst of the metal-ligand complex of formula (I) can be made catalytically active by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. In addition, the metal-ligand complex of formula (I) includes both a neutral procatalyst form and a catalyst form that can be positively charged by loss of a monoanionic ligand such as benzyl or phenyl. Suitable activating cocatalysts for use herein include oligomeric alumoxanes or modified alkylaluminoxanes.

[0060] 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.

[0061] 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.

[0062] In some embodiments, the ethylene-based polymer can comprise at least 90 mole percent 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 can comprise at least 93 mole percent units derived from ethylene, at least 96 mole percent units, at least 97 mole percent units derived from ethylene, or alternatively, 90 to 100 mole percent units derived from ethylene, 90 to 99.5 mole percent units derived from ethylene, or 97 to 99.5 mole percent units derived from ethylene.

[0063] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50 mol %, other embodiments include at least 1 mole percent (mol %) to 25 mol %, and in further embodiments, the amount of additional α-olefin is at least 5 mol % to 103 mol %, hi some embodiments, the additional α-olefin is 1-octene.

[0064] Any conventional polymerization process may be used to produce the ethylene-based polymers, including, but not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof, using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, and the like, in parallel, series, or any combination thereof.

[0065] 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.

[0066] In another embodiment, an 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.

[0067] 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 contain 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 the 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.

[0068] 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 ~0.950g / cm 3 , 0.860g / cm 3 ~0.920g / cm 3 , 0.865g / cm 3 ~0.900g / cm 3 , 0.860g / cm 3 ~0.900g / cm 3 , 0.860g / cm 3 ~0.890g / cm 3 , or 0.865 g / cm 3 ~0.890g / cm 3 The density may be

[0069] In another embodiment, the polymer obtained from the catalyst system according to the present disclosure has a melt flow ratio (I10 / I2), where the melt index I2 is measured at 190°C and a load of 2.16 kg in accordance with 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.

[0070] 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.

[0071] 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. 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: Less than 25 mole percent of trihydrocarbyl aluminum compounds AlR, based on total moles of aluminum A1 R B1 R C1 wherein R A1 , R B1 , and R C1 However, independently, linear (C1-C 40 ) Alkyl, branched (C1-C 40) alkyl, or (C6-C 40 ) aryl hydrocarbyl-modified methylaluminoxane; One or more procatalysts comprising a metal-ligand complex according to formula (I): [ka] During the ceremony, Ti is titanium, n is 1, 2, or 3; Each X is independently 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 -NCOR C is a monodentate or bidentate ligand selected from the metal-ligand complex is overall charge neutral; Cp is cyclopentadienyl and R S substituted cyclopentadienyl, wherein Cp is selected from the group consisting of η 5 bonded to Ti in a bonding mode and R S However, independently, (C1-C 20 ) alkyl, (C1-C 20 ) heteroalkyl, (C1-C 20 ) aryl, or R S Substituent (C1-C 20 ) aryl, (C1-C 20 ) heteroaryl, or R S Substituent (C1-C 20 ) heteroaryl, wherein two adjacent R S groups are optionally linked to form a ring; N is nitrogen; Y is carbon or silicon and is covalently bonded to Cp; R1 and R 2 However, independently, -H, (C1-C 40 ) hydrocarbyl, and (C-C 40 ) heterohydrocarbyl; R 3 However, independently, (C1-C 40 ) hydrocarbyl, and (C-C 40 and one or more procatalysts selected from: Section 2. 3. The polymerization process of claim 1 or 2, wherein the hydrocarbyl-modified methylaluminoxane has less than 20 mole percent trihydrocarbyl aluminum, based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane. Section 3. 3. The polymerization process of claim 1 or 2, wherein the hydrocarbyl-modified methylaluminoxane has less than 15 mole percent trihydrocarbyl aluminum, based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane. Section 4. 3. The polymerization process of paragraph 1 or 2, wherein the hydrocarbyl-modified methylaluminoxane has less than 10 mole percent trihydrocarbyl aluminum, based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane. Section 5. Item 5. The polymerization process according to any one of Items 1 to 4, wherein the hydrocarbyl-modified methylaluminoxane is a modified methylaluminoxane. Section 6. R A1 , R B1 , and R C1 However, independently, linear (C1-C 20 ) Alkyl, Linear (C1-C 15 ) alkyl, or linear (C1-C 12 Item 6. The polymerization process according to any one of items 1 to 5, wherein the alkyl is alkyl. Section 7. R A1 , R B1 , and R C1Item 7. The polymerization process according to any one of items 1 to 6, wherein is methyl, ethyl, propyl, 2-propyl, butyl, n-octyl, nonyl, decyl, undecyl, or dodecyl. Section 8. The polyolefin has a viscosity of 0.865 to 0.890 g / cm 3 Item 8. The polymerization process according to any one of items 1 to 7, wherein the density is in the range of Section 9. Item 9. The polymerization process according to any one of items 1 to 8, wherein the polyolefin has a molecular weight in the range of 30,000 to 100,000 g / mol. Section 10. Item 10. The polymerization process of any one of items 1 to 9, wherein the catalyst system does not contain a borate activator. Section 11. The olefin monomer is (C3-C 20 11. The polymerization process according to any one of items 1 to 10, wherein the olefin is an α-olefin. Section 12. The olefin monomer is (C3-C 20 Item 7. The polymerization process according to any one of items 1 to 6, wherein the olefin is not an α-olefin. Section 13. Item 13. The polymerization process according to any one of Items 1 to 12, wherein the olefin monomer is a cyclic olefin. Section 14. R 1 and R 2 However, independently, (C1-C 12 ) alkyl or (C6-C 20 Item 14. The polymerization process according to any one of items 1 to 13, wherein the aryl is aryl. Section 15. R 1 and R 2 Item 15. The polymerization process according to any one of items 1 to 14, wherein is methyl, ethyl, propyl, or phenyl. Section 16. R 3 However, independently, (C1-C 12 Item 16. The polymerization process according to any one of items 1 to 15, wherein the alkyl is alkyl. Section 17. R3 Item 17. The polymerization process according to any one of items 1 to 16, wherein each is independently tert-butyl, tert-octyl, or n-octyl. Section 18. Item 18. The polymerization process of any one of items 1 to 17, wherein Cp is independently tetramethylcyclopentadienyl. Section 19. Item 19. The polymerization process according to any one of items 1 to 18, wherein Cp is selected from the following: [ka] Section 20. Item 20. The polymerization process according to any one of items 1 to 19, wherein the polymerization process is a solution polymerization reaction.

[0072] One or more features of the present disclosure will be illustrated in light of the following examples. [Example]

[0073] Procedure for batch reactor polymerization. The feedstocks (ethylene, 1-octene) and process solvent (a narrow-boiling range, high-purity isoparaffinic solvent commercially available from ExxonMobil Corporation under the trademark ISOPAR E) were purified with molecular sieves. A 1-gallon (3.79 L) stirred autoclave reactor was charged with ISOPAR E and 1-octene. The reactor was then heated to the desired temperature and charged with ethylene to reach the desired pressure. If necessary, hydrogen was also added at this point. The catalyst composition was prepared in a drybox under an inert atmosphere by mixing the desired procatalyst, and optionally one or more additives as needed, with additional solvent to obtain a total volume of approximately 15-20 mL. The activated catalyst mixture was then rapidly injected into the reactor. The reactor pressure and temperature were maintained 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.

[0074] Test Method Unless otherwise indicated herein, the following analytical methods are used in describing aspects of the present disclosure.

[0075] 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 loads of 2.16 kg and 10 kg, respectively. The values are reported in g / 10 min. Fractions of the polymer sample were measured by collecting the product polymer from the reactor producing that particular fraction or portion of the polymer composition. For example, a first polyethylene fraction can be collected from the reactor producing the lower density, higher molecular weight component of the polymer composition. Prior to the melt index measurement, the polymer solution is dried under vacuum.

[0076] 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.

[0077] 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 with 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.

[0078] 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 10-fold spacing 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 above 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights below 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)).

[0079]

number

[0080] 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.

[0081] Total plate counts for the GPC column set were performed using decane (prepared at 0.04 g in 50 mL of TCB and dissolved for 20 minutes with gentle stirring). Plate counts (Equation 2) and symmetry (Equation 3) were measured with a 200-microliter injection according to the following equations:

[0082]

number

[0083]

number

[0084] 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 a PolymerChar high-temperature autosampler to a pre-nitrogen-sparged septa-capped vial. Samples were dissolved at 160°C for 2 hours under "slow" shaking.

[0085] 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) in Equation 1, according to Equations 4-6, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph.

[0086]

number

[0087] 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 (Apparent)) for each sample by RV-matching the respective decane peak in the sample (RV (FM Sample)) with that of the decane peak in the narrow standard calibration (RV (FM Calibrated)). Any change in the time of the decane marker peak is then assumed to be related to a linear shift in flow rate (Flow Rate (Effective)) throughout the run. To facilitate the highest accuracy in RV measurements of the flow rate marker peaks, a least-squares fitting routine is used to fit the peaks in the flow rate marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is 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) is calculated as shown in Equation 7. Processing of the flow rate marker peaks was performed via PolymerChar GPCOne™ software. An acceptable flow correction is such that the effective flow rate should be within + / - 0.5% of the apparent flow rate.

[0088]

number

[0089] Hydrocarbyl-modified methylaluminoxane (MMAO) is commercially available from Nouryon, with offices in Chicago, Illinois, USA, and Albemarle, headquartered in Charlotte, North Carolina, USA.

[0090] Analysis of Hydrocarbyl-Modified Methylaluminoxane Activators. In a nitrogen atmosphere glove box, A1 R B1 R C1The 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. The sample was further hydrolyzed by the addition of 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 and subsequent back-titration with ZnCl2 using xylenol orange as an indicator.

[0091] AlR in hydrocarbyl-modified methylaluminoxane A1 R B1 R C1 Compound calculations

[0092]

number

[0093] AlR A1 R B1 R C1 The compound content is analyzed using previously described methods (Macromol. Chem. Phys. 1996, 197, 1537, WO2009029857A1, Analytical Chemistry 1968, 40(14), 2150-2153, and Organometallics 2013, 32(11), 3354-3362).

[0094] The metal complexes are conveniently prepared by standard metallation and ligand exchange procedures involving a transition metal source and a neutral polyfunctional ligand source. In addition, the complexes can also be prepared by an amide removal and hydrocarbylation process starting from the corresponding transition metal tetraamide and a hydrocarbylating agent such as trimethylaluminum. The techniques employed are similar to those disclosed in U.S. Patent Nos. 6,320,005, 6,103,657, WO 02 / 38628, WO 03 / 40195, and U.S. Patent No. 2004 / 0220050.

[0095] A general synthesis for CGC catalysts can be found in US6884857B1. A procedure for the synthesis of complex A can be found in US5,470,993A. A procedure for the synthesis of complex B can be found in US5,965,756A. A procedure for the synthesis of complex C can be found in PCT Application No. WO1998 / 006726A1. A procedure for the synthesis of complex D can be found in US6,268,444. A procedure for the synthesis of complex E can be found in PCT Application No. WO2001 / 042315A1.

[0096] Suitable cocatalysts include those compounds previously known in the art for use with Group 4 metal olefin polymerization complexes. Examples of suitable activating cocatalysts include (C1-C 30Neutral Lewis acids such as .) hydrocarbyl-substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum or tri(hydrocarbyl)boron compounds and their halogenated (including perhalogenated) derivatives having 1 to 10 carbons in each hydrocarbyl or hydrocarbyl halide group, more especially perfluorinated tri(aryl)boron compounds, most especially tris(pentafluorophenyl)borane; non-polymeric, compatible, non-coordinating ion-forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium, phosphonium, oxonium, carbonium, silylium, or sulfonium salts of compatible non-coordinating anions, or ferrocenium, lead, or silver salts of compatible non-coordinating anions; and combinations of the foregoing cation-forming cocatalysts and techniques. The aforementioned activating cocatalysts and activation techniques have been previously taught in the following references for different metal complexes for olefin polymerization: EP-A-277,003, US-A-5,153,157, US-A-5,064,802, US-A-5,321,106, US-A-5,721,185, US-A-5,350,723, US-A-5,425,872, US-A-5,625,087, US-A-5,883,204, US-A-5,919,983, US-A-5,783,512, WO 99 / 15534, and WO 99 / 42467.

[0097] Procatalysts A, B, C, D, and E have a structure according to formula (I) and are as follows:

[0098] [ka]

[0099] [Table 1]

[0100] Cocatalysts C3 and C4 are hydrocarbyl-modified methylaluminoxanes (MMAOs) containing a combination of isobutyl and methyl groups in a ratio of about 1:2.

[0101] Cocatalyst I1 is a modified methylaluminoxane (MMAO) containing a combination of octyl and methyl groups in a ratio of about 1:6.

[0102] Example 1 - Batch reactor polymerization reaction using CGC procatalyst and comparative activators and modified aluminoxanes.

[0103] Procatalysts A and B were tested in a batch reactor using C1, C2, C3, or C4 as activators, and the data are summarized in Tables 1-2. Dry weight efficiencies are higher when the catalysts are activated with inventive cocatalyst I1 compared to comparative activator C1 or comparative activator C3.

[0104] [Table 2]

[0105] Run conditions: 120° C., ISOPAR E (1470 g), 1-octene (100 g), hydrogen (40 mmol), and pressurized with ethylene to a total pressure of 410 psi. a. This run was carried out with an Al:Ti ratio of 50 and with the addition of C3.

[0106] The molar ratio of catalyst to comparative cocatalyst C1 is 1.2 and 4 for the comparative cocatalyst. For each example of the present invention, the molar ratio of activator to catalyst is 100 or 500. The catalyst system of the present invention is a linear modified alkyl and a low mole percent of AlR A1 R B1 R C1 The aluminoxane contains a borane activator, C1, or a branched alkyl group and a high mole percentage of AlR A1 R B1 R C1Compared to aluminoxane systems with higher aluminum loadings (such as C3), I1 showed increased efficiency when used to activate constrained geometry catalysts. At higher aluminum loadings, I1 also provided better activity than the borate activator C2. Overall, the use of these aluminoxanes resulted in increased catalyst activity and narrower molecular weight distributions.

[0107] [Table 3]

[0108] Run conditions: 120°C, ISOPAR E (1470 g), 1-octene (150 g), hydrogen (40 mmol), pressurized with ethylene to a total pressure of 150 psi. a. This run was carried out with an Al:Ti ratio of 50 and with the addition of C3. b Modified run using with ethylene (175 psi).

[0109] All manipulations of air-sensitive materials were performed using a high vacuum line (10 -6Sequential purification was performed in oven-dried Schlenk glassware on a dual-manifold Schlenk line interfaced with a 5000 psi (2000 psi) refrigerant (Torr) or in an N-filled MBraun glove box (<1 ppm O) equipped with a large-volume recirculator, with rigorous removal of O and moisture. Argon (Airgas, pre-purified grade) was purified by passage through a supported MnO oxygen scavenging column and an activated Davison 4 Å molecular sieve column. Ethylene (Airgas) was purified by passage through an oxygen / moisture trap (Matheson, model MTRP-0042-XX). Hydrocarbon solvents (n-pentane, n-hexane, 1-hexene, methylcyclohexane, and toluene) were dried using activated alumina columns according to the method described by Grubbs (see Pangborn, AB; Giardello, MA; Grubbs, RH; Rosen, RK; Timmers, FJ, Safe and Convenient Procedure for Solvent Purification. Organometallics 1996, 15(5), 1518-1520) and then vacuum-transferred from Na / K alloys. Benzene-d6 and toluene-d8 (Cambridge Isotope Laboratories, 99+ atom % D) were stored in vacuo on Na / K alloys and vacuum-transferred immediately before use. 1,2-Difluorobenzene and chlorobenzene-d5 were dried over CaH2 and distilled under vacuum. Chloroform-d3 and 1,1,2,2-tetrachloroethane-d2 were used as received (Cambridge Isotope Laboratories, 99+ atom % D).

[0110] 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). 1 Chemical 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. A process for polymerizing olefin monomers to prepare polyolefins, comprising reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system, wherein the catalyst system is Less than 25 mole percent of trihydrocarbyl aluminum compounds AlR, based on the total moles of aluminum Ａ１ R Ｂ１ R Ｃ１ wherein R Ａ１ , R Ｂ１ , and R Ｃ１ are independently linear (C １ -C ４０ ) alkyl, branched (C 3 -C 40 ) alkyl, or (C ６ -C ４０ ) aryl hydrocarbyl-modified methylaluminoxane; One or more procatalysts comprising a metal-ligand complex according to formula (I): 【Chemical 1】 During the ceremony, Ti is titanium, n is 1, 2, or 3; Each X is independently an unsaturated (C ２ -C ５０ ) hydrocarbons, unsaturated (C ２ -C ５０ ) heterohydrocarbon, saturated (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 ) a monodentate or bidentate ligand selected from dienes and halogens; the metal-ligand complex is overall charge neutral; Cp is cyclopentadienyl and R Ｓ substituted cyclopentadienyl, wherein Cp is selected from the group consisting of η ５ bonded to Ti in a bonding mode, and R Ｓ But independently, (C １ -C ２０ ) alkyl, (C 1 -C 20 ) heteroalkyl, (C １ -C ２０ ) aryl, or (C １ -C ２０ ) heteroaryl, wherein two adjacent R Ｓ groups are optionally linked to form a ring; N is nitrogen; Y is carbon or silicon and is covalently bonded to Cp; R １ and R ２ are independently -H, (C １ -C ４０ ) hydrocarbyl, and (C １ -C ４０ ) heterohydrocarbyl; R ３ But independently, (C １ -C ４０ ) hydrocarbyl, and (C １ -C ４０ and one or more procatalysts selected from:

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

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

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

5. R Ａ１ , R Ｂ１ , and R Ｃ１ are independently linear (C １ -C ２０ ) alkyl, linear (C １ -C １５ ) alkyl, or linear (C １ -C １２ 5. The polymerization process of claim 1, wherein the alkyl is 2-(2-methyl-2-propanol).

6. R Ａ１ , R Ｂ１ , and R Ｃ１ The polymerization process of any one of claims 1 to 5, wherein is methyl, ethyl, propyl, 2-propyl, butyl, n-octyl, nonyl, decyl, undecyl, or dodecyl.

7. The polyolefin has a viscosity of 0.865 to 0.890 g / cm ３ The polymerization process of any one of claims 1 to 6, wherein the polymer has a density in the range of

8. The polymerization process of any one of claims 1 to 7, wherein the catalyst system does not contain a borate activator.

9. The olefin monomer is (C ３ -C ２０ 9. The polymerization process according to claim 1, wherein the olefin is an α-olefin.

10. The olefin monomer is (C ３ -C ２０ 6. The polymerization process of claim 1, wherein the olefin is not an α-olefin.

11. The polymerization process of any one of claims 1 to 8 and 10, wherein the olefin monomer is a cyclic olefin.

12. R １ and R ２ But independently, (C １ -C １２ ) alkyl or (C ６ -C ２０ 12. The polymerization process of claim 1, wherein the aryl is aryl.

13. R １ and R ２ The polymerization process of any one of claims 1 to 12, wherein is methyl, ethyl, propyl, or phenyl.

14. R ３ But independently, (C １ -C １２ 14. The polymerization process of claim 1, wherein the alkyl is .

15. R ３ is independently tert-butyl, tert-octyl, or n-octyl.

16. The polymerization process of any one of claims 1 to 15, wherein Cp is independently tetramethylcyclopentadienyl.

17. 16. The polymerization process of any one of claims 1 to 15, wherein Cp is selected from: 【Chemistry 2】

18. The polymerization process according to any one of claims 1 to 17, wherein the polymerization process is a solution polymerization reaction.

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