Hydrocarbyl-modified methylaluminoxane cocatalyst for bisphenylphenoxy metal-ligand complexes

Abstract

A method for polymerizing olefin monomers. The method comprises reacting ethylene and optionally one or more olefin monomers in the presence of a catalytic system, wherein the catalytic system comprises: AlR having a content of less than 50 mol% based on the total molar amount of aluminum. A1 R B1 R C1 Modified hydrocarbon methylaluminoxane, wherein R A1 R B1 and R C1 Independently for straight chains (C1-C) 40 Alkyl groups, branched (C1-C) 40 )alkyl or (C6-C 40 ) aryl; and one or more metal-ligand complexes according to formula (I).

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 053,354, filed July 17, 2020, the entire disclosure of which is hereby incorporated by reference. Technical Field

[0003] The embodiments disclosed herein generally relate to modified hydrocarbon methylaluminoxane activators for catalyst systems comprising a diphenylphenoxy metal-ligand complex having a three-atom ether joint. Background Technology

[0004] Since Ziegler and Natta discovered heterogeneous olefin polymerization, global polyolefin production reached approximately 150 million tons per year in 2015 and continues to rise due to increasing market demand. This success is partly based on a series of significant breakthroughs in cocatalyst technology. Discovered cocatalysts include aluminoxanes, boranes, and borates with triphenylcarbium or ammonium cations. These cocatalysts activate homogeneous single-point olefin polymerization catalysts and are already being used industrially to produce polyolefins.

[0005] As part of the catalyst composition in α-olefin polymerization, the activator may possess characteristics that favor the production of α-olefin polymers and the final polymer composition including α-olefin polymers. Activator properties that increase α-olefin polymer yield include, but are not limited to: rapid activation of the main catalyst, high catalyst efficiency, high temperature resistance, consistent polymer composition, and selective deactivation.

[0006] Borate-based cocatalysts have significantly contributed to a fundamental understanding of the mechanisms of olefin polymerization and have enhanced the ability to precisely control the microstructure of polyolefins through intentional tuning of catalyst structure and methods. This has led to a surge of interest in mechanistic studies and the development of novel homogeneous olefin polymerization catalyst systems with precise control over the microstructure and properties of polyolefins. However, once the cation of the activator or cocatalyst activates the main catalyst, the ionic ions of the activator can remain in the polymer composition. As a result, the borate anion can influence the polymer composition. In particular, the size of the borate anion, its charge, its interaction with the surrounding medium, and the dissociation energy of the borate anion with available counterions will affect the ability of ions to diffuse through the surrounding medium (such as solvents, gels, or polymer materials).

[0007] Modified methylaluminoxane (MMAO) can be described as a mixture of aluminoxane structures and trialkylaluminate compounds. Trialkylaluminate compounds, such as trimethylaluminum, are used as scavengers to remove impurities that may deactivate olefin polymerization catalysts during polymerization. However, trialkylaluminate compounds are believed to be active in some polymerization systems. Catalyst inhibition was observed when trimethylaluminum was present in propylene homopolymerization with a hafnium thiocyanate catalyst at 60 °C (Busico, V. et al., Macromolecules, 2009, 42, 1789-1791). However, these observations suggest a difference between MAO activation and borate activation, and even in direct comparisons, only some difference between trimethylaluminum and the absence of trimethylaluminum may be captured. Furthermore, it is unclear whether these observations extend to other catalyst systems, ethylene polymerization, or polymerization at higher temperatures. In any case, the preference for soluble MAO necessitates the use of MMAO and therefore the presence of trialkylaluminate compounds.

[0008] Modified methylaluminoxane (MMAO) is used as an activator in some PE processes, replacing borate-based activators. However, MMAO has been found to negatively impact the performance of some catalysts (e.g., bisphenylphenoxy metal-ligand complexes) and the production of polyethylene resin: negative impacts on polymerization methods include reduced catalyst activity, broadened compositional distribution of the resulting polymer, and negative impacts on pellet handling. Summary of the Invention

[0009] There is a ongoing need to develop a catalyst system that maintains catalyst efficiency, reactivity, and the ability to produce polymers with good physical properties. The production of homogeneous polymer compositions is also required.

[0010] Embodiments of this disclosure include a method for polymerizing olefin monomers. In one or more embodiments, the method includes reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system. The catalyst system comprises a modified hydrocarbon methylaluminoxane and a main catalyst. Based on the total molar number of aluminum, AlR has less than 50 moles. A R B R C Modified hydrocarbon methylaluminoxane, wherein R A R B and R C Independently for straight chains (C1-C) 40 Alkyl, branched (C1-C) 40 )alkyl or (C6-C 40 aryl; and one or more metal-ligand complexes according to formula (I):

[0011]

[0012] In formula (I), M is titanium, zirconium, or hafnium. (X) n The subscript n is 1, 2, or 3. Each X is independently selected from unsaturated (C2-C3) 50 Hydrocarbons, unsaturated (C2-C) 50 ( ) heterohydrocarbons, (C1-C 50 ) hydrocarbon group, (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 monodentate ligand; and the metal-ligand complex is electrically neutral overall.

[0013] In equation (I), R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 and R 15 Independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -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 halogens.

[0014] In equation (I), R 1 and R 16 Independently select the group consisting of the following items: –H, (C1-C) 40 ) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -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)-, halogens, free radicals having formula (II), free radicals having formula (III), and free radicals having formula (IV):

[0015]

[0016] In equations (II), (III), and (IV), R 31 To R 35 R 41 To R 48 and R 51 To R 59 Each of them is independently selected from –H, (C1-C 40 ) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -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.

[0017] In equation (I), Y represents CH2 and CHR. 21 CR 21 R 22 SiR 21 R 22 or GeR 21 R 22 , where R21 and R 22 It is (C1-C) 20 Alkyl group; the prerequisite is that when Y is CH2, R 8 and R 9 At least one of them is not –H.

[0018] In equations (I), (II), (III), and (IV), each R in equation (I) C R P and R N Independently for (C1-C 30 ) hydrocarbon group, (C1-C 30 () Heterohydrocarbon group or -H. Attached Figure Description

[0019] Figure 1 The graph shows the catalytic efficiency of metal-ligand complexes I1, I3, and I7 as a function of MMAO cocatalyst type. Detailed Implementation

[0020] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of this disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure. Rather, the provision of embodiments makes this disclosure thorough and complete, and the embodiments will fully convey the scope of the subject matter to those skilled in the art.

[0021] The following is a list of common abbreviations:

[0022] Me: Methyl; Et: Ethyl; Ph: Phenyl; Bn: Benzyl; i-Pr: Isopropyl; t-Bu: Tert-Butyl; t-Oct: Tert-Octyl (2,4,4-Trimethylpentan-2-yl); Tf: Trifluoromethanesulfonate; THF: Tetrahydrofuran; Et2O: Diethyl ether; CH2Cl2: Dichloromethane; CV: Column volume (used in column chromatography); EtOAc: Ethyl acetate; C6D6: Deuterated benzene or benzene-d6; CDCl3: Deuterium Chloroform substitute; Na2SO4: Sodium sulfate; MgSO4: Magnesium sulfate; HCl: Hydrogen chloride; n-BuLi: n-Butyllithium; t-BuLi: Tert-Butyllithium; MAO: Methylaluminoxane; MMAO: Modified methylaluminoxane; GC: Gas chromatography; LC: Liquid chromatography; NMR: Nuclear magnetic resonance; MS: Mass spectrometry; mmol: Millimole; mL: Milliliter; M: Mole; min or mins: Minute; h or hrs: Hour; d: Day.

[0023] The term "independently selected" is used in this document to refer to R groups, such as R 1 R 2 R 3 R 4 and R5 They can be the same or different (e.g., R) 1 R 2 R 3 R 4 and R 5 All can be substituted alkyl groups or R 1 and R 2 It can be a substituted alkyl group and R 3 (This could be an aryl group, etc.). Chemical names associated with the R group are intended to convey the chemical structure that is generally accepted in the art as corresponding to the chemical structure of the chemical name. Therefore, chemical names are intended to supplement and describe, rather than exclude, structural definitions known to those skilled in the art.

[0024] The term "pre-catalyst" refers to a transition metal compound that, when combined with an activator, exhibits catalytic activity for olefin polymerization. The term "activator" refers to a compound that chemically reacts with the main catalyst in a manner that converts the main catalyst into a catalytically active catalyst. As used herein, the terms "co-catalyst" and "activator" are interchangeable.

[0025] When used to describe certain carbon-containing chemical groups, it has the form "(C x -C y The insertion of ")" indicates that the unsubstituted form of the chemical group has x to y carbon atoms, including both x and y. For example, (C1-C 50 Alkyl groups are alkyl groups having 1 to 50 carbon atoms in their unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted with one or more substituents such as RS. (Using "(C") x -C y Insert the defined R S The substituted chemical group can contain more than y carbon atoms, depending on any group R. S The identity. For example, "using exactly one group R..." S Replacement (C1-C) 50 ) alkyl, wherein R S "Phenyl (-C6H5)" can contain 7 to 56 carbon atoms. Therefore, it is common practice to use "(C6H5)" when referring to phenyl groups. x -C y The inserted chemical group is replaced by one or more carbon-containing substituents R. S During substitution, both x and y are added with substituents R from all carbon atoms. S The minimum and maximum total number of carbon atoms in a chemical group are determined by the sum of the combinations of carbon atoms.

[0026] The term "substitution" means that at least one hydrogen atom (-H) bonded to a carbon atom in the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R).S (Substitution). The term "-H" refers to a hydrogen atom or hydrogen group covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless explicitly stated otherwise.

[0027] The term "(C1-C)" 50 "alkyl" refers to a saturated straight-chain or branched hydrocarbon group with 1 to 50 carbon atoms. The term "C1-C..." 30 "Alkyl" refers to a saturated straight-chain or branched hydrocarbon group with 1 to 30 carbon atoms. Each (C1-C2) 50 )alkyl and (C1-C 30 Each alkyl group may be unsubstituted or substituted with one or more R groups. S Replacement. In some examples, each hydrogen atom in the hydrocarbon group can be replaced by R. S Substitution, such as, for example, trifluoromethyl. Unsubstituted (C1-C2) 50 Examples of alkyl groups are unsubstituted (C1-C1) alkyl groups. 20 )alkyl; unsubstituted (C1-C 10 Alkyl; unsubstituted (C1-C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Substituted (C1-C5)alkyl 40 Examples of alkyl groups are substituted (C1-C2) 20 )alkyl, substituted (C1-C 10 )alkyl, trifluoromethyl and [C 45 Alkyl group. The term "[C]" 45 "Alkyl" means that the group including the substituent has a maximum of 45 carbon atoms and is, for example, an R of a (C1-C5) alkyl group (such as, for example, methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl). S Replacement (C) 27 -C 40 )alkyl.

[0028] Terminology (C3-C) 50 Alkenyl refers to a branched or unbranched, cyclic or acyclic monovalent hydrocarbon group containing 3 to 50 carbon atoms, at least one double bond, and is unsubstituted or bonded by one or more R groups. S Substitution. Unsubstituted (C3-C) 50 Examples of alkenyl groups: n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, and cyclohexadienyl. Substituted (C3-C) 50Examples of alkenyl groups: (2-trifluoromethyl)pent-1-enyl, (3-methyl)hex-1-enyl, (3-methyl)hex-1,4-dienyl and (Z)-1-(6-methylhept-3-en-1-yl)cyclohex-1-enyl.

[0029] The term "(C3-C)" 50 "Cycloalkyl" refers to a saturated cyclic hydrocarbon group with 3 to 50 carbon atoms that is not substituted or is surrounded by one or more R groups. S Substitution. Other cycloalkyl groups (e.g., (C x -C y Cycloalkyl groups are defined in a similar manner as having x to y carbon atoms and being unsubstituted or derived from one or more R groups. S Replaced. Unreplaced (C3-C) 40 Examples of cycloalkyl groups are unsubstituted (C3–C4) cycloalkyl groups. 20 )cycloalkyl, unsubstituted (C3–C 10 Cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substituted (C3–C) 40 Examples of cycloalkyl groups are substituted (C3–C4) cycloalkyl groups. 20 )cycloalkyl, substituted (C3–C 10 )cycloalkyl and 1-fluorocyclohexyl.

[0030] The term "halogen atom" or "halogen" refers to a free radical of a fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) atom. The term "halide" refers to the anionic form of a halogen atom: the fluoride ion (F...). - ), chloride ions (Cl) - ), bromide ions (Br) - ) or iodide ions (I - ).

[0031] The term "saturation" refers to the absence of carbon-carbon double bonds, carbon-carbon triple bonds, and (in groups containing heteroatoms) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. In saturated chemical groups, the presence of one or more substituents R... S In the case of substitution, one or more double or triple bonds may optionally be present in the substituent R. S In this context, the term "unsaturated" means containing one or more carbon-carbon double or triple bonds, or (in groups containing heteroatoms) one or more carbon-nitrogen, carbon-phosphorus, or carbon-silicon double bonds, excluding those that may exist in the substituent R. S (If any) double bonds in an aromatic ring or a heteroaromatic ring.

[0032] Embodiments of this disclosure include methods for polymerizing olefin monomers. In one or more embodiments, the method includes reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system.

[0033] In various implementation schemes, the catalyst system does not contain borate activators.

[0034] In some implementations, the olefin monomer is (C3-C4) 20 α-olefins. In other embodiments, the olefin monomer is not (C3-C4). 20 α-olefins. In various embodiments, the olefin monomer is a cyclic olefin.

[0035] In one or more embodiments, the catalyst system comprises a hydrocarbon-modified methylaluminoxane and a main catalyst. Based on the total molar number of aluminum, the hydrocarbon-modified methylaluminoxane has less than 50 mol% AlR. A1 R B1 R C1 In the formula AlR A1 R B1 R C1 In the middle, R A1 R B1 and R C1 Independently for straight chains (C1-C) 40 Alkyl, branched (C1-C) 40 )alkyl, (C1-C 40 ) aryl or combinations thereof.

[0036] The term "hydrocarbon-modified methylaluminoxane" refers to a methylaluminoxane (MMAO) structure containing a certain amount of trialkylaluminum. Hydrocarbon-modified methylaluminoxanes comprise a combination of a hydrocarbon-modified methylaluminoxane base and trialkylaluminum. The total molar amount of aluminum in a hydrocarbon-modified methylaluminoxane consists of the aluminum contribution from the molar amount of aluminum from the hydrocarbon-modified methylaluminoxane base and the aluminum contribution from the trialkylaluminum. Based on the total molar amount of aluminum in a hydrocarbon-modified methylaluminoxane, it comprises more than 2.5 mol% trialkylaluminum. These additional hydrocarbon substituents can influence the subsequent aluminoxane structure and lead to differences in the distribution and size of the aluminoxane clusters (Bryliakov, KP et al., Macromolecular Chemistry and Physics (Macromol. Chem. Phys. 2006, 207, 327-335). Additional hydrocarbon substituents can also impart increased solubility of the aluminoxane in hydrocarbon solvents such as, but not limited to, hexane, heptane, methylcyclohexane, and ISOPAR E. TM As demonstrated in US5777143. Modified methylaluminoxane compositions are generally disclosed and can be prepared as described in US5066631 and US5728855, which are incorporated herein by reference.

[0037] In embodiments of this disclosure, the catalyst system comprises one or more metal-ligand complexes according to formula (I).

[0038]

[0039] In formula (I), M is titanium, zirconium, or hafnium with an oxidation state of +2, +3, or +4. (X) n The subscript n is 1, 2, or 3. Each X is independently selected from unsaturated (C2-C3) 50 Hydrocarbons, unsaturated (C2-C) 50 ( ) heterohydrocarbons, (C1-C 50 ) hydrocarbon group, (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 monodentate ligand; and the metal-ligand complex is electrically neutral overall.

[0040] In equation (I), R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 and R 15 Independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -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 halogens.

[0041] In equation (I), R 1 and R 16 Independently select the group consisting of the following items: –H, (C1-C) 40 ) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -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)-, halogens, free radicals having formula (II), free radicals having formula (III), and free radicals having formula (IV):

[0042]

[0043] In equations (II), (III), and (IV), R 31 To R 35 R 41 To R 48 and R 51 To R 59 Each of them is independently selected from –H, (C1-C 40 ) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -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.

[0044] In equation (I), Y represents CH2 and CHR. 21 CR 21 R 22 SiR 21 R 22 or GeR 21 R 22 , where R 21 and R 22 It is (C1-C) 20 Alkyl group; the prerequisite is that when Y is CH2, R 8 and R 9 At least one of them is not –H.

[0045] Unbound by theory, these preferred substitution modes containing triatomic bridges (-CH2YCH2-) are believed to be consistent with the R of this disclosure. 8 and R 9 The combination of substitution patterns at the group sites results in mostly single-center behavior. Second polymerization sites, frequently observed under MMAO activation, do not bind to these catalyst systems of the present invention. These second polymerization sites can adversely produce additional morphologies in the resulting polymer. These morphologies manifest as a broadening of the molecular weight distribution profile or through a non-uniform distribution of comonomers.

[0046] In equations (I), (II), (III), and (IV), each R in equation (I) C R P and R N Independently for (C1-C 30 ) hydrocarbon group, (C1-C 30 () Heterohydrocarbon group or -H.

[0047] In some embodiments, based on the total molar amount of aluminum in the hydrocarbon-modified methylaluminoxane, the modified hydrocarbon-modified methylaluminoxane in the polymerization method has less than 20 mol% and more than 5 mol% trialkylaluminum. In some embodiments, based on the total molar amount of aluminum in the hydrocarbon-modified methylaluminoxane, the modified hydrocarbon-modified methylaluminoxane has less than 15 mol% trialkylaluminum. In one or more embodiments, based on the total molar amount of aluminum in the hydrocarbon-modified methylaluminoxane, the modified hydrocarbon-modified methylaluminoxane has less than 10 mol% trialkylaluminum. In various embodiments, the modified hydrocarbon-modified methylaluminoxane is a modified methylaluminoxane.

[0048] In some implementations, trialkylaluminum has the formula AlR A1 R B1 R C1 , where R A1 R B1 and R C1 Independently for straight chains (C1-C) 40Alkyl, branched (C1-C) 40 )alkyl or (C6-C 40 )Aryl. In one or more embodiments, R A1 R B1 and R C1 Independently, it is methyl, ethyl, propyl, 2-propyl, butyl, tert-butyl, or octyl. In some embodiments, R A1 R B1 and R C1 They are the same. In other implementations, R A1 R B1 and R C1 At least one of them is different from the other R A1 R B1 and R C1 .

[0049] The group R in the metal-ligand complex of formula (I) 1 and R 16 They choose independently of each other. For example, R 1 It can be selected from free radicals having formula (II), (III) or (IV), and R 16 It can be (C1-C) 40 ) hydrocarbon group; or R 1 It can be selected from free radicals having formula (II), (III) or (IV), and R 16 Can be selected from R 1 Free radicals of the same or different formulas (II), (III), or (IV). R 1 and R 16 Both can be free radicals having formula (II), wherein the group R 31-35 In R 1 and R 16 The same or different. In other examples, R 1 and R 16 Both can be groups having formula (III), where group R 41-48 In R 1 and R 16 The same or different in; or R 1 and R 16 Both can be groups having formula (IV), where group R 51-59 In R 1 and R 16 The same or different.

[0050] In some implementation schemes, R 1 and R 16 At least one of them is a free radical having formula (II), where R 32 and R 34It is tert-butyl. In one or more embodiments, R 32 and R 34 For (C1-C 12 ) hydrocarbon group or -Si[(C1-C 10 [alkyl]3.

[0051] In some implementations, when R 1 Or R 16 When at least one of them is a free radical having formula (III), R 43 and R 46 One or both of them are tert-butyl, and R 41-42 R 44-45 and R 47 - is -H. In other implementations, R 42 and R 47 One or both of them are tert-butyl, and R 41 R 43-46 And R is -H. In some implementations, R 42 and R 47 Both are -H. In various implementation schemes, R 42 and R 47 For (C1-C 20 ) hydrocarbon group or -Si[(C1-C 10 [alkyl]3. In other embodiments, R 43 and R 46 For (C1-C 20 ) hydrocarbon group or –Si(C1-C 10 [alkyl]3.

[0052] In the implementation plan, when R 1 Or R 16 When at least one of them is a free radical having formula (IV), each R 52 R 53 R 55 R 57 and R 58 For –H, (C1-C 20 ) hydrocarbon group, -Si[(C1-C 20 [(C1-C)]3 or -Ge[(C1-C) 20 [3. Hydrocarbon group]. In some implementations, R 52 R 53 R 55 R 57 and R 58 At least one of them is (C3-C) 10 )alkyl, -Si[(C3-C 10 )alkyl]3 or -Ge[(C3-C 10[alkyl]3. In one or more embodiments, R 52 R 53 R 55 R 57 and R 58 At least two of them are (C3-C) 10 )alkyl, -Si[(C3-C 10 )alkyl]3 or -Ge[(C3-C 10 [alkyl]3. In various embodiments, R 52 R 53 R 55 R 57 and R 58 At least three of them are (C3-C) 10 )alkyl, -Si[(C3-C 10 )alkyl]3 or -Ge[(C3-C 10 [alkyl]3.

[0053] In some implementations, when R 1 Or R 16 When at least one of them is a free radical having formula (IV), R 52 R 53 R 55 R 57 and R 58 At least two of them are (C1-C 20 ) hydrocarbon group or -C(H)2Si[(C1-C 20 [3] )hydrocarbon group.

[0054] (C3-C 10 Examples of alkyl groups include, but are not limited to: propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl.

[0055] In equation (I), R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 and R 15 Independently selected from -H, (C1-C 40) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -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 halogens.

[0056] In one or more implementations, R 2 R 4 R 5 R 12 R 13 and R 15 It is hydrogen;

[0057] In various implementation schemes, R 5 R 6 R 7 and R 8 At least one of them is a halogen atom; and R 9 R 10 R 11 and R 12 At least one of them is a halogen atom. In some implementations, R 8 and R 9 It is independently a (C1-C4) alkyl group.

[0058] In some implementation schemes, R 3 and R 14 It is (C1-C) 20 )alkyl. In one or more embodiments, R 3 and R 14 It is methyl; and R 6 and R 11 It is a halogen. In the implementation plan, R 6 and R 11 It is tert-butyl. In other embodiments, R 3 and R 14 It is either tert-singyl or octyl.

[0059] In various implementation schemes, R 3 and R 14 It is (C1-C)24 )alkyl. In one or more embodiments, R 3 and R 14 It is (C4-C) 24 )alkyl. In some embodiments, R 3 and R 14 The compounds are 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl. In the embodiments, R 3 and R 14 For -OR C , where R C For (C1-C 20 ) hydrocarbons, and in some embodiments, R C It can be methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl) or 1,1-dimethylethyl.

[0060] In one or more implementations, R 8 and R 9 One of them is not –H. In various implementation schemes, R 8 and R 9 At least one of them is (C1-C 24 )alkyl. In some embodiments, R 8 and R 9 Both are (C1-C 24 )alkyl. In some embodiments, R 8 and R 9 It is methyl. In other embodiments, R 8 and R 9 It is a halogen.

[0061] In some implementation schemes, R 3 and R 14 R is methyl; in one or more embodiments, R 3 and R 14 It is (C4-C) 24 )alkyl. In some embodiments, R 8 and R 9 It is 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl.

[0062] In various implementation schemes, in the metal-ligand complex of formula (I), R 6 and R 11 It is a halogen. In some implementations, R 6 and R 11 For (C1-C 24 )alkyl. In various embodiments, R 6 and R 11 Independently selected from methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl. In some embodiments, R 6 and R 11 It is tert-butyl. In the implementation plan, R 6 and R 11 For -OR C , where R C For (C1-C 20 ) hydrocarbon group, and in some embodiments, R C It is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), or 1,1-dimethylethyl. In other embodiments, R 6 and R 11 -SiR C 3, where each R C Independently for (C1-C 20 ) hydrocarbon group, and in some embodiments, R C It can be methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl) or 1,1-dimethylethyl.

[0063] In some embodiments, the chemical groups (e.g., X and R) of the metal-ligand complex of formula (I) 1-59 Any or all of them may be unsubstituted. In other embodiments, the chemical groups X and R of the metal-ligand complex of formula (I) are... 1-59 None of them were controlled by one or more Rs. S Replacement, or any one or all of them being replaced by one or more R S Replacement. When two or more R S When bonded to the same chemical group of a metal-ligand complex of formula (I), each R of the chemical group S It can be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, chemical groups X and R 1-59 None of them were R S Total substitution, or any or all of them, can be replaced by R. SComplete replacement. In the case of R S In fully substituted chemical groups, each R S They can all be the same or can be chosen independently. In one or more implementations, R S Selected from (C1-C) 20 ) hydrocarbon group, (C1-C 20 )alkyl, (C1-C 20 ) heterohydrocarbon group or (C1-C 20 Heteroalkyl groups.

[0064] In equations (I), (II), (III), and (IV), each R C R P and R N Independently for (C1-C 30 ) hydrocarbon group, (C1-C 30 () Heterohydrocarbon group or -H.

[0065] In some implementations, in the metal-ligand complex according to formula (I), R 8 and R 9 All are methyl. In other embodiments, R 8 and R 9 One of them is methyl, and R 8 and R 9 The other one is –H.

[0066] In the metal-ligand complex according to formula (I), X is bonded to M via a covalent or ionic bond. In some embodiments, X may be a monoanionic ligand with a net oxidation state of -1. Each monoanionic ligand may independently be a hydride, (C1-C2) 40 ) hydrocarbon-based carbanion, (C1-C 40 Heteroalkyl carbanions, halide ions, nitrate ions, carbonate ions, phosphate ions, sulfate ions, HC(O)O - HC(O)N(H) - (C1-C) 40 )hydrocarbon C(O)O - (C1-C) 40 )hydrocarbon group C(O)N((C1-C 20 (hydrocarbon group) - (C1-C) 40 Hydrocarbon group 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 - , where each R K R L and R M Independently hydrogen, (C1-C 40 ) hydrocarbon group or (C1-C 40 ) heterohydrocarbon group, or R K and R L Together they form (C2-C) 40 ) alkylene group or (C1-C 20 ) heterohydrocarbon group and R M As defined above.

[0067] In some implementations, X is a halogen, unsubstituted (C1-C2) 20 ) hydrocarbon group, unsubstituted (C1-C) 20 ) hydrocarbon group C(O)O– or R K R L N-, where R K and R L Each of them is independently unsubstituted (C1-C) 20 ) hydrocarbon group. In some embodiments, each monodentate ligand X is a chlorine atom, (C1-C 10 ) hydrocarbon group (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C6) 10 ) hydrocarbon group C(O)O– or R K R L N-, where R K and R L Each of them is independently unsubstituted (C1-C) 10 ) hydrocarbon group.

[0068] In another embodiment, X is selected from: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chlorine. X is methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chlorine. In one embodiment, n is 2, and at least two X groups are independently monoanionic monodentate ligands. In a specific embodiment, n is 2, and the two X groups are coupled to form a bidentate ligand. In another embodiment, the bidentate ligand is 2,2-dimethyl-2-dimethylsilane-1,3-diyl or 1,3-butadiene.

[0069] In one or more embodiments, each X is independently –(CH2)SiR X 3, where each R X Independently for (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, and at least one R X For (C1-C 30 )alkyl. In some embodiments, when R X One of them is (C1-C) 30 When it is a heteroalkyl group, the heteroatom is silicon dioxide or an oxygen atom. In some embodiments, R X It can be methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl.

[0070] In one or more embodiments, X is –(CH2)Si(CH3)3, –(CH2)Si(CH3)2(CH2CH3); –(CH2)Si(CH3)(CH2CH3)2, –(CH2)Si(CH2CH3)3, –(CH2)Si(CH3)2 (n-butyl), –(CH2)Si(CH3)2 (n-hexyl), –(CH2)Si(CH3)(n-octyl)R X –(CH2)Si(n-octyl)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, according to the metal-ligand complex of formula (I), exactly two R X Covalent connection or exactly three R X Covalent connection.

[0071] In some implementations, X is -CH2Si(R) C ) 3-Q (OR C ) Q 、-Si(R C ) 3-Q (OR C ) Q -OSi(R) C ) 3-Q (OR C ) Q Where the subscript Q is 0, 1, 2 or 3, and each R C Independently substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, or substituted or unsubstituted (C1-C)30 ) heterohydrocarbon group.

[0072] co-catalyst components

[0073] Catalytic activity can be achieved by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions, including metal-ligand complexes of formula (I). For example, the main catalyst of a metal-ligand complex according to formula (I) can be made catalytically active by contacting the complex with an activated co-catalyst or by combining the complex with an activated co-catalyst. Furthermore, the metal-ligand complex according to formula (I) comprises both a neutral main catalyst form and a catalytic form that may be positively charged due to the loss of monomeric ionic ligands (such as benzyl or phenyl). Suitable activated co-catalysts herein include oligomeric aluminoxanes or modified alkylaluminoxanes.

[0074] Polyolefins

[0075] The catalytic system described in the preceding paragraphs is used in the polymerization of olefins (primarily ethylene and propylene) to form ethylene-based or propylene-based polymers. In some embodiments, the polymerization scheme contains only a single type of olefin or α-olefin, thereby forming a homopolymer. However, additional α-olefins may be incorporated into the polymerization process. These additional α-olefin comonomers typically have no more than 20 carbon atoms. For example, α-olefin comonomers 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.

[0076] Ethylene-based polymers, such as homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers (such as α-olefins), may contain at least 50 mol% of ethylene-derived monomer units. All individual values ​​and subranges covered by “at least 50 mol%” are disclosed herein as separate embodiments; for example, ethylene-based polymers, i.e., homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as α-olefins, may contain at least 60 mol% of ethylene-derived monomer units; at least 70 mol% of ethylene-derived monomer units; at least 80 mol% of ethylene-derived monomer units; or 50 mol% to 100 mol% of ethylene-derived monomer units; or 80 mol% to 100 mol% of ethylene-derived monomer units.

[0077] In some embodiments, the ethylene-based polymer may comprise at least 90 mol% of ethylene-derived units. All individual values ​​and subranges from at least 90 mol% are included herein and disclosed herein as separate examples. For example, the ethylene-based polymer may comprise at least 93 mol% of ethylene-derived units; at least 96 mol% of units; at least 97 mol% of ethylene-derived units; or alternatively, 90 mol% to 100 mol% of ethylene-derived units; 90 mol% to 99.5 mol% of ethylene-derived units; or 97 mol% to 99.5 mol% of ethylene-derived units.

[0078] In some embodiments of the ethylene-based polymer, the additional α-olefin is less than 50 mol%; other embodiments include at least 1 mol% to 25 mol%; and in still other embodiments, the additional α-olefin includes at least 5 mol% to 103 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0079] Ethylene polymers can be produced using any conventional polymerization process. Such conventional polymerization methods include, but are not limited to, solution polymerization, slurry polymerization, and combinations thereof, using one or more conventional reactors such as ring reactors, isothermal reactors, stirred tank reactors, parallel or series batch reactors, or any combination thereof.

[0080] In one embodiment, the ethylene-based polymer can be produced via solution polymerization in a dual-reactor system, such as a dual-loop reactor system, wherein ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system as described herein and optionally one or more co-catalysts. In another embodiment, the ethylene-based polymer can be produced via solution polymerization in a dual-reactor system, such as a dual-loop reactor system, wherein ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein and optionally one or more other catalysts. The catalyst system described herein can optionally be used in combination with one or more other catalysts in either the first or second reactor. In one embodiment, the ethylene-based polymer can be produced via solution polymerization in a dual-reactor system, such as a dual-loop reactor system, wherein ethylene and optionally one or more α-olefins are polymerized in both reactors in the presence of a catalyst system as described herein.

[0081] In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single-reactor system (e.g., a monocyclic reactor system), wherein ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system as described in this disclosure and optionally one or more co-catalysts as described in the preceding paragraphs.

[0082] Ethylene-based polymers may further include one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. Ethylene-based polymers may contain any amount of additives. Ethylene-based polymers may contain a combined weight of about 0 to about 10% of such additives based on the weight of the ethylene-based polymer and one or more additives. Ethylene-based polymers may further include fillers, which may include, but are not limited to, organic or inorganic fillers. Based on the combined weight of the ethylene-based polymer and all additives or fillers, the ethylene-based polymer may contain about 0 to about 20% by weight of fillers, such as calcium carbonate, talc, or Mg(OH)₂. Ethylene-based polymers may further be blended with one or more polymers to form blends.

[0083] In some embodiments, polymerization methods for producing ethylene-based polymers may include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system according to this disclosure. According to ASTM D792 (in its entirety incorporated herein by reference), the density of polymers produced by such catalyst systems incorporating metal-ligand complexes of formula (I) may be, for example, 0.850 g / cm³. 3 Up to 0.970 g / cm 3 0.880 g / cm 3 Up to 0.920 g / cm 3 0.880 g / cm 3 Up to 0.910 g / cm 3 Or 0.880 g / cm 3 Up to 0.900 g / cm 3 .

[0084] In another embodiment, the polymer produced by the catalyst system according to this disclosure has a melt flow ratio (I 10 The melt index I2 is between 5 and 15, where the melt index I2 is measured according to ASTM D1238 (incorporated herein by reference in its entirety) at 190°C and a load of 2.16 kg, and the melt index I... 10 Measured according to ASTM D1238 at 190°C and a 10kg load. In other embodiments, the melt flow ratio (I 10The melt flow ratio is 5 to 10, and in another embodiment, the melt flow ratio is 5 to 9.

[0085] In some embodiments, the polymer produced by the catalyst system according to the present disclosure has a molecular weight distribution (MWD) of 1 to 25, wherein MWD is defined as M w / M n M w The weight-average molecular weight and M n The molecular weight is the number average. In other embodiments, the polymer produced by the catalyst system has a molecular weight distribution (MWD) of 1 to 6. Another embodiment includes a MWD of 1 to 3; and other embodiments include a MWD of 1.5 to 2.5.

[0086] Gel permeation chromatography (GPC)

[0087] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector. The autosampler oven chamber was set to 160°C, and the column chamber to 150°C. Four Agilent "MixedA" 30cm 20µm linear mixed-bed columns were used. The chromatographic solvent was 1,2,4-trichlorobenzene containing 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen injection. The injection volume was 200 μL, and the flow rate was 1.0 mL / min.

[0088] The calibration of the GPC column was performed using at least 20 narrowly distributed polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in six “cocktail” mixtures with at least ten-fold intervals between each molecular weight. The standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 g of polystyrene standard was prepared in 50 mL of solvent; for molecular weights less than 1,000,000, 0.05 g of polystyrene standard was prepared in 50 mL of solvent. The polystyrene standards were dissolved at 80°C and gently stirred for 30 minutes. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, *Journal of Polymer Science*, Vol. 6, p. 621 (1968)).

[0089] M 聚乙烯 =A×(M) 聚苯乙烯 ) B (EQ 1)

[0090] Where M is the molecular weight, A has a value of 0.4315, and B equals 1.0.

[0091] The fifth-order multi-top was used to fit the corresponding polyethylene equivalent calibration point. A small adjustment to A (from approximately 0.40 to 0.44) was made to correct for column resolution and band broadening effects, resulting in NIST standard NBS 1475 at 52,000 Mw.

[0092] High-temperature thermal gradient interaction chromatography (HT-TGIC or TGIC)

[0093] High-temperature thermal gradient interaction chromatography (HT-TGIC or TGIC) measurements were performed using a commercially available crystallization elution fractionation (CEF) instrument (Polymer Char, Spain) (Cong et al., Macromolecules, 2011, 44(8), 3062-3072). The CEF instrument was equipped with an IR-5 detector. Graphite has been used as the stationary phase in HT TGIC columns (Freddy, A. Van Damme et al., US Patent 8,476,076; Winniford et al., US 8,318,896). Separation was performed using a single graphite column (250 × 4.6 mm). Graphite was packed into the column using a dry packing technique followed by a wet packing technique (Cong et al., EP 2714226B1 and cited references). The experimental parameters were as follows: top oven / delivery tube / needle temperature 150℃, dissolution temperature 150℃, dissolution stirring setting 2, pump stabilization time 15 seconds, column cleaning pump flow rate 0.500 mL / min, column loading pump flow rate 0.300 mL / min, stabilization temperature 150℃, stabilization time (pre-, before column loading) 2.0 min, stabilization time (post-, after column loading) 1.0 min, SF (soluble fraction) time 5.0 min, cooling rate from 150℃ to 30℃ 3.00℃ / min, flow rate during cooling 0.04 mL / min, heating rate from 30℃ to 160℃ 2.00℃ / min, isothermal time at 160℃ 10 min, elution flow rate 0.500 mL / min, and injection loop size 200 μL.

[0094] The flow rate during the cooling process is adjusted according to the length of the graphite column so that all polymer fractions must remain on the column at the end of the cooling cycle.

[0095] Samples were prepared using a PolymerChar autosampler at a concentration of 4.0 mg / mL in ODCB (defined below) maintained at 150°C for 120 minutes. Before use, silica gel 40 (particle size 0.2-0.5 mm, catalog number 10181-3, EMD) was dried in a vacuum oven at 160°C for approximately two hours. For CEF instruments equipped with an autosampler with N2 purge capability, silica gel 40 was packed into two 300 mm × 7.5 mm GPC-sized stainless steel columns, and the silica gel 40 columns were installed at the inlet of the CEF instrument's pump to purify ODCB. BHT was not added to the mobile phase. ODCB dried with silica gel 40 is now referred to as "ODCB". TGIC data were processed on the PolymerChar (Spain) "GPC One" software platform. Temperature calibration was performed using a mixture of approximately 4 to 6 mg of eicosane and 14.0 mg of isotactic homopolymer polypropylene (iPP) with a polydispersity of 3.6 to 4.0, a molecular weight (Mw) reported as 150,000 to 190,000 polyethylene equivalents, and a polydispersity (Mw / Mn) of 3.6 to 4.0, wherein the iPP DSC melt temperature was measured at 158–159 °C (DSC method described below). 14.0 mg of polyethylene homopolymer HDPE (zero comonomer content, weight-average molecular weight (Mw) of 115,000 to 125,000 polyethylene equivalents, and a polydispersity of 2.5 to 2.8) was added to a 10 mL vial containing 7.0 mL of ODCB. The dissolution time was 2 hours at 160 °C.

[0096] HT-TGIC Data Processing of Polymer Samples

[0097] Solvent blanks (pure solvent injection) were run under the same experimental conditions as the polymer samples. Data processing for the polymer samples included: subtraction of the solvent blank for each detector channel, temperature extrapolation as described in the calibration process, temperature compensation using the delay volume determined by the calibration process, and adjustment of the elution temperature axis to the 30°C and 160°C ranges as calculated by the calibrated heating rate.

[0098] The chromatogram (measurement channel of the IR-5 detector) is integrated with PolymerChar "GPC One" software. A linear baseline is plotted based on the visible differences when the peak decreases to a flat baseline (approximately zero in the blank chromatogram) at high elution temperatures and in the minimum or flat region of the detector signal on the high-temperature side of the soluble fraction (SF).

[0099] The width index (B-index) of the TGIC spectrum

[0100] TGIC chromatograms are related to the content and distribution of comonomers. They can also be related to the number of active sites on the catalyst. Chromatographic experimental factors can influence TGIC spectra to some extent (Stregel et al., "Modern size-exclusion liquid chromatography," Wiley, 2nd ed., Chapter 3). The TGIC width index (B-index) can be used for quantitative comparison of the width of TGIC chromatograms of samples with different compositions and distributions. The B-index can be calculated for any portion of the maximum spectral height. For example, the "N" B-index can be obtained by measuring the spectral width at 1 / N of the maximum spectral height using the following equation:

[0101]

[0102] Where Tp is the temperature at which the maximum height is observed in the spectrum, and N is an integer of 2, 3, 4, 5, 6, or 7. In the case of multiple peaks with similar heights in a TGIC chromatogram, the peak at the highest elution temperature is defined as the spectral temperature (Tp).

[0103] The U-index of the TGIC spectrum (U-index)

[0104] TGIC is used to measure the compositional distribution of polymers. To assess the uniformity of the compositional distribution, the resulting chromatogram is fitted to a Gaussian distribution according to the following equation:

[0105]

[0106] This fitting is achieved using the least squares method with the function described above. The residual f(x) between the data and the function is... i ,β) are squared and then summed, where xi is the elution temperature above 35℃, i = 0, and n is the final elution temperature of the TGIC spectrum.

[0107]

[0108] The fitting function is adjusted to provide a minimum value for summation. In addition to the least squares method, the fitting equation is further combined with a weighting function to prevent overestimation of the peak shape.

[0109]

[0110] Where for (y) i -f(x i All positive instances of ,β)), w i It equals 1, and for (y i -f(x iAll negative values ​​of β are equal to 11. Using this method, the fitting function prevents overestimation of the peak shape and provides a better approximation of the area covered by the single-center catalyst. When fitting this curve, the total area of ​​the distribution covered by the fitting can be compared with the total area of ​​the sample chromatogram excluding the fractions remaining at 30°C at the end of the cooling step of the TGIC experiment. Multiplying this value by 100 yields the homogeneity index (U-index).

[0111]

[0112] As discussed earlier, low-density polymers typically have a broader molecular weight distribution (MWD) than high-density polymers due to elution temperature. TGIC spectra can be influenced by polymer MWD (Abdulaal et al., Macromolecular Chem Phy, 2017, 218, 1600332). Therefore, when using TGIC to analyze the width of MWD curves, the width of the curve is not an accurate indicator of the polymer's chemical composition.

[0113] Due to the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer, the embodiments of the catalyst system described in this disclosure produce unique polymer properties.

[0114] One or more features of this disclosure are illustrated by the following embodiments:

[0115] Example

[0116] The procedure for continuous reactor polymerization is as follows: Raw materials (ethylene, 1-octene) and process solvents (narrow boiling range, high-purity isoparaffin solvent, commercially available under the brand name ISOPAR E from ExxonMobil Corporation) are purified using molecular sieves and then introduced into the reaction environment. Hydrogen is supplied at a high purity level in a pressurized cylinder without further purification. The reactor monomer feed (ethylene) stream is pressurized to above the reaction pressure. The solvent and comonomer feed streams are pressurized to above the reaction pressure. The catalyst components (metal-ligand complexes and cocatalysts) are manually diluted batch-wise to specified concentrations using the purified solvent and then pressurized to above the reaction pressure. All reaction feed streams are measured by mass flow meters and independently controlled by a computer-automated valve control system.

[0117] Continuous solution polymerization is carried out in a continuous stirred tank reactor (CSTR). The combined solvent, monomer, comonomer, and hydrogen feed into the reactor are controlled at temperatures between 5°C and 50°C, typically between 15°C and 25°C. All components are fed into the polymerization reactor along with the solvent feed. A catalyst is fed into the reactor to achieve the specified ethylene conversion. The cocatalyst component is fed separately based on a calculated specified molar ratio or ppm amount. The effluent from the polymerization reactor (including solvent, monomer, comonomer, hydrogen, catalyst component, and polymer) exits the reactor and comes into contact with water. Additionally, various additives, such as antioxidants, can be added at this point. The feed stream is then passed through a static mixer to uniformly disperse the mixture.

[0118] After the addition of additives, the effluent (including solvent, monomers, comonomers, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the flow temperature, thus preparing the polymer for separation from other lower-boiling-point components. The flow then passes through a reactor pressure control valve, across which the pressure is significantly reduced. From here, the effluent enters a two-stage separation system consisting of a devolve and a vacuum extruder, where the solvent and unreacted hydrogen, monomers, comonomers, and water are removed from the polymer. At the extruder outlet, the resulting molten polymer filament is passed through a cold water bath, where it solidifies. The filament is then fed through a filament shredder, where the polymer is air-dried and cut into pellets.

[0119] Procedure for batch reactor polymerization. The feedstock (ethylene, 1-octene) and process solvent (ISOPAR E) are purified using molecular sieves before being introduced into the reaction environment. ISOPAR E and 1-octene are charged into a stirred autoclave reactor. The reactor is then heated to a specific temperature and ethylene is added to reach pressure. Optionally, hydrogen is also added. A catalyst system is prepared in an inert atmosphere in a drying oven by mixing a metal-ligand complex and optionally one or more additives with a separate solvent. The catalyst system is then injected into the reactor. The reactor pressure and temperature are kept constant by feeding ethylene during the polymerization reaction and cooling the reactor as needed. After 10 minutes, the ethylene feed is shut off and the solution is transferred to a nitrogen-purged resin bath. The polymer is thoroughly dried in a vacuum oven, and the reactor is thoroughly rinsed with hot ISOPAR E between polymerization runs.

[0120] Test methods

[0121] Unless otherwise indicated herein, the following analytical methods are used to describe various aspects of this disclosure:

[0122] Melt Flow Index

[0123] The melt index I2 (or I2) and I of the polymer sample10 (Or I10) Measured according to ASTM D-1238 at 190°C and under loads of 2.16 kg and 10 kg respectively. The values ​​are reported in g / 10 min.

[0124] density

[0125] Samples for density measurement are prepared according to ASTM D4703. According to ASTM D792, Method B involves measuring the sample within one hour of pressing it.

[0126] Analysis of hydrocarbon-modified methylaluminoxanes

[0127] Example 1 It is an analytical procedure used to determine the concentration of aluminum in a solution. .

[0128] In a nitrogen atmosphere glove box, AlR will be used. A1 R B1 R C1 The aluminum-based analyte was transferred to a balanced flask and the mass of the sample was recorded. The sample was diluted with methylcyclohexane and then quenched with methanol. The mixture was vortexed and allowed to react for more than 15 minutes, then the sample was removed from the glove box. The sample was further hydrolyzed by adding H₂SO₄. The flask was capped and shaken for five minutes. Periodic venting of the flask may be necessary depending on the aluminum concentration. The solution was transferred to a separatory funnel. The flask was rinsed repeatedly with water, adding each rinse from the process to the separatory funnel. The organic layer was discarded, and the remaining aqueous solution was transferred to a volumetric flask. The separatory funnel was rinsed further with water, adding each rinse to the volumetric flask. The flask was diluted to a known volume, thoroughly mixed, and analyzed by complexation with excess EDTA followed by back titration with ZnCl₂ using xylenol orange as an indicator.

[0129] AlR in hydrocarbon-modified alkylaluminoxanes A1 R B1 R C1 Compound calculations

[0130]

[0131]

[0132] Analyze AlR using the previously described method. A1 R B1 R C1Compound content (Macromol.Chem.Phys.1996,197,1537; WO2009029857A1; Analytical Chemistry 1968,40(14),2150-2153; and Organometallics 2013,32(11),3354-3362)

[0133] Metal complexes are conveniently prepared via standard metallization and ligand exchange procedures involving transition metal sources and neutral multifunctional ligand sources. Alternatively, complexes can be prepared from corresponding transition metal tetraamides and alkylating agents (such as trimethylaluminum) via amide elimination and alkylation methods. The techniques employed are identical or similar to those disclosed in U.S. Patent Nos. 6,320,005, 6,103,657, WO 02 / 38628, WO 03 / 40195, and US-A-2004 / 0220050.

[0134] Synthetic procedures for synthesizing metal-ligand complexes I1 to 18 and C1 to C3 can be found in the following procedures, and in the case of prior disclosures, in the following disclosures: US20040010103A1, WO2007136494A2, WO2012027448A1, WO2016003878A1, WO2016014749A1, WO2017058981A1, WO2018022975A1.

[0135] Preparation of ligands for I1 (disclosed in WO2018022975 A1)

[0136]

[0137] Synthesis of 6',6”'-(((diisopropylsilanediyl)bis(methylene))bis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol)dimethylzirconium (I1): A solution of MeMgBr in diethyl ether (3.00 M, 5.33 mL, 16.0 mmol) was added to a solution of ZrCl4 (0.895 g, 3.84 mmol) in toluene (60 mL) at -30 °C. After stirring for 3 minutes, solid ligands (5.00 g, 3.77 mmol) were added in portions. The mixture was stirred for 8 h, and then the solvent was removed overnight under reduced pressure to give a dark residue. Hexane / toluene (10:1) was added... 70 mL was added to the residue, and the solution was shaken at room temperature for a few minutes. The material was then passed through the CELITE stopper of a sintered funnel. The glass frit was extracted with hexane (2 × 15 mL). The combined extracts were concentrated to dryness under reduced pressure. Pentane (20 mL) was added to the yellowish-brown solid, and the heterogeneous mixture was placed in 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 I1 (4.50 g, yield: 83%) as a white powder.

[0138] 1 H NMR (400MHz, C6D6) δ8.65–8.56(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.

[0139] Synthesis of I5 :

[0140]

[0141] ZrCl4 (798 mg, 3.43 mmol), toluene (30 mL), and a stir bar were added to a 100 mL oven-dried glass flask. The solution was placed in a refrigerator and cooled to -30 °C for 20 minutes. The solution was removed from the refrigerator and treated with MeMgBr (4.35 mL, 13.1 mmol, 3 M, in Et2O) and stirred for 15 minutes. Solid I5 ligand (5.00 g, 3.26 mmol) was added to this cold suspension. The reaction mixture was stirred at room temperature for 3 h and then filtered through a sintered plastic funnel. The filtrate was dried under vacuum. The resulting solid was washed with hexane and dried under vacuum to give I5 (3.31 g, 62%) as a grayish-white powder.

[0142] 1 H NMR (400MHz, benzene-d6) δ8.19(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=2.5 Hz,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 =9.9,4.9Hz,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).

[0143] Synthetic route of I6

[0144]

[0145] Synthesis of 2-bromo-4-fluoro-6-methylphenol: Acetonitrile (400 mL), 4-fluoro-6-methylphenol (50 g, 396.4 mmol), and p-toluenesulfonic acid (monohydrate) (75.6 g, 396 mmol) were added to a 1-liter glass vial, ensuring all substances were in solution. The solution was cooled to 0°C with ice for 25 minutes (to form a precipitate). The cooled solution was then slowly treated with N-bromosuccinimide (70.55 g, 396.4 mmol) (over approximately 5 minutes) while stirring overnight and allowing it to reach room temperature. 19The reaction was analyzed by 1F NMR spectroscopy and GC / MS to confirm complete conversion. Volatiles were removed under vacuum, and the resulting solid was treated with dichloromethane (600 mL), cooled in a refrigerator (0 °C), and filtered through a large silica gel stopper. The silica gel was washed several times with cold CH2Cl2. Volatiles were removed under vacuum (first-stage yield: 46 g, 56%). 1 ¹H NMR (400MHz, chloroform-d) δ 7.05 (ddd, J = 7.7, 3.0, 0.7Hz, 1H), 6.83 (ddt, J = 8.7, 3.0, 0.8Hz, 1H), 5.35 (s, 1H), 2.29 (d, J = 0.7Hz, 3H). 19 F NMR (376MHz, chloroform-d) δ-122.84.

[0146]

[0147] Synthesis of bis((2-bromo-4-fluoro-6-methylphenoxy)methyl)diisopropylgermanium: In a glove box, in a 250 mL flask equipped with a magnetic stir bar, 95% NaH (1.76 g) (carefully generating H2) was slowly added to a solution of 2-bromo-4-fluoro-6-methylphenol (15 g, 73.2 mmol) in N,N-dimethylformamide (DMF) (35 mL) until hydrogen evolution ceased. This mixture was stirred at room temperature for 30 minutes. Then, diisopropylgermanium dichloride (6.29 g, 24.4 mmol) was added. The mixture was heated to 55 °C and maintained at this temperature for 18 hours. The reaction mixture was removed from the glove box and quenched with a saturated aqueous solution of NH4Cl (20 mL) and H2O (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 Et2O (20 mL), and the combined organic extracts were washed with brine (10 mL). The organic layer was then dried (MgSO4), filtered, and concentrated to dryness. The crude residue was dried and loaded onto silica gel, and then purified by rapid column chromatography (100 mL / min, pure hexane, ethyl acetate added to increase to 10% within 20 min) to give a pale yellow oil as the product. All clean fractions (some fractions containing <10% starting phenol) were combined, and the final product was left under vacuum overnight (yield: 9 g, 62%).

[0148] 1 ¹H NMR (400MHz, chloroform-d) δ 7.10 (dd, J = 7.7, 3.0Hz, 2H), 6.84 (ddd, J = 8.8, 3.1, 0.8Hz, 2H), 4.14 (s, 4H), 2.33 (s, 6H), 1.74 (hept, J = 7.4Hz, 2H), 1.35 (d, J = 7.4Hz, 12H);19 F NMR (376MHz, chloroform-d) δ-118.03.

[0149] Synthesis of I6 ligands

[0150]

[0151] 2,7-Di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (disclosed in WO2014105411 A1) (29.0 g, 41.9 mmol), bis((2-bromo-4-fluoro-6-methylphenoxy)methyl)diisopropylgermanium (6.00 g, 8.65 mmol, containing 10% 2-bromo-4-fluoro-2-methylphenol) and THF (80 mL) were added to a 500 mL glass bottle equipped with a stir bar. The solution was heated to 55°C and treated with chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) (tBu3P-PdG2) (199 mg, 0.346 mmol, 4 mol%) while stirring. NaOH aqueous solution (17.3 mL, 51.9 mmol, 3 M) was purged with nitrogen for 20 min, and then added to THF solution. The reaction mixture was stirred overnight at 55°C. The aqueous phase was separated and discarded, and the remaining organic phase was diluted with diethyl ether and washed twice with brine. The solution was passed through a short silica gel stopper. The filtrate was dried on a rotary evaporator, dissolved in THF / MeOH (40 mL / 40 mL), treated with HCl (2 mL), and stirred overnight at 70°C. The solution was dried under vacuum and purified by C18 reversed-phase column chromatography to provide an I6 ligand as a grayish-white solid (yield: 6.5 g, 54%).

[0152] 1 H NMR (400MHz, chloroform-d) δ8.01(d,J=8.2Hz,4H),7.42(dd,J=25.5,2.4Hz,4H),7.32(dd,J=8.2,1.6Hz,4H),7.17(s,4H),6.87(ddd,J=16.4 ,8.8,3.0Hz,4H),6.18(s,2H),3.79(s,4H),2.12(s,6H),1.71(s,6H),1.56(s,4H),1.38(s,12H),1.31(s,36H),0.83–0.73(m,30H); 19 F NMR (376MHz, chloroform-d) δ-119.02.

[0153] Synthesis of I6 :

[0154]

[0155] ZrCl4 (402 mg, 1.72 mmol), toluene (83 mL), and a stir bar were added to a 100 mL oven-dried glass flask. The solution was placed in a refrigerator and cooled to -30 °C for 20 minutes. The solution was removed from the refrigerator and treated with MeMgBr (2.4 mL, 7.1 mmol, 3 M, in Et2O) and stirred for 3 minutes. Solid form of I6 ligand (2.3 g, 1.64 mmol) was added to this cold suspension, and the remaining powder was dissolved in cold toluene (3 mL) and added to the reactants. The reactants were stirred overnight at room temperature and then filtered through a sintered plastic funnel. The filtrate was dried under vacuum, dissolved again in toluene (40 mL), filtered again through a CELITE stopper, and dried again under vacuum. The resulting solid was washed with pentane (approximately 5 mL), dried under vacuum, and yielded I10 (2.1 g, 84%) as a grayish-white powder.

[0156] 1 H NMR (400MHz, benzene-d6) δ8.20(dd,J=8.2,0.5Hz,2H),8.11(dd,J=8.2,0.6Hz,2H),7.88–7.82(m,4H),7.77(d, J=2.6Hz,2H),7.50(dd,J=8.3,1.7Hz,2H),7.42–7.37(m,4H),6.99(dd,J=8.7,3.1Hz,2H),6.20–6.10(m,2 H),4.29(d,J=12.2Hz,2H),3.90(d,J=12.2Hz,2H),1.56(s,4H),1.53(s,18H),1.29(s,24H),1.27(s,6H), 1.18(s,6H),1.04–0.94(m,2H),0.81(d,J=7.4Hz,6H),0.80(s,18H),0.74(d,J=7.4Hz,6H),-0.47(s,6H); 19 F NMR (376MHz, benzene-d6) δ-116.24.

[0157] I7 synthesis scheme

[0158] Preparation of bis((2-bromo-4-tert-butylphenoxy)methyl)diisopropylsilane

[0159]

[0160] In a glove box, diisopropylchlorosilane (3.703 g, 20 mmol, 1.0 equivalent) was dissolved in anhydrous THF (120 mL) in a 250 mL single-necked round-bottom flask. The flask was capped with a diaphragm, sealed, removed from the glove box, and cooled to -78 °C in a dry ice-acetone bath. Bromochloromethane (3.9 mL, 60 mmol, 3.0 equivalent) was added. Using a syringe pump, a hexane solution of butyllithium (18.4 mL, 46 mmol, 2.3 equivalent) was added to the cooling wall of the flask over 3 h. The mixture was warmed to room temperature overnight (16 h), and saturated NH4Cl (30 mL) was added. The two layers were separated. The aqueous layer was extracted with diethyl ether (2 × 50 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under reduced pressure. The crude product was used for the next step without further purification.

[0161] In a glove box, bis(chloromethyl)diisopropylsilane (2.14 g, 10 mmol, 1.0 equivalent), 4-tert-butyl-2-bromophenol (6.21 g, 27 mmol, 2.7 equivalent), K-3PO4 (7.46 g, 35 mmol, 3.5 equivalent), and DMF (10 mL) were added to a 40 mL vial. The reaction mixture was stirred overnight at 80 °C. After cooling to room temperature, the reaction mixture was purified by column chromatography using ether / hexane (0 / 100 -> 30 / 70) as the eluent. 4.4 g of colorless oil was collected, with an overall yield of 73% after two steps.

[0162] 1 H NMR (400MHz, CDCl3) δ7.51(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).

[0163] 6 " ,6 "" '-(((diisopropylsilanediyl)bis(methylene))bis(oxy))bis(3,3 " ,5-Uncle Dingji-5'- Preparation of methyl-[1,1':3',1”-terphenyl]-2'-ol

[0164]

[0165] In a glove box, bis((2-bromo-4-tert-butylphenoxy)methyl)diisopropylsilane (1.20 g, 2.0 mmol, 1.0 equivalent), 2-(3',5'-di-tert-butyl-5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane (2.54 g, 5.0 mmol, 2.5 equivalent), tBu3P Pd G2 (0.031 g, 0.06 mmol, 0.03 equivalent), THF (3 mL), and 4M NaOH solution (3.0 mL, 12.0 mmol, 6.0 equivalent) were added to a 40 mL vial equipped with a stir bar. The vial was heated at 55 °C for 2 hours under nitrogen. After completion, the top organic layer was extracted with ether and filtered through a short silica gel stopper. The solvent was removed under reduced pressure. The residue was dissolved in THF (10 mL) and MeOH (10 mL). Then concentrated HCl (0.5 mL) was added. The resulting mixture was heated at 75 °C for 2 hours and then cooled to room temperature. The solvent was removed under reduced pressure. The residue was purified by reversed-phase column chromatography using THF / MeCN (0 / 100->100 / 0) as the eluent. 1.62 g of white solid was collected, yield 78%.

[0166] 1 H NMR (400MHz, CDCl3) δ7.39(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).

[0167] Preparation of I7

[0168]

[0169] In a glove box, add ZrCl4 (47 mg, 0.2 mmol, 1.0 equivalent) and anhydrous toluene (6.0 mL) to an oven-dried 40 mL vial equipped with a stir bar. Cool the vial to -30°C in a refrigerator for at least 30 minutes. Remove the vial from the refrigerator. Add MeMgBr (3 M, 0.29 mL, 0.86 mmol, 4.3 equivalent) to the stirred suspension. Two minutes later, 206 mg (0.2 mmol, 1.0 equivalent) of 6”,6””'-(((diisopropylsilanediyl)bis(methylene))bis(oxy))bis(3,3”,5-tri-tert-butyl-5'-methyl-[1,1':3',1”-terphenyl]-2'-ol (as solid) was added. The resulting mixture was stirred overnight at room temperature. The solvent was removed under vacuum to give a dark solid, which was washed with hexane (10 mL) and then extracted with toluene (12 mL). After filtration, the toluene extract was dried under vacuum. 170 mg of white solid was collected, yield 74%.

[0170] 1 H NMR (400MHz, C6D6) δ8.20–7.67(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=8.6H z,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).

[0171] The metal-ligand complexes I1 to I8 have the structure according to formula (I) and are as follows:

[0172]

[0173]

[0174] Metal-ligand complexes C1 to C3 are comparative examples and are as follows:

[0175]

[0176] Example 2— Polymerization reaction

[0177] Metal-ligand complexes (MLCs) I1 to I8 were tested in a continuous polymerization process using MMAO-A1, MMAO-B, MMAO-C, MMAO-D1, MMAO-D2, MMAO-E, or MMAO-F as activators, and compared with comparative metal-ligand complexes C1 to C3. The data are summarized in Tables 2-9.

[0178] Table 1: Alkyl aluminum oxane compositions

[0179]

[0180]

[0181] *MMAO-A1 and A2 are modified with n-octyl substituents to achieve a methyl:n-octyl ratio of approximately 6:1. MMAO-B is modified with n-octyl substituents to achieve a methyl:n-octyl ratio of approximately 19:1.

[0182] Table 2: Continuous Process Ethylene / 1-Octene Copolymerization

[0183]

[0184] Polymerization was carried out in a reactor at a temperature of 160°C, with a continuous feed flow rate of 3.4 kg / h ethylene, 3.3 kg / h 1-octene, and 21 kg / h ISOPAR E. [A] % solids refers to the concentration of the polymer in the reactor. [B] H2 (mol%) is defined as the mole fraction of hydrogen in the reactor relative to ethylene, expressed as a percentage. [C] Efficiency (Eff.) is measured as 10. 6 g polymer / g metal. 1 Reactor temperature = 153℃, continuous feed flow rate = 2.5 kg / h ethylene, 3.3 kg / h 1-octene, 21 kg / h ISOPAR E. A molar ratio of 1.2 relative to the complex is used. 2 [HNMe(C 18 H 37 [2][B(C6F5)4], MMAO-D was used in the reactor at the reported Al concentration. 3 The reactor temperature is 190℃, and the continuous feed flow rate is 4.6 kg / h ethylene, 2.0 kg / h 1-octene, and 22 kg / h ISOPAR E.

[0185] Table 3: Polymer data generated under continuous operation .

[0186]

[0187] Item numbering is referenced in Table 2.

[0188] Table 4: Polymer data generated under continuous operation .

[0189]

[0190] Item numbering is referenced in Table 2.

[0191] The data recorded in Tables 2 to 4 show that the combination of the catalyst of the present invention with the MMAO activator produces polymers with narrow MWD, as shown by the U index, which is independent of the MMAO activator.

[0192] When the U-index approaches 100, the fitted area is similar to the sample area, indicating a single-center catalyst. As previously stated, the substitution mode of the catalyst system of the present invention is believed to prevent the formation of a second active site and thus result in a narrower compositional distribution. Furthermore, a narrower compositional distribution will lead to a smaller expected B-index. The embodiments of the present invention given in Tables 3 and 4 all show smaller B-indexes than the comparative examples with unsubstituted bridges.

[0193] To demonstrate the advantages of MMAO-A1, MMAO-B, and MMAO-C, continuous process data are shown in Tables 5 through 8. H2 was adjusted to achieve the desired polymer melt index, and density variations were permitted.

[0194] Table 5: Continuous Process Ethylene / 1-Octene Copolymerization

[0195]

[0196] Polymerization was carried out at 160°C with a continuous feed flow rate of 3.4 kg / h ethylene, 3.3 kg / h 1-octene, and 21 kg / h ISOPARE, 14% solids, and 81% ethylene conversion. The efficiency (Eff.) was measured to be 10. 6 g polymer / g metal.

[0197] Table 6: Continuous Process Ethylene / 1-Octene Copolymerization

[0198]

[0199] Polymerization was carried out at 160°C with a continuous feed flow rate of 3.4 kg / h ethylene, 3.3 kg / h 1-octene, and 21 kg / h ISOPARE, 14% solids, and 81% ethylene conversion. The efficiency (Eff.) was measured to be 10. 6 g polymer / g metal.

[0200] Table 7: Continuous Process Ethylene / 1-Octene Copolymerization

[0201]

[0202] Polymerization was carried out at 175°C with a continuous feed rate of 3.3 kg / h ethylene, 1.6 kg / h 1-octene, and 22 kg / h ISOPARE, 14% solids, and 87% C2 conversion. The efficiency (Eff.) was measured to be 10. 6 g polymer / g metal.

[0203] Figure 1 This is a graph showing catalyst efficiency as a function of co-catalyst type. When used in combination with MMAO-A1, MMAO-B, and MMAO-C, the metal-ligand complexes I1, I3, and I7 are more efficient than when used in combination with the comparative co-catalyst MMAO-D / borate.

[0204] Table 8: Continuous Process Ethylene / 1-Octene Copolymerization

[0205]

[0206] Polymerization was carried out at 175°C with a continuous flow rate of 140 lbs / h ethylene, 30.7-35.0 lbs / h 1-octene, and 900 lbs / h ISOPAR E, 14% solids, and 93.8% ethylene conversion. The efficiency (Eff.) was measured to be 10. 6 g polymer / g metal.

[0207] Equipment Standards

[0208] Unless otherwise stated, all solvents and reagents were obtained from commercial sources and used as is. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by activated alumina, and in some cases by Q-5 reactants. Solvents used in experiments conducted in a nitrogen-filled glove box were purified by activated alumina. The samples were stored on molecular sieves and then further dried. Glassware used for moisture-sensitive reactions was dried overnight in an oven before use. NMR spectra were recorded on a Varian 400-MR and VNMRS-500 spectrometer. LC-MS analysis was performed using a Waters e2695 SeparationsModule coupled with a Waters 2424ELS detector, a Waters 2998PDA detector, and a Waters 3100ESI mass detector. LC-MS separation was performed on an XBridge C18 3.5μm 2.1×50mm column using a gradient of acetonitrile to water from 5:95 to 100:0, with 0.1% formic acid as the ionizing agent. HRMS analysis was performed using an Agilent 1290 Infinity LC with a Zorbax EclipsePlus C18 1.8μm 2.1×50mm column coupled to an Agilent 6230TOF Mass Spectrometer with electrospray ionization. 1 The H NMR data are reported as follows: chemical shifts (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quadruplet, p = quintuplet, sex = hexatuplet, sept = heptet and m = multiplicity), integration, and assignment). Low-field data from the inner tetramethylsilane (TMS, scale δ) are reported using the protons remaining in the deuterated solvent as a reference. 1 Chemical shifts (in ppm) from H NMR data. 1 H-decoupling method was used to determine 13 C NMR data were used, and chemical shifts (in ppm) were reported from the low field of tetramethylsilane (TMS, scale δ) compared to using protons remaining in the deuterated solvent as a reference.

Claims

1. A method for polymerizing olefin monomers, the method comprising reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system, wherein the catalyst system comprises: A hydrocarbon-modified methylaluminoxane having an AlR content of less than 50 mol% and greater than or equal to 11 mol% based on the total molar percentage of aluminum in the hydrocarbon-modified methylaluminoxane. A1 R B1 R C1 , where R A1 R B1 and R C1 Independently for straight-chain C1-C 40 Alkyl, branched C1-C 40 Alkyl or C6-C 40 Aryl; and One or more metal-ligand complexes according to formula (I): in: M represents titanium, zirconium, or hafnium; n is 1, 2, or 3; Each X is independently selected from C1−C 20 Hydrocarbon groups, phenyl groups, benzyl groups, and halogens; The metal-ligand complex is electrically neutral overall; R 1 and R 16 Independently select the group consisting of the following: free radicals having formula (II), free radicals having formula (III), and free radicals having formula (IV): Where R 31-35 R 41-48 and R 51-59 Each of them is independently selected from –H, C1−C 20 Hydrocarbon group, –Si[C1−C 20 [Hydrocarbon group]3、−Si(R C 3. −OR C 、−SR C -CN, -CF3 or halogen; R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 and R 15 Independently selected from −H, C1−C 40 hydrocarbon group, C1−C 40 heterohydrocarbon group, −Si(R) C 3. −OR C 、−SR C -CN, -CF3 and halogens; Y represents CH2 and CHR. 21 CR 21 R 22 SiR 21 R 22 or GeR 21 R 22 , where R 21 and R 22 It is C1-C 20 alkyl; The prerequisite is: (1) If Y is CH2, then R 8 and R 9 At least one of them is not –H; R C Independently C1−C 30 hydrocarbon group, C1−C 30 heteroalkyl groups or −H; and The catalyst system described herein does not contain borate activators.

2. The polymerization method according to claim 1, wherein, based on the total molar amount of aluminum in the hydrocarbon-modified methylaluminoxane, the hydrocarbon-modified methylaluminoxane contains less than 25 mol% AlR. A1 R B1 R C1 .

3. The polymerization method according to claim 1, wherein the hydrocarbon-modified methylaluminoxane is a modified methylaluminoxane.

4. The polymerization method according to claim 1, wherein R 8 and R 9 At least one of them is C1−C 40 hydrocarbon group, C1−C 40 heterohydrocarbon groups or halogen atoms.

5. The polymerization method according to claim 1, wherein R 8 and R 9 At least one of them is a C1-C5 alkyl group.

6. The polymerization method according to claim 1, wherein R 1 and R 16 At least one of them is a free radical having formula (III).

7. The polymerization method according to claim 6, wherein R 42 and R 47 For C1−C 20 Hydrocarbon group or –Si[C1−C 20 [Hydrocarbon group]3, or R 43 and R 46 For C1−C 20 Hydrocarbon group or –Si[C1−C 20 [Hydrocarbon group]3.

8. The polymerization method according to claim 1, wherein R 1 and R 16 At least one of them is a free radical having formula (II).

9. The polymerization method according to claim 8, wherein R 32 and R 34 For C1−C 12 Hydrocarbon group or –Si[C1−C 20 [Hydrocarbon group]3.

10. The polymerization method according to claim 1, wherein R 1 and R 16 At least one of them is a free radical having formula (IV).

11. The polymerization method according to claim 10, wherein R 52 R 53 R 55 R 57 and R 58 At least two of them are C1−C 20 Hydrocarbon group or –Si[C1−C 20 [Hydrocarbon group]3.

12. The polymerization method according to claim 1, wherein R 3 and R 14 For C1−C 20 alkyl.

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

14. The polymerization method according to claim 1, wherein R 3 and R 14 It is either tert-singyl or octyl.

15. The polymerization method according to claim 1, wherein the olefin monomer is C3−C 20 α-olefins.

16. The polymerization method according to claim 1, wherein the olefin monomer is a cyclic olefin.

17. The polymerization method according to claim 1, wherein the polymerization method is a solution polymerization reaction.

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