Heteroatom-crosslinked bis-phenyl-phenoxy catalyst and ethylene copolymer with improved features

Abstract

An embodiment relates to a catalyst system comprising a metal-ligand complex having the following structure:, In the above formula, R17 and R18 are independently (C5-C40)hydrocarbyl. The embodiment also relates to an ethylene-based polymer comprising a polymerization reaction product of an ethylene monomer and a 1-butene comonomer, wherein the ethylene-based polymer has a density of 0.854 g / cm3 to 0.875 g / cm3, a melt index I2 of 0.1 to 30 dg / min, a melt flow ratio (I10 / I2) of 5 to 15, a molecular weight distribution (MWD) of 1.5 to 5, and an HCC (high comonomer content) value of less than 1.4 wt%.

Description

Technology Field

[0001] Cross-reference of related applications

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 625,518, filed on January 26, 2024, with the title of "Performance of heteroatom-crosslinked bis-phenyl-phenoxy catalysts," the entire contents of which are incorporated herein by reference.

[0003] Technology field

[0004] The embodiments of the present disclosure generally relate to olefin polymerization catalyst systems and processes, and more specifically to heteroatom-crosslinked bis-phenyl-phenoxy catalyst systems for olefin polymerization. Background Technology

[0005] Olefinic polymers, such as polyethylene and / or polypropylene, are manufactured using various catalyst systems. The selection of these catalyst systems used in the polymerization process of olefinic polymers is an important factor contributing to the characteristics and properties of these olefinic polymers.

[0006] Polyethylene and polypropylene are manufactured for a wide variety of articles. Polyethylene and polypropylene polymerization processes can vary in many respects and can produce a very diverse range of resulting polyethylene resins with different physical properties, realizing various resins suitable for use in different applications. Ethylene monomers and, optionally, one or more comonomers are present in a liquid diluent (e.g., solvent), such as an alkane or isoalkane, e.g., isobutane. Hydrogen may also be added to the reactor. Catalyst systems for producing polyethylene typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (either metallocene or non-metallocene (molecules)) catalyst systems. The reactants in the catalyst system and the diluent are circulated at an elevated polymerization temperature around the reactor, thereby producing a polyethylene homopolymer or copolymer. Periodically or continuously, a portion of the reaction mixture containing the polyethylene product dissolved in the diluent is removed from the reactor along with unreacted ethylene and one or more optional comonomers. The reaction mixture may be treated to remove the polyethylene product from the diluent and unreacted reactants when removed from the reactor, at which point the diluent and unreacted reactants are typically recirculated back into the reactor. Alternatively, the reaction mixture may be sent to a second reactor connected in series with the first reactor, and a second polyethylene fraction may be produced.

[0007] Despite research efforts to develop catalyst systems suitable for olefin polymerization, such as polyethylene or polypropylene polymerization, there remains a need to reduce operating costs by increasing the efficiency of the catalyst system without compromising other important properties, particularly intrinsic molecular weight, comonomer incorporation rate, and solubility in alkane solvents. Previously reported heteroatom-crosslinked bis-phenyl-phenoxy catalyst systems primarily relate to metal-ligand complexes containing silicon or germanium crosslinks, where two isopropyl groups are bonded to the silicon or germanium atoms of the respective silicon or germanium crosslinks. However, a systematic investigation of the structure-performance relationship of germanium- or silicon-crosslinked bis-phenyl-phenoxy catalyst systems revealed that substituents on the silicon and germanium crosslink atoms can have a significant influence on important properties of the catalyst system, including catalytic activity, intrinsic molecular weight, comonomer incorporation rate, and solubility in alkane solvents, without limitation. In fact, it has been found that catalytic efficiency can be significantly improved, for example, by up to 2 to 3 times in some cases, by changing isopropyl substituents to specific alkyl groups. Furthermore, the activity achieved by the germanium- or silicon-crosslinked bis-phenyl-phenoxy catalyst systems described herein can be obtained without impairing other important properties, such as intrinsic molecular weight, comonomer incorporation rate, and solubility in alkane solvents. In fact, intrinsic molecular weight, comonomer incorporation rate, and solubility in alkane solvents were improved or maintained in most of the catalyst systems described herein.

[0008] Accordingly, through the catalyst system described herein and the polymerization process including it, an improved olefin polymerization process with high catalytic efficiency can be realized. The high catalytic efficiency achieved by the catalyst system described herein enables a reduction in catalyst usage costs and thus can enhance the commercial potential of heteroatom-crosslinked bis-phenyl-phenoxy catalysts. Furthermore, the catalyst system described herein is particularly useful for the development of new catalysts with low usage costs.

[0009] In addition, the catalyst system described herein and the polymerization process containing it have been found to be capable of producing ethylene / butene copolymers with a short-chain branching distribution (SCBD) at high temperatures and high production rates. Conventional catalyst systems used for ethylene / butene copolymerization tend to produce ethylene / butene copolymers with a wide SCBD and high comonomer content (HCC) fraction when reactor configuration or process conditions deviate from ideal conditions. Under these circumstances, the plant is forced to operate by lowering the production rate or increasing the target density, which results in reduced profits and / or degraded product performance.

[0010] Low-density ethylene / α-olefin copolymers, such as ethylene / butene copolymers, tend to become blocked during storage and / or transport. Specifically, for polymers with specific density and melt index specifications, a wide SCBD and high HCC fraction can lead to pellet massing and make material handling difficult. The HCC fraction represents the weight fraction of a polymer sample consisting of chains with high comonomer content and / or low molecular weight, and can be measured using thermal gradient interaction chromatography. In addition to poor solid handling performance, polymers with a wider SCBD also often have higher oligomer and / or BBB triad content, which can negatively affect curing performance in various applications. Therefore, improved catalyst systems and polymerization processes are required to produce copolymers with reduced HCC fraction and a narrow SCBD.

[0011] As mentioned above, surprisingly, the catalyst system described herein has been found to be capable of producing ethylene / α-olefin copolymers, such as ethylene / butene copolymers, having excellent comonomer incorporation ability and a long half-life, reduced HCC fraction, narrow SCBD, low vinyl unsaturation, and low levels of BBB terebinary. The combination of these features provides copolymers that exhibit a good curing reaction using peroxide as a curing agent without sacrificing the weather resistance or durability typically seen in polymers with excellent curing performance achieved due to high levels of unsaturation. Furthermore, due to the efficient comonomer incorporation exhibited by the catalyst system described herein, the butene concentration at the downstream end of the reactor is lowered, and thus liquid-liquid equilibrium and / or gas-liquid equilibrium problems at the downstream heater of the reactor can be avoided, thereby improving the transition time between comonomer grades. The polymer stream maintains a single phase, thus enabling efficient heat transfer at the reactor downstream heater and increasing the production speed while minimizing the expansion of the SCBD.

[0012] An embodiment of the present disclosure comprises a catalytic system comprising a metal-ligand complex according to the following formula (I):

[0013]

[0014] In formula (I), M is a metal selected from titanium, zirconium, or hafnium; n is 1 or 2; when n is 1, X is a monodentate or bidentate ligand; when n is 2, each X is a monodentate ligand, and is the same or different; the metal-ligand complex is charge-neutral as a whole; each Z is independently selected from silicon or germanium; and R 1 and R 16 is a radical having the following chemical formula (II):

[0015]

[0016] In chemical formula (II), R 31-35 are respectively (C1-C 40 )hydrocarbyl, (C1-C 40 )heterohydrocarbil, -Si(R C )3, -OR C , -SR C , -CN, -CF3, halogen, and -H are independently selected.

[0017] In chemical formula (I), R 2-4 , R 5-8 , R 9-12 , and R 13-15 are respectively (C1-C 40 )hydrocarbyl, (C1-C 40 )heterohydrocarbil, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -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 Independently selected from )2NC(O)-, halogen, and -H; R 17 and R 18 is independently (C5-C 40 )hydrocarbil and; R 23 and R 24 is -(CR C 2) m - is selected independently from, where m is 1 or 2; and each R C , R P , and R N (C1-C 30 )hydrocarbyl, (C1-C 30) It is independently selected from heterohydrocarbil, or -H. Brief explanation of the drawing

[0018] The following detailed description of specific embodiments of the present disclosure is best understood when read together with the following drawings. FIG. 1a is a graph showing the thermal gradient interaction chromatography (TGIC) short-chain branch distribution (SCBD) curves for copolymer designs having a melt index I2 of approximately 0.26 dg / min for the inventive example and comparative example according to one or more embodiments described in the present disclosure. FIG. 1b is a graph of TGIC SCBD curves for other copolymer designs having a melt index I2 of approximately 5 dg / min for inventive examples and comparative examples according to one or more embodiments described in the present disclosure. FIG. 1c is a graph of a TGIC SCBD curve for another copolymer design having a melt index I2 of approximately 1.2 dg / min for the inventive example and comparative example according to one or more embodiments described in the present disclosure. FIG. 2 is a graph showing the HCC value (weight%) versus density (g / cc) for an ethylene / 1-butene copolymer produced in an ethylene / butene copolymer study according to one or more embodiments described in the present disclosure. FIG. 3 is a graph showing the BBB trimer content (BBB trimer per 1,000 carbon atoms) versus density (g / cc) for an ethylene / 1-butene copolymer produced in an ethylene / butene copolymer study according to one or more embodiments described in the present disclosure. FIG. 4 is a graph showing the vinyl content (vinyl per 1,000 carbon atoms) versus density (g / cc) for an ethylene / 1-butene copolymer produced in an ethylene / butene copolymer study according to one or more embodiments described in the present disclosure. Figure 5 shows the extrapolation result of the elution temperature for TGIC temperature correction. Specific details for implementing the invention

[0019] Specific embodiments of a catalytic system will be described below. It should be understood that the catalytic system of this disclosure may be implemented in different forms and should not be interpreted as being limited to the specific embodiments presented in this disclosure. Rather, embodiments are provided to ensure that this disclosure is thorough and complete and to fully convey the scope of the subject matter of the invention to those skilled in the art.

[0020] Common abbreviations are as follows:

[0021] R, Z, M, X, and n : As defined above; Me : Methyl; Et : Ethyl; Ph : Phenyl; Bn : Benzyl; i -Pr : Iso -profile; t -Bu : tert -butyl; t -Oct : tert -Octyl (2,4,4-trimethylpent-2-yl); n -Oct : n -Octyl; Ts : Toluene sulfonate; THF : Tetrahydrofuran; Et 2 O : Diethyl ether; MeOH : Methanol; DMA : Dimethylacetamide; DME : Dimethoxyethanol; CH 2 Cl2 or DCM : Dichloromethane; CCl 4 : Carbon tetrachloride; EtOH : Ethanol; CH 3 CN : Acetonitrile; EtOAc : Ethyl acetate; C 6 D 6 : Deuterium benzene or benzene- d 6 : CDCl 3 : Deuteriumized chloroform; DMSO- d 6 : Deuterium dimethyl sulfoxide; DBA : Dibenzylideneacetone; PPh 3 : Triphenylphosphine; tBu 3 P : Tri-t-butylphosphine; tBu 3 P Pd G2 : ; SiO 2 : Silica gel; Me 4 Si : Tetramethylsilane; NaOH : Sodium hydroxide; HCl : Hydrochloric acid; NaHCO 3 : Sodium bicarbonate; NaO t Bu : Sodium tert -Butoxide; K 3 PO 4 : tribasic potassium phosphate; brine : Saturated aqueous sodium chloride; Na 2 SO 4 : Sodium sulfate; MgSO 4 : Magnesium sulfate; n -BuLi : n - Butyl lithium; CuI : Copper iodide(I); Cs 2 CO 3 : Cesium carbonate; HfCl 4 : Hafnium(IV) chloride; HfBn 4 : Hafnium(IV) tetrabenzyl; ZrCl 4 : Zirconium(IV) chloride; ZrBn 4 : Zirconium(IV) tetrabenzyl; N 2 : Nitrogen gas; PhMe : Toluene; MAO : Methylaluminoxan; MMAO : Modified methylaluminoxane; PTFE : Polytetrafluoroethylene; GC : Gas chromatography; LC : Liquid chromatography; NMR : Nuclear magnetic resonance; HRMS High-resolution mass spectrometry; mmol : millimoles; mL : milliliters; M : Mol; min : minute; h : hour; d : Day; equiv : Equivalents.

[0022] The term "independently selected" is R 1 , R 2 , R 3 , R 4 , and R 5 R groups such as can be the same or different (e.g., R 1 , R 2 , R 3 , R 4 , and R 5 All of can be substituted alkyls, or R 1 and R 2 is a substituted alkyl and R 3The singular is used herein to indicate that it may be an aryl, etc. The singular use includes the plural use, and vice versa (e.g., hexane solvents include hexanes). The named R group will generally have a structure recognized in the art as corresponding to the R group bearing that name. These definitions are intended to supplement and exemplify definitions known to those skilled in the art, rather than to exclude them.

[0023] The term "procatalyst" refers to a compound that exhibits catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with a procatalyst in a manner that catalytically converts the procatalyst into an active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable.

[0024] When used to describe a specific carbon atom-containing chemical group, "(C x -C y An interpolation expression of the form )" implies that the unsubstituted chemical group has x to y carbon atoms, including x and y. For example, (C1-C 50 )alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, a specific chemical group is R S It can be substituted with one or more substituents such as. "(C x -C y R of a chemical group defined using the )" insertion S The substituted version is any R S Depending on the identity of the group, it can contain more than y carbon atoms. For example, "R S Exactly one R that is phenyl (-C6H5). S (C1-C 50 )alkyl" can contain 7 to 56 carbon atoms. Therefore, generally "(Cx -C y A chemical group defined using the )" insertion is one or more carbon atom-containing substituents R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group is all carbon atom-containing substituents R S It is determined by adding both x and y to the combined sum of the number of carbon atoms from.

[0025] In some embodiments, each chemical group (e.g., X, R, Z, etc.) of the metal-ligand complex of formula (I) may be unsubstituted as long as the above-mentioned conditions are satisfied, i.e., substituent R S It can be defined without the use of. In another embodiment, at least one of the chemical groups of the metal-ligand complex of formula (I) is independently one or more substituents R S It contains. In most embodiments, the metal-ligand complex of formula (I) contains a total of 20 or fewer R S ...exists, and in other embodiments, a total of 10 or fewer R S There exists, and in some embodiments, a total of 5 or fewer R S is present. The compound has two or more substituents R S In the case containing, each R S is independently bonded to the same or different substituted chemical groups. Two or more R S When bonded to the same chemical group, they are independently bonded to the same or different carbon atoms or heteroatoms in the same chemical group, including persubstitution of the chemical group.

[0026] The term "oversubstitution" refers to each hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group being a substituent (e.g., R). SIt means that it is replaced by ). The term "polysubstituted" means that at least two (but not all) of the hydrogen atoms bonded to the carbon atom or heteroatom of the corresponding unsubstituted compound or functional group are each replaced by a substituent.

[0027] The term "-H" refers to hydrogen or a hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and refer to the same thing unless explicitly stated otherwise.

[0028] term "(C1-C 40 "Hydrocarbyl" refers to a hydrocarbon radical having 1 to 40 carbon atoms, and the term "(C1-C 40 "Hydrocarbylene" means a hydrocarbon deradical having 1 to 40 carbon atoms, and each hydrocarbon radical and each hydrocarbon deradical is aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic including acyclic; 3 or more carbon atoms), or acyclic, and each hydrocarbon is unsubstituted or has one or more R S It is replaced with.

[0029] In the present disclosure, (C1-C 40 )hydrocarbil is unsubstituted or substituted (C1-C 40 )alkyl, (C3-C 40 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 )alkylene, (C6-C 40 )aryl, or (C6-C 20 )aryl-(C1-C 20 It may be an alkylene. The aforementioned (C1-C 40 Each hydrocarbyl group has up to 20 carbon atoms (i.e., (C1-C 20 )hydrocarbyl).

[0030] term "(C1-C 40)alkyl" and "(C1-C 18 )alkyl" are each unsubstituted or one or more R S It refers to a saturated straight-chain or branched-chain hydrocarbon radical having 1 to 40 carbon atoms or 1 to 18 carbon atoms substituted with . Unsubstituted (C1-C 40 Examples of )alkyl groups include unsubstituted (C1-C 20 )alkyl; unsubstituted (C1-C 10 )alkyl; unsubstituted (C1-C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Substituted (C1-C 40 Examples of )alkyl groups include substituted (C1-C 20 )alkyl, substituted (C1-C 10 )alkyl, trifluoromethyl and [C 45 ]alkyl. The term "[C 45 ]alkyl (with square brackets) refers to radicals where up to 45 carbon atoms are present in the radical, including substituents, for example, each R being a (C1-C5)alkyl. S Replaced with (C 27 -C 40 )means that it is an alkyl. Each (C1-C5)alkyl is independently methyl, trifluoromethyl, ethyl, 1-propyl, 2-propyl (also known as 1-methylethyl and Iso -propyl), or 1,1-dimethylethyl (also so-called tert -butyl)

[0031] term "(C6-C 40 )aryl" is unsubstituted or (one or more R SIt means a mono-, non-, or tricyclic aromatic hydrocarbon radical having 6 to 40 carbon atoms substituted by, wherein at least 6 to 14 carbon atoms are aromatic ring carbon atoms, and the mono-, non-, or tricyclic radical each comprises 1, 2, or 3 rings; 1 ring is aromatic, and 2 or 3 rings are independently fused or non-fused rings, and at least one of the 2 or 3 rings is aromatic. Unsubstituted (C6-C 40 An example of an aryl is an unsubstituted (C6-C 20 )aryl, unsubstituted (C6-C 18 )aryl; 2-(C1-C5)alkyl-phenyl; 2,4-bis(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C6-C 40 An example of an aryl is a substituted (C6-C 20 )aryl; substituted (C6-C 18 )aryl; 2,4-bis([C 20 ]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluorene-9-on-1-yl.

[0032] term "(C3-C 40 )cycloalkyl" is unsubstituted or has one or more R S It refers to a saturated cyclic hydrocarbon radical having 3 to 40 carbon atoms substituted by. Other cycloalkyl groups (e.g., (C3-C 12 )alkyl) has x to y carbon atoms and is unsubstituted or has one or more R S It is defined in a similar way to being substituted. Unsubstituted (C3-C 40 Examples of )cycloalkyls are unsubstituted (C3-C 20 )cycloalkyl, unsubstituted (C3-C 10) are cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substituted (C3-C 40 Examples of )cycloalkyls are substituted (C3-C 20 )cycloalkyl, substituted (C3-C 10 ) These are cycloalkyl, cyclopentanone-2-yl, and 1-fluorocyclohexyl.

[0033] (C1-C 40 Examples of )hydrocarbylenes include unsubstituted or substituted (C6-C 40 )arylene, ( C3-C 40 )cycloalkylene and (C1-C 40 )alkylene (e.g., (C1-C 20 It includes alkylenes. In some embodiments, the deradical exists on the same carbon atom (e.g., -CH2-) or adjacent carbon atoms (i.e., 1,2-deradical), or is separated by one, two, or more than two intervening carbon atoms (e.g., 1,3-deradical, 1,4-deradical, etc.). Some deradicals include α,ω-deradicals. α,ω-deradicals are deradicals having the maximum carbon skeleton spacing between radical carbons. (C2-C 20 Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CH2CH2-), propane-1,3-diyl (i.e., -CH2CH2CH2-), and 2-methylpropane-1,3-diyl (i.e., -CH2CH(CH3)CH2-). (C6-C 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0034] term "(C1-C 40 )alkylene" is unsubstituted or has one or more R S It refers to a saturated straight-chain or branched-chain diradical having 1 to 40 carbon atoms substituted by (i.e., the radical does not exist on the ring atom). Unsubstituted (C1-C50 Examples of alkylenes include unsubstituted (C1-C) including -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3). 20 It is an alkylene, where "C*" indicates a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Substituted (C1-C 50 Examples of )alkylenes are substituted (C1-C 20 )alkylene, -CF2-, -C(O)-, and -(CH2) 14 It is C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosilene). As previously mentioned, two R groups S is together (C1-C 18 Because it can form alkylenes, substituted (C1-C 50 Examples of alkylenes also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0035] term "(C3-C 40 )cycloalkylene" is unsubstituted or has one or more R S It refers to a cyclic diradical having 3 to 40 carbon atoms substituted with (i.e., the radical exists on the ring atom).

[0036] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of heteroatoms are O, S, S(O), and S(O). 2, Si(R C ) 3, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2-, or -Si(R C Includes )2-, and each R C and each RP is unsubstituted (C1-C 18 )hydrocarbyl or -H, and each R N It is unsubstituted (C1-C 18 ) It is hydrocarbyl. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms are replaced by heteroatoms. The term "(C1-C 50 ")heterohydrocarbyl" refers to a heterohydrocarbon radical having 1 to 50 carbon atoms, and the term "(C1-C 50 "Heterohydrocarbylene" refers to a heterohydrocarbon diradical having 1 to 50 carbon atoms. (C1-C 50 )heterohydrocarbil or (C1-C 50 The heterohydrocarbon of )heterohydrocarbylene has one or more heteroatoms. The radical of heterohydrocarbylene exists on a carbon atom or a heteroatom, and the diradical of heterohydrocarbylene may exist on: (1) one or two carbon atoms, (2) one or two heteroatoms, or (3) a carbon atom and a heteroatom. Each (C1-C 50 )heterohydrocarbil and (C1-C 50 )heterohydrocarbylene is unsubstituted or (one or more R S It may be an aromatic or non-aromatic, saturated or unsaturated, straight or branched chain substituted by) cyclic (including monocyclic and polycyclic, fused and unfused polycyclic) or acyclic.

[0037] In some embodiments, (C1-C 40 )heterohydrocarbil is independently unsubstituted or substituted (C1-C 40 )heteroalkyl, (C1-C 40 )hydrocarbyl-O-, (C1-C 40 )hydrocarbyl-S-, (C1-C 40 )hydrocarbil-S(O)-, (C1-C 40)hydrocarbyl-S(O)2-, (C1-C 40 )hydrocarbyl-Si(R C )2-, (C1-C 40 )hydrocarbyl-N(R N )-, (C1-C 40 )Hydrocarbil-P(R P )-, (C2-C 40 )heterocycloalkyl, (C2-C 19 )heterocycloalkyl-(C1-C 20 )alkylene, ( C3-C 20 )cycloalkyl-(C1-C 19 )heteroalkylene, (C2-C 19 )heterocycloalkyl-(C1-C 20 )heteroalkylene, (C1-C 40 )heteroaryl, (C1-C 19 )heteroaryl-(C1-C 20 )alkylene, (C6-C 20 )aryl-(C1-C 19 )heteroalkylene or (C1-C 19 )heteroaryl-(C1-C 20 It is a heteroalkylene.

[0038] The term "heteroaromatic hydrocarbon" refers to an aromatic hydrocarbon molecule or molecular skeleton in which 1 to 4 carbon atoms are replaced by heteroatoms. The term "(C4-C 50 )heteroaryl" is an unsubstituted or (one or more R) having a total of 4 to 50 carbon atoms. S It refers to a mono-, non-, or tricyclic heteroaromatic hydrocarbon radical substituted with (o), wherein the mono-, non-, or tricyclic radical comprises 1, 2, or 3 rings, respectively, and the 2 or 3 rings are independently fused or non-fused, and at least one of the 2 or 3 rings is heteroaromatic. Another heteroaryl group (e.g., generally (C x -C y )heteroaryl, e.g. (C4-C 12)heteroaryl) has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or has one or more than one R S It is defined in a manner similar to being substituted by. Monocyclic heteroaromatic hydrocarbon radicals are 5-membered or 6-membered rings. The 5-membered ring has 1 to 4 carbon atoms and 4 to 1 heteroatom, each heteroatom being O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon radicals are pyrrole-1-yl; pyrrole-2-yl; furan-3-yl; thiophene-2-yl; pyrazole-1-yl; isoxazole-2-yl; isothiazol-5-yl; imidazole-2-yl; oxazole-4-yl; thiazole-2-yl; 1,2,4-triazole-1-yl; 1,3,4-oxadiazole-2-yl; 1,3,4-thiadiazole-2-yl; tetrazole-1-yl; tetrazole-2-yl; and tetrazole-5-yl. The 6-membered ring has 4 or 5 carbon atoms and 2 or 1 heteroatom, and the heteroatom is N or P. Examples of 6-membered heteroaromatic hydrocarbon radicals are pyridine-2-yl; pyrimidine-2-yl; and pyrazine-2-yl. Acyclic heteroaromatic hydrocarbon radicals can be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring system acyclic heteroaromatic hydrocarbon radicals are indole-1-yl; and benzimidazole-1-yl. Examples of fused 6,6-ring system acyclic heteroaromatic hydrocarbon radicals are quinoline-2-yl; and isoquinoline-1-yl. Tricyclic heteroaromatic hydrocarbon radicals can be fused 5,6,5-; 5,6,6-; 6,5,6-; or 6,6,6-ring systems. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indole-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indole-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazole-9-yl. An example of a fused 6,6,6-ring system is acridin-9-yl.

[0039] The aforementioned heteroalkyl is (C1-C50 ) It may be a saturated straight-chain or branched-chain radical containing one or more carbon atoms and one or more heteroatoms. Likewise, heteroalkylene may be a saturated straight-chain or branched-chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatom is, as defined above, Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C , S, SR C It may include , S(O), and S(O)2, wherein each heteroalkyl and heteroalkylene group is unsubstituted or one or more R S It is replaced with.

[0040] Unsubstituted (C2-C 40 Examples of )heterocycloalkyls are unsubstituted (C2-C 20 )heterocycloalkyl, unsubstituted (C2-C 10 )heterocycloalkyl, aziridine-l-yl, oxetane-2-yl, tetrahydrofuran-3-yl, pyrrolidine-l-yl, tetrahydrothiophene-S,S-dioxide-2-yl, morpholine-4-yl, 1,4-dioxane-2-yl, hexahydroazepine-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0041] The term "halogen atom" or "halogen" refers to the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I). The term "halide" refers to the anionic form of a halogen atom: fluoride (F - ), chloride (Cl - ), bromide (Br - ) or iodide(I - It means ).

[0042] The term "saturated" means the absence of carbon-carbon double bonds, carbon-carbon triple bonds, and carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds (in heteroatom-containing groups). A saturated chemical group has one or more substituents R S In the case of substitution, one or more double and / or triple bonds are optionally substituted with substituent R S It may or may not be present in. The term "unsaturated" refers to one or more carbon-carbon double bonds, carbon-carbon triple bonds, or one or more carbon-nitrogen, carbon-phosphorus, or carbon-silicon double bonds (if present, substituent R) (in heteroatom-containing groups). S This means that it contains (not including any double bonds such as the above that may exist in the (hetero)aromatic ring, or if present).

[0043] An embodiment of the present disclosure comprises a catalytic system comprising a metal-ligand complex according to the following formula (I):

[0044]

[0045] In formula (I), M is a metal selected from titanium, zirconium, or hafnium; n is 1 or 2; when n is 1, X is a monodentate or bidentate ligand; when n is 2, each X is a monodentate ligand, and is the same or different; the metal-ligand complex is charge-neutral as a whole; each Z is independently selected from silicon or germanium; and R 1 and R 16 is a radical having the following chemical formula (II):

[0046]

[0047] In chemical formula (II), R 31-35 are respectively (C1-C 40 )hydrocarbyl, (C1-C 40 )heterohydrocarbil, -Si(RC )3, -OR C , -SR C , -CN, -CF3, halogen, and -H are independently selected.

[0048] In chemical formula (I), R 2-4 , R 5-8 , R 9-12 , and R 13-15 are respectively (C1-C 40 )hydrocarbyl, (C1-C 40 )heterohydrocarbil, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -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 Independently selected from )2NC(O)-, halogen, and -H; R 17 and R 18 is independently (C5-C 40 )hydrocarbil and; R 23 and R 24 is -(CR C 2) m - is selected independently from, where m is 1 or 2; and each R C , R P , and R N (C1-C 30 )hydrocarbyl, (C1-C 30 ) It is independently selected from heterohydrocarbil, or -H.

[0049] Surprisingly, R of chemical formula (I) 17 and R 18 This independently (C5-C 40 )hydrocarbil and R1 and R 16 It was found that for a radical having this chemical formula (II), improved catalytic efficiency can be achieved without impairing other important properties such as intrinsic molecular weight, comonomer incorporation rate, and solubility in alkane solvents. That is, R 1 and R 16 In the case of a radical having this chemical formula (II), R 17 and R 18 This independently (C5-C 40 The effect on catalyst efficiency in the case of hydrocarbyl is R 1 and R 16 This is considered to be more significant than in the case of radicals having structures other than this chemical formula (II), especially when M is zirconium.

[0050] In some embodiments of the metal-ligand complex of formula (I), R 17 and R 18 is independently (C5-C 20 )alkyl. In some embodiments, R 17 and R 18 is pentyl, hexyl, heptyl, octyl, or nonyl. In some embodiments, R 17 and R 18 It is pentane-3-1.

[0051] In some embodiments, R 17 and R 18 is independently (C5-C 20 )is a cycloalkyl. In some embodiments, R 17 and R 18 It is cyclopentyl, cyclohexyl, cycloheptyl, or bicyclo[2.2.1]heptyl.

[0052] In some embodiments, R 17 and R 18 They are connected to form a ring structure having at least five carbon atoms. In some embodiments, R 17 and R 18They are connected to form a ring structure with 5, 6, or 7 carbon atoms.

[0053] In some embodiments of the metal-ligand complex of formula (I), R 6 and R 11 is independently (C2-C 12 )alkyl. In some embodiments, R 6 and R 11 silver tert - It is butyl.

[0054] In some embodiments of the metal-ligand complex of formula (I), R 1 and R 16 At least one of them is a radical having the chemical formula (II), and R 32 and R 34 Is tert - It is butyl.

[0055] In some embodiments of the metal-ligand complex of formula (I), R 3 and R 14 is independently (C1-C 12 )alkyl. In some embodiments, R 3 and R 14 is independently tert -Octyl, n - It is octyl or methyl.

[0056] In some embodiments of the metal-ligand complex of formula (I), R 8 and R 9 is -H.

[0057] In some embodiments of the metal-ligand complex of formula (I), R 7 and R 10 is a halogen. In some embodiments of the metal-ligand complex of formula (I), R 5 and R 12 is a halogen. In some embodiments of the metal-ligand complex of formula (I), R 5 , R 7 , R 10 and R 12 is a halogen.

[0058] In some embodiments of the metal-ligand complex of formula (I), each X is (C1-C 40 )hydrocarbyl, (C1-C 40 )heterohydrocarbil, -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -CH2Ge(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -NH(R C ), -N(Si(R C )3)2, -NR C Si(R C )3, -NHSi(R C )3, -OR C A ligand independently selected from , -CN, -CF3, and halogen, and each R C is independently substituted or unsubstituted (C1-C 30 )hydrocarbyl, or substituted or unsubstituted (C1-C 30 )heterohydrocarbyl, and each Q is 0, 1, 2 or 3, and each W is 0, 1, or 2.

[0059] In some embodiments of the metal-ligand complex of formula (I), R 6 , R 7 , R10 and R 11 is not a halogen. Although not bound by theory, R is not a halogen. 6 , R 7 , R 10 , and R 11 ...in some embodiments, independently (C5-C 40 ) Hydrocarbyl R 17 and R 18 R, a radical having the chemical formula (II). 1 and R 16 It is believed that when combined with, it can improve catalytic efficiency without impairing other important properties such as intrinsic molecular weight and solubility in alkane solvents. Although not bound by theory, the presence of halogens in this position is considered advantageous for comonomer incorporation but detrimental to activity (leading to increased usage costs), particularly R 6 and R 11 This is especially true in the case of this halogen.

[0060] In a specific embodiment of the catalytic system, the metal-ligand complex according to formula (I) may, without limitation, comprise a complex having the structure of any of the following precursor catalysts 1 to 5:

[0061]

[0062] The metal-ligand complexes of precatalysts 1 to 5 each contain a germanium crosslink connecting one oxygen atom to another oxygen atom by a covalent bond. Each substituent R of the metal-ligand complexes of precatalysts 1 to 5 17 and R 18 is independently (C5-C 40 It is hydrocarbyl.

[0063] In a specific embodiment of the catalytic system, the metal-ligand complex according to formula (I) may, without limitation, comprise a complex having the structure of any of the following precursor catalysts 6 to 9:

[0064]

[0065] The metal-ligand complexes of precatalysts 6 to 9 each contain silicon crosslinks connecting one oxygen atom to another oxygen atom by a covalent bond. Each substituent R of the metal-ligand complexes of precatalysts 6 to 9 17 and R 18 is independently (C5-C 40 It is hydrocarbyl.

[0066] Pre-catalyst activation

[0067] The catalytic system of the present disclosure comprises a metal-ligand complex according to formula (I). The metal-ligand complex according to formula (I) may exist in a catalytically active form, or in a precatalytic form that is catalytically inactive or at least substantially less catalytically active than the catalytically active form. Precatalytics 1 to 9 are catalytically inactive forms of various metal-ligand complexes according to formula (I). A precatalytic system comprising a metal-ligand complex of formula (I) in the form of a precatalytic can be catalytically activated by any technique known in the art for activating a metal-based catalyst for an olefin polymerization reaction. For example, the metal-ligand complex of formula (I) may be catalytically activated by contacting the metal-ligand complex with an activating cocatalytic or by combining the metal-ligand complex with an activating cocatalytic. Another example of a suitable activation technique includes bulk electrolysis. Combinations of one or more of the aforementioned activating cocatalytics and techniques are also considered. When a metal-ligand complex according to chemical formula (I) in the form of a pre-catalyst is applied to any of these activation techniques, a catalytically activated form of the metal-ligand complex according to chemical formula (I) is obtained. In some embodiments, the catalytically activated form of the metal-ligand complex according to formula (I) may be the result of cutting at least one X from the precatalytic form of the metal-ligand complex according to formula (I) by any of the activation techniques described above.

[0068] Co-catalyst components

[0069] In embodiments of the present disclosure, the catalyst system may include a co-catalyst component. A catalyst system comprising a metal-ligand complex of formula (I) may be catalytically activated by any technique known in the art for activating a metal-based catalyst for an olefin polymerization reaction. For example, a procatalyst according to formula (I) may be made catalytically active by contacting the procatalyst with one or more activating co-catalysts (also referred to herein as "activators") or by combining the procatalyst with them. Additionally, the metal-ligand complex of formula (I) includes both a neutral procatalyst form and a catalyst form that may become positively charged due to the loss of a monoanionic ligand such as benzyl or phenyl. Activating co-catalysts suitable for use herein include alkyl aluminum; polymeric or oligomeric aluminoxane (also known as aluminoxane); modified alkyl aluminoxane; hydrocarbyl-modified methylaluminoxane; neutral Lewis acid; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions), but are not limited thereto. Combinations of one or more of the aforementioned activation co-catalysts and techniques are also considered. The term "alkyl aluminum" means monoalkyl aluminum dihydride or monoalkylaluminum dihalide, dialkyl aluminum hydride or dialkyl aluminum halide, or trialkylaluminum. Examples of polymeric or oligomeric alumonic acids include methylalumonic acid, triisobutylaluminum-modified methylalumonic acid, hydrocarbyl-modified methylaluminoxane (e.g., MMAO-7), and isobutylalumonic acid.

[0070] Lewis acid activators (co-catalysts) include 1 to 3 (C1-C) as described herein. 20It includes a Group 13 metal compound containing a )hydrocarbyl substituent. In one embodiment, the Group 13 metal compound is tri((C1-C 20 )hydrocarbyl)-substituted-aluminum, tree((C1-C 20 )hydrocarbyl)-boron compound, tri((C1-C 10 )alkyl)aluminum, tri((C6-C 18 It is an aryl)boron compound or a halogenated (including perhalogenated) derivative thereof. In additional embodiments, the Group 13 metal compound is tris(fluoro-substituted phenyl)borane or tris(pentafluorophenyl)borane. In some embodiments, the activating co-catalyst is tetrakis((C1-C 20 )hydrocarbyl borate or tri((C1-C 20 )hydrocarbyl)ammonium tetrakis((C1-C 20 )hydrocarbyl)borate (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" refers to ((C1-C 20 )Hydrocarbil)4N + , ((C1-C 20 )Hydrocarbil)3N(H) + , ((C1-C 20 )hydrocarbil)2N(H)2 + , (C1-C 20 )hydrocarbyl N(H)3 + , or N(H)4 + It refers to nitrogen cations, and each (C1-C 20 Hydrocarbyl, if present in two or more, may be the same or different.

[0071] The combination of neutral Lewis acid activators (co-catalysts) is tri((C1-C4)alkyl)aluminum and tri((C6-C4) halides 18It comprises a mixture comprising a combination of aryl)borone compounds, in particular tris(pentafluorophenyl)borane. Other embodiments are a combination of such neutral Lewis acid mixtures with polymeric or oligomeric alumonic acids, and a combination of a single neutral Lewis acid, in particular tris(pentafluorophenyl)borane, with polymeric or oligomeric alumonic acids. The ratio of moles of (metal-ligand complex):(tris(pentafluorophenylborane):(alumonic acid) [e.g., (group 4 metal-ligand complex):(tris(pentafluorophenylborane):(alumonic acid)] is 1:1:1 to 1:10:100, and in other embodiments, 1:1:1.5 to 1:5:30.

[0072] A catalytic system comprising a metal-ligand complex of formula (I) can be activated to form an active catalytic composition by combining with one or more co-catalysts, e.g., a cation-forming co-catalyst, a strong Lewis acid, or a combination thereof. Suitable activating co-catalysts include polymeric or oligomeric aluminoxanes, particularly methyl aluminoxane, as well as inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable co-catalysts include modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl tetrakis(pentafluorophenyl)borate (1 - ) amine (i.e., [HNMe(C 18 H 37 )2][B(C6F5)4]), and combinations of the two, but not limited thereto.

[0073] In some embodiments, one or more of the aforementioned activation co-catalysts are used in combination with one another. A particularly preferred combination is a mixture of an oligomeric or polymeric alumonic acid compound and tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate. The ratio of the total moles of one or more metal-ligand complexes of Formula (I) to the total moles of one or more activation co-catalysts is 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, and in some other embodiments at least 1:1000; and 10:1 or less, and in some other embodiments 1:1 or less. When alumonic acid is used alone as an activation co-catalyst, the moles of alumonic acid used are preferably at least 100 times the moles of the metal-ligand complex of Formula (I). When tris(pentafluorophenyl)borane is used alone as an activation co-catalyst, in some other embodiments, the ratio of the moles of tris(pentafluorophenyl)borane used to the total moles of one or more metal-ligand complexes of formula (I) is 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1. The remaining activation co-catalyst is generally used in a molar amount approximately equivalent to the total molar amount of one or more metal-ligand complexes of formula (I).

[0074] In one or more embodiments, the catalytic system described herein comprises a metal-ligand complex according to formula (I) and hydrocarbyl-modified methylaluminoxane. The term "hydrocarbyl-modified methylaluminoxane" refers to a methylaluminoxane (MMAO) structure comprising a predetermined amount of trihydrocarbyl aluminum. Hydrocarbyl-modified methylaluminoxane comprises a combination of a hydrocarbyl-modified methylaluminoxane matrix and trihydrocarbyl aluminum. The total molar amount of aluminum in the hydrocarbyl-modified methylaluminoxane consists of the amount of aluminum contributed from the moles of aluminum from the hydrocarbyl-modified methylaluminoxane matrix and the moles of aluminum from the trihydrocarbyl aluminum. Hydrocarbyl-modified methylaluminoxane may contain more than 2.5 mol% of trihydrocarbylaluminum based on the total molar amount of aluminum in the hydrocarbyl-modified methylaluminoxane. These additional hydrocarbyl substituents may affect the subsequent aluminoxane structure and may cause differences in the distribution and size of aluminoxane clusters (Reference [Bryliakov, KP et. al. Macromol. Chem. Phys. [2006, 207, 327-335]). Additional hydrocarbyl substituents are also, as demonstrated in U.S. Patent No. 5,777,143, but are not limited to, hexane, heptane, methylcyclohexane, and isophar E TM The solubility of aluminoxane in hydrocarbon solvents such as can be increased. Modified methylaluminoxane compositions are generally disclosed and can be prepared as described in U.S. Patents No. 5,066,631 and No. 5,728,855, both of which are incorporated herein by reference in their entirety.

[0075] In some embodiments of the catalytic systems and processes described herein, the hydrocarbyl-modified methylaluminoxane may have less than 25 mol% trihydrocarbyl aluminum based on the total molar amount of aluminum in the hydrocarbyl-modified methylaluminoxane. Trihydrocarbyl aluminum is AlR A1 R B1 R C1 It has the chemical formula, and in the above formula, R A1 , R B1 , and R C1 is independently (C1-C 40 It is an alkyl.

[0076] In some embodiments of the catalytic system and process described herein, the hydrocarbyl-modified methylaluminoxane has more than 5 mol% and less than 20 mol% of trihydrocarbyl aluminum based on the total molar amount of aluminum in the hydrocarbyl-modified methylaluminoxane. In some embodiments, the hydrocarbyl-modified methylaluminoxane has less than 15 mol% of trihydrocarbyl aluminum based on the total molar amount of aluminum in the hydrocarbyl-modified methylaluminoxane. In one or more embodiments, the hydrocarbyl-modified methylaluminoxane has less than 10 mol% of trihydrocarbyl aluminum based on the total molar amount of aluminum in the hydrocarbyl-modified methylaluminoxane. In various embodiments, the hydrocarbyl-modified methylaluminoxane is modified methylaluminoxane.

[0077] In some embodiments, trihydrocarbyl aluminum is AlR A1 R B1 R C1 It has the chemical formula, and in the above formula, R A1 , R B1 , and R C1 is independently (C1-C 10 )alkyl. In one or more embodiments, R A1 , R B1 , and R C1 is independently methyl, ethyl, propyl, 2-propyl, butyl, tert - It is butyl or octyl. In some embodiments, R A1 , R B1 , and R C1 is identical. In another embodiment, R A1 , R B1 , and R C1 At least one of them is at least another R A1 , R B1 , and R C1 It is different from.

[0078] polyolefin

[0079] The catalyst system described in the above paragraph is used for the polymerization of olefins, primarily ethylene and propylene. In some embodiments, only a single type of olefin or α-olefin is present in the polymerization scheme to produce a homopolymer. However, additional α-olefins may be incorporated into the polymerization process. Additional α-olefin comonomers typically have 20 or fewer 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, ethylidene norbornene. 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.

[0080] Ethylene and optionally one or more comonomers, for example, ethylene-based polymers of α-olefins, for example, homopolymers and / or copolymers (including copolymers) may comprise at least 50 weight% of units derived from ethylene. All individual values ​​and sub-ranges included in “at least 50 weight%” are disclosed herein as separate embodiments; for example, ethylene and optionally one or more comonomers, for example, ethylene-based polymers of α-olefins, homopolymers and / or copolymers (including copolymers) may comprise at least 60 weight% of units derived from ethylene; at least 70 weight% of units derived from ethylene; at least 80 weight% of units derived from ethylene; or units derived from 50 to 100 weight% of ethylene; or units derived from 80 to 100 weight% of ethylene.

[0081] In some embodiments, the ethylene-based polymer may comprise a unit derived from at least 50 mol% of ethylene. All individual values ​​and sub-ranges of at least 90 mol% are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer may comprise a unit derived from at least 93 mol% of ethylene; a unit derived from at least 96 mol% of ethylene; a unit derived from at least 97 mol% of ethylene; or alternatively, a unit derived from 90 to 100 mol% of ethylene; a unit derived from 90 to 99.5 mol% of ethylene; or a unit derived from 97 to 99.5 mol% of ethylene.

[0082] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50%; other embodiments comprise at least 1 mole percent (mol%) to 20 mole%; and in further embodiments, the amount of additional α-olefin comprises at least 5 mole% to 10 mole%. In some embodiments, the additional α-olefin is 1-octene.

[0083] In some embodiments, the additional α-olefin comonomer comprises 1-butene, and the ethylene-based polymer is an ethylene / 1-butene copolymer, e.g., an ethylene / 1-butene copolymer, wherein the ethylene-based polymer comprises 20% to 40% by weight of units derived from 1-butene based on the total weight of the ethylene-based polymer. In some embodiments, the ethylene-based polymer comprises, based on the total weight of the ethylene-based polymer, a unit derived from 1-butene in an amount of 22% to 40% by weight, a unit derived from 1-butene in an amount of 22% to 38% by weight, a unit derived from 1-butene in an amount of 24% to 38% by weight, a unit derived from 1-butene in an amount of 24% to 36% by weight, a unit derived from 1-butene in an amount of 26% to 36% by weight, a unit derived from 1-butene in an amount of 26% to 34% by weight, a unit derived from 1-butene in an amount of 28% to 34% by weight, a unit derived from 1-butene in an amount of 28% to 33% by weight, or a unit derived from 1-butene in an amount of 29% to 33% by weight.

[0084] Any conventional polymerization process may be used to produce ethylene-based polymers. Such conventional polymerization processes include, but are not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof, using one or more conventional reactors in parallel or in series, such as, for example, loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, continuous stirred tank reactors, batch reactors, and combinations thereof.

[0085] In one embodiment, an ethylene-based polymer may be produced by solution polymerization in a dual reactor system, e.g., a double-loop reactor system, and 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, an ethylene-based polymer may be produced by solution polymerization in a dual reactor system, e.g., a double-loop reactor system, and ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system as described in this disclosure and herein and optionally one or more other catalysts. The catalyst system described herein may be used in combination with one or more other catalysts in a first reactor or a second reactor, optionally. In one embodiment, an ethylene-based polymer may be produced by solution polymerization in a dual reactor system, e.g., a double-loop reactor system, and ethylene and optionally one or more α-olefins are polymerized in both reactors in the presence of a catalyst system as described herein. In another embodiment, the ethylene-based polymer may be produced by solution polymerization in a single reactor system, for example, a single-loop reactor system, and ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system as described in the present disclosure and optionally one or more co-catalysts as described in the preceding paragraph.

[0086] In some embodiments, a polymerization process for producing an ethylene-based polymer comprises the step of polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system. In one or more embodiments, the catalyst system may comprise a metal-ligand complex according to Formula (I) in a catalytically active form without a co-catalyst or an additional catalyst. In further embodiments, the catalyst system may comprise a metal-ligand complex according to Formula (I) in a pre-catalyst form, a catalytically active form, or a combination of both forms in combination with at least one co-catalyst. In further embodiments, the catalyst system may comprise a metal-ligand complex according to Formula (I) in a pre-catalyst form in combination with at least one co-catalyst and at least one additional catalyst. In further embodiments, the catalyst system may comprise a first catalyst and at least one additional catalyst, and, optionally, at least one co-catalyst, wherein the first catalyst is a metal-ligand complex according to Formula (I) in a catalytically active form.

[0087] The ethylene-based polymer may additionally contain one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymer may contain any amount of additives. The ethylene-based polymer may contain about 0 to about 10 weight percent of these additives by total weight, based on the weight of the ethylene-based polymer and one or more additives. The ethylene-based polymer may additionally contain fillers, which may include organic or inorganic fillers, but are not limited thereto. The ethylene-based polymer may contain, for example, about 0 to about 20 weight percent of fillers, 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 additionally blend with one or more polymers to form a blend.

[0088] In some embodiments, the polymerization process for producing an ethylene-based polymer comprises ethylene and optionally (C3-C 12 The method may include the step of polymerizing an α-olefin in the presence of a catalyst system, wherein the catalyst system comprises at least one metal-ligand complex of formula (I). In some embodiments, the ethylene-based polymer of the present disclosure, comprising the ethylene-based polymer produced from the polymerization process and catalyst system described herein, has a g / cm³ value when measured according to ASTM D792 (the entirety of which is incorporated herein by reference). 3 Up to 0.970 g / cm³ 3 Density of; melt flow ratio of 5 to 15 (I 10 / I2) - Melt index I2 is measured at 190°C and a 2.16 kg load according to ASTM D1238 (the entirety of which is incorporated herein by reference), and melt index I 10It is measured at 190°C and a 10 kg load according to ASTM D1238 -; and may have a molecular weight distribution (MWD) of 1 to 5 - MWD is the ratio of weight average molecular weight to number average molecular weight -.

[0089] In some embodiments, the ethylene-based polymer of the present disclosure, comprising the ethylene-based polymer produced from the polymerization process and catalyst system described herein, has a g / cm³ value when measured according to ASTM D792. 3 Up to 0.970 g / cm³ 3 , 0.880 g / cm 3 Up to 0.920 g / cm³ 3 , 0.880 g / cm 3 Up to 0.910 g / cm³ 3 , or 0.880 g / cm³ 3 Up to 0.900 g / cm³ 3 It may have a density. In some embodiments, the ethylene-based polymer of the present disclosure, comprising the ethylene-based polymer produced from the polymerization process and catalyst system described herein, has a density of 0.850 g / cm³ when measured according to ASTM D792. 3 Up to 0.880 g / cm³ 3 , 0.854 g / cm 3 Up to 0.880 g / cm³ 3 , 0.854 g / cm 3 Up to 0.875 g / cm³ 3 , 0.856 g / cm 3 Up to 0.875 g / cm³ 3 , 0.856 g / cm 3 Up to 0.872 g / cm³ 3 , 0.858 g / cm 3 Up to 0.872 g / cm³ 3 , 0.858 g / cm 3 Up to 0.870 g / cm³ 3 , 0.858 g / cm 3 Up to 0.868 g / cm³ 3 , 0.860 g / cm 3 Up to 0.868 g / cm³3 , or 0.860 g / cm³ 3 Up to 0.866 g / cm³ 3 It can have a density of.

[0090] In some embodiments, the ethylene-based polymer of the present disclosure, comprising an ethylene-based polymer produced from the polymerization process and catalyst system described herein, may have a weight-average molecular weight Mw of 50 kg / mol to 200 kg / mol, e.g., 50 kg / mol to 190 kg / mol, 55 kg / mol to 190 kg / mol, 55 kg / mol to 180 kg / mol, 60 kg / mol to 180 kg / mol, 60 kg / mol to 170 kg / mol, 65 kg / mol to 170 kg / mol, 65 kg / mol to 160 kg / mol, 70 kg / mol to 160 kg / mol, or 70 kg / mol to 150 kg / mol. In some embodiments, the ethylene-based polymer of the present disclosure, comprising an ethylene-based polymer produced from the polymerization process and catalyst system described herein, may have a molecular weight of 0.854 g / cm³ 3 Up to 0.875 g / cm³ 3 It may have a density and a weight-average molecular weight of 50 kg / mol to 200 kg / mol. In some embodiments, the ethylene-based polymer of the present disclosure, comprising the ethylene-based polymer produced from the polymerization process and catalyst system described herein, has a density of 0.854 g / cm³. 3 Up to 0.875 g / cm³ 3 It can have a density of 70 kg / mol to 150 kg / mol and a weight-average molecular weight.

[0091] In some embodiments, the ethylene-based polymer of the present disclosure, comprising an ethylene-based polymer produced from the polymerization process and catalyst system described herein, when measured according to ASTM D1238, has a gamma of 0.1 dg / min to 30 dg / min, 0.1 dg / min to 25 dg / min, 0.1 dg / min to 30 dg / min, 0.1 dg / min to 20 dg / min, 0.1 dg / min to 15 dg / min, 0.1 dg / min to 10 dg / min, 0.2 dg / min to 10 dg / min, 0.1 dg / min to 9 dg / min, 0.2 dg / min to 9 dg / min, 0.1 dg / min to 8 dg / min, 0.2 dg / min to 8 dg / min. It may have a melt index I2 of dg / min, 0.1 dg / min to 7 dg / min, 0.2 dg / min to 7 dg / min, 0.1 dg / min to 6 dg / min, 0.15 dg / min to 6 dg / min, or 0.2 dg / min to 6 dg / min. In some embodiments, the ethylene-based polymer of the present disclosure, comprising the ethylene-based polymer produced from the polymerization process and catalyst system described herein, has a melt index of 0.854 g / cm³ 3 Up to 0.875 g / cm³ 3 It may have a density and a melt index I2 of 0.1 to 30 dg / min. In some embodiments, the ethylene-based polymer of the present disclosure, comprising the ethylene-based polymer produced from the polymerization process and catalyst system described herein, has a density of 0.854 g / cm³. 3 Up to 0.875 g / cm³ 3 It can have a density of 0.1 to 10 dg / min and a melt index I2 of 0.1 to 10 dg / min.

[0092] In some embodiments, the ethylene-based polymer of the present disclosure, comprising the ethylene-based polymer produced from the polymerization process and catalyst system described herein, has a melt flow ratio (I) of 5 to 15, 5 to 10, or 5 to 9.10 Can have / I2).

[0093] In some embodiments, the ethylene-based polymer of the present disclosure, comprising the ethylene-based polymer produced from the polymerization process and catalyst system described herein, may have a molecular weight distribution (MWD) of 1 to 10, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3.5, 1.5 to 3, or 1.5 to 2.5.

[0094] In some embodiments, the ethylene-based polymer of the present disclosure, comprising the ethylene-based polymer produced from the polymerization process and catalyst system described herein, may have an HCC value of 3.0 wt% or less, 2.8 wt% or less, 2.4 wt% or less, 2.2 wt% or less, 2.0 wt% or less, 1.8 wt% or less, 1.6 wt% or less, 1.4 wt% or less, or 1.2 wt% or less when measured according to the HCC measurement method described herein.

[0095] In some embodiments, the ethylene-based polymer of the present disclosure, comprising the ethylene-based polymer produced from the polymerization process and catalyst system described herein, may have a BBB tritium content of 0.0075 or fewer BBB tritiums per 1,000 carbons, or 0.007 or fewer BBB tritiums per 1,000 carbons, when measured according to the BBB tritium measurement method described herein.

[0096] In some embodiments, the ethylene-based polymer of the present disclosure, comprising an ethylene-based polymer produced from the polymerization process and catalyst system described herein, may have low vinyl unsaturation, which is demonstrated to have 0.01 or fewer vinyls per 1,000 carbons. In some embodiments, the ethylene-based polymer of the present disclosure, comprising an ethylene-based polymer produced from the polymerization process and catalyst system described herein, may have 0.009 or fewer vinyls per 1,000 carbons, or 0.008 or fewer vinyls per 1,000 carbons, when measured according to the vinyl content measurement method described herein.

[0097] In some embodiments, the ethylene-based polymer of the present disclosure, comprising an ethylene-based polymer produced from the polymerization process and catalyst system described herein, may have a total unsaturation of 0.1 or less per 1,000 carbons, a total unsaturation of 0.09 or less per 1,000 carbons, a total unsaturation of 0.08 or less per 1,000 carbons, or a total unsaturation of 0.075 or less per 1,000 carbons when measured according to the total unsaturation measurement method described herein.

[0098] Embodiments of the catalyst systems described herein enable improved olefin polymerization processes with high catalytic efficiency. The high catalytic efficiency achieved by the catalyst systems described herein enables a reduction in catalyst usage costs, which can enhance the commercial potential of heteroatom-crosslinked bis-phenyl-phenoxy catalysts. Furthermore, the catalyst systems described herein exhibit enhanced catalytic activity without compromising other important properties such as intrinsic molecular weight, comonomer incorporation rate, and solubility in alkane solvents. Indeed, intrinsic molecular weight, comonomer incorporation rate, and solubility in alkane solvents were improved or maintained in most of the catalyst systems described herein.

[0099] In addition, the catalyst system described herein can produce ethylene / α-olefin copolymers, such as ethylene / butene copolymers, having a reduced HCC fraction, narrow SCBD, low vinyl unsaturation, and low levels of BBB teromers. The combination of these features provides a copolymer that exhibits a good curing reaction using peroxide as a curing agent without sacrificing the weather resistance or durability typically seen in polymers with excellent curing performance achieved due to high levels of unsaturation.

[0100] One or more features of the present disclosure are illustrated with reference to the following embodiments:

[0101] Examples

[0102] Example 1: Preparation of dicyclopentylbis(iodomethyl)german

[0103]

[0104] In a glove box, a 40 mL vial was filled with GeCl4 (2.16 g, 10 mmol, 1.0 equivalent) and dry THF (20 mL) under a nitrogen atmosphere and then cooled to -30°C. A solution of cyclopentyl magnesium chloride in diethyl ether (2 M, 10.5 mL, 21 mmol, 2.1 equivalent) was added dropwise to the pre-cooled solution. The reaction mixture was maintained at -30°C for 30 minutes and then slowly warmed to room temperature. The reaction mixture was filtered to remove the precipitate (washed with hexane). The filtrate was concentrated, diluted with ether, and filtered again. This process was repeated several times to remove the Mg salt. The product was used in the next step without further purification.

[0105] An n-BuLi solution in hexane (2.5 M, 8.4 mL, 21 mmol, 2.1 equivalents) was added dropwise at 0°C to a solution of methyl p-tolyl thioether (3.18 g, 23 mmol, 2.3 equivalents) in THF (20 mL). The reaction mixture was stirred at the same temperature for 1 hour, then slowly heated to room temperature for 2 hours. The resulting solution was added dropwise at -10°C to 0°C to a pre-cooled solution of dichlorodicyclopentylgerman prepared in THF (10 mL). After 30 minutes, MeOH (2 mL) was added to stop the reaction, diluted with ether (250 mL), and washed with brine. The organic layer was dried over MgSO4, filtered through a short silica gel pad, and concentrated under reduced pressure. The residue was purified by column chromatography using ether / hexane (0 / 100 -> 50 / 50) as the eluent. 2.6 g of colorless oil was collected, and the yield was 53%.

[0106] In a glove box, an 8 mL arc sphere was filled with dicyclopentylbis((p-tolyltio)methyl)german (0.973 g, 2.0 mmol, 1.0 equivalent), LiI (0.268 g, 2.0 mmol, 1.0 equivalent), MeI (3.0 mL, 48.0 mmol, 24.0 equivalent), and DMF (2 mL), sealed, and then removed from the glove box. The reaction mixture was stirred at 120°C for 24 hours. After cooling to room temperature, the reaction mixture was filtered through a short plug of silica gel (washed with DCM). After removing the solvent under reduced pressure, the residue was purified by column chromatography using pentane / ether (100 / 0 -> 80 / 20) as the eluent to obtain a light brown oil. 0.34 g was collected, and the yield was 34%.

[0107] 1H NMR (400 MHz, CDCl3) δ 2.23 (s, 4H), 2.00 - 1.89 (m, 4H), 1.71 - 1.60 (m, 4H), 1.58 - 1.43 (m, 10H).

[0108] Example 2: Preparation of bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dicyclopentylgermane

[0109]

[0110] In a glove box, a 40 mL vial was filled with dicyclopentylbis(iodomethyl)german (0.34 g, 0.69 mmol, 1.0 equivalent), 2-bromo-4-(tert-butyl)phenol (0.474 g, 2.1 mmol, 3.0 equivalent), K2CO3 (0.381 g, 2.76 mmol, 4.0 equivalent), and acetone (2 mL). The reaction mixture was stirred overnight at 65°C. After cooling to room temperature, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography using ether / hexane (0 / 100 -> 30 / 70) as the eluent. 0.44 g of product was collected, with a yield of 92%.

[0111] 1 H NMR (400 MHz, CDCl3) δ 7.50 (d, J = 2.4 Hz, 2H), 7.24 - 7.22 (m, 2H), 6.98 (dd, J = 8.7, 2.1 Hz, 2H), 4.11 (s, 4H), 2.01 - 1.92 (m, 4H), 1.68 - 1.58 (m, 10H), 1.54 - 1.48 (m, 4H), 1.27 (s, 18H).

[0112] Example 3: Preparation of Ligand 1

[0113]

[0114] In a glove box, a 40 mL vial equipped with a stirring bar was filled with Compound A (0.962 g, 1.9 mmol, 3.0 equivalents, purchased from Boulder Scientific), bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dicyclopentylgermane (0.44 g, 0.63 mmol, 1.0 equivalent), tBu3P Pd G2 (0.01 g, 0.02 mmol, 0.03 equivalents), THF (2 mL), and an aqueous NaOH solution (4 M, 0.95 mL, 3.8 mmol, 6.0 equivalents). The vial was heated overnight at 55°C under nitrogen. Upon completion, the upper organic layer was extracted with ether and filtered through a short plug of silica gel. The solvent was removed under reduced pressure. The residue was dissolved in THF (10 mL) and MeOH (10 mL). Then, concentrated HCl (0.5 mL) was added. The resulting mixture was heated at 75°C for 2 hours and then cooled to room temperature. The solvent was removed under reduced pressure. The residue was purified by reverse-phase column chromatography using THF / MeCN (0 / 100 -> 100 / 0) as the eluent. 0.51 g of white solid was collected, and the yield was 72%.

[0115] 1 H NMR (400 MHz, CDCl3) δ 7.39 (t, J = 1.8 Hz, 2H), 7.36 (d, J = 1.8 Hz, 4H), 7.31 (d, J = 2.6 Hz, 2H), 7.22 (dd, J = 8.6, 2.6 Hz, 2H), 7.11 (d, J = 2.3 Hz, 2H), 6.95 (d, J = 2.2, 2H), 6.71 (d, J = 8.6 Hz, 2H), 5.54 (s, 2H), 3.80 (s, 4H), 2.33 (s, 6H), 1.48 - 1.41 (m, 4H), 1.33 (s, 36H), 1.30 (s, 18H), 1.27 - 1.09 (m, 10H), 1.07 - 0.98 (m, 6H).

[0116] Example 4: Preparation of Precursor Catalyst 1

[0117]

[0118] In a glove box, an oven-dried 40 mL vial was filled with ZrCl4 (0.047 g, 0.2 mmol, 1.0 equivalent) and anhydrous toluene (6 mL) and cooled to -30°C in a freezer. After removing the vial from the freezer, MeMgBr (3 M, 0.29 mL, 0.86 mmol, 4.3 equivalent) in diethyl ether was added while stirring. After stirring for 2 minutes (when the solution darkened), Ligand 1 (0.226 g, 0.2 mmol, 1.0 equivalent) was added. The mixture was heated to room temperature and stirred overnight. The solvent was removed under vacuum to obtain a dark brown solid, which was washed with hexane (10 mL) and filtered. The remaining solid was extracted with toluene (12 mL). The toluene extract was dried under vacuum to obtain a white solid. 0.21 g of white solid was collected, and the yield was 84%.

[0119] 1 H NMR (400 MHz, C6D6) δ 8.14 (br s, 2H), 7.79 (t, J = 1.9 Hz, 2H), 7.56 (d, J = 2.5 Hz, 2H), 7.28 - 7.17 (m, 6H), 5.68 (d, J = 8.6) Hz, 2H), 4.82 (d, J = 11.5 Hz, 2H), 3.66 (d, J = 11.5 Hz, 2H), 2.27 (s, 6H), 1.62 - 1.18 (m, 66H), 0.83 - 0.68 (m, 4H), 0.55 - 0.43 (m, 2H), -0.04 (s, 6H).

[0120] Example 5: Preparation of dicyclohexylbis(iodomethyl)german

[0121]

[0122] In a glove box, a 40 mL vial was filled with GeCl4 (2.16 g, 10 mmol, 1.0 equivalent) and dry toluene (20 mL) under a nitrogen atmosphere and then cooled to -30°C. A solution of cyclohexyl magnesium chloride in diethyl ether (2 M, 10.5 mL, 21 mmol, 2.1 equivalent) was added dropwise to the pre-cooled solution. The reaction mixture was maintained at -30°C for 30 minutes and then slowly heated to room temperature. The reaction mixture was filtered to remove the precipitate (washed with hexane). The filtrate was concentrated, diluted with ether, and filtered again. This process was repeated several times to remove the Mg salt. The product was used in the next step without further purification.

[0123] An n-BuLi solution in hexane (2.5 M, 8.4 mL, 21 mmol, 2.1 equivalents) was added dropwise at 0°C to a solution of methyl p-tolyl thioether (3.46 g, 25 mmol, 2.5 equivalents) in THF (20 mL). The reaction mixture was stirred at the same temperature for 1 hour, then slowly heated to room temperature for 2 hours. The resulting solution was added dropwise at -10°C to a pre-cooled solution of dichlorodicyclohexylgerman prepared in THF (10 mL) at 0°C. After 30 minutes, MeOH (2 mL) was added to stop the reaction, diluted with ether (250 mL), and washed with brine. The organic layer was dried over MgSO4, filtered through a short silica gel pad, and concentrated under reduced pressure. The residue was purified by column chromatography using ether / hexane (0 / 100 -> 50 / 50) as the eluent. 3.67 g of colorless oil was collected, and the yield was 71%.

[0124] In a glove box, an 8 mL arc sphere was filled with dicyclohexylbis((p-tolyltio)methyl)german (1.03 g, 2.0 mmol, 1.0 equivalent), LiI (0.268 g, 2.0 mmol, 1.0 equivalent), MeI (3.0 mL, 48.0 mmol, 24.0 equivalent), and DMF (2 mL), sealed, and then removed from the glove box. The reaction mixture was stirred at 120°C for 24 hours. After cooling to room temperature, the reaction mixture was filtered through a short plug of silica gel (washed with DCM). After removing the solvent under reduced pressure, the residue was purified by column chromatography using pentane / ether (100 / 0 -> 80 / 20) as the eluent to obtain a light brown oil. 0.47 g was collected, and the yield was 45%.

[0125] 1 H NMR (400 MHz, CDCl3) δ 2.22 (s, 4H), 1.84 - 1.68 (m, 10H), 1.51 - 1.38 (m, 6H), 1.32 - 1.22 (m, 6H).

[0126] Example 6: Preparation of bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dicyclohexylgerman

[0127]

[0128] In a glove box, a 40 mL vial was filled with dicyclohexylbis(iodomethyl)german (0.5 g, 0.96 mmol, 1.0 equivalent), 2-bromo-4-(tert-butyl)phenol (0.77 g, 3.36 mmol, 3.5 equivalent), K2CO3 (0.66 g, 4.8 mmol, 5.0 equivalent), and acetone (2 mL). The reaction mixture was stirred overnight at 65°C. After cooling to room temperature, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography using ether / hexane (0 / 100 -> 30 / 70) as the eluent. 0.69 g of product was collected, with a yield of 99%.

[0129] 1H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 2.3 Hz, 2H), 7.26 - 7.22 (m, 2H), 6.97 (d, J = 8.6 Hz, 2H), 4.10 (s, 4H), 1.94 - 1.85 (m, 4H), 1.76 - 1.66 (m, 6H), 1.60 - 1.50 (m, 6H), 1.33 - 1.23 (m, 6H), 1.27 (s, 18H).

[0130] Example 7: Preparation of Ligand 2

[0131]

[0132] In a glove box, a 40 mL vial equipped with a stirring bar was filled with Compound A (1.45 g, 2.86 mmol, 3.0 equivalents, purchased from Boulder Scientific), bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dicyclohexylgermane (0.69 g, 0.95 mmol, 1.0 equivalent), tBu3P Pd G2 (0.01 g, 0.02 mmol, 0.02 equivalents), THF (2 mL), and an aqueous NaOH solution (4 M, 1.43 mL, 5.72 mmol, 6.0 equivalents). The vial was heated overnight at 55°C under nitrogen. Upon completion, the upper organic layer was extracted with ether and filtered through a short plug of silica gel. The solvent was removed under reduced pressure. The residue was dissolved in THF (10 mL) and MeOH (10 mL). Then, concentrated HCl (0.5 mL) was added. The resulting mixture was heated at 75°C for 2 hours and then cooled to room temperature. The solvent was removed under reduced pressure. The residue was purified by reverse-phase column chromatography using THF / MeCN (0 / 100 -> 100 / 0) as the eluent. 0.65 g of white solid was collected, and the yield was 59%.

[0133] 1H NMR (400 MHz, CDCl3) δ 7.40 (t, J = 1.8 Hz, 2H), 7.35 (d, J = 1.8 Hz, 4H), 7.33 (d, J = 2.5 Hz, 2H), 7.21 (dd, J = 8.6, 2.6 Hz, 2H), 7.11 (d, J = 2.3 Hz, 2H), 6.97 (d, J = 2.3 Hz, 2H), 6.64 (d, J = 8.7 Hz, 2H), 5.54 (s, 2H), 3.76 (br s, 4H), 2.34 (s, 6H), 1.38 - 1.25 (m, 64H), 1.00 - 0.78 (m, 12H).

[0134] Example 8: Preparation of Precursor Catalyst 2

[0135]

[0136] In a glove box, an oven-dried 40 mL vial was filled with ZrCl4 (0.047 g, 0.2 mmol, 1.0 equivalent) and anhydrous toluene (6 mL), and then cooled to -30°C in a freezer. After removing the vial from the freezer, MeMgBr (3 M, 0.29 mL, 0.86 mmol, 4.3 equivalent) in diethyl ether was added while stirring. After stirring for 2 minutes (when the color of the solution darkened), Ligand 2 (0.231 g, 0.2 mmol, 1.0 equivalent) was added. The mixture was heated to room temperature and stirred overnight. The solvent was removed under vacuum to obtain a dark brown solid, which was extracted with hexane (12 mL) and filtered. The hexane extract was concentrated to about 2 to 3 mL and then left at -30°C for 1 day. After pouring off the supernatant, the remaining solid was dried under vacuum to obtain a white solid. 0.18 g of white solid was collected, and the yield was 74%.

[0137] 1H NMR (400 MHz, C6D6) δ 8.16 (br s, 2H), 7.80 (t, J = 1.9 Hz, 2H), 7.58 (d, J = 2.5 Hz, 2H), 7.30 - 7.24 (m, 4H), 7.19 (dd, J = 8.6, 2.5 Hz, 2H), 5.69 (d, J = 8.6 Hz, 2H), 4.82 (d, J = 11.6 Hz, 2H), 3.70 (d, J = 11.6 Hz, 2H), 2.32 (s, 6H), 1.63 - 1.35 (m, 40H), 1.30 - 1.21 (m, 20H), 1.19 - 0.95 (m, 10H), 0.73 - 0.53 (m, 4H).

[0138] Example 9: Preparation of bis(iodomethyl)di(pentane-3-yl)german

[0139]

[0140] In a glove box, a 40 mL vial was filled with CuCl (0.7 g, 7.0 mmol, 1.0 equivalent), GeCl4 (1.51 g, 7.0 mmol, 1.0 equivalent), and dry THF (15 mL) under a nitrogen atmosphere, and then cooled to -30°C. A solution of 3-pentyl magnesium bromide in diethyl ether (1 M, 14.0 mL, 14.0 mmol, 2.0 equivalent) was added dropwise to the pre-cooled solution. The reaction mixture was maintained at -30°C for 30 minutes and then slowly warmed to room temperature. The reaction mixture was filtered to remove the precipitate (washed with hexane). The filtrate was concentrated, diluted with ether, and filtered again. This process was repeated several times to remove the Mg salt. The product was used in the next step without further purification.

[0141] An n-BuLi solution in hexane (2.5 M, 12.6 mL, 31.5 mmol, 2.1 equivalents) was added dropwise to a solution of methyl p-tolyl thioether (4.77 g, 34.5 mmol, 2.3 equivalents) in THF (20 mL) at 0°C. The reaction mixture was stirred at the same temperature for 1 hour, then slowly heated to room temperature for 2 hours. The resulting solution was added dropwise to a pre-cooled solution of dichlorodi(pentane-3-yl)german (3.87 g, 15.0 mmol, 1.0 equivalent) in THF (15 mL) at -10°C to 0°C. After 30 minutes, the reaction was stopped by adding MeOH (2 mL), diluted with ether (250 mL), and washed with brine. The organic layer was dried over MgSO4, filtered through a short silica gel pad, and concentrated under reduced pressure. The residue was purified by column chromatography using ether / hexane (0 / 100 -> 50 / 50) as the eluent. 2.3 g of colorless oil was collected, and the yield was 31%.

[0142] In a glove box, 8 mL of arc sphere was filled with di(pentane-3-yl)bis((p-tolyltio)methyl)german (0.98 g, 2.0 mmol, 1.0 equivalent), LiI (0.268 g, 2.0 mmol, 1.0 equivalent), MeI (3.0 mL, 48.0 mmol, 24.0 equivalent), and DMF (2 mL), sealed, and then removed from the glove box. The reaction mixture was stirred at 120°C for 24 hours. After cooling to room temperature, the reaction mixture was filtered through a short plug of silica gel (washed with DCM). After removing the solvent under reduced pressure, the residue was purified by column chromatography using pentane / ether (100 / 0 -> 80 / 20) as the eluent to obtain a light brown oil. 0.56 g of product was collected, and the yield was 56%.

[0143] 1H NMR (400 MHz, CDCl3) δ 2.34 (s, 4H), 1.71 - 1.56 (m, 8H), 1.33 - 1.22 (m, 2H), 0.97 (t, J = 7.4 Hz, 12H).

[0144] Example 10: Preparation of bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dicyclohexylgerman

[0145]

[0146] In a glove box, a 40 mL vial was filled with bis(iodomethyl)di(pentane-3-yl)german (0.56 g, 1.1 mmol, 1.0 equivalent), 2-bromo-4-(tert-butyl)phenol (1.03 g, 4.5 mmol, 4.0 equivalent), K2CO3 (0.94 g, 6.8 mmol, 6.0 equivalent), and acetone (2 mL). The reaction mixture was stirred overnight at 65°C. After cooling to room temperature, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography using ether / hexane (0 / 100 -> 30 / 70) as the eluent. 0.78 g of product was collected, with a yield of 99%.

[0147] 1 H NMR (400 MHz, CDCl3) δ 7.50 (d, J = 2.3 Hz, 2H), 7.26 - 7.23 (m, 2H), 6.98 (d, J = 8.6 Hz, 2H), 4.13 (s, 4H), 1.81 - 1.60 (m, 8H), 1.53 - 1.45 (m, 2H), 1.27 (s, 18H), 0.97 (t, J = 7.4 Hz, 12H).

[0148] Example 11: Preparation of Ligand 3

[0149]

[0150] In a glove box, a 40 mL vial equipped with a stirring bar was filled with Compound A (1.70 g, 3.35 mmol, 3.0 equivalents, purchased from Boulder Scientific), bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dicyclohexylgermane (0.78 g, 1.1 mmol, 1.0 equivalents), tBu3P Pd G2 (0.017 g, 0.03 mmol, 0.03 equivalents), THF (3 mL), and aqueous NaOH solution (4 M, 1.70 mL, 6.7 mmol, 6.0 equivalents). The vial was heated overnight at 55°C under nitrogen. Upon completion, the upper organic layer was extracted with ether and filtered through a short plug of silica gel. The solvent was removed under reduced pressure. The residue was dissolved in THF (10 mL) and MeOH (10 mL). Then, concentrated HCl (0.5 mL) was added. The resulting mixture was heated at 75°C for 2 hours and then cooled to room temperature. The solvent was removed under reduced pressure. The residue was purified by reverse-phase column chromatography using THF / MeCN (0 / 100 -> 100 / 0) as the eluent. 0.86 g of white solid was collected, and the yield was 68%.

[0151] 1 H NMR (400 MHz, CDCl3) δ 7.42 - 7.38 (m, 2H), 7.36 (d, J = 1.8 Hz, 4H), 7.29 (d, J = 2.5 Hz, 2H), 7.19 (dd, J = 8.7, 2.5 Hz, 2H), 7.12 (d, J = 2.3 Hz, 2H), 6.98 - 6.92 (m, 2H), 6.66 (d, J = 8.6 Hz, 2H), 5.47 (s, 2H), 3.78 (br s, 4H), 2.33 (s, 6H), 1.36 - 1.27 (m, 54H), 1.26 - 1.11 (m, 8H), 0.95 - 0.86 (m, 2H), 0.59 (t, J = 7.3 Hz, 12H).

[0152] Example 12: Preparation of Precursor Catalyst 3

[0153]

[0154] In a glove box, an oven-dried 40 mL vial was filled with ZrCl4 (0.047 g, 0.2 mmol, 1.0 equivalent) and anhydrous toluene (6 mL) and cooled to -30°C in a freezer. After removing the vial from the freezer, MeMgBr (3 M, 0.29 mL, 0.86 mmol, 4.3 equivalent) in diethyl ether was added while stirring. After stirring for 2 minutes (when the solution darkened), Ligand 3 (0.226 g, 0.2 mmol, 1.0 equivalent) was added. The mixture was heated to room temperature and stirred overnight. The solvent was removed under vacuum to obtain a dark brown solid, which was washed with hexane (10 mL) and filtered. The remaining solid was extracted with toluene (12 mL). The toluene extract was dried under vacuum to obtain a white solid. 0.19 g of white solid was collected, and the yield was 76%.

[0155] 1 H NMR (400 MHz, C6D6) δ 8.14 (br s, 2H), 7.78 (t, J = 1.8 Hz, 2H), 7.57 (d, J = 2.4 Hz, 2H), 7.29 - 7.23 (m, 4H), 7.20 - 7.17 (m, 2H), 5.71 (d, J = 8.6 Hz, 2H), 4.88 (d, J = 11.6 Hz, 2H), 3.80 (d, J = 11.6 Hz, 2H), 2.28 (s, 6H), 1.64 - 1.35 (m, 36H), 1.24 (s, 18H), 1.18 - 0.94 (m, 12H), 0.69 - 0.56 (m, 12H), 0.55 - 0.46 (m, 2H), -0.06 (s, 6H).

[0156] Example 13: Preparation of dicycloheptylbis(iodomethyl)german

[0157]

[0158] In a glove box, a 40 mL vial was filled with CuCl (0.7 g, 7.0 mmol, 1.0 equivalent), GeCl4 (1.51 g, 7.0 mmol, 1.0 equivalent), and dry THF (15 mL) under a nitrogen atmosphere, and then cooled to -30°C. A solution of cycloheptyl magnesium bromide in diethyl ether (2 M, 7.0 mL, 14.0 mmol, 2.0 equivalent) was added dropwise to the pre-cooled solution. The reaction mixture was maintained at -30°C for 30 minutes and then slowly warmed to room temperature. The reaction mixture was filtered to remove the precipitate (washed with hexane). The filtrate was concentrated, diluted with ether, and filtered again. This process was repeated several times to remove the Mg salt. The product was used in the next step without further purification.

[0159] An n-BuLi solution in hexane (2.5 M, 12.6 mL, 31.5 mmol, 2.1 equivalents) was added dropwise at 0°C to a solution of methyl p-tolyl thioether (4.77 g, 34.5 mmol, 2.3 equivalents) in THF (20 mL). The reaction mixture was stirred at the same temperature for 1 hour, then slowly heated to room temperature for 2 hours. The reaction mixture was cooled back to 0°C, and the solution of dichlorodicycloheptylgermane (3.87 g, 15.0 mmol, 1.0 equivalents) prepared above was added dropwise. After 30 minutes, MeOH (2 mL) was added to stop the reaction, diluted with ether (250 mL), and washed with brine. The organic layer was dried over MgSO4, filtered through a short silica gel pad, and concentrated under reduced pressure. The residue was purified by column chromatography using ether / hexane (0 / 100 -> 50 / 50) as the eluent. 2.6 g of colorless oil was collected, and the yield was 35%.

[0160] In a glove box, 8 mL of arc sphere was filled with dicycloheptylbis((p-tolyltio)methyl)german (1.08 g, 2.0 mmol, 1.0 equivalent), LiI (0.268 g, 2.0 mmol, 1.0 equivalent), MeI (3.0 mL, 48.0 mmol, 24.0 equivalent), and DMF (2 mL), sealed, and then removed from the glove box. The reaction mixture was stirred at 120°C for 24 hours. After cooling to room temperature, the reaction mixture was filtered through a short plug of silica gel (washed with DCM). After removing the solvent under reduced pressure, the residue was purified by column chromatography using pentane / ether (100 / 0 - 80 / 20) as the eluent to obtain a light brown oil. 0.52 g of product was collected, and the yield was 47%.

[0161] 1 H NMR (400 MHz, CDCl3) δ 2.24 (s, 4H), 1.91 - 1.82 (m, 4H), 1.81 - 1.71 (m, 4H), 1.68 - 1.57 (m, 4H), 1.54 - 1.40 (m, 12H), 1.35 - 1.22 (m, 2H).

[0162] Example 14: Preparation of bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dicycloheptylgerman

[0163]

[0164] In a glove box, a 40 mL vial was filled with dicycloheptylbis(iodomethyl)german (0.52 g, 0.95 mmol, 1.0 equivalent), 2-bromo-4-(tert-butyl)phenol (0.65 g, 2.84 mmol, 3.0 equivalent), K2CO3 (0.52 g, 3.8 mmol, 4.0 equivalent), and acetone (2 mL). The reaction mixture was stirred overnight at 65°C. After cooling to room temperature, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography using ether / hexane (0 / 100 -> 30 / 70) as the eluent. 0.61 g of product was collected, with a yield of 86%.

[0165] 1 H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 2.4 Hz, 2H), 7.26 - 7.22 (m, 2H), 6.98 (d, J = 8.7 Hz, 2H), 4.10 (s, 4H), 2.03 - 1.93 (m, 4H), 1.80 - 1.69 (m, 4H), 1.66 - 1.57 (m, 10H), 1.54 - 1.40 (m, 8H), 1.28 (s, 18H).

[0166] Example 15: Preparation of Ligand 4

[0167]

[0168] In a glove box, a 40 mL vial equipped with a stirring bar was filled with Compound A (1.23 g, 2.43 mmol, 3.0 equivalents, purchased from Boulder Scientific), bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dicycloheptylgerman (0.61 g, 0.81 mmol, 1.0 equivalent), tBu3P Pd G2 (0.012 g, 0.02 mmol, 0.03 equivalents), THF (3 mL), and aqueous NaOH solution (4 M, 1.22 mL, 4.9 mmol, 6.0 equivalents). The vial was heated overnight at 55°C under nitrogen. Upon completion, the upper organic layer was extracted with ether and filtered through a short plug of silica gel. The solvent was removed under reduced pressure. The residue was dissolved in THF (10 mL) and MeOH (10 mL). Then, concentrated HCl (0.5 mL) was added. The resulting mixture was heated at 75°C for 2 hours and then cooled to room temperature. The solvent was removed under reduced pressure. The residue was purified by reverse-phase column chromatography using THF / MeCN (0 / 100 -> 100 / 0) as the eluent. 0.71 g of white solid was collected, and the yield was 74%.

[0169] 1H NMR (400 MHz, CDCl3) δ 7.39 (t, J = 1.7 Hz, 2H), 7.34 (d, J = 1.8 Hz, 4H), 7.33 (d, J = 2.5 Hz, 2H), 7.22 (dd, J = 8.6, 2.5 Hz, 2H), 7.10 (d, J = 2.4 Hz, 2H), 6.97 (d, J = 2.2 Hz, 2H), 6.71 - 6.63 (m, 2H), 5.55 (s, 2H), 3.77 (br s, 4H), 2.34 (s, 6H), 1.49 - 1.40 (m, 4H), 1.38 - 1.26 (m, 60H), 1.23 - 1.12 (m, 6H), 1.08 - 0.94 (m, 10H).

[0170] Example 16: Preparation of Precursor Catalyst 4

[0171]

[0172] In a glove box, an oven-dried 40 mL vial was filled with ZrCl4 (0.047 g, 0.2 mmol, 1.0 equivalent) and anhydrous toluene (6 mL), and then cooled to -30°C in a freezer. After removing the vial from the freezer, MeMgBr (3 M, 0.29 mL, 0.86 mmol, 4.3 equivalent) in diethyl ether was added while stirring. After stirring for 2 minutes (when the color of the solution darkened), Ligand 4 (0.237 g, 0.2 mmol, 1.0 equivalent) was added. The mixture was heated to room temperature and stirred overnight. The solvent was removed under vacuum to obtain a dark brown solid, which was extracted with hexane (12 mL) and filtered. The hexane extract was concentrated to about 2 to 3 mL and left at -30°C for 1 day. After pouring off the supernatant, the remaining solid was dried under vacuum to obtain a white solid. 0.22 g of white solid was collected, and the yield was 84%.

[0173] 1H NMR (400 MHz, C6D6) δ 8.15 (br s, 2H), 7.80 (t, J = 1.8 Hz, 2H), 7.59 (d, J = 2.5 Hz, 2H), 7.32 - 7.23 (m, 4H), 7.19 (dd, J = 8.6, 2.5 Hz, 2H), 5.69 (d, J = 8.6 Hz, 2H), 4.84 (d, J = 11.5 Hz, 2H), 3.75 (d, J = 11.6 Hz, 2H), 2.32 (s, 6H), 1.64 - 1.11 (m, 66H), 1.08 - 0.96 (m, 2H), 0.93 - 0.84 (m, 4H), 0.74 - 0.63 (m, 2H), -0.05 (s, 6H).

[0174] Example 17: Preparation of dinorbornilbis(iodomethyl)german

[0175]

[0176] In a glove box, a 150 mL bottle was filled with CuCl (0.76 g, 7.7 mmol, 0.5 equivalents), GeCl4 (3.3 g, 15.4 mmol, 1.0 equivalent), and dry THF (15 mL), and then cooled to -30°C. A solution of 2-norbornyl magnesium chloride in diethyl ether (0.77 M, 44.0 mL, 33.9 mmol, 2.2 equivalents) was added dropwise to the pre-cooled solution. The reaction mixture was maintained at -30°C for 30 minutes and then slowly warmed to room temperature. The reaction mixture was filtered to remove the precipitate (washed with hexane). The filtrate was concentrated, diluted with ether, and filtered again. This process was repeated several times to remove the Mg salt. The product was used in the next step without further purification.

[0177] An n-BuLi solution in hexane (2.5 M, 12.6 mL, 31.5 mmol, 2.1 equivalents) was added dropwise at 0°C to a solution of methyl p-tolyl thioether (4.77 g, 34.5 mmol, 2.3 equivalents) in THF (20 mL). The reaction mixture was stirred at the same temperature for 1 hour, then slowly heated to room temperature for 2 hours. The reaction mixture was cooled back to 0°C, and the dichlorodinorbornylgerman (3.87 g, 15.0 mmol, 1.0 equivalent) solution prepared above was added dropwise. After 30 minutes, MeOH (2 mL) was added to stop the reaction, diluted with ether (250 mL), and washed with brine. The organic layer was dried over MgSO4, filtered through a short silica gel pad, and concentrated under reduced pressure. The residue was purified by column chromatography using ether / hexane (0 / 100 -> 50 / 50) as the eluent. 4.8 g of colorless oil was collected, and the yield was 59%.

[0178] In a glove box, 8 mL of ARC spheres were filled with dinorbornilbis((p-tolyltio)methyl)german (1.61 g, 3.0 mmol, 1.0 equivalent), LiI (0.40 g, 3.0 mmol, 1.0 equivalent), MeI (3.74 mL, 60.0 mmol, 20.0 equivalent), and DMF (3 mL), sealed, and then removed from the glove box. The reaction mixture was stirred at 120°C for 24 hours. After cooling to room temperature, the reaction mixture was filtered through a short plug of silica gel (washed with DCM). After removing the solvent under reduced pressure, the residue was purified by column chromatography using pentane / ether (100 / 0 -> 80 / 20) as the eluent to obtain a light brown oil. 1.02 g of product was collected, and the yield was 62%.

[0179] 1H NMR (400 MHz, CDCl3) δ 2.36 - 2.23 (m, 4H), 1.94 - 1.46 (m, 10H), 1.37 - 1.17 (m, 12H).

[0180] Example 18: Preparation of bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dinorbornylgerman

[0181]

[0182] In a glove box, a 40 mL vial was filled with dinorbornilbis(iodomethyl)german (1.02 g, 1.87 mmol, 1.0 equivalent), 2-bromo-4-(tert-butyl)phenol (1.5 g, 6.55 mmol, 3.5 equivalent), K3PO4 (1.79 g, 8.4 mmol, 4.5 equivalent), and DMF (3 mL). The reaction mixture was stirred overnight at 80°C. After cooling to room temperature, the reaction mixture was diluted with ether (15 mL), filtered, and the filtrate concentrated under reduced pressure. The residue was purified by column chromatography using ether / hexane (0 / 100 -> 30 / 70) as the eluent. 1.0 g of product was collected, and the yield was 71%.

[0183] 1 H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 2.5, 2H), 7.26 - 7.22 (m, 2H), 7.01 - 6.94 (m, 2H), 4.15 - 4.06 (m, 4H), 2.50 - 2.42 (m, 2H), 2.33 - 2.25 (m, 2H), 1.94 - 1.70 (m, 2H), 1.64 - 1.46 (m, 8H), 1.44 - 1.109 (m, 30H).

[0184] Example 19: Preparation of Ligand 5

[0185]

[0186] In a glove box, a 40 mL vial equipped with a stirring bar was filled with Compound A (2.03 g, 4.0 mmol, 3.0 equivalents, purchased from Boulder Scientific), bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dinorbornylgerman (1.0 g, 1.34 mmol, 1.0 equivalent), tBu3P Pd G2 (0.021 g, 0.04 mmol, 0.03 equivalents), THF (3 mL), and aqueous NaOH solution (4 M, 2.0 mL, 8.0 mmol, 6.0 equivalents). The vial was heated overnight at 55°C under nitrogen. Upon completion, the upper organic layer was extracted with ether and filtered through a short plug of silica gel. The solvent was removed under reduced pressure. The residue was dissolved in THF (10 mL) and MeOH (10 mL). Then, concentrated HCl (0.5 mL) was added. The resulting mixture was heated at 75°C for 2 hours and then cooled to room temperature. The solvent was removed under reduced pressure. The residue was purified by reverse-phase column chromatography using THF / MeCN (0 / 100 -> 100 / 0) as the eluent. 1.12 g of white solid was collected, and the yield was 71%.

[0187] 1 H NMR (400 MHz, CDCl3) δ 7.41 - 7.34 (m, 6H), 7.34 - 7.29 (m, 2H), 7.13 - 7.09 (m, 2H), 6.99 - 6.93 (m, 2H), 6.77 - 6.65 (m, 2H), 5.54 - 5.47 (m, 2H), 3.85 - 3.67 (m, 4H), 2.34 (s, 6H), 2.01 - 1.79 (m, 4H), 1.35 - 1.28 (m, 54H), 1.27 - 1.13 (m, 8H), 1.10 - 0.99 (m, 2H), 0.91 - 0.75 (m, 8H).

[0188] Example 20: Preparation of Precursor Catalyst 5

[0189]

[0190] In a glove box, an oven-dried 40 mL vial was filled with ZrCl4 (0.047 g, 0.2 mmol, 1.0 equivalent) and anhydrous toluene (6 mL), and then cooled to -30°C in a freezer. After removing the vial from the freezer, MeMgBr (3 M, 0.29 mL, 0.86 mmol, 4.3 equivalent) in diethyl ether was added while stirring. After stirring for 2 minutes (when the color of the solution darkened), ligand 5 (0.236 g, 0.2 mmol, 1.0 equivalent) was added. The mixture was heated to room temperature and stirred overnight. The solvent was removed under vacuum to obtain a dark brown solid, which was extracted with hexane (12 mL) and filtered. The hexane extract was concentrated to about 2 to 3 mL and left at -30°C for 1 day. After pouring off the supernatant, the remaining solid was dried under vacuum to obtain a white solid. 0.21 g of white solid was collected, and the yield was 81%.

[0191] 1 H NMR (400 MHz, C6D6) δ 8.12 (br s, 2H), 7.82 - 7.75 (m, 2H), 7.70 - 7.50 (m, 4H), 7.31 - 7.18 (m, 6H), 5.83 - 5.65 (m, 2H), 4.88 - 4.70 (m, 2H), 3.78 - 3.51 (m, 2H), 2.34 - 2.23 (m, 6H), 2.09 - 1.94 (m, 2H), 1.84 - 1.69 (m, 2H), 1.64 - 1.32 (m, 36H), 1.29 - 1.20 (m, 20H), 1.13 - 0.82 (m, 14H), 0.69 - 0.45 (m, 2H), -0.01 - -0.14 (m, 6H).

[0192] Example 21: Preparation of Bis(chloromethyl)dicyclohexylsilane

[0193]

[0194] In a glove box, a 100 mL round-bottom flask (RBF) was filled with dichlorodicyclohexylsilane (5.33 g, 20.0 mmol, 1.0 equivalent) and THF (30 mL). The flask was sealed and then removed from the glove box. Bromochloromethane (5.2 mL, 80.0 mmol, 4.0 equivalent) was added, and the reaction mixture was cooled to -78°C in a dry ice-acetone bath. Subsequently, an n-BuLi solution in hexane (2.5 M, 18.5 mL, 46.2 mmol, 2.3 equivalent) was added to the cooled wall of the flask over a period of 2 hours using a syringe pump. The mixture was heated to room temperature overnight. Then, a saturated aqueous solution of NH4Cl (30 mL) was added. Two layers were separated. The aqueous layer was extracted with ether (2 × 60 mL). The combined organic layer was dried over MgSO4, filtered through a short pad of silica gel, concentrated under reduced pressure, and then dried under vacuum. The unrefined product was used in the next step without further purification.

[0195] Example 22: Preparation of bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dicyclohexylsilane

[0196]

[0197] In a glove box, a 40 mL vial was filled with bis(chloromethyl)dicyclohexylsilane (1.47 g, 5.0 mmol, 1.0 equivalent), 2-bromo-4-(tert-butyl)phenol (3.44 g, 15.0 mmol, 3.0 equivalent), K3PO4 (4.26 g, 20.0 mmol, 4.0 equivalent), and DMF (6 mL). 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. 2.8 g of colorless oil was collected, with a yield of 82%.

[0198] 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 2.4 Hz, 2H), 7.44 (d, J = 2.3 Hz, 2H), 6.96 (dd, J = 8.6, 5.2 Hz, 2H), 3.89 (s, 4H), 1.90 - 1.81 (m, 6H), 1.78 - 1.66 (m, 8H), 1.51 - 1.39 (m, 6H), 1.28 (s, 18H), 1.17 - 1.22 (m, 2H).

[0199] Example 23: Preparation of Ligand 6

[0200]

[0201] In a glove box, the compound in a 40 mL vial equipped with a stirring bar B The vial was packed with bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dicyclohexylsilane) (1.02 g, 1.5 mmol, 1.0 equivalent), tBu3P Pd G2 (0.023 g, 0.05 mmol, 0.03 equivalent), THF (3 mL), and an aqueous NaOH solution (2.25 mL, 9.0 mmol, 6.0 equivalent). The vial was heated under nitrogen at 55°C for 2 hours. Upon completion, the upper organic layer was extracted with ether and filtered through a short plug of silica gel. The solvent was removed under reduced pressure. The residue was purified by reverse-phase column chromatography using THF / MeCN (0 / 100 -> 100 / 0) as the eluent. 1.2 g of product was collected, and the yield was 72%.

[0202] 1H NMR (400 MHz, CDCl3) δ 7.40 (t, J = 1.8 Hz, 2H), 7.35 (d, J = 1.8 Hz, 4H), 7.33 (d, J = 2.5 Hz, 2H), 7.20 (dd, J = 8.6, 2.5 Hz, 2H), 7.10 (d, J = 2.2 Hz, 2H), 6.97 (d, J = 2.3, 2H), 6.62 (d, J = 8.7 Hz, 2H), 5.48 (s, 2H), 3.56 (br s, 4H), 2.34 (s, 6H), 1.50 - 1.40 (m, 2H), 1.32 (s, 36H), 1.31 (s, 18H), 1.38 - 1.24 (m, 10H), 0.89 - 0.75 (m, 10H).

[0203] Example 24: Preparation of Precursor Catalyst 6

[0204]

[0205] In a glove box, an oven-dried 40 mL vial was filled with ZrCl4 (0.047 g, 0.2 mmol, 1.0 equivalent) and anhydrous toluene (6 mL), and then cooled to -30°C in a freezer. After removing the vial from the freezer, MeMgBr (3 M, 0.29 mL, 0.86 mmol, 4.3 equivalent) in diethyl ether was added while stirring. After stirring for 2 minutes (when the color of the solution darkened), ligand 6 (0.22 g, 0.2 mmol, 1.0 equivalent) was added. The mixture was heated to room temperature and stirred overnight. The solvent was removed under vacuum to obtain a dark brown solid, which was extracted with hexane (12 mL) and filtered. The hexane extract was concentrated to about 2 to 3 mL and left at -30°C for 1 day. After pouring off the supernatant, the remaining solid was dried under vacuum to obtain a white solid. 0.17 g of white solid was collected, and the yield was 69%.

[0206] 1H NMR (400 MHz, C6D6) δ 8.16 (br s, 2H), 7.80 (t, J = 1.9 Hz, 2H), 7.59 (d, J = 2.5 Hz, 2H), 7.59 (br s, 2H), 7.26 (br s, 4H), 7.22 - 7.17 (m, 2H), 5.67 (d, J = 8.6 Hz, 2H), 4.62 (d, J = 13.5 Hz, 2H), 3.48 (d, J = 13.5 Hz, 2H), 2.31 (s, 6H), 1.67 - 1.34 (m, 44H), 1.31 - 1.17 (m, 28H), 1.13 - 0.92 (m, 10H), 0.77 - 0.49 (m, 6H), 0.27 - 0.16 (m, 2H), - 0.05 (s, 6H).

[0207] Example 25: Preparation of Bis(chloromethyl)dicycloheptylsilane

[0208]

[0209] In a glove box, a 40 mL vial was filled with (C6F5)3B (0.07 g, 0.14 mmol, 0.07 equivalents), Ph2SiH2 (0.37 g, 2.0 mmol, 1.0 equivalents), cycloheptene (1.16 g, 12.0 mmol, 6.0 equivalents), and 1,2-dichloroethane (2 mL). The resulting mixture was heated overnight at 70°C. Volatile substances were removed under vacuum. The unpurified product was used in the next step without further purification.

[0210] In a glove box, a 40 mL vial was filled with AlCl3 (0.67 g, 5.0 mmol, 2.5 equivalents), dicycloheptyldiphenylsilane (0.75 g, 2.0 mmol, 1.0 equivalent), and hexane (5 mL). A solution of AcCl in hexane (0.39 g, 5.0 mmol, 2.5 equivalents) was added dropwise at room temperature. The mixture was stirred for 3 hours. The supernatant was decanted, and volatile substances were removed under vacuum. The unpurified product was used in the next step without further purification.

[0211] In a glove box, 100 mL of RBF was filled with dichlorodicycloheptylsilane (2.55 g, 8.7 mmol, 1.0 equivalent) and THF (20 mL). The flask was sealed and then removed from the glove box. Bromochloromethane (2.26 mL, 35.0 mmol, 4.0 equivalent) was added, and the reaction mixture was cooled to -78°C in a dry ice-acetone bath. Subsequently, an n-BuLi solution in hexane (2.5 M, 7.65 mL, 19.1 mmol, 2.2 equivalent) was added to the cooled wall of the flask over a period of 2 hours using a syringe pump. The mixture was heated to room temperature overnight. Then, a saturated aqueous solution of NH4Cl (30 mL) was added. Two layers were separated. The aqueous layer was extracted with ether (2 × 60 mL). The combined organic layer was dried over MgSO4, filtered through a short pad of silica gel, concentrated under reduced pressure, and then dried under vacuum. The unrefined product was used in the next step without further purification.

[0212] Example 26: Preparation of bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dicycloheptylsilane

[0213]

[0214] In a glove box, a 40 mL vial was filled with bis(chloromethyl)dicycloheptylsilane (0.64 g, 2.0 mmol, 1.0 equivalent), 2-bromo-4-(tert-butyl)phenol (1.38 g, 6.0 mmol, 3.0 equivalent), K3PO4 (1.7 g, 8.0 mmol, 4.0 equivalent), and DMF (6 mL). 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. 1.12 g of colorless oil was collected, with a yield of 79%.

[0215] 1H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 2.4 Hz, 2H), 7.26 (dd, J = 8.6, 2.2 Hz, 2H), 6.96 (d, J = 8.6 Hz, 2H), 3.89 (s, 4H), 1.99 - 1.85 (m, 4H), 1.81 - 1.71 (m, 6H), 1.65 - 1.57 (m, 4H), 1.52 - 1.38 (m, 10H), 1.28 (s, 18H).

[0216] Example 27: Preparation of Ligand 7

[0217]

[0218] In a glove box, the compound in a 40 mL vial equipped with a stirring bar C The vial was filled with bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dicycloheptylsilane)(1.66 g, 3.6 mmol, 3.0 equivalents), bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dicycloheptylsilane)(0.84 g, 1.2 mmol, 1.0 equivalents), tBu3P Pd G2(0.018 g, 0.04 mmol, 0.03 equivalents), THF (4 mL), and aqueous NaOH solution (1.8 mL, 7.1 mmol, 6.0 equivalents). The vial was heated under nitrogen at 60°C for 2 hours. Upon completion, the upper organic layer was extracted with ether and filtered through a short plug of silica gel. The solvent was removed under reduced pressure. The residue was dissolved in THF (10 mL) and MeOH (10 mL). Then, concentrated HCl (0.3 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 reverse-phase column chromatography using THF / MeCN (0 / 100 -> 100 / 0) as the eluent. 1.00 g of product was collected, and the yield was 74%.

[0219] 1H NMR (400 MHz, CDCl3) δ 7.39 (t, J = 1.9 Hz, 2H), 7.34 (d, J = 1.9 Hz, 4H), 7.33 (d, J = 2.5 Hz, 2H), 7.24 - 7.18 (m, 2H), 7.10 (d, J = 2.2 Hz, 2H), 6.97 (d, J = 2.2 Hz, 2H), 6.65 (d, J = 8.5 Hz, 2H), 5.49 (s, 2H), 3.57 (br s, 4H), 2.34 (s, 6H), 1.42 - 1.22 (m, 64H), 1.23 - 1.10 (m, 6H), 1.06 - 0.89 (m, 6H), 0.76 - 0.65 (m, 2H).

[0220] Example 28: Preparation of Precursor Catalyst 7

[0221]

[0222] In a glove box, an oven-dried 40 mL vial was filled with ZrCl4 (0.047 g, 0.2 mmol, 1.0 equivalent) and anhydrous toluene (6 mL), and then cooled to -30°C in a freezer. After removing the vial from the freezer, MeMgBr (3 M, 0.29 mL, 0.86 mmol, 4.3 equivalent) in diethyl ether was added while stirring. After stirring for 2 minutes (when the color of the solution darkened), ligand 7 (0.228 g, 0.2 mmol, 1.0 equivalent) was added. The mixture was heated to room temperature and stirred overnight. The solvent was removed under vacuum to obtain a dark brown solid, which was extracted with hexane (12 mL) and filtered. The hexane extract was concentrated to about 2 to 3 mL and left at -30°C for 1 day. After pouring off the supernatant, the remaining solid was dried under vacuum to obtain a white solid. 0.18 g of white solid was collected, and the yield was 71%.

[0223] 1H NMR (400 MHz, C6D6) δ 8.15 (br s, 2H), 7.79 (t, J = 1.8 Hz, 2H), 7.59 (d, J = 2.5 Hz, 2H), 7.59 (br s, 2H), 7.31 - 7.23 (m, 4H), 7.20 - 7.15 (m, 2H), 5.68 (d, J = 8.6 Hz, 2H), 4.64 (d, J = 13.6 Hz, 2H), 3.56 (d, J = 13.4 Hz, 2H), 2.31 (s, 6H), 1.73 - 1.04 (m, 70H), 1.02 - 0.73 (m, 6H), 0.39 - 0.28 (m, 2H), -0.06 (s, 6H).

[0224] Example 29: Preparation of Bis(chloromethyl)dinorbornylsilane

[0225]

[0226] In a glove box, a 40 mL vial was filled with (C6F5)3B (0.23 g, 0.45 mmol, 0.15 equivalents), PhSiH3 (0.325 g, 3.0 mmol, 1.0 equivalents), norbornene (1.70 g, 18.0 mmol, 6.0 equivalents), and 1,2-dichloroethane (3 mL). The resulting mixture was heated overnight at 85°C. Volatile substances were removed under vacuum. The unpurified product was used in the next step without further purification.

[0227] In a glove box, a 40 mL vial was filled with AlCl3 (0.67 g, 5.0 mmol, 2.5 equivalents), dinorbornylphenylsilane (0.59 g, 2.0 mmol, 1.0 equivalent), and hexane (5 mL). A solution of AcCl in hexane (0.39 g, 5.0 mmol, 2.5 equivalents) was added dropwise at room temperature. The mixture was stirred for 3 hours. The supernatant was decanted, and volatile substances were removed under vacuum. The unpurified product was used in the next step without further purification.

[0228] In a glove box, 100 mL of RBF was filled with dichlorodinorbornylsilane (2.90 g, 10.0 mmol, 1.0 equivalent) and THF (20 mL). The flask was sealed and then removed from the glove box. Bromochloromethane (2.6 mL, 40.0 mmol, 4.0 equivalent) was added, and the reaction mixture was cooled to -78°C in a dry ice-acetone bath. Subsequently, an n-BuLi solution in hexane (2.5 M, 9.2 mL, 23.0 mmol, 2.3 equivalent) was added to the cooled wall of the flask over a period of 2 hours using a syringe pump. The mixture was heated to room temperature overnight. Then, a saturated aqueous solution of NH4Cl (30 mL) was added. Two layers were separated. The aqueous layer was extracted with ether (2 × 60 mL). The combined organic layer was dried over MgSO4, filtered through a short pad of silica gel, concentrated under reduced pressure, and then dried under vacuum. The unrefined product was used in the next step without further purification.

[0229] Example 30: Preparation of Bis((2-Bromo-4-(tert-butyl)phenoxy)methyl)dinorbornylsilane

[0230]

[0231] In a glove box, a 40 mL vial was filled with bis(chloromethyl)dinorbornylsilane (1.59 g, 5.0 mmol, 1.0 equivalent), 2-bromo-4-(tert-butyl)phenol (2.87 g, 12.0 mmol, 3.0 equivalent), K2CO3 (2.77 g, 20.0 mmol, 4.0 equivalent), and DMSO (6 mL). 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. 2.7 g of colorless oil was collected, with a yield of 77%.

[0232] 1H NMR (400 MHz, CDCl3) δ 7.54 - 7.49 (m, 2H), 7.29 - 7.22 (m, 2H), 7.00 - 6.92 (m, 2H), 3.97 - 3.82 (m, 4H), 2.52 - 2.42 (m, 2H), 2.36 - 2.02 (m, 6H), 1.52 - 0.99 (m, 32H).

[0233] Example 31: Preparation of Ligand 8

[0234]

[0235] In a glove box, the compound in a 40 mL vial equipped with a stirring bar B The vial was filled with bis((2-bromo-4-(tert-butyl)phenoxy)methyl)dinorbornylsilane) (2.08 g, 4.8 mmol, 2.8 equivalents), tBu3P Pd G2 (0.026 g, 0.05 mmol, 0.03 equivalents), THF (4 mL), and aqueous NaOH solution (2.6 mL, 10.2 mmol, 6.0 equivalents). The vial was heated under nitrogen at 60°C for 2 hours. Upon completion, the upper organic layer was extracted with ether and filtered through a short plug of silica gel. The solvent was removed under reduced pressure. The residue was purified by reverse-phase column chromatography using THF / MeCN (0 / 100 -> 100 / 0) as the eluent. 1.27 g of product was collected, and the yield was 66%.

[0236] 1H NMR (400 MHz, CDCl3) δ 7.42 - 7.29 (m, 8H), 7.24 - 7.16 (m, 2H), 7.14 - 7.08 (m, 2H), 7.02 - 6.92 (m, 2H), 6.79 - 6.62 (m, 2H), 5.50 - 5.40 (m, 2H), 3.66 - 3.47 (m, 4H), 2.37 - 2.30 (m, 6H), 2.04 - 1.93 (m, 2H), 1.91 - 1.80 (m, 2H), 1.40 - 1.23 (m, 62H), 1.21 - 1.08 (m, 4H), 1.05 - 0.92 (m, 4H), 0.91 - 0.70 (m, 8H), 0.52 (t, J = 8.7 Hz, 2H).

[0237] Example 32: Preparation of Precursor Catalyst 8

[0238]

[0239] In a glove box, an oven-dried 40 mL vial was filled with ZrCl4 (0.047 g, 0.2 mmol, 1.0 equivalent) and anhydrous toluene (6 mL), and then cooled to -30°C in a freezer. After removing the vial from the freezer, MeMgBr (3 M, 0.29 mL, 0.86 mmol, 4.3 equivalent) in diethyl ether was added while stirring. After stirring for 2 minutes (when the color of the solution darkened), ligand 8 (0.227 g, 0.2 mmol, 1.0 equivalent) was added. The mixture was heated to room temperature and stirred overnight. The solvent was removed under vacuum to obtain a dark brown solid, which was extracted with hexane (12 mL) and filtered. The hexane extract was concentrated to about 2 to 3 mL and left at -30°C for 1 day. After pouring off the supernatant, the remaining solid was dried under vacuum to obtain a white solid. 0.17 g of white solid was collected, and the yield was 68%.

[0240] 1H NMR (400 MHz, C6D6) δ 8.11 (br s, 2H), 7.83 - 7.75 (m, 2H), 7.64 (br s, 2H), 7.63 - 7.54 (m, 2H), 7.33 - 7.16 (m, 6H), 5.83 - 5.66 (m, 2H), 4.72 - 4.50 (m, 2H), 3.58 - 3.36 (m, 2H), 2.29 (s, 6H), 2.19 - 1.86 (m, 4H), 1.74 - 0.80 (m, 80H), 0.06 - - 0.07 (m, 6H).

[0241] Example 33: Preparation of bis((2-bromo-4-(tert-butyl)-3,5-difluorophenoxy)methyl)dicyclohexylsilane

[0242]

[0243] In a glove box, a 40 mL vial was filled with bis(chloromethyl)dicyclohexylsilane (1.77 g, 6.0 mmol, 1.0 equivalent), 2-bromo-4-(tert-butyl)-3,5-difluorophenol (4.0 g, 15.0 mmol, 2.5 equivalent), K3PO4 (4.48 g, 21.1 mmol, 3.5 equivalent), and DMSO (10 mL). The reaction mixture was stirred at 80°C for 2 hours. After cooling to room temperature, the reaction mixture was purified by column chromatography using ether / hexane (0 / 100 -> 30 / 70) as the eluent. 2.75 g of colorless oil was collected, with a yield of 61%.

[0244] 1 H NMR (400 MHz, CDCl3) δ 6.55 (dd, J = 14.7, 2.1 Hz, 2H), 3.85 (s, 4H), 1.85 - 1.79 (m, 2H), 1.78 - 1.68 (m, 10H), 1.45 - 1.41 (m, 18H), 1.28 - 1.18 (m, 10H).

[0245] 19 F{1H} NMR (376 MHz, CDCl3) δ -98.07 (d, J = 7.5 Hz, 2F), -105.68 (d, J = 7.5 Hz, 2F).

[0246] Example 34: Preparation of Ligand 9

[0247]

[0248] In a glove box, a 40 mL vial equipped with a stirring bar was filled with bis((2-bromo-4-(tert-butyl)-3,5-difluorophenoxy)methyl)dicyclohexylsilane (0.78 g, 1.0 mmol, 1.0 equivalent), top group (1.47 g, 2.9 mmol, 2.8 equivalent), aliquat 336 (10 mg), tBu3P Pd G2 (0.016 g, 0.03 mmol, 0.03 equivalent), toluene (3 mL), and 4N NaOH solution (1.56 mL, 6.2 mmol, 6.0 equivalent). The vial was heated overnight at 80°C under nitrogen. Upon completion, the top organic layer was extracted with ether and filtered through a short plug of silica gel. The solvent was removed under reduced pressure. The residue was dissolved in THF (10 mL) and MeOH (10 mL). Then, concentrated HCl (0.3 mL) was added. The resulting mixture was heated at 70°C for 2 hours and then cooled to room temperature. The solvent was removed under reduced pressure. The residue was purified by reverse-phase column chromatography using THF / MeCN (0 / 100 -> 100 / 0) as the eluent. 0.75 g of product was collected, and the yield was 61%.

[0249] 1H NMR (400 ㎒, CDCl3) δ 7.41 (t, J = 1.8 ㎐, 2H), 7.29 (d, J = 1.8 ㎐, 4H), 7.14 - 7.08 (m, 2H), 6.91 (dd, J = 6.0, 2.2 ㎐, 2H), 6.31 (td, J = 16.1, 15.4, 2.4 ㎐, 2H), 5.15 (s, 1H), 5.11 (s, 1H), 3.53 - 3.35 (m, 4H), 2.34 (d, J = 5.9 ㎐, 6H), 1.45 (t, J = 2.0 ㎐, 18H), 1.41 - 1.23 (m, 10H), 1.32 (s, 36H), 0.96 - 0.70 (m, 12H).

[0250] 19 F{1H} NMR (376 ㎒, CDCl3) δ -104.78 (d, J = 7.6 ㎐, 1F), -104.94 (d, J = 7.6 ㎐, 1F), -105.79 (dd, J = 13.8, 7.7 ㎐, 2F).

[0251] Example 35: Preparation of Precursor Catalyst 9

[0252]

[0253] In a glove box, an oven-dried 40 mL vial was filled with ZrCl4 (0.047 g, 0.2 mmol, 1.0 equivalent) and anhydrous toluene (6 mL). It was cooled to -30°C in a freezer. After removing the vial from the freezer, 3 M MeMgBr in ether (0.29 mL, 0.88 mmol, 4.4 equivalents) was added while stirring. After 2 minutes, the solution turned dark. A ligand (0.237 g, 0.2 mmol, 1.0 equivalent) was added, and the mixture was heated to room temperature overnight while stirring. The solvent was removed under vacuum to obtain a dark brown solid, which was extracted with hexane (12 mL) and filtered. The hexane extract was concentrated to about 2 to 3 mL and left at -30°C for 1 day. After pouring off the supernatant, the remaining solid was dried under vacuum to obtain a white solid. 0.2 g of product was collected, and the yield was 77%.

[0254] 1 H NMR (400 MHz, C6D6) δ 8.08 (br s, 2H), 7.84 (q, J = 1.7 Hz, 2H), 7.51 (br s, 2H), 7.27 (t, J = 3.0 Hz, 2H), 7.20 (d, J = 2.3 Hz, 2H), 5.32 (dd, J = 13.0, 1.8 Hz, 2H), 4.50 (d, J = 13.3 Hz, 2H), 3.45 (d, J = 13.4 Hz, 2H), 2.23 (s, 6H), 1.68 - 1.33 (m, 60H), 1.22 (d, J = 13.0 Hz, 2H), 1.10 - 0.92 (m, 8H), 0.75 - 0.63 (m, 2H), 0.60 - 0.47 (m, 2H), 0.22 - 0.13 (m, 2H), 0.10 (s, 6H).

[0255] 19 F{1H} NMR (376 MHz, C6D6) δ -101.95 (d, J = 7.1 Hz, 2F), -104.66 (d, J = 7.1 Hz, 2F).

[0256] Batch reactor polymerization procedure

[0257] Raw materials (ethylene, 1-octene) and process solvent (high-purity isoparaffin solvent with a narrow boiling range, trade name ISOPAR ® E (commercially available from ExxonMobil Corporation) was purified using a molecular sieve before being introduced into the reaction environment. A 1-gallon (3.79 L) stirred autoclave reactor was used for the ISOPAR ® It was charged with E and 1-octene. Subsequently, the reactor was heated to the desired temperature and then charged with ethylene until the total pressure reached 410 psig. The catalyst composition was prepared in a dry box under an inert atmosphere using the desired metal-ligand complex and co-catalyst ([HNMe(C 18 H 37 )2][B(C6F5)4] was mixed with modified methylaluminoxane (MMAO), and additional solvent was added to provide a total volume of about 15 to about 20 mL. Subsequently, the activated catalyst mixture was rapidly injected into the reactor. Reactor pressure and temperature were maintained constant by supplying ethylene during polymerization and cooling the reactor as necessary. After 10 minutes, the ethylene supply was stopped, and the solution was transferred to a nitrogen-purged resin kettle. The polymer was completely dried in a vacuum oven, and the reactor was transferred to a hot ISOPAR oven between polymerization runs. ® It was completely washed with E.

[0258] Continuous polymerization procedure

[0259] Raw materials (ethylene, 1-octene) and process solvent (high-purity isoparaffin solvent with a narrow boiling range, trade name ISOPAR ®E (commercially available from ExxonMobil Corporation) is purified using a molecular sieve before being introduced into the reaction environment. MMAO, commercially available from AkzoNobel, was used as an impurity scavenger. Individual catalyst components (pre-catalysts or co-catalysts) were prepared using the purified solvent (ISOPAR ® Using E), it was manually batch-diluted to a specific component concentration and pressurized to exceed the reaction pressure. The co-catalyst was [HNMe(C 18 H 37 )2][B(C6F5)4], which was used at a molar ratio of 1.2 for the metal-ligand complex of formula (I). All reaction feed flows were measured with a mass flow meter and controlled independently using a computer automated valve control system.

[0260] High-purity hydrogen is supplied using a shared pipeline and dried using a molecular sieve. The reactor monomer feed stream is pressurized to excess reaction pressure via a mechanical compressor. The solvent feed is pressurized to excess reaction pressure via a pump. The comonomer feed is pressurized to excess reaction pressure via a pump. Individual catalyst components are manually batch-diluted to specific concentrations using purified solvent and pressurized to excess reaction pressure. All reaction feed flows are measured by mass flow meters and controlled independently by metering pumps.

[0261] The comonomer feed is mechanically pressurized and can be injected into the process at several potential locations depending on the reactor configuration, which includes only a feed stream for the first reactor, only a feed stream for the second reactor, or both a first reactor feed stream and a second reactor feed stream independently.

[0262] The continuous solution polymerization reactor consists of a liquid-filled adiabatic continuous stirred tank reactor (CSTR). All solvent, monomer, comonomer, hydrogen, and catalyst component feeds can be controlled independently. The temperature of the entire feed stream (solvent, monomer, comonomer, and hydrogen) into the reactor is controlled by passing the feed stream through a heat exchanger. The entire feed into the polymerization reactor is injected into the reactor from a single location. The catalyst component is injected into the polymerization reactor separately from the other feeds. A stirrer within the reactor serves to continuously mix the reactants. The reactor temperature can be finely tuned by providing an oil bath.

[0263] The final reactor effluent is introduced into a zone where the effluent is deactivated by the addition and reaction with a suitable reagent (typically water). At this same reactor outlet location, other additives (octadecyl 3,5-di-Tert-butyl-4-hydroxyhydrocinnamate, tetrakis(methylene(3,5-di-Tert-butyl-4-hydroxyhydrocinnamate))methane, and tris(2,4-di-Tert-butyl-phenyl)phosphite) are added for polymer stabilization.

[0264] After catalyst deactivation and the addition of optional additives, the reactor effluent is fed into a devolatilization system that removes the polymer from the non-polymer stream. The non-polymer stream is removed from the system. The isolated polymer melt is pelletized and collected. Catalytic efficiency and characteristics of the resulting polymers were evaluated for the inventive precatalysts 1 to 8 and comparative precatalysts C1 and C2. Precatalysts 1 to 8 (see above) each had a structure according to Formula (I), and precatalysts 1 to 5 each had germanium crosslinks, while precatalysts 6 to 8 each had silicon crosslinks. For each of precatalysts 1 to 8, R on the germanium or silicon crosslink 17 and R 18 Substituents are independently (C5-C 40 It was hydrocarvil.

[0265] Comparative precursor catalysts C1, C2, and C3 (see below) are each R on a germanium (C1) or silicon (C2) crosslink. 17 and R 18 Substituents are independent (C5-C 40 It has a structure different from chemical formula (I) in that it is isopropyl rather than hydrocarbyl. In addition, the comparative precatalyst C3 is R 1 and R 16 It differs from chemical formula (I) in that it is not a radical having chemical formula (II).

[0266]

[0267] R of the germanium-crosslinked metal-ligand complex according to chemical formula (I) 17 and R 18 This independently isopropyl (C5-C 40 To investigate the effect in the case of hydrocarbyl, polymerization reactions were carried out according to the conditions for a single reactor system as described above, and in each reaction, one of precatalysts 1 to 5 or comparative precatalyst C1 was added as a metal-ligand complex of the catalyst system. The properties of the polymers produced using one of precatalysts 1 to 5 or comparative precatalyst C1 having germanium crosslinking, respectively, are recorded in Tables 1 to 3.

[0268] [Table 1]

[0269]

[0270] [Table 2]

[0271]

[0272] [Table 3]

[0273]

[0274] As can be seen in Tables 1 to 3, each has a metal-ligand complex according to formula (I) having a germanium crosslink, and R 17 and R 18This independently (C5-C 40 The polymerization process using hydrocarbyl precursor catalysts 1 to 5 is R 3 and R 14 Roof Tile R 17 and R 18 Improved catalytic efficiency was exhibited compared to the same polymerization process using comparative precatalyst C1, which has the same metal-ligand complex as precatalysts 1 to 5 except for the group (when comparing batch reactor polymerization data within the same campaign). R of comparative precatalyst C1 17 and R 18 Silver (C5-C 40 It was a conventional isopropyl group rather than a hydrocarbyl group, and due to this difference, the catalytic efficiency of comparative precatalyst C1 is believed to be lower than that of precatalysts 1 to 5. Although not bound by theory, regarding the n-octyl R for comparative precatalyst C1 3 and R 14 Groups are considered to have minimal effect on catalyst efficiency (long-chain alkyl groups are mainly used for better solubility). Larger R 17 and R 18 It can also be seen in Tables 1 to 3 that there is a tendency for the group to produce polymers with a higher molecular weight.

[0275] For a metal-ligand complex having a structure according to chemical formula (I) with germanium crosslinking, R 17 and R 18 This independently (C5-C 40 To further demonstrate the advantages of hydrocarbyl, continuous polymerization data for precatalyst 4 and comparative precatalyst C1 are shown in Table 4. The data were obtained at the same C2 conversion rate (10 g / L C2 discharge). The H2 supply was adjusted to reach the desired polymer melt index, and the density was allowed to vary according to the 1-octene sensitivity of the catalyst.

[0276] [Table 4]

[0277]

[0278] The continuous polymerization data of pre-catalyst 4 and comparative pre-catalyst C1 support the results presented above for batch reactor polymerization. In particular, the data R 17 and R 18 This independently isopropyl (C5-C 40 This shows that precatalyst 4, having a metal-ligand complex according to chemical formula (I) which was hydrocarbyl, exhibits improved catalytic efficiency compared to comparative precatalyst C1. Furthermore, the lower density of precatalyst 4 compared to comparative precatalyst C1 indicates that similar I2 and I 10 Considering the / I2 value, it indicates that pre-catalyst 4 has a similar long-chain branching structure and a better comonomer incorporation rate.

[0279] R of the silicon-crosslinked metal-ligand complex according to chemical formula (I) 17 and R 18 This independently isopropyl (C5-C 40 To investigate the effect in the case of hydrocarbyl, the polymerization reaction was carried out according to the conditions for a single reactor system as described above, and in each reaction, one of precatalysts 6 to 8 or comparative precatalyst C2 was added as a metal-ligand complex to the catalyst system. The characteristics of the polymers produced using one of precatalysts 6 to 8 or comparative precatalyst C2, each having silicon crosslinking, are recorded in Tables 5 and 6, along with the batch reactor polymerization results for precatalyst 9 (Table 6).

[0280] [Table 5]

[0281]

[0282] [Table 6]

[0283]

[0284] As can be seen in Tables 5 and 6, each has a metal-ligand complex according to chemical formula (I) having silicon crosslinking and R 17 and R 18 This independently (C5-C 40 The polymerization process using hydrocarbyl precursor catalysts 6 to 8 is R 17 and R 18 Improved catalytic efficiency was exhibited compared to the same polymerization process using comparative precatalyst C2, which has the same metal-ligand complex as precatalysts 6 to 8 except for the group. R of comparative precatalyst C2 17 and R 18 Silver (C5-C 40 It was a conventional isopropyl group rather than a hydrocarbyl group, and this difference is explained by the lower catalytic efficiency of comparative precatalyst C2 compared to precatalysts 6 to 8. As with the case of Ge-crosslinked precatalysts 1 to 5, a larger R 17 and R 18 It can also be seen in Tables 5 and 6 that the group tends to produce polymers with a higher molecular weight.

[0285] For a metal-ligand complex having a structure according to chemical formula (I) with silicon crosslinking, R 17 and R 18 This independently (C5-C 40 To further demonstrate the advantages of hydrocarbyl, continuous polymerization data for precatalyst 6 and comparative precatalyst C2 are shown in Table 7. The data were obtained at the same C2 conversion rate (10 g / L C2 discharge). The H2 supply was adjusted to reach the desired polymer melt index, and the density was allowed to vary according to the 1-octene sensitivity of the catalyst.

[0286] [Table 7]

[0287]

[0288] The continuous polymerization data of precatalyst 6 and comparative precatalyst C2 support the results presented above for batch reactor polymerization. In particular, the data R 17 and R 18 This independently isopropyl (C5-C 40 This shows that the precatalyst 6, having a metal-ligand complex according to chemical formula (I) which was hydrocarbyl, exhibits improved catalytic efficiency compared to the comparative precatalyst C2. Furthermore, the lower density of precatalyst 6 compared to the comparative precatalyst C2 indicates that precatalyst 6 has a better comonomer incorporation rate.

[0289] To investigate the ethylene / 1-butene copolymerization capability of the catalyst system described herein, R 17 and R 18 This independently (C5-C 40 )a precatalyst 9 having a metal-ligand complex according to the chemical formula (I) of hydrocarbyl, and (C5-C 40 Instead of the )hydrocarbil group, the usual R 17 and R 18 A study was conducted to produce a series of ethylene / butene copolymer designs with specific density and melt index specifications using a comparative precursor catalyst C3 having a group. The process conditions used in the ethylene / 1-butene copolymer study are recorded in Table 8, and various characteristics of the copolymers produced in this study are recorded in Tables 9 and 10 and presented as graphs in Figures 1a to 4.

[0290] [Table 8]

[0291]

[0292] [Table 9]

[0293]

[0294] [Table 10]

[0295]

[0296] As can be seen in Table 9 above, the ethylene / butene copolymerization process using precatalyst 9, which has a metal-ligand complex according to chemical formula (I), can produce an ethylene / butene copolymer with a reduced HCC fraction, narrow SCBD, low vinyl unsaturation, and low levels of BBB teromers. Although not bound by theory, comparative precatalyst C3 has R on silicon crosslinking 17 and R 18 Giga independently (C5-C 40 In that it is not )hydrocarbyl, and R 1 and R 16 It is believed that the HCC fraction increases, SCBD widens, vinyl unsaturation increases, and the level of BBB trimer increases because it differs from chemical formula (I) in that it is not a radical having chemical formula (II).

[0297] Figures 1a to 1c show TGIC SCBD curves for samples of similar copolymer designs, and it can be seen that the precatalyst 9 having a metal-ligand complex according to formula (I) provides a narrower SCBD curve than the comparative precatalyst C3 for each tested density and melt index specification.

[0298] Figure 2 is a graph showing the relationship between HCC value (weight%) and density (g / cc) for ethylene / 1-butene copolymers produced in an ethylene / butene copolymerization study. It can be seen that the precatalyst 9 of the present invention consistently produces HCC values ​​of less than 1.4 weight% across the tested density range, whereas the comparative precatalyst C3 consistently produces high HCC values ​​of more than 1.4 weight%. As previously mentioned, these low HCC values ​​improve the solid handling performance of the polymer.

[0299] Figure 3 is a graph showing the relationship between BBB trimer content (number of BBB trimers per 1,000 carbon atoms) and density (g / cc) for ethylene / 1-butene copolymers produced in an ethylene / butene copolymerization study. It can be seen that the precatalyst 9 of the present invention consistently produces polymers having 0.0075 or fewer BBB trimers per 1,000 carbon atoms, whereas the comparative precatalyst C3 consistently produces polymers having 0.0075 or more BBB trimers per 1,000 carbon atoms. The reduced BBB trimer content of the polymer produced by the precatalyst 9 of the present invention is expected to improve solid handling and curing performance.

[0300] Figure 4 is a graph showing the relationship between vinyl content (number of vinyl atoms per 1,000 carbon atoms) and density (g / cc) for ethylene / 1-butene copolymers produced in an ethylene / butene copolymerization study. It can be seen that the precatalyst 9 of the present invention consistently produces polymers having less than 0.01 vinyl atoms per 1,000 carbon atoms, whereas the comparative precatalyst C3 consistently produces polymers having more than 0.01 vinyl atoms per 1,000 carbon atoms. The reduced vinyl unsaturation of the polymer produced by the precatalyst 9 of the present invention is expected to improve the environmental aging performance of the polymer.

[0301] Test method

[0302] density

[0303] Samples for density measurement were prepared according to ASTM D-1928 (the whole of which is incorporated herein by reference). Measurements were performed within one hour of pressurizing the sample using ASTM D-792, Method B (the whole of which is incorporated herein by reference).

[0304] Melting index

[0305] The melt index (I2) was measured according to ASTM-D 1238 (the entirety of which is incorporated herein by reference) at 190°C / 2.16 kg and recorded in grams eluted per 10 minutes. Melt flow rate (I 10 ) was measured according to ASTM-D 1238 at 190℃ / 10 kg and recorded in grams eluted per 10 minutes.

[0306] Gel Permeation Chromatography (GPC)

[0307] 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 and detector compartments were set to 150°C. The columns used were four Agilent "Mixed A" 30 cm 20-micron linear mixed-bed columns. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm of butylated hydroxytoluene (BHT). Nitrogen was used as the solvent source for sparging. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters / min.

[0308] Calibration of the GPC column set was performed with at least 21 polystyrene standards with a narrow molecular weight distribution having molecular weights ranging from 580 to 8,400,000, said standards were arranged in six "cocktail" mixtures spaced at least 10-fold apart from 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 greater than 1,000,000 and at 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards were pre-dissolved at 80°C with gentle stirring for 30 minutes and then cooled; the room temperature solution was then transferred to an autosampler dissolution oven at 160°C for 30 minutes while cooled. The standard peak molecular weight of polystyrene was converted to the molecular weight of polyethylene using Formula 1 (described in the literature [Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)]):

[0309] M 폴리에틸렌 = A × ( M 폴리스티렌 ) B (Equation 1)

[0310] In the above formula, M is the molecular weight, A has a value of 0.4163, and B is 1.0.

[0311] Each polyethylene equivalent correction point was fitted using a fifth-order polynomial.

[0312] The total plate count of the GPC column set was performed using decane introduced into the blank sample via a micropump controlled by the PolymerChar GPC-IR system. The plate count of the chromatography system must exceed 18,000 for four Agilent "Mixed A" 30 cm 20-micron linear mixed-bed columns.

[0313] Samples were prepared semi-automatically using PolymerChar "Instrument Control" software, gravimetrically targeted to 2 mg / ml, and a solvent (containing 200 ppm BHT) was added to pre-nitrogen-sparged, septic-capped via a PolymerChar high-temperature autosampler. Samples were dissolved at 160°C for 2 hours under "low-speed" shaking.

[0314] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculation was based on the GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 2 to 4, using the PolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram at each equally spaced data acquisition point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard correction curve for point (i) from Equation 1.

[0315] (Equation 2)

[0316] (Equation 3)

[0317] (Equation 4)

[0318] To monitor deviations over time, a flow marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. Using this flow marker (FM), the pump flow rate (flow rate (nominal)) of each sample was linearly corrected by aligning the RV of the decane peak within each sample (RV (FM sample)) to the RV of the decane peak in the narrow standard correction (RV (FM corrected)). Subsequently, any change in the decane marker peak over time is assumed to be associated with a linear shift in the flow rate (flow rate (effective)) over the entire run. After calibrating the system based on the flow marker peak, the effective flow rate (for the narrow standard correction) is calculated according to Equation 5. Processing of the flow marker peak was performed using PolymerChar GPC One™ software. An acceptable flow rate correction is that the effective flow rate must be within + / -0.5% of the nominal flow rate.

[0319] Flow Rate (Effective) = Flow Rate (Nominal) * (RV (FM Corrected) / RV (FM Sample)) (Equation 5)

[0320] Differential Scanning Calorimetry (DSC)

[0321] Baseline calibration of the DSC Q1000 is performed using the software's calibration wizard. First, a baseline is obtained by heating the cell from -80°C to 280°C without placing any sample in the aluminum DSC pan. Then, sapphire standard material is used according to the wizard's instructions. Next, approximately 1 to 2 mg of a new indium sample is analyzed by heating the sample to 180°C, cooling it to 120°C at a cooling rate of 10°C / min, maintaining the sample isothermally at 120°C for 1 minute, and then heating the sample from 120°C to 180°C at a heating rate of 10°C / min. The heat of fusion and the melting point of the indium sample are measured, and the melting point was confirmed to be within 0.5°C from 156.6°C, and the heat of fusion within 0.5 J / g from 28.71 J / g. Then, a small drop of the fresh sample is placed in the DSC pan, and the deionized water is analyzed by cooling from 25°C to -30°C at a cooling rate of 10°C / min. The sample is held isothermally at -30°C for 2 minutes, then heated to 30°C at a heating rate of 10°C / min. The melting initiation point is measured and verified to be within 0.5°C of 0°C. Then, the polymer sample is compressed into a thin film at a temperature of 350°F. Approximately 5 to 8 mg of the sample is weighed and placed in the DSC pan. The lid of the pan is tightly closed to maintain a sealed atmosphere. The sample pan is placed in the DSC cell, and then heated to a temperature approximately 30°C higher than the polymer melting temperature at a rapid rate of approximately 100°C / min. The sample is held at this temperature for 5 minutes. Then, the sample is cooled to -40°C at a rate of 10°C / min and held isothermally at that temperature for 5 minutes. Consequently, the sample is heated at a rate of 10°C / min until it is completely melted. The resulting enthalpy curve is analyzed.

[0322] Efficiency measurement

[0323] Catalytic efficiency was measured as the amount of polymer produced relative to the amount of catalyst (active metal) used in the solution polymerization process.

[0324] 1 H NMR and 13 C NMR

[0325] 1 H and 13 A method for measuring comonomer content (method for measuring comonomer content), total unsaturation (method for measuring total unsaturation), vinyl / 1000C (method for measuring vinyl content), and BBB trimer (method for measuring BBB trimer) using 1 / 3 C NMR spectroscopy is provided below.

[0326] Total unsaturation and vinyl / 1000C 1 Measurements are performed via ¹H NMR analysis. Approximately 3.25 g of a tetrachloroethane-d2 / perchloroethylene 50 / 50 mixture containing 0.001 M chromium acetylacetonate as a relaxant is added to 0.130 g of sample in a 10 mm NMR tube containing 100 ppm I-168. The tube and its contents are heated to 110°C to dissolve and homogenize the sample. Data are collected using a Bruker 600 MHz spectrometer equipped with a multinuclear high-temperature cryoprobe. Desaturation data are collected using 16 scans per data file, a pulse repetition delay of 15.8 seconds, and a sample temperature of 120°C. The spectral width is set to 12,019 Hz, and the file size is 32K data points. Pre-saturation experiments are performed using 100 scans per data file.

[0327] Total degree of unsaturation and vinyl / 1000C 1 Two experiments are performed for H NMR calculation: one is a control spectrum to quantify total polymer protons, and the other is a double pre-saturation experiment to obtain a high-sensitivity spectrum for quantifying the degree of unsaturation by suppressing strong polymer backbone peaks. Residue in TCE-d2 (6.0 ppm) 1The signal from H is integrated and set to a value of 100, and the integration from 3 ppm to -0.5 ppm is used as the signal from the total polymer in the control experiment. In the pre-saturation experiment, the TCE signal is also set to 100, and the corresponding integration values ​​for unsaturation (vinylene, trisubstituted unsaturation, vinyl, and vinylidene) are calculated. The integration values ​​of the areas for cis- and trans-vinylene (about 5.40 to 5.60 ppm), trisubstituted (about 5.16 to 5.35 ppm), vinyl (about 4.95 to 5.15 ppm), and vinylidene (about 4.70 to 4.90 ppm) are calculated. The BHT-OH signal, or any other additive signals if present, were not included in the integrated area.

[0328] The integral value of the entire polymer obtained from the control experiment is divided by 2 to obtain a value representing X thousand carbons. The value obtained by dividing the integral value of the unsaturated group by the number of protons contributing to that integral value represents the number of moles of each type of unsaturated group per X thousand carbons. The number of moles of each type of unsaturated group is divided by X to obtain the number of moles of unsaturated groups per 1,000 moles of carbons. The total degree of unsaturation is the sum of cis- and trans-vinylene, trisubstituted, vinyl, and vinylidene, all expressed in units of the number of moles of unsaturated groups per 1,000 moles of carbons.

[0329] 13 C NMR

[0330] The comonomer content and sequence distribution are 13Measurements are performed via 3C NMR analysis. Approximately 2.6 g of a 75 / 25 mixture of tetrachloroethane / tetrachloroethane-d2 containing 0.025 M chromium acetylacetonate as a relaxant is added to 0.2 g of sample in a 10 mm NMR tube. The tube and its contents are heated to 150°C to dissolve and homogenize the sample. Data are collected using a Bruker 600 MHz spectrometer equipped with a multinuclear high-temperature cryoprobe. Data acquisition includes 256 scans per data file, a pulse repetition delay of 7.8 seconds, and a sample temperature of 120°C. The spectral width is set to 35,700 Hz, and the file size is 131K data points.

[0331] For the analysis of comonomer content and BBB trimer molar fraction, 13 The 3C NMR spectrum is integrated and analyzed using the matrix method. This method uses vector equations s=fM Includes solving, M is the assignment matrix, s is the row vector representation of the spectrum, and f is the mole fraction composition vector. f The elements of represent a triad of C2 and C4 containing all permutations of C2 and C4. Assignment matrix M silver f It consists of one row for each tripr and one column for each integrated NMR signal. The elements of the matrix are integral values ​​determined by referring to the assignments established in the literature ["Multidimensional NMR Studies of Poly(ethylene-co-1-butene) Microstructures," Sahoo, SK et al., Macromolecules, Volume 34, Issue 2001, Pages 4757-67 (2003)], the entirety of which is incorporated herein by reference. These equations are for each sample s and the integrated 13 To minimize the error function between C data fIt was solved by changing the elements of. This process is executed using the Solver function of Microsoft Excel.

[0332] Thermal gradient interaction chromatography (HCC measurement method)

[0333] A commercial crystallization elution fractionation (CEF) instrument (Polymer Char, Spain) is used to perform high-temperature thermal gradient interaction chromatography (HT-TGIC or TGIC) measurements (Reference [Cong, et al., Macromolecules, 2011, 44 (8), 3062-3072.]). The CEF instrument is equipped with an IR-5 detector. Graphite was used as the stationary phase in the HT-TGIC column (U.S. Patent No. 8,476,076 by Freddy, A. Van Damme et al.; U.S. Patent No. 8,318,896 by Winniford et al.). A single graphite column (250 × 4.6 mm) is used for separation. Graphite is packed into the column using dry packing followed by slurry packing technology (European Patent EP 2714226B1 (Cong et al.) and cited reference). The experimental parameters are as follows: top oven / transport line / needle temperature of 150°C, dissolution temperature of 150°C, dissolution stirring setting of 2, pump stabilization time of 15 seconds, pump flow rate for column washing of 0.500 mL / min, pump flow rate for column loading of 0.300 ml / min, stabilization temperature of 150°C, stabilization time of 1.0 min (pre-loading to column), stabilization time of 1.0 min (post-loading to column), SF (soluble fraction) time of 5.0 min, cooling rate of 3.00°C / min from 150°C to 30°C, flow rate during the cooling process of 0.03 ml / min, heating rate of 2.00°C / min from 30°C to 160°C, isothermal time of 10 min at 160°C, elution flow rate of 0.500 mL / min, and injection loop size of 200 microliters.

[0334] The flow rate during the cooling process is adjusted according to the length of the graphite column, which must ensure that all polymer fractions remain on the column at the end of the cooling cycle.

[0335] Samples are prepared by a PolymerChar autosampler at 150°C for 120 minutes at a concentration of 4.0 mg / ml in ODCB (defined below). Silica Gel 40 (particle size 0.2 to 0.5 mm, catalog number 10181-3, EMD) is dried in a vacuum oven at 160°C for about 2 hours prior to use. For a CEF instrument equipped with an autosampler with an N2 purging function, 5.0 grams of Silica Gel 40 were added to 2 liters of ortho-dichlorobenzene (ODCB, 99% anhydrous grade, Sigma-Aldrich), or Silica Gel 40 was packed into three "300 × 7.5 mm" GPC-sized stainless steel columns, and the Silica Gel 40 columns were installed at the pump inlet of the CEF instrument to dry the ODCB. Such "ODCB containing silica gel" or ODCB dried with silica gel 40 is hereinafter referred to as "ODCB". TGIC data is processed on the PolymerChar (Spain) "GPC One" software platform. Temperature correction is performed with a mixture of about 4 to 6 mg of eicosan, 14.0 mg of isotactic homopolymer polypropylene iPP (polydispersity of 3.6 to 4.0, molecular weight Mw reported as polyethylene equivalent of 150,000 to 190,000, and polydispersity of 3.6 to 4.0 (Mw / Mn), iPP DSC melting temperature measured to be 158 to 159°C (DSC method described herein below)). 14.0 mg of homopolymer polyethylene HDPE (unmeasurable comonomer content, weight average molecular weight (Mw) reported as 115,000 to 125,000 polyethylene equivalents, and polydispersity of 2.5 to 2.8) was filled into a 10 mL vial with 7.0 mL of ODCB. The dissolution time was 2 hours at 160°C.

[0336] For the correction process, a solution of eicosan and HDPE is used. For elution temperatures in the range of 30°C to 150°C, the process consists of the following steps:

[0337] 1. A step of extrapolating the elution temperature for each isothermal step during elution according to the heating rate (described in FIG. 5).

[0338] 2. Step for calculating the delay volume. The temperature (x-axis) corresponding to the IR measurement channel chromatogram (y-axis) is shifted so that the peak maximum value of eicosan (y-axis) matches the elution temperature of 30.0°C. The delay volume is calculated from the temperature difference (actual elution temperature of the peak maximum value of eicosan from 30°C) obtained by dividing by the heating rate of the method and then multiplying by the elution flow rate.

[0339] 3. A step of adjusting each recorded elution temperature by this same delay volume adjustment.

[0340] 4. A step of linearly changing the heating rate so that the maximum eucosan elution peak temperature is maintained at 30.0℃, while the observed HDPE reference material has a maximum elution peak temperature of 150.0℃.

[0341] The comonomer content versus elution temperature of HT-TGIC is constructed using at least 20 reference materials (ethylene homopolymers and ethylene-octene random copolymers prepared using a single-site metallocene catalyst, having an ethylene equivalent weight-average molecular weight in the range of 35,000 to 236,000 g / mol and a polydispersity of 2.0 to 2.5). Reference [Cong et al., Macromolecule, 2011, 44 (8), 3062-3072)] is referenced. All these reference materials are prepared at a concentration of 4 mg / mL and analyzed in the same manner as previously described. Mathematical fit of the reported elution peak temperature as a function of octene mol% is performed using linear regression to R 2 Equation 6 (EQ6) was derived, in which is greater than 0.99.

[0342] (Elution temperature (°C)) = -4.0831 × (Octene mol%) + 149.6 (Equation 6)

[0343] Data processing for the polymer samples of HT-TGIC is described below.

[0344] The solvent blank (pure solvent injection) is performed under the same experimental conditions as the polymer sample. Data processing for the polymer sample includes: subtraction of the solvent blank for each detector channel, temperature extrapolation described in the calibration process, temperature compensation by the delayed volume measured from the calibration process, and adjustment on the elution temperature axis for the 30°C and 160°C ranges calculated from the heating rate of the calibration.

[0345] The chromatogram (measurement channel of the IR-5 detector) is integrated into the PolymerChar "GPC One" software. If the peak falls within the minimum or flat region of the detector signal on the low-temperature side of the soluble fraction (SF) and the flat baseline (a value of nearly zero in the chromatogram excluding the blank) at the high elution temperature, a straight baseline is plotted from the visible difference.

[0346] When the peak falls into the above-mentioned baseline region (a value of nearly zero in the chromatogram excluding the blank), the upper limit of the temperature integration is set based on the visible difference. The lower limit of the temperature integration is set based on the intersection of the baseline and the chromatogram containing the soluble fraction.

[0347] "High comonomer content (HCC)" is defined as the polymer fraction that elutes between the lower temperature integration limit and 52.0°C. The HCC value is calculated by dividing the area from approximately 27.0°C to 52.0°C by the total area (from approximately 27.0°C to 160°C) and multiplying the quotient by 100.

[0348] Below is the DSC method used to measure the melting temperature of homopolymer polypropylene as specified in HT-TGIC.

[0349] The melting point of iPP is measured using differential scanning calorimetry (DSC). The temperature at the maximum heat flow rate relative to the linear baseline is used as the melting point. The linear baseline consists of the melting start point (above the glass transition temperature) and the melting end point. The temperature is raised from room temperature to 200°C at a rate of 10°C / min, held at 200°C for 5 minutes, lowered to 0°C at 10°C / min, held at 0°C for 5 minutes, and then raised from 0°C to 200°C at 10°C / min, and data is obtained from this second heating cycle.

[0350] Throughout this specification, references to “one embodiment,” “a specific embodiment,” “various embodiments,” “one or more embodiments,” or “an embodiment” mean that a specific feature, structure, material, or property described in relation to an embodiment is included in at least one embodiment of this disclosure. Accordingly, the appearance of phrases such as “in an embodiment,” “in one or more embodiments,” “in a specific embodiment,” “in various embodiments,” “in one embodiment,” or “in an embodiment” in various places throughout this specification does not necessarily refer to the same embodiment or to only a single embodiment. Furthermore, a specific feature, structure, material, or property may be combined in any suitable manner in one or more embodiments.

[0351] It should be obvious to those skilled in the art that various modifications may be made to the described embodiments without departing from the spirit and scope of the claimed technical gist. Accordingly, this specification is deemed to include modifications and changes to the described embodiments insofar as such modifications and changes fall within the scope of the appended claims and their equivalents.

Claims

Claim 1 Catalytic system comprising a metal-ligand complex according to the following chemical formula (I): In the above formula, M is a metal selected from titanium, zirconium, or hafnium; n is 1 or 2; when n is 1, X is a monodentate or bidentate ligand; when n is 2, each X is an independently selected monodentate ligand; the metal-ligand complex is charge-neutral as a whole; each Z is independently selected from silicon or germanium; and R 1 and R 16 is independently a radical having the following chemical formula (II): In the above formula, R 31-35 are respectively (C1-C 40 )hydrocarbyl, (C1-C 40 )heterohydrocarbil, -Si(R C )3, -OR C , -SR C Independently selected from -CN, -CF3, halogen, and -H, and R 2-4 , R 5-8 , R 9-12 , and R 13-15 are respectively (C1-C 40 )hydrocarbyl, (C1-C 40 )heterohydrocarbil, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -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 Independently selected from )2NC(O)-, halogen, and -H; R 17 and R 18 is independently (C5-C 40 It is hydrocarbil; R 23 and R 24 is -(CR C 2) m - is selected independently from, and m is 1 or 2; In chemical formula (I), each R C , R P , and R N is independently (C1-C 30 )hydrocarbyl, (C1-C 30 )heterohydrocarbyl, or -H. Claim 2 In paragraph 1, R 17 and R 18 is independently (C5-C 20 )alkyl, catalyst system. Claim 3 In paragraph 1 or 2, R 17 and R 18 A catalytic system in which the atoms are connected to form a ring structure having at least five carbon atoms. Claim 4 In any one of paragraphs 1 to 3, R 6 and R 11 is independently (C2-C 12 )alkyl, catalyst system. Claim 5 In any one of paragraphs 1 through 4, R 1 and R 16 At least one of them is a radical having the chemical formula (II), and R 32 and R 34 Is tert - Butyl phosphorus, catalyst system. Claim 6 In any one of paragraphs 1 through 5, R 3 and R 14 is independently (C1-C 12 )alkyl, catalyst system. Claim 7 In any one of paragraphs 1 through 6, R 3 and R 14 is independently tert -Octyl, n - Octyl, or methyl, catalyst system. Claim 8 In any one of paragraphs 1 through 7, R 6 and R 11 silver tert - Butyl phosphorus, catalyst system. Claim 9 In any one of paragraphs 1 through 8, R 8 and R 9 is a catalyst system that is -H. Claim 10 In any one of paragraphs 1 through 9, R 7 and R 10 A halogen-based catalytic system. Claim 11 In any one of paragraphs 1 through 10, R 5 and R 12 is a halogen, catalytic system. Claim 12 In any one of paragraphs 1 through 11, each X is (C1-C 40 )hydrocarbyl, (C1-C 40 )heterohydrocarbil, -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -CH2Ge(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -NH(R C ), -N(Si(R C )3)2, -NR C Si(R C )3, -NHSi(R C )3, -OR C A ligand independently selected from , -CN, -CF3, and halogen, and each R C is independently substituted or unsubstituted (C1-C 30 )hydrocarbyl, or substituted or unsubstituted (C1-C 30 A catalytic system that is heterohydrocarbyl, where each Q is 0, 1, 2 or 3 and each W is 0, 1, or 2. Claim 13 In any one of paragraphs 1 through 12, R 17 and R 18 is independently (C5-C 20 )Cycloalkyl, catalyst system. Claim 14 As a polymerization process for manufacturing ethylene-based polymers, ethylene and optionally (C3-C 12 ) comprising the step of polymerizing an α-olefin in the presence of a catalyst system according to any one of claims 1 to 13, wherein the ethylene-based polymer is: 0.850 g / cm³ when measured according to ASTM D792 3 Up to 0.970 g / cm³ 3 Density of; A melt flow ratio of 5 to 15 (I 10 / I2) - Melt index I2 is measured at 190°C and a 2.16 kg load according to ASTM D1238, and melt index I 10 ...was measured at 190°C and a 10 kg load according to ASTM D1238 -; and A polymerization process for producing an ethylene-based polymer having a molecular weight distribution (MWD) of 1 to 5 - MWD is the ratio of weight average molecular weight to number average molecular weight. Claim 15 In claim 14, the catalyst system further comprises at least one co-catalyst, a polymerization process for producing an ethylene-based polymer. Claim 16 In claim 15, the polymerization process for producing an ethylene-based polymer, wherein at least one co-catalyst comprises modified methylaluminoxane (MMAO). Claim 17 In claim 16, the polymerization process for producing an ethylene-based polymer, wherein the modified methylaluminoxan (MMAO) comprises 10 to 20% of trialkyl aluminum species. Claim 18 In any one of claims 14 to 17, the ethylene and the (C3-C 12 A polymerization process for producing ethylene-based polymers, wherein α-olefins are polymerized through solution polymerization. Claim 19 In paragraph 18, the above ethylene and the above (C3-C 12 A polymerization process for producing ethylene-based polymers, wherein α-olefins are polymerized via solution polymerization in a loop reactor system. Claim 20 In any one of paragraphs 14 to 19, the above (C3-C 12 )α-olefin is 1-butene, a polymerization process for manufacturing ethylene-based polymers. Claim 21 A polymerization process for producing an ethylene-based polymer, wherein the ethylene-based polymer comprises 20% to 40% by weight of units derived from 1-butene based on the total weight of the ethylene-based polymer. Claim 22 In any one of claims 14 to 21, the density of the ethylene-based polymer is 0.854 g / cm³ 3 Up to 0.875 g / cm³ 3 A polymerization process for producing an ethylene-based polymer, wherein the melt index I2 of the ethylene-based polymer is 0.1 to 30 dg / min. Claim 23 In any one of claims 14 to 21, the density of the ethylene-based polymer is 0.854 g / cm³ 3 Up to 0.875 g / cm³ 3 A polymerization process for producing an ethylene-based polymer, wherein the ethylene-based polymer has a weight average molecular weight of 50 kg / mol to 200 kg / mol. Claim 24 A polymerization process for producing an ethylene-based polymer, wherein, in any one of claims 14 to 23, the ethylene-based polymer comprises less than 0.01 vinyl per 1,000 carbon atoms. Claim 25 A polymerization process for producing an ethylene-based polymer, wherein, in any one of claims 18 to 24, the ethylene-based polymer has an HCC (high comonomer content) value of less than 3.0 wt%, and the HCC value is measured using thermal gradient interaction chromatography (TGIC) according to an HCC measurement method. Claim 26 A polymerization process for producing an ethylene-based polymer, wherein, in any one of claims 18 to 25, the ethylene-based polymer has less than 0.0075 BBB trimers per 1,000 carbon atoms, and the BBB trimer content is measured according to the BBB measurement method. Claim 27 An ethylene-based polymer comprising the polymerization reaction product of an ethylene monomer and a 1-butene comonomer, with 0.854 g / cm³ when measured according to ASTM D792 3 Up to 0.875 g / cm³ 3 Density of; melt index I2 of 0.1 to 30 dg / min - melt index I2 is measured at 190°C and a 2.16 kg load according to ASTM D1238 -; melt flow ratio (I) of 5 to 15 10 / I2) - Melt Index I 10 An ethylene-based polymer having: - measured at 190°C and a 10 kg load according to ASTM D1238; - a molecular weight distribution (MWD) of 1.5 to 5 - MWD is the ratio of weight-average molecular weight to number-average molecular weight -; - a high comonomer content (HCC) value of less than 1.4 wt% - HCC values ​​are measured using thermal gradient interaction chromatography (TGIC) according to the HCC measurement method -; and - a BBB trimer content of less than 0.0075 BBB trimers per 1,000 carbons - BBB trimer content is measured according to the BBB measurement method - Claim 28 In claim 27, an ethylene-based polymer comprising 20% ​​to 40% by weight of a unit derived from a 1-butene comonomer based on the total weight of the ethylene-based polymer. Claim 29 An ethylene-based polymer comprising less than 0.01 vinyl per 1,000 carbons in claim 27 or 28.

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