A substituted pyridine-2,6-bis(phenylene phenolate) complex with increased solubility, which is useful as a catalyst component for olefin polymerization

Abstract

The present disclosure relates to a bis(aryl phenolate) Lewis base transition metal complex, a catalyst system containing the bis(aryl phenolate) Lewis base transition metal complex, and a polymerization method for producing polyolefin polymers such as polyethylene-based polymers and polypropylene-based polymers.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefit and priority of U.S. Provisional Application No. 63 / 338,167, filed on May 4, 2022, the disclosure of which is incorporated herein by reference. The present disclosure relates to bis(arylphenolate) Lewis base transition metal complexes, catalyst systems comprising bis(arylphenolate) Lewis base transition metal complexes, and polymerization processes for producing polyolefin polymers such as polyethylene - based polymers and polypropylene - based polymers.

Background Art

[0002] Polyolefins such as polyethylene typically have comonomers such as hexene incorporated into the polyethylene backbone. These copolymers provide various physical properties compared to polyethylene alone and are typically produced in low - pressure reactors using, for example, solution polymerization, slurry polymerization, or gas - phase polymerization processes. The polymerization can be carried out in the presence of a catalyst system such as a Ziegler - Natta catalyst, a chromium - based catalyst, or a catalyst system using a metallocene catalyst. Furthermore, since pre-catalysts (neutral, non-activated complexes) are often stored for several weeks before use, the pre-catalysts should be thermally stable at ambient temperature and above. The performance of a given catalyst is closely affected by reaction conditions such as monomer concentration and temperature. For example, solution processes that offer advantages due to being carried out at temperatures above 120 °C are, in particular, a challenge for catalyst development. At such high reactor temperatures, both high catalyst activity and high molecular weight capabilities decline very consistently with increasing reactor temperature, so it is often difficult to maintain high catalyst activity and high molecular weight capabilities. For a wide range of desired polyolefin products ranging from high-density polyethylene (HDPE) to elastomers (e.g., thermoplastic elastomers (TPE); ethylene-propylene-diene (EPDM)), a single catalyst is likely to be unable to address all that is required for the production of these various polyolefin products, so a number of different catalyst systems may be required. Due to the strict set of requirements necessary for the development and production of new polyolefin products, the effort to identify a catalyst suitable for a given product and production process is very difficult.

[0003] Aromatic solvents are typically used to dissolve catalyst components in industrial olefin polymerization processes. However, usually, the solubility of catalyst components in non-aromatic solvents is poor, so replacing aromatic solvents with non-aromatic solvents such as isohexane is a challenge. Further information on the general state of the art regarding non-metallocene olefin polymerization catalysts can be found in Baier, M. C. (2014) “Post-Metallocenes in the Industrial Production of Poly-olefins,” Angew. Chem. Int. Ed., v.53, pp. 9722-9744, the entire contents of which are incorporated herein by reference.

[0004] Further information regarding the complex can be found in Goryunov, G. P. et al. (2021) “Rigid Postmetallocene Catalysts for Propylene Polymerization: Ligand Design Prevents the Temperature-Dependent Loss of Stereo- and Regioselectivities,” ACS Catalysis, v.11(13), pp. 8079-8086; US2020 / 0255556; US2020 / 0255555; US2020 / 0254431; and US2020 / 0255553, each of which is incorporated herein by reference in its entirety. SUMMARY OF THE INVENTION

[0005] A catalyst compound represented by formula (I).

Chemical formula

[0006] An aliphatic hydrocarbon solvent; and a homogeneous solution containing at least one complex of formula (I), wherein the concentration of the complex is 0.20% by mass or more (alternatively 0.25% by mass or more, alternatively 0.30% by mass or more, alternatively 0.35% by mass or more, alternatively 0.40% by mass or more, alternatively 0.50% by mass or more, alternatively 1.0% by mass or more, alternatively 2.0% by mass or more). A method for producing a propylene-based polymer, comprising polymerizing propylene by contacting propylene with a catalyst system prepared from formula (I) at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30 °C to 230 °C in one or more continuous stirred tank reactors or loop reactors in series or parallel to form a propylene-based polymer. A method for producing an ethylene-based polymer, comprising polymerizing ethylene by contacting ethylene with a catalyst system prepared from formula (I) in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30 °C to 230 °C to form a propylene-based polymer.

Embodiments for Carrying Out the Invention

[0007] Exemplary embodiments of the industrial progress of the present invention include pyridine-2,6-bis(phenylene phenolate) complexes that are useful as catalyst components for olefin polymerization and have improved solubility in non-aromatic hydrocarbons (e.g., isohexane). The improved solubility of these complexes was achieved by modifying the ligand framework that provides improved solubility at specific positions, but did not adversely affect the performance of this complex when used as a catalyst for olefin polymerization. For the purposes of this disclosure, the numbering scheme for groups of the periodic table is used as described in Chemical and Engineering News, v.63(5), pg. 27 (1985). Thus, "Group 4 metals" refers to the elements of Group 4 of the periodic table, e.g., Hf, Ti, or Zr. The following abbreviations may be used herein: Me is methyl, Et is ethyl, Ph is phenyl, tBu is tertiary butyl, MAO is methylalumoxane, NMR is nuclear magnetic resonance, t is time, s is second, h is hour, psi is pounds per square inch, psig is pounds per square inch gauge, equiv is equivalent, and RPM is revolutions per minute.

[0008] This specification describes transition metal complexes. The term complex is used to describe a molecule in which auxiliary ligands are coordinated to a central transition metal atom. The ligands are bulky and stably bound to the transition metal so as to maintain their influence during the use of the catalyst, such as polymerization. The ligands can be coordinated to the transition metal by covalent bonds and / or electron-donating coordination or intermediate bonds. Transition metal complexes are generally activated using an activator to exert their polymerization or oligomerization function. The activator, without being bound by theory, often generates a cation as a result of the removal of a leaving group and an anionic group often referred to as such from the transition metal. The terms "substituent", "radical", "group" and "moiety" may be used interchangeably. "Conversion rate" refers to the amount of monomer converted to the polymer product, reported as mol% and calculated based on the amount of polymer yield and the amount of monomer fed to the reactor.

[0009] "Catalytic activity" is a measure of how active a catalyst is, and is reported as the number of grams of product polymer (gP.mmolcat -1 .h -1 ) produced per millimole of catalyst (cat) per hour. The term "heteroatom" refers to any of the Group 13-17 elements excluding carbon. Heteroatoms can include B, Si, Ge, Sn, N, P, As, O, S, Se, Te, F, Cl, Br and I. The term "heteroatom" can include the above elements having attached hydrogen, e.g., BH, BH 2 , SiH 2 , OH, NH, NH 2 . The term "substituted heteroatom" describes a heteroatom in which one or more of these hydrogen atoms have been replaced by a hydrocarbyl group or a substituted hydrocarbyl group.

[0010] Unless otherwise indicated (e.g., definitions such as "substituted hydrocarbyl", "substituted aromatic", etc.), the term "substituted" means that at least one hydrogen atom is replaced by a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group, such as -NR * 2 、-OR * 、-SeR * 、-TeR * 、-PR * 2 、-AsR * 2 、-SbR * 2 、-SR * 、-BR * 2 、-SiR * 3 、-GeR * 3 、-SnR * 3 、-PbR * 3 wherein each R * is independently a hydrocarbyl radical or a halocarbyl radical, and two or more R * may be joined together to form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or at least one hydrogen atom is replaced by at least one non-hydrogen group such as those described above, or at least one heteroatom is inserted within the hydrocarbyl ring.

[0011] The term "substituted hydrocarbyl" means that at least one hydrogen atom of a hydrocarbyl radical is replaced by at least one heteroatom (e.g., a halogen such as Br, Cl, F, or I) or a heteroatom-containing group (e.g., a functional group such as -NR * 2 、-OR * 、-SeR * 、-TeR * 、-PR * 2 、-AsR * 2 、-SbR *2 、 -SR * 、 -BR * 2 、 -SiR * 3 、 -GeR * 3 、 -SnR * 3 、 -PbR * 3 and R * are each, independently, a hydrocarbyl radical or a halocarbyl radical, and two or more R * may be joined together to form a substituted or unsubstituted, fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), a hydrocarbyl radical substituted thereby, or a hydrocarbyl radical in which at least one heteroatom is inserted into the hydrocarbyl ring. The term "hydrocarbyl-substituted phenyl" means a phenyl group in which one, two, three, four or five hydrogen groups are replaced by a hydrocarbyl group or a substituted hydrocarbyl group. For example, a "hydrocarbyl-substituted phenyl" group has the formula:

[0012] [Chemical formula] (R a 、R b 、R c 、R d and R e are each, independently, hydrogen, C 1 -C 40 hydrocarbyl or C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group (provided that at least one of R a 、R b 、R c 、R d and R e is not H), or two or more of R a 、R b 、R c 、R d and R e may combine together to form C 4 -C62 (which can form a cyclic or polycyclic hydrocarbyl ring structure or a combination thereof) can be represented by The term "substituted aromatic" means an aromatic group in which one or more hydrogen groups are replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing group.

[0013] The term "substituted phenyl" means a phenyl group in which one or more hydrogen groups are replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing group.

[0014] The term "substituted carbazole" means a carbazolyl group in which one or more hydrogen groups are replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing group. The term "substituted naphthyl" means a naphthyl group in which one or more hydrogen groups are replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing group. The term "substituted anthracenyl" means an anthracenyl group in which one or more hydrogen groups are replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing group. The term "substituted fluorenyl" means a fluorenyl group in which one or more hydrogen groups are replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing group.

[0015] The terms "trihydrocarbylsilyl" and "trihydrocarbylgermyl" mean a silyl group or a germyl group bonded to three hydrocarbyl groups. Examples of suitable trihydrocarbylsilyl groups and trihydrocarbylgermyl groups can include all isomers of trimethylsilyl, trimethylgermyl, triethylsilyl, triethylgermyl, and tripropylsilyl, tripropylgermyl, tributylsilyl, tributylgermyl, tripentylsilyl, tripentylgermyl, trihexylsilyl, butyldimethylsilyl, butyldimethygermyl, dimethyloctylsilyl, dimethyloctylgermyl, etc. The terms "dihydrocarbylamino" and "dihydrocarbylphosphino" mean a nitrogen group or a phosphorus group bonded to two hydrocarbyl groups which may be bonded together. Examples of suitable dihydrocarbylamino groups and dihydrocarbylphosphino groups can include dimethylamino, dimethylphosphino, diethylamino, N - pyrrolidinyl, diethylphosphino, and all isomers of dipropylamino, dipropylphosphino, dibutylamino, dibutylphosphino, etc.

[0016] The term "substituted adamantanyl" means an adamantanyl group in which one or more hydrogen groups are replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom - containing group. The terms "alkoxy" and "alkoxide" mean an alkyl group or an aryl group bonded to an oxygen atom, e.g., an alkyl ether group or an aryl ether group / a radical bonded to an oxygen atom, and the alkyl group / aryl group can be a C 1 ~C 10 hydrocarbyl (also referred to as a hydrocarbyloxy group). The alkyl group may be straight - chain, branched or cyclic. The alkyl group may be saturated or unsaturated. Examples of suitable alkoxy radicals can include methoxy, ethoxy, n - propoxy, iso - propoxy, n - butoxy, iso - butoxy, sec - butoxy, tert - butoxy, phenoxy.

[0017] The term "thiolate" means an alkyl or aryl group bonded to a sulfur atom, e.g., an alkylthioether group or an arylthioether group / a radical containing a sulfur atom, where the alkyl group / aryl group is a C 1 ~C 10 hydrocarbyl (also referred to as a hydrocarbylthiolate group). The alkyl group may be straight-chain, branched, or cyclic. The alkyl group may be saturated or unsaturated. Examples of suitable thiolate radicals include methanethiolate, ethanethiolate, n-propanethiolate, iso-propanethiolate, n-butanethiolate, iso-butanethiolate, sec-butanethiolate, tert-butanethiolate, benzenethiolate. The term "aryl" or "aryl group" means an aromatic ring and its substituted variants, e.g., phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Similarly, heteroaryl means an aryl group in which a ring carbon atom (or two or three ring carbon atoms) is replaced by a heteroatom such as N, O, or S. As used herein, the term "aromatic" also refers to a pseudoaromatic heterocyclic group, a heterocyclic substituent having properties and structure (nearly planar) similar to those of an aromatic heterocyclic ligand but not falling within the definition of aromatic. Similarly, the term aromatic also refers to a substituted aromatic.

[0018] The term "arylalkyl" means an aryl group in which hydrogen is replaced by an alkyl group or a substituted alkyl group. For example, 3,5'-di-tert-butyl-phenylindenyl is indene substituted by an arylalkyl group. When an arylalkyl group is a substituent on another group, the arylalkyl group is bonded to that other group through the aryl. The term "alkylaryl" means an alkyl group in which hydrogen is replaced by an aryl group or a substituted aryl group. For example, phenethylindenyl is indene substituted by an ethyl group bonded to a benzene group. When an alkylaryl group is a substituent on another group, the alkylaryl group is bonded to that other group through the alkyl. The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, the benzyl group has 6 ring atoms and tetrahydrofuran has 5 ring atoms.

[0019] A heterocyclic ring is a ring having heteroatoms within the ring structure, as opposed to a ring in which hydrogen on a ring atom is replaced by a heteroatom. For example, tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Another example of a heterocyclic ring can include pyridine, imidazole, and thiazole.

[0020] The terms "hydrocarbyl radical", "hydrocarbyl group", or "hydrocarbyl" can be used interchangeably and are defined to mean a group consisting of only hydrogen atoms and carbon atoms. For example, a hydrocarbyl can be linear, branched, or cyclic, and in the case of cyclic, can be aromatic or non-aromatic, C 1 -C 100It can be a radical. Examples of such radicals include, but are not limited to, alkyl groups such as methyl, ethyl, propyl (e.g., n-propyl, isopropyl, cyclopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., iso-amyl, cyclopentyl), hexyl (e.g., cyclohexyl), octyl (e.g., cyclooctyl), nonyl, decyl (e.g., adamantanyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or tricontyl, and aryl groups such as phenyl, benzyl and naphthyl.

[0021] The terms "adamantyl" and "adamantanyl" may be used interchangeably. Unless otherwise indicated, "C m -C y " refers to the corresponding moiety containing the total number of carbon atoms from m to y. Thus, examples of "C 2 -C 40 substituted hydrocarbyl" without further definition include one or more heteroatom-containing groups containing additional carbon (e.g., -NR * 2 , -OR * , -SeR * , -TeR * , -PR * 2 , -AsR * 2 , -SbR * 2 , -SR * , -BR * 2 , -SiR * 3 , -GeR * 3 , -SnR * 3 , -PbR * 3 ) and are further substituted by C1 It can contain a hydrocarbyl group, and thus the resulting substituted hydrocarbyl moiety contains a total of 2 to 40 carbon atoms. As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, Mz is the z average molecular weight, mass % is the mass percentage, and mol % is the mole percentage. The molecular weight distribution (MWD), also referred to as the polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol.

[0022] Unless otherwise indicated, as used herein, "high molecular weight" is defined as a number average molecular weight (Mn) value of 100,000 g / mol or greater. "Low molecular weight" is defined as an Mn value of less than 100,000 g / mol. Unless otherwise specified, all melting points (Tm) are the second melting point of differential scanning calorimetry (DSC).

[0023] The "catalyst system" is a combination consisting of at least one catalyst compound, at least one activator, an optional co-activator, and an optional support material. The terms "catalyst compound", "catalyst complex", "transition metal complex", "transition metal compound", "pre-catalyst compound", and "pre-catalyst complex" are used interchangeably. When the "catalyst system" is used to describe such a pair before activation, the "catalyst system" means an unactivated catalyst complex (pre-catalyst) together with an activator, which may be together with a co-activator. When the "catalyst system" is used to describe such a pair after activation, the "catalyst system" means an activated complex and an activator or a moiety that balances other charges. The transition metal compound may be neutral as in the pre-catalyst or a charged chemical species containing a counterion as in the activated catalyst system. For the purposes of the present disclosure and its claims, when the catalyst system is described as including the neutral stable form of the components, it is well understood by those skilled in the art that the ionic form of the components is in a form that reacts with the monomer to produce a polymer. A polymerization catalyst system is a catalyst system capable of polymerizing a monomer into a polymer. Further, the catalyst compounds and activators represented by the formulas herein are intended to include both the neutral and ionic forms of the catalyst compounds and activators.

[0024] In the description herein, the catalyst may be described as a catalyst, a catalyst precursor, a pre-catalyst compound, a catalyst compound, or a transition metal compound, and these terms are used interchangeably. The term "anionic ligand" refers to a negatively charged ligand that donates one or more pairs of electrons to a metal ion. The term "Lewis base" refers to a neutrally charged ligand that donates one or more pairs of electrons to a metal ion. Examples of Lewis bases include diethyl ether, trimethylamine, pyridine, tetrahydrofuran, dimethyl sulfide, and triphenylphosphine. The term "heterocyclic Lewis base" refers to a Lewis base that is also a heterocycle. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan. A bis(arylphenolate) Lewis base ligand is a tridentate ligand that binds to a metal through two anionic donors (phenolate) and one heterocyclic Lewis base donor (e.g., a pyridinyl group). A bis(arylphenolate) heterocyclic ligand is a tridentate ligand that binds to a metal through two anionic donors (phenolate) and one heterocyclic Lewis base donor. The term "continuously" means a system that operates without interruption or stoppage. For example, a continuous process for producing a polymer is one in which reactants are continuously introduced into one or more reactors and the polymer product is continuously withdrawn.

[0025] Transition metal complex In at least one embodiment, the catalyst compound represented by formula (I) is as follows. [Chemical formula] (I) (wherein M is a metal of Group 3, 4, or 5; L is a Lewis base; X is an anionic ligand; n is 1, 2, or 3; m is 0, 1, or 2; n + m is 4 or less; R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R7 and R 8 each independently is hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 R 2 and R 3 R 3 and R 4 R 5 and R 6 R 6 and R 7 or R 7 and R 8 one or more of which may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring or an unsubstituted heterocyclic ring, each having 5, 6, 7 or 8 ring atoms, R 9 R 10 R 11 and R 12 each independently is hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 9 and R 10 R 10 and R 11 or R 11 and R 12 one or more of which may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring or an unsubstituted heterocyclic ring, each having 5, 6, 7 or 8 ring atoms, R 13 R 14 R 15 and R 16 each independently is hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40is a substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R 13 and R 14 , R 14 and R 15 or R 15 and R 16 one or more of which may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring or an unsubstituted heterocyclic ring, each having 5, 6, 7 or 8 ring atoms, R 17 , R 18 and R 19 are each, independently, hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 a substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 or R 17 and R 19 one or more of which may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring or an unsubstituted heterocyclic ring, each having 5, 6, 7 or 8 ring atoms, Any two L groups may be joined together to form a bidentate Lewis base, The X group may be attached to the L group to form a monoanionic bidentate group, Any two X groups may be joined together to form a dianionic ligand, Provided that at least one of R 17 , R 18 and R 19 contains at least 2 or more saturated or unsaturated carbon atoms)

[0026] For example, M in formula (I) can be a Group 3, Group 4 or Group 5 metal, for example, M can be a Group 4 metal. Group 4 metals can include zirconium, titanium, and hafnium. In at least one embodiment, M is zirconium or hafnium.

[0027] Each L in formula (I) can be independently selected from ether, amine, phosphine, thioether, ester, Et 2 O, MeOtBu, Et 3 N, PhNMe 2 , MePh 2 N, tetrahydrofuran, and dimethyl sulfide, and each X can be independently selected from methyl, benzyl, trimethylsilyl, methyl(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydride, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate ion, dimethylamide, diethylamide, dipropylamide, and diisopropylamide. In at least one embodiment, n in formula (I) is 2, and each X is independently chloro, benzyl, or methyl.

[0028] R in formula (I) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 can each be independently selected from hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, hydrocarbyloxy, trihydrocarbylsilyl, trihydrocarbylgermyl, dihydrocarbylamino, dihydrocarbylphosphino, or halogen, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6and R 7 or R 7 and R 8 One or more of them may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring or an unsubstituted heterocyclic ring, each having 5, 6, 7 or 8 ring atoms.

[0029] For example, R 4 and R 5 in formula (I) can independently be C 1 -C 20 alkyl, for example, R 4 and R 5 can be tert-butyl or adamantanyl. In at least one embodiment, R 4 and R 5 are independently selected from unsubstituted phenyl, substituted phenyl, unsubstituted carbazole, substituted carbazole, unsubstituted naphthyl, substituted naphthyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted fluorenyl or substituted fluorenyl, a heteroatom or a heteroatom-containing group, for example, R 4 and R 5 can independently be unsubstituted phenyl or 3,5-di-tert-butylbenzyl. Further, (1) R 4 can be C 1 -C 20 alkyl (for example, R 4 can be tert-butyl), R 5 can be aryl, or (2) R 5 can be C 1 -C 20 alkyl (for example, R 5 can be tert-butyl) and R 4 can be aryl, either one of them. Alternatively, R 4 and / or R 5 can independently be a heteroatom, for example, R 4 and R 5can be a halogen atom (e.g., Br, Cl, F or I). Alternatively, R 4 and / or R 5 can independently be a silyl group. For example, R 4 and R 5 can be a trialkylsilyl group or a triarylsilyl group, where alkyl is C 1 ~C 30 alkyl (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl, cyclopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., iso-amyl, cyclopentyl), hexyl (e.g., cyclohexyl), octyl (e.g., cyclooctyl), nonyl, decyl (e.g., adamantanyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or tricontyl), and aryl is C 6 ~C 30 aryl (e.g., phenyl, benzyl and naphthyl). Advantageously, R 4 and R 5 can be triethylsilyl.

[0030] In some embodiments, R 4 and R 5 are each independently C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, and more preferably, R 4 and R 5are each independently selected from a tertiary hydrocarbyl group (e.g., tert-butyl, tert-pentyl, tert-hexyl, tert-heptyl, tert-octyl, tert-nonyl, tert-decyl, tert-undecyl, tert-dodecyl) and a cyclic tertiary hydrocarbyl group (e.g., 1-methylcyclohexyl, 1-norbornyl, 1-adamantanyl or substituted 1-adamantanyl).

[0031] In some embodiments, R 4 and R 5 are each independently a C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, and more preferably, R 4 and R 5 are each independently a non-aromatic cyclic alkyl group (e.g., cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, adamantanyl, norbornyl or 1-methylcyclohexyl or substituted adamantanyl), most preferably a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, 1-adamantanyl, substituted 1-adamantanyl or 1-norbornyl). In some embodiments, R 4 and R 5 are adamantanyl. R 4 and R 5 can be used to control the molecular weight of the polymer product. For example, when one or both of R 4 and R 5 is tert-butyl, a high molecular weight polymer can be obtained with this catalyst compound. In contrast, when R 4 , R 5 , or R 4 and R 5 is phenyl, a low molecular weight polymer can be obtained with this catalyst compound.

[0032] In at least one embodiment, R 2 and R 7 of formula (I) are each independently a C 1 -C10 is alkyl, for example, R 2 and R 7 are, independently, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dimethyl-pentyl, tert-butyl, isopropyl or their isomers. R of formula (I) 1 、R 3 、R 6 、R 8 、R 9 、R 11 、R 12 、R 13 、R 15 、R 16 、R 17 、R 18 and R 19 are each, independently, hydrogen or C 1 -C 10 alkyl can be, for example, R 1 、R 3 、R 6 、R 8 、R 9 、R 11 、R 12 、R 13 、R 15 、R 16 、R 17 、R 18 and R 19 are, independently, hydrogen, methyl, ethyl, propyl or isopropyl. In at least one embodiment, R 1 、R 3 、R 6 、R 8 、R 9 、R 11 、R 12 、R 13 、R 15 and R 16 are hydrogen. Alternatively, R of formula (I) 1 、R 3 、R 6 、R 8 、R 9 、R 11 、R 12 、R 13 、R 15 and R 16can each independently be hydrogen, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy or trimethylsilyl.

[0033] In some embodiments, R 17 , R 18 or R 19 is at least one of C 2 -C 40 hydrocarbyl, C 2 -C 40 substituted hydrocarbyl or C 2 -C 40 heteroatom-containing group containing one or more heteroatoms. In some embodiments, R 17 , R 18 or R 19 is at least one of C 2 -C 40 hydrocarbyl, C 2 -C 40 substituted hydrocarbyl or C 2 -C 40 heteroatom-containing group containing one or more heteroatoms, and R 17 、 R 18 or R 19 is at least one of hydrogen. In some embodiments, one of R 17 , R 18 or R 19 is C 2 -C 40 hydrocarbyl, C 2 -C 40 substituted hydrocarbyl or C 2 -C 40 heteroatom-containing group containing one or more heteroatoms, and two of R 17 , R 18 or R 19 are hydrogen. In some embodiments, R 18 is C 2 -C 40 hydrocarbyl, C 2 -C 40A substituted hydrocarbyl or a C containing one or more heteroatoms 2 -C 40 is a heteroatom-containing group, and R 17 and R 19 are hydrogen.

[0034] In some embodiments, one of R 17 or R 19 is a C 2 -C 40 hydrocarbyl, a C 2 -C 40 substituted hydrocarbyl or a C containing one or more heteroatoms 2 -C 40 heteroatom-containing group, R 18 is hydrogen, and one of R 17 or R 19 is hydrogen.

[0035] In some embodiments, R 17 and R 19 are independently a C 2 -C 40 hydrocarbyl, a C 2 -C 40 substituted hydrocarbyl or a C containing one or more heteroatoms 2 -C 40 heteroatom-containing group, and R 18 is hydrogen.

[0036] In some embodiments, at least one of R 17 , R 18 or R 19 is a moiety containing at least two or more saturated or unsaturated carbon atoms, for example, a C 2 -C 40Hydrocarbyl (e.g., ethyl, ethenyl, propyl (e.g., n-propyl, isopropyl, cyclopropyl), propenyl, propynyl, butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), butenyl, butynyl, pentyl (e.g., iso-amyl, cyclopentyl), pentenyl, pentynyl, hexyl (e.g., cyclohexyl), hexenyl, hexynyl, heptyl, heptenyl (hepentyl), heptynyl, octyl (e.g., cyclooctyl), octenyl, octynyl, nonyl, nonenyl, nonynyl, decyl (e.g., adamantanyl), decenyl, decynyl, undecyl, undecenyl, undecynyl, dodecyl, dodecenyl, dodecynyl, tridecyl, tridecenyl, tridecynyl, tetradecyl, tetradecenyl, tetradecynyl, pentadecyl, pentadecenyl, pentadecynyl, hexadecyl, hexadecenyl, hexadecynyl, heptadecyl, heptadecenyl, heptadecynyl, octadecyl, octadecenyl, octadecynyl, nonadecyl, nonadecenyl, nonadecynyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, tricontyl and their isomers), C 2 -C 40 substituted hydrocarbyl or C containing one or more heteroatoms 2 -C 40 heteroatom-containing group (e.g., hydrocarbyloxy, trihydrocarbylsilyl, trihydrocarbylgermyl, dihydrocarbylamino, dihydrocarbylphosphino).

[0037] In some embodiments, at least one of R 17 , R 18 and R 19 contains a moiety having at least three non-hydrogen atoms, e.g., C 3 -C 40Hydrocarbyl (e.g., propyl (e.g., n-propyl, isopropyl, cyclopropyl), propenyl, propynyl, butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), butenyl, butynyl, pentyl (e.g., iso-amyl, cyclopentyl), pentenyl, pentynyl, hexyl (e.g., cyclohexyl), hexenyl, hexynyl, heptyl, heptenyl (hepentyl), heptynyl, octyl (e.g., cyclooctyl), octenyl, octynyl, nonyl, nonenyl, nonynyl, decyl (e.g., adamantanyl), decenyl, decynyl, undecyl, undecenyl, undecynyl, dodecyl, dodecenyl, dodecynyl, tridecyl, tridecenyl, tridecynyl, tetradecyl, tetradecenyl, tetradecynyl, pentadecyl, pentadecenyl, pentadecynyl, hexadecyl, hexadecenyl, hexadecynyl, heptadecyl, heptadecenyl, heptadecynyl, octadecyl, octadecenyl, octadecynyl, nonadecyl, nonadecenyl, nonadecynyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, tricontyl and their isomers), C 2 -C 40 Substituted hydrocarbyl (e.g., hydrocarbylene trihydrocarbylsilane, hydrocarbylene trihydrocarbylgermane, (dihydrocarbylamino)hydrocarbylene, (dihydrocarbylphosphino)hydrocarbylene, (hydrocarbyloxy)hydrocarbylene, (hydrocarbylthio)hydrocarbylene) or C containing one or more heteroatoms 2 -C 40 Heteroatom-containing group (e.g., hydrocarbyloxy, trihydrocarbylsilyl, trihydrocarbylgermyl, dihydrocarbylamino, dihydrocarbylphosphino).

[0038] In some embodiments, R 17 、R 18 or R 19At least one of them contains a moiety having at least two or more saturated carbon atoms, for example, propyl (e.g., n-propyl, isopropyl, cyclopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., iso-amyl, cyclopentyl), hexyl (e.g., cyclohexyl), heptyl, octyl (e.g., cyclooctyl), nonyl, decyl (e.g., adamantanyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, tricontyl and their isomers.

[0039] In some embodiments, R 17 , R 18 or R 19At least one of them is a moiety containing at least two or more partially unsaturated carbon atoms, such as propenyl (e.g., n-propenyl), butenyl (e.g., n-butenyl), pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icosanyl, henicosanyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, tricontenyl, propynyl (e.g., n-propynyl), butynyl (e.g., n-butynyl), pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, icosynyl, henicosynyl, docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, tricontynyl, butadienyl, pentadienyl, hexadienyl, heptadienyl, octadienyl, nonadienyl, decadienyl, undecadienyl, dodecadienyl, substituted phenyl (e.g., methylphenyl, ethylphenyl, propyphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, dodecylphenyl, undecylphenyl and dodecylphenyl) and their isomers.

[0040] In some embodiments, R 17 , R 18 or R 19 At least one of them includes, but is not limited to, C 2 -C 40A substituted hydrocarbyl: a hydrocarbylene trihydrocarbylsilane (e.g., methylene trimethylsilane, methylene triethylsilane, methylene tripropylsilane, methylene tributylsilane, methylene tripentylsilane, methylene trihexylsilane, methylene dimethylbutylsilane, ethylene trimethylsilane, ethylene triethylsilane, ethylene tripropylsilane, ethylene tributylsilane, ethylene tripentylsilane, ethylene trihexylsilane, ethylene dimethylbutylsilane, and their isomers), a hydrocarbylene trihydrocarbylgermane (e.g., methylene trimethylgermane, methylene triethylgermane, methylene tripropylgermane, methylene tributylgermane, methylene tripentylgermane, methylene trihexylgermane, methylene dimethylbutylgermane, ethylene trimethylgermane, ethylene triethylgermane, ethylene tripropylgermane, ethylene tributylgermane, ethylene tripentylgermane, ethylene trihexylgermane, ethylene dimethylbutylgermane, and their isomers), a (di hydrocarbylamino) hydrocarbylene (e.g., (dimethylamino)methylene, (diethylamino)methylene, (dipropylamino)methylene, (dibutylamino)methylene, (dipentylamino)methylene, (dihexylamino)methylene, (diheptylamino)methylene, (dioctylamino)methylene, (dinonylamino)methylene, (didecylamino)methylene, (diundecylamino)methylene, (didodecylamino)methylene, (methyethylamino)methylene, (dimethylamino)ethylene, (diethylamino)ethylene, (dipropylamino)ethylene, (dibutylamino)ethylene, (dipentylamino)ethylene, (dihexylamino)ethylene, (diheptylamino)ethylene, (dioctylamino)ethylene, (dinonylamino)ethylene, (didecylamino)ethylene, (diundecylamino)ethylene, (didodecylamino)ethylene, (methyethylamino)ethylene, imidazolidin - 1 - yl, imidazol - 1 - yl, 1,5 - diazabicyclo[3.2.1] Octan-8-yl and their isomers), (dihydrocarbylphosphino)hydrocarbylene (e.g., (dimethylphosphino)methylene, (diethylphosphino)methylene, (dipropylphosphino)methylene, (dibutylphosphino)methylene, (dipentyl)phosphinomethylene, (dihexylphosphino)methylene, (diheptylphosphino)methylene, (dioctylphosphino)methylene ((dioctyphosphino)methylene), (dinonylphosphino)methylene, (didecylphosphino)methylene, (diundecylphosphino)methylene, (didodecylphosphino)methylene, (dimethylphosphino)ethylene, (diethylphosphino)ethylene, (dipropylphosphino)ethylene, (dibutylphosphino)ethylene, (dipentyl)phosphinoethylene, (dihexylphosphino)ethylene, (diheptylphosphino)ethylene, (dioctylphosphino)ethylene ((dioctyphosphino)ethylene), (dinonylphosphino)ethylene, (didecylphosphino)methylene, (diundecylphosphino)ethylene, (didodecylphosphino)ethylene and their isomers), (hydrocarbyloxy)hydrocarbylene (e.g., methoxymethylene, ethoxymethylene, propoxymethylene, butoxymethylene, pentoxymethylene, hexoxymethylene, heptoxymethylene, octoxymethylene, nonoxymethylene, decoxymethylene, undecoxymethylene, dodecoxymethylene, methoxyethylene, ethoxyethylene, propoxyethylene, butoxyethylene, pentoxyethylene, hexoxyethylene, heptoxyethylene, octoxyethylene, nonoxyethylene, decoxyethylene, undecoxyethylene, dodeoxyethylene, (phenoxy)methylene, (toloxy)methylene, (ethylphenoxy)methylene, (propylphenoxy)methylene, (butylphenoxy)methylene, (pentylphenoxy)methylene, (hexylphenoxy)methylene, 2,6,7-trioxabicyclo[2.2.2]octan-1-yl, 4-methyl-2,6,7-trioxabicyclo[2.2.2) octan-1-yl and their isomers), (hydrocarbylthio)hydrocarbylene (e.g., (methylthio)methylene, (ethylthio)methylene, (propylthio)methylene, (butylthio)methylene, (pentylthio)methylene, (hexylthio)methylene, (heptylthio)methylene, (octylthio)methylene, (nonylthio)methylene, (decylthio)methylene, (dodecylthio)methylene, (methylthio)ethylene, (ethylthio)ethylene, (propylthio)ethylene, (butylthio)ethylene, (pentylthio)ethylene, (hexylthio)ethylene, (heptylthio)ethylene, (octylthio)ethylene, (nonylthio)ethylene, (decylthio)ethylene, (dodecylthio)ethylene and their isomers).

[0041] In some embodiments, R 17 , R 18 or R 19 of which at least one contains one or more heteroatoms including but not limited to C 2 -C 40Heteroatom-containing groups: Hydrocarbyloxy (e.g., ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, phenoxy, and substituted phenoxy, e.g., phenoxy-4-(2,4,4-trimethylpentan-2-yl), and (1R,2S,5R)-2-isopropyl-5-methylcyclohexan-1-oxy and their isomers), hydrocarbylthio (e.g., ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio, undecylthio, dodecylthio, phenylthio, substituted phenylthio and their isomers), trihydrocarbylsilyl (e.g., trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, trinonylsilyl, tridecylsilyl, dimethyloctylsilyl, butyldimethylsilyl (including tert-butyldimethylsilyl, n-butyldimethylsilyl) and their isomers), trihydrocarbylgermyl (e.g., trimethylgermyl, triethylgermyl, tripropylgermyl, tributylgermyl, trihexylgermyl, triheptylgermyl, trioctylgermyl, trinonylgermyl, tridecylgermyl, dimethyloctylgermyl, butyldimethylgermyl and their isomers), dihydrocarbylamino (e.g., dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino, methylethylamino, pyrrolidinyl, piperidinyl and their isomers) and dihydrocarbylphosphino (e.g., dimethylphosphino, diethylphosphino, dipropylphosphino, dibutylphosphino, dipentylphosphino, dihexylphosphino, methylethylphosphino, phosphoranyl, phosphinanyl and their isomers).

[0042] In some embodiments of formula (I), R 4 and R 5 can be adamantanyl or substituted adamantanyl, R 2 and R7 is C 1 -C 20 which can be hydrocarbyl, R 1 , R 3 , R 6 , R 8 , R 9 , R 11 , R 12 , R 13 , R 15 , R 16 , R 17 and R 19 are hydrogen, and R 18 is C 2 -C 40 hydrocarbyl, C 2 -C 40 substituted hydrocarbyl or C containing one or more heteroatoms 2 -C 40 heteroatom-containing group. In some embodiments of formula (I), R 4 and R 5 can be adamantanyl or substituted adamantanyl, and R 2 and R 7 are C 1 -C 20 which can be hydrocarbyl, and R 1 , R 3 , R 6 , R 8 , R 9 , R 11 , R 12 , R 13 , R 15 , R 16 and R 18 are hydrogen, and one of R 18 and R 19 is C 2 -C 40 hydrocarbyl, C 2 -C 40 substituted hydrocarbyl or C containing one or more heteroatoms 2 -C 40 heteroatom-containing group, and the other of R 18 and R 19 is hydrogen.

[0043] In some embodiments of formula (I), R 4 and R 5 can be adamantanyl or substituted adamantanyl, and R 2 and R 7 can be C 1 -C 20 hydrocarbyl, and R 1 , R 3 , R 6 , R 8 , R 9 , R 11 , R 12 , R 13 , R 15 , R 16 and R 18 are hydrogen, and R 18 and R 19 are independently C 2 -C 40 hydrocarbyl, C 2 -C 40 substituted hydrocarbyl or C 2 -C 40 heteroatom-containing group containing one or more heteroatoms. In some embodiments, R 18 is C 2 -C 40 hydrocarbyl, C 2 -C 40 substituted hydrocarbyl or C 2 -C 40 heteroatom-containing group containing one or more heteroatoms.

[0044] In some embodiments, R 18 is a linear chain having a length of at least 3 non-hydrogen atoms and having a terminal bonded to pyridine. In some embodiments, R 17 is C 2 -C 40 hydrocarbyl, C 2 -C 40 substituted hydrocarbyl or C 2 -C 40 heteroatom-containing group containing one or more heteroatoms. In some embodiments, R 17It contains a linear chain with at least 3 non-hydrogen atoms in length and a terminal bonded to pyridine. In some embodiments, R 19 is C 2 -C 40 hydrocarbyl, C 2 -C 40 substituted hydrocarbyl or C containing one or more heteroatoms 2 -C 40 heteroatom-containing group.

[0045] In some embodiments, R 19 is a linear chain with at least 3 non-hydrogen atoms in length and a terminal bonded to pyridine.

[0046] In some embodiments, R 18 is not methyl, methoxy or trifluoromethyl. In at least one embodiment, the catalyst compound is

Chemical formula

[0047] In at least one embodiment, one or more various catalyst compounds are present in the catalyst system. One or more various catalyst compounds can be present in the reaction zone where the methods described herein are carried out. The same activator can be used for the transition metal compound, but two different activators such as non-coordinating anion activators and aluminoxanes can be used in combination.

[0048] Further exemplary embodiments of the industrial progress of the present invention include the following. R 4 and R 5 are adamantanyl, and R 18 is C2 -C 40 Hydrocarbyl, C 2 -C 40 Substituted hydrocarbyl or C containing one or more heteroatoms 2 -C 40 A composition of formula (I) which is a heteroatom-containing group. R 4 And R 5 Is adamantanyl, R 18 Is a composition of formula (I) containing a linear chain having a length of at least 3 non-hydrogen atoms and a terminal bonded to pyridine. R 4 And R 5 Is adamantanyl, R 18 Is of formula A(R a )(R b )(R c (wherein A is Si or Ge, and R a , R b And R c Are each independently C 1 -C 40 Hydrocarbyl or C 1 -C 40 Substituted hydrocarbyl, or one or more of R a And R b , R a And R c Or R b And R c May together form one or more substituted or unsubstituted hydrocarbyl rings) containing a silyl group or a germyl group of formula (I).

[0049] Exemplary embodiments of the industrial progress of the present invention may also be a homogeneous solution containing an aliphatic hydrocarbon solvent and a complex of formula (I), wherein the concentration of the complex is 0.20% by mass or more (alternatively 0.25% by mass or more, alternatively 0.30% by mass or more, alternatively 0.35% by mass or more, alternatively 0.40% by mass or more, alternatively 0.50% by mass or more, alternatively 1.0% by mass or more, alternatively 2.0% by mass or more). Without intending to be bound by theory, R 17 , R 18 And R19 In at least one of them, when there are at least two or more saturated or unsaturated carbon atoms, alone or R 4 and R 5 substituents and / or R 2 and R 7 in combination with substituents is considered to assist the solubility of the complex of formula (I) in an aliphatic solvent.

[0050] Another exemplary embodiment of the industrial progress of the present invention is a method for producing a propylene-based polymer, in one or more continuous stirred tank reactors or loop reactors in series or parallel, at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30 °C to 230 °C, contacting propylene and one or more optional C 3 -C 40 olefins with a catalyst system comprising the composition of formula (I) to polymerize propylene and one or more optional C 3 -C 40 olefins to form a propylene-based polymer. Another exemplary embodiment of the industrial progress of the present invention is a method for producing an ethylene-based polymer, in one or more continuous stirred tank reactors or loop reactors in series or parallel, at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30 °C to 230 °C, contacting ethylene and one or more optional C 4 -C 40 olefins with a catalyst system comprising the composition of formula (I) to polymerize ethylene and one or more optional C 4 -C 40 olefins to form a propylene-based or ethylene-based polymer.

[0051] Method for preparing a transition metal complex U.S. Patent Application No. 16 / 787,909 (Publication No. US2020 / 255553) describes a general method for preparing bis(phenolate) ligands and bis(phenolate) complexes that can be used in the industrial progress of the present invention. Synthesis of substituted pyridine precursors The preparation of the substituted pyridine precursor can include, but is not limited to, the method shown in Scheme 1. Such a substituted pyridine precursor may subsequently be used in the method for preparing the bis(phenolate) ligand described in U.S. Patent Application No. 16 / 787,909 (Publication No. US2020 / 255553). The formation of Compound B (Method 1) can be achieved by deprotonation of Compound A with a strong base such as lithium diisopropylamide (LDA) followed by the addition of a primary or secondary alkyl halide (R-X). The formation of Compound D or E (Method 2) can be achieved by the addition of M-OR’ or M-SR’ to Compound C, respectively, where M’ is a Group 1 element such as Na and R’ is a hydrocarbyl. The formation of Compound G (Method 3) can be achieved by the addition of a Turbo Grignard (e.g., isopropylmagnesium chloride lithium chloride complex) followed by the addition of a trihydrocarbylsilyl halide (R * 3 Si-X).

[0052] The formation of Compound I (where “aryl” refers to a substituted aryl moiety) by the coupling of Compound G with a substituted aryllithium compound (“aryllithium”) (Method 4) can be achieved by a known Pd-catalyzed coupling such as a Negishi coupling.

[0053] The formation of Compound J (Method 5) can be achieved by the addition of a nucleophile (e.g., diisopropylamide, substituted aryloxide) to Compound I. Scheme 1

Chemical formula

[0054] Activators and optional scavengers, co-activators and chain transfer agents U.S. Patent Application No. 16 / 788,088 (Publication No. US2020 / 254431) describes an activator, an optional scavenger, an optional co-activator, and an optional chain transfer agent that can be used due to the industrial progress of the present invention. In particular, useful activators are also non-aromatic hydrocarbon-soluble activator compounds, such as N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(pentafluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(heptafluoronaphthalenyl)borate], N-methyl-N-octadecyl-4-(octadecyloxy)anilinium [tetrakis(pentafluorophenyl)borate], N-methyl-N-octadecyl-4-(octadecyloxy)anilinium [tetrakis(heptafluoronaphthalenyl)borate], N,N-di(tallow)methylammonium [tetrakis(pentafluorophenyl)borate], N,N-di(tallow)methylammonium [tetrakis(heptafluoronaphthalenyl)borate], N,N-di(octadecyl)methylammonium [tetrakis(pentafluorophenyl)borate], N,N-di(octadecyl)methylammonium [tetrakis(heptafluoronaphthalenyl)borate], N,N-di(hexadecyl)methylammonium [tetrakis(pentafluorophenyl)borate], N,N-di(hexadecyl)methylammonium [tetrakis(heptafluoronaphthalenyl)borate], N-octadecyl-N-hexadecylmethylammonium [tetrakis(pentafluorophenyl)borate], and N-octadecyl-N-hexadecylmethylammonium [tetrakis(heptafluoronaphthalenyl)borate], as described in PCT Application No. US2020 / 044865 (Publication No. WO2021 / 086467), U.S. Patent Application No. 16 / 394,174 (published as US2019 / 0330394), and PCT Application No. US2019 / 029056 (published as WO2019 / 210026).

[0055] It is preferred to use an activator that is soluble in the non-aromatic hydrocarbon solvent, but an activator that has poor solubility or is insoluble in the non-aromatic hydrocarbon solvent can be used. When used, these activators can be fed to the reactor as a slurry or as a solid. Particularly useful activators in this class include triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, and the like.

[0056] A typical activator-to-catalyst ratio is a molar ratio of about 1:1. Alternative preferred ranges include 0.1:1 to 100:1, alternatively 0.5:1 to 200:1, alternatively 1:1 to 500:1, alternatively 1:1 to 1000:1. Particularly useful ranges are 0.5:1 to 10:1, preferably 1:1 to 1:10. Particularly useful optional scavengers or co-activators or chain transfer agents include, for example, trialkylaluminums such as triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and dialkylzincs such as diethylzinc. Further, hydrocarbon-soluble aluminoxanes and modified aluminoxanes "free of" trimethylaluminum can be used or may be used.

[0057] Furthermore, one of ordinary skill in the art can select suitable known activators and optional scavengers or co-activators or chain transfer agents for that particular purpose without undue experimentation. Combinations of multiple activators can be used. Similarly, combinations of multiple optional scavengers or co-activators or chain transfer agents may be used.

[0058] Solvent The catalyst constituent components of the present invention can be used together with an aromatic solvent such as toluene. Preferably, however, the catalyst constituent components are absent when used in the polymerization process. Solvents useful for dissolving the catalyst compound, the activator compound, or for combining the catalyst compound and the activator, and / or for introducing the catalyst system or any of their components into the reactor, and / or for use in the polymerization process, include, but are not limited to, aliphatic hydrocarbon solvents: butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, or combinations thereof. Preferred solvents can include normal paraffins (e.g., Norpar™ solvents available from ExxonMobil Chemical Company (Houston, TX)), isoparaffin solvents (e.g., Isopar™ solvents available from ExxonMobil Chemical Company (Houston, TX)), non-aromatic cyclic solvents (e.g., Nappar™ solvents available from ExxonMobil Chemical Company (Houston, TX)), and combinations thereof.

[0059] Preferably, the aliphatic hydrocarbon solvent is C 4 ~C 10 a linear, branched, or cyclic alkane. Alternatively, it is selected from C 5 ~C 8 linear, branched, or cyclic alkanes. Preferably, the aliphatic hydrocarbon solvent is substantially free of all aromatic solvents. Preferably, the solvent is substantially free of toluene. By "substantially free of all aromatic solvents such as toluene" is meant that the solvent contains substantially no aromatic solvents (e.g., present at 0 mol%, alternatively, present at less than 1 mol%), preferably the polymerization reaction and / or the resulting polymer contains no "detectable aromatic hydrocarbon solvents" such as toluene. Preferred aliphatic hydrocarbon solvents include, in addition to commercially available solvent mixtures such as Nappar6 (trademark) and IsoparE (trademark), isohexane, cyclohexane, methylcyclohexane, pentane, isopentane, heptane, and combinations thereof. However, one of ordinary skill in the art can select other suitable non-aromatic hydrocarbon solvents without undue experimentation. Highly preferred aliphatic hydrocarbon solvents include isohexane, methylcyclohexane, and commercially available solvent mixtures such as Nappar6 (trademark) and IsoparE (trademark). Regarding the testing of the solubility of the compound, preferred solvents include isohexane and methylcyclohexane.

[0060] Optional support material In embodiments herein, the catalyst system may include an inert support material. The support material can be a porous support material such as talc and inorganic oxides. U.S. Patent Application No. 16 / 788,088 (Publication No. US2020 / 0254431) describes optional support materials that can be used with the industrial progress of the present invention. Further, one of ordinary skill in the art can select a suitable known support for that particular purpose without undue experimentation.

[0061] Polymerization method The present disclosure relates to a polymerization method of contacting a monomer (e.g., ethylene; propylene) and optionally one or more comonomers (e.g., C 2 -C 20 alpha-olefin, C 4 -C 40 cyclic olefin, C 5 -C 20 non-conjugated diene) with a catalyst system comprising an activator and at least one of the above catalyst compounds. The catalyst compound and the activator may be combined together in any order. The catalyst compound and the activator may be combined together before contacting with the monomer. Alternatively, the catalyst compound and the activator may be introduced separately into the polymerization reactor, in which case they subsequently react to form an active catalyst. U.S. Patent Application No. 16 / 788,088 (Publication No. US2020 / 0254431) describes monomers that can be used by the industrial progress of the present invention and describes polymerization methods that can be used by the industrial progress of the present invention. Furthermore, a catalyst that is highly soluble in aliphatic hydrocarbon solvents may be used as a trim catalyst in well-known polymerization methods, such as those described in WO2015 / 123177 and WO2020 / 092587.

[0062] Blends and Films The polymers produced by the industrial progress of the present invention can be used to produce the blends and films described in U.S. Patent Application No. 16 / 788,088 (Application No. US2020 / 0254431) without undue experimentation. Examples

[0063] General Considerations Regarding Synthesis The following chemical substances may be abbreviated as shown, either in lowercase or by their initials. 1,2-dimethoxyethane (dme), ethyl ether (ether), tetrahydrofuran (thf), Celite, methylcyclohexane (MeCy), 1,4-dioxane (dioxane), hexamethyldisiloxane (hmdso), N,N-dimethylformamide (DMF), N-bromosuccinimide (NBS), n-butyllithium (BuLi). Room temperature is 23 °C unless otherwise specified.

[0064] Complexes 1, 2, and 3 (shown below) are comparative complexes. The following chemical substances may be abbreviated as shown, either in lowercase or by their initials. 1,2-dimethoxyethane (dme), ethyl ether (ether), tetrahydrofuran (thf), Celite, methylcyclohexane (MeCy), 1,4-dioxane (dioxane), hexamethyldisiloxane (hmdso).

[0065] Complex 1 (dimethylzirconium [2’,2’’’-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-methyl-[1,1’-biphenyl]-2-olate]) and 2 (dimethylzirconium [2’,2’’’-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1’-biphenyl]-2-olate]) were prepared as described in U.S. Patent Application Publication No. 2020 / 0255553. [Chemical Formula]

[0066] All reagents were purchased from commercial suppliers (Sigma Aldrich, Fisher Scientific, Oakwood Chemical or Combi-Blocks) and used as received unless otherwise specified. For solvents, N 2 was bubbled through and dehydrated over 3 Å molecular sieves. Lithium diisopropylamide (LDA) was prepared as described in Org. Synth. 1986, v.64, 68. 2,6-Dibromo-4-nitropyridine and 2,6-dibromo-4-(pyrrolidin-1-yl)pyridine were prepared as described in [Organic Letters, 2010, v.12(22), p. 5242 - 5245]. All chemical operations were carried out under a nitrogen atmosphere unless otherwise specified. Flash column chromatography was performed using the specified solvent system on Sigma Aldrich silica gel 60 Å (70 mesh - 230 mesh). All anhydrous solvents were purchased from Fisher Chemical, degassed and dehydrated over molecular sieves before use. Deuterated solvents were purchased from Cambridge Isotope Laboratories, degassed and dehydrated over molecular sieves before use. 1 1H NMR spectroscopic data were obtained on a C 6 D 6 、CD 2 Cl 2 、CDCl 3 、D 8-Obtained at 250 MHz, 400 MHz or 500 MHz using a solution prepared by dissolving approximately 10 mg of the sample in either toluene or another deuterated solvent. The chemical shifts (δ) shown are relative to the residual protium in the deuterated solvent at 7.15 ppm, 5.32 ppm, 7.24 ppm and 2.09 ppm for C 6 D 6 , CD 2 Cl 2 , CDCl 3 , D 8 -toluene, respectively.

[0067] Preparation of Catalyst Precursors and Ligands ZrCl 4 (ether) 2 . Dichloromethane (100 mL) and ZrCl 4 (10.0 g, 42.9 mmol) were combined to form a slurry. Ether (9.54 g, 129 mmol) was added dropwise over 60 minutes. The mixture was stirred for 1 hour. The insoluble solid was precipitated, and then the supernatant was decanted and filtered through celite on a fritted disk. The filtrate was evaporated to near dryness to obtain a slurry. Isohexane (60 mL) was added to this slurry, and the mixture was stirred thoroughly. The resulting off-white solid was collected on a frit, washed with isohexane, and dried under reduced pressure. Yield: 12.5 g, 76.6%.

[0068] 2-(2-(1-Adamantanyl)-4-tert-butylphenoxy)tetrahydro-2H-pyran

Chemical Structure

[0069] (3-(1-Adamantanyl)-5-(tert-butyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)lithium ether complex

Chemical formula

[0070] 2-((3-(1-adamantanyl)-2'-bromo-5-(tert-butyl)-[1,1'-biphenyl]-2-yl)oxy)tetrahydro-2H-pyran

Chemical formula

[0071] 4-(1-Adamantanyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinine

Chemical formula

[0072] Isopropanol (150 mL) was added to the resulting residue and the resulting solution was refluxed for 16 hours. After cooling the reaction to ambient temperature, the reaction was concentrated and cooled to -20 °C for 1 hour, and the product was obtained as a white solid (16.6 g, 80%), which was isolated by filtration. 1 H NMR (400 MHz, CDCl 3 ) δ 8.17 (d, J = 8.2 Hz, 1H), 8.09 - 8.02 (m, 2H), 7.65 (t, J = 8.0 Hz, 1H), 7.45 - 7.40 (m, 2H), 5.24 (p, J = 6.1 Hz, 1H), 2.30 (br, 6H), 2.16 (br, 3H), 1.84 (br, 6H), 1.43 - 1.39 (m, 15H).

[0073] 2’,2’’’-(Pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0074] 2’,2’’’-(4-Methylpyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0075] 2,6-Dibromo-4-ethylpyridine

Chemical Structure

[0076] 2’,2’’’-(4-Ethylpyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0077] 2,6-Dibromo-4-(ethylthio)pyridine

Chemical Structure

[0078] 2-(Adamantan-1-yl)-6-bromo-4-methylphenol

Chemical Structure

[0079] (1-(3-Bromo-5-methyl-2-(methoxymethoxy)phenyl)adamantane

Chemical Structure

[0080] 2-(3-Adamantan-1-yl)-5-methyl-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Chemical formula

[0081] 1-(2'-Bromo-5-methyl-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane [Chemical formula] To a solution of 10.0 g (24.3 mmol) of 2-(3-adamantan-1-yl)-5-methyl-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane in 1,4-dioxane (100 mL) were successively added 7.22 g (25.5 mmol) of 2-bromoiodobenzene, 8.38 g (60.6 mmol) of potassium carbonate and 50 mL of water. The resulting mixture was purged with argon for 10 minutes and then 1.40 g (1.21 mmol) of Pd(PPh 3 ) 4 was added. The mixture was stirred at 100 °C for 12 hours, then cooled to room temperature and diluted with 100 mL of water. The crude product was extracted with dichloromethane (3 × 150 mL), and the combined organic extracts were dehydrated with Na 2 SO 4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40 - 63 μm, eluent: hexane - dichloromethane = 10:1, v / v). Yield 10.7 g (quantitative) of a white solid. 1 1H NMR (CDCl 3 , 400 MHz): δ 7.72 (d, J = 7.9 Hz, 1H), 7.35 - 7.44 (m, 3H), 7.19 - 7.26 (m, 1H), 6.94 (m, 1H), 4.53 (dd, J = 20.0, 4.6 Hz, 2H), 3.24 (s, 3H), 2.38 (s, 3H), 2.23 (m, 6H), 2.15 (m, 3H), 1.84 (m, 6H). 1313C NMR (CDCl 3 , 100 MHz): δ 151.51, 142.78, 141.11, 134.63, 132.76, 132.16, 132.13, 129.83, 128.57, 127.76, 127.03, 124.05, 98.85, 56.95, 41.21, 37.18, 36.94, 29.07, 21.00.

[0082] 4-((3r,5r,7r)-Adamantan-1-yl)-6-isopropoxy-2-methyl-6H-dibenzo[c,e][1,2]oxaborinine

Chemical Structure

[0083] 2’,2’’’-(4-(Ethylthio)pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-methyl-[1,1’-biphenyl]-2-ol) [Chemical Structure] To a solution of 770 mg (2.00 mmol) of 4-((3r,5r,7r)-adamantan-1-yl)-6-isopropoxy-2-methyl-6H-dibenzo[c,e][1,2]oxaborinine in 1,4-dioxane (5 mL) were successively added 290 mg (0.98 mmol) of 2,6-dibromo-4-(ethylthio)pyridine, 1.63 g (5.00 mmol) of cesium carbonate, and 3 mL of water. The resulting mixture was purged with argon for 1 minute, and then 112 mg (0.10 mmol) of Pd(PPh 3 ) 4was added. This mixture was stirred at 100 °C for 12 h, then cooled to room temperature and diluted with 50 mL of water. The mixture thus obtained was extracted with dichloromethane (3 × 50 mL), and the combined organic extracts were dried over Na 2 SO 4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40 - 63 μm, eluent: hexane - dichloromethane = 1:1, v / v). Yield 580 mg (77%) as a mixture of two isomers as a colorless glassy solid. 1 1H NMR (CDCl 3 , 400 MHz): δ 7.65 (s, 1H), 7.58 - 7.62 (m, 2H), 7.45 - 7.51 (m, 4H), 7.32 - 7.41 (m, 3H), 6.92 (s, 1H), 6.86 - 6.88 (m, 2H), 6.79 - 6.81 (m, 2H), 6.21 (s, 1H), 2.41 - 2.70 (m, 2H), 2.26 (s, 3H), 2.00 (s, 3H), 1.57 - 1.98 (m, 30H), 1.14 - 1.20 (m, 3H). 13 13C NMR (CDCl 3 , 100 MHz) δ 157.3, 157.2, 151.3, 150.3, 150.2, 149.7, 139.5, 138.3, 138.0, 137.9, 137.6, 137.5, 132.4, 131.3, 130.4, 130.2, 130.15, 129.5, 129.0, 128.8, 128.6, 127.83, 127.76, 127.0, 126.7, 119.6, 118.6, 40.5, 40.1, 37.09, 37.03, 36.83, 36.75, 36.5, 29.1, 29.0, 25.0, 24.6, 20.8, 20.6, 13.6, 13.4.

[0084] 2,6 - Dichloro - 4 - butylpyridine

Chemical Structure

[0085] 2’,2’’’-(4-Butylpyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol) [Chemical formula] To a solution of 4-(1-adamantanyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinine (2.97 g, 6.39 mmol) in 1,4-dioxane (20 mL) were successively added 2,6-dichloro-4-butylpyridine (0.69 g, 3.38 mmol), cesium carbonate (6.61 g, 20.2 mmol), Buchwald RuPhos precatalyst, 1st generation (Strem, CAS 1028206-60-1, 60.0 mg, 0.08 mmol), and water (10 mL). The reaction mixture was stirred at 100 °C for 16 h, then cooled to ambient temperature and diluted with water (30 mL). The resulting mixture was diluted with hexane (20 mL). After separating the two phases, the aqueous phase was extracted with dichloromethane (2 × 50 mL). The combined organic extracts were dried over MgSO 4 and filtered through a small amount of silica gel, then concentrated in vacuo to dryness. The crude product was dissolved in hexane, followed by the addition of ethanol (100 mL). The solution was concentrated at 40 °C under reduced pressure and then cooled to ambient temperature. The precipitate was isolated as an ethanol adduct, which was dissolved in toluene and concentrated to dryness to remove all the ethanol. The product was isolated as a mixture of two isomers (1.95 g, 35%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.29 (s, 2H in A), 7.59 - 7.35 (m, 8H), 6.94 (s, 2H in B), 6.80 (s, 2H in B), 6.75 (m), 6.56 - 6.53 (s, 2H), 2.35 - 2.19 (m, 2H), 2.06 - 1.85 (m, 18H), 1.66 (br, 12H), 1.25 - 1.17 (m, 4H), 1.17 (s, 9H in B), 1.00 (s, 9H in A), 0.86 (t, J = 6.8 Hz, 3H).

[0086] 2,6-Dichloro-4-((tert-butyldimethylsilyl)methyl)pyridine

Chemical Structure

[0087] 2’,2’’’-(4-((tert-Butyldimethylsilyl)methyl)pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0088] 2,6-Dichloro-4-((triethylsilyl)methyl)pyridine

Chem.

[0089] 2’,2’’’-(4-((Triethylsilyl)methyl)pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0090] 2,6-Dichloro-4-((trihexylsilyl)methyl)pyridine

Chemical Structure

[0091] 2’,2’’’-(4-((Trihexylsilyl)methyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0092] 2’,2’’’-(4-(Pyrrolidin-1-yl)pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-methyl-[1,1’-biphenyl]-2-ol) [Chemical formula] To a solution of 2.00 g (5.18 mmol) of 4-((3r,5r,7r)-adamantan-1-yl)-6-isopropoxy-2-methyl-6H-dibenzo[c,e][1,2]oxaborinine in 1,4-dioxane (13 mL) were successively added 792 mg (2.59 mmol) of 2,6-dibromo-4-(pyrrolydin-1-yl)pyridine, 4.22 g (12.9 mmol) of cesium carbonate and 7 mL of water. The resulting mixture was purged with argon for 10 minutes and then 299 mg (0.260 mmol) of Pd(PPh 3 ) 4 was added. The mixture was stirred at 100 °C for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The mixture thus obtained was extracted with dichloromethane (3 × 50 mL), and the combined organic extracts were dried over Na 2 SO 4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40 - 63 μm, eluent: hexane - ethyl acetate = 10:1, v / v). The resulting glassy solid was triturated with 30 mL of n-pentane, and the precipitate thus obtained was filtered off (G3), washed with 2 × 10 mL of n-pentane and dried in vacuo. Yield 990 mg (47%) of a mixture of two isomers as a white powder. 1 1H NMR (CDCl 3, 400 MHz): δ 8.65 (br.s, 2H in B), 8.21 (br.s, 2H in A), 7.64 - 7.66 (m, 2H in A), 7.57 - 7.59 (m, 2H in B), 7.40 - 7.49 (m, 4H in A, 4H in B), 7.26 - 7.34 (m, 2H in A, 2H in B), 6.84 - 6.89 (m, 3H in A, 3H in B), 6.27 (s, 2H in B), 6.06 (s, 2H in A), 5.99 (s, 2H in A), 2.95 - 3.10 (m, 4H in A), 2.80 - 2.93 (m, 4H in B), 2.24 (s, 6H in A), 2.00 (s, 6H in B), 1.50 - 1.99 (m, 30H in A, 30H in B). 13 C NMR (CDCl 3 , 100 MHz) δ 157.25, 157.18*, 150.6, 150.2*, 140.3*, 139.1, 138.1*, 137.9, 137.7, 137.6*, 132.2, 131.4*, 130.8*, 130.1, 130.0, 129.1, 129.0, 128.98, 128.4*, 128.3 128.2*, 127.5, 127.4*, 126.5, 126.3*, 105.9*, 105.7, 47.0*, 46.7, 40.5*, 40.1, 37.0*, 36.8, 36.7*, 36.4, 29.1, 29.0, 25.33, 25.27, 25.0*, 20.8, 20.6*.

[0093] 2,6-Dichloro-4-(tert-butoxy)pyridine

Chemical Structure

[0094] 2’,2’’’-(4-(tert-Butoxy)pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical formula

[0095] 2,6-Dichloro-4-(3-butenyl)pyridine

Chemical formula

[0096] 2’,2’’’-(4-(3-Butenyl)pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0097] 2,6-Dichloro-4-propylpyridine

Chemical formula

[0098] 2’,2’’’-(4-Propylpyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0099] 2,6-Dichloro-4-(tert-butyldimethylsilyl)pyridine

Chemical Structure

[0100] 2’,2’’’-(4-(tert-Butyldimethylsilyl)pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0101] 2,6-Dichloro-4-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)pyridine

Chemical Structure

[0102] 2’,2’’’-(4-(4-(2,4,4-Trimethylpentan-2-yl)phenoxy)pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol) [Chemical Structure] To a solution of 4-(1-adamantanyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinine (0.584 g, 1.36 mmol) in 1,4-dioxane (6 mL) were successively added 2,6-dichloro-4-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)pyridine (0.240 g, 0.68 mmol), cesium carbonate (1.33 g, 4.09 mmol), Buchwald RuPhos palladacycle second generation precatalyst (Strem, CAS 1375325-68-0, 20.0 mg, 0.03 mmol), and water (3 mL). The reaction mixture was stirred at 100 °C for 16 h, then cooled to ambient temperature and diluted with water (10 mL). The resulting mixture was diluted with hexane (10 mL). After separating the two phases, the aqueous phase was extracted with dichloromethane (2 × 10 mL). The combined organic extracts were dried over MgSO 4 and then concentrated in vacuo. Purification by flash chromatography on silica gel (50% dichloromethane in hexane) gave the product (0.637 g, 93.4%) as a mixture of two isomers. 1 H NMR (400 MHz, CDCl 3 ) δ 8.24 (s, 2H in A), 7.45 - 7.30 (m, 10H), 7.08 (s, 2H), 6.95 (s, 2H in B), 6.86 - 6.77 (m, 2H), 6.62 (s, 2H in B), 6.59 (s, 2H in A), 6.54 (s, 2H), 1.97 - 1.79 (m, 18H), 1.75 - 1.55 (m, 14H), 1.36 (br, 6H), 1.16 (s, 18H in B), 1.08 (s 18H in A), 0.71 (s, 9H).

[0103] 4-(tert-Butyl)thio-2,6-dichloropyridine

Chem.

[0104] 2’,2’’’-(4-tert-Butyl)thiopyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chem.

[0105] 4-(butylthio)-2,6-dichloropyridine

Chemical Structure

[0106] 2’,2’’’-(4-(Butylthio)-pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical formula

[0107] Lithium dodecaneethiolate

Chemical Structure

[0108] 2,6-Dichloro-4-dodecylthio-pyridine

Chemical Structure

[0109] 2’,2’’’-(4-(Dodecylthio)-pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0110] 4-(4-(tert-Butyl)phenyl)-2,6-dichloropyridine

Chem.

[0111] 2’,2’’’-(4-(4-(tert-Butyl)phenyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chem.

[0112] 2,6-Dibromoisonicotinic acid

Chemical Structure

[0113] (2,6-Dibromopyridin-4-yl)methanol

Chemical Structure

[0114] 4-(Bromomethyl)-2,6-dibromopyridine

Chemical Structure

[0115] 4-(N,N-Diisopropylaminomethyl)-2,6-dibromopyridine

Chem.

[0116] 2’,2’’’-(4-(N,N-Diisopropylaminomethyl)pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chem.

[0117] 2,6-Dibromo-4-(4-methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl)pyridine

Chemical Structure

[0118] 2’,2’’’-(4-(4-Methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl)pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0119] 2,6-Dibromo-4-((p-tolyloxy)methyl)pyridine

Chemical Structure

[0120] 2’,2’’’-(4-((p-Tolyloxy)methyl)pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0121] 2,6 - Dichloro - 4-(n - butyldimethylsilyl)pyridine

Chemical Structure

[0122] 2’,2’’’-(4-(n-Butyldimethylsilyl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0123] Lithium [(1R,2S,5R)-2-isopropyl-5-methyl-cyclohexan-1-olate]

Chemical Structure

[0124] 2,6-Dichloro-4-(((1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl)oxy)pyridine

Chemical Structure

[0125] 2’,2’’’-((4-(((1R,2S,5R)-2-Isopropyl-5-methylcyclohexyl)oxy)pyridine)-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-pentyl)-[1,1’-biphenyl]-2-ol) [Chemical Structure] 2,6-Dichloro-4-(((1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl)oxy)pyridine (148 mg, 0.490 mmol), 4-((1s,3s)-adamantan-1-yl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinine (420 mg, 0.979 mmol, 2 equiv), cesium carbonate (957 mg, 2.94 mmol, 6 equiv) and chloro(2-dicyclohexylphosphino-2’,6’-diisopropoxy-1,1’-biphenyl)[2-(2’-amino-1,1’-biphenyl)]palladium(II) (15 mg, 19 μmol, 4 mol%) in dioxane (5 mL) were stirred, and degassed water (2.5 mL) was added. The reaction was stirred and heated to 100 °C for 4.5 h. The reaction was cooled to room temperature. The reaction was partitioned between dichloromethane (50 mL) and water (50 mL) in a separatory funnel. The organic phase was collected and the aqueous phase was further extracted with additional dichloromethane (20 mL). The combined organic phases were filtered through a thin pad of silica. The filtrate was concentrated in vacuo. The crude was stirred with pentane (5 mL) and the resulting solution was concentrated under a nitrogen stream and then under high vacuum to give the product (441 mg, 94% yield, a mixture of diastereomers). 1 H NMR (400 MHz, C 6 D 6 ), the diastereomers were integrated as one: δ 8.69 - 8.53 (m, 1H), 7.47 - 7.19 (m, 7H), 7.14 - 7.08 (m, 3H), 6.86 - 6.53 (m, 3H), 3.92 - 3.70 (m, 1H), 2.44 - 1.72 (m, 31H), 1.58 - 0.96 (m, 24H), 0.95 - 0.58 (11H).

[0126] 2’,2’’’-(4-Ethoxypyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0127] 2,6-dichloro-3-(n-butyldimethylsilyl)pyridine

Chemical Structure

[0128] 2’,2’’’-(3-(n-Butyldimethylsilyl)pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0129] 2,6-Dichloro-4-(hept-1-yn-1-yl)pyridine

Chemical Structure

[0130] 2’,2’’’-(4-(Hepta-1-yn-1-yl)pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0131] 2,6-Dichloroisonicotinic acid

Chemical formula

[0132] (2,6-Dichloropyridin-4-yl)methanol

Chem.

[0133] 2,6-Dichloroisonicotinaldehyde

Chem.

[0134] 8-(2,6-Dichloropyridin-4-yl)-1,5-diazabicyclo[3.2.1]octane

Chem.

[0135] Hypothetical synthesis of 2’,2’’’-(4-(1,5-diazabicyclo[3.2.1]octan-8-yl)pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol)

Chem.

[0136] 1,3,5-Trimethyladamantane [Chemical formula] In a Parr pressure reactor, 2.3 mL (64.0 mmol) of 2.9 M MeMgBr in diethyl ether was added all at once to a solution of 15.0 g (62.0 mmol) of 1-bromo-3,5-dimethyladamantane in diethyl ether (80 mL). The resulting solution was heated to 105 °C and stirred at this temperature overnight. Then, the reactor was cooled to room temperature and the pressure was released. Further, 100 mL of 10% HCl was carefully added. The resulting mixture was extracted with diethyl ether (3 × 30 mL), and the combined organic extracts were dried over Na 2 SO 4 and then evaporated to dryness. Yield 11.3 g (99%) of a colorless oil. 1 H NMR (CDCl 3, 400 MHz): δ 1.98 - 2.03 (m, 1H), 1.25 - 1.28 (m, 6H), 1.00 - 1.12 (m, 6H), 0.78 (s, 9H). 13 C NMR (CDCl 3 , 100 MHz) δ 51.1, 43.2, 31.4, 30.7, 30.0.

[0137] 3,5,7-Trimethyladamantan-1-ol

Chemical Structure

[0138] 4-Methyl-2-(3,5,7-trimethyladamantan-1-yl)phenol

Chemical Structure

[0139] 2-Bromo-4-methyl-6-(3,5,7-trimethyladamantan-1-yl)phenol [Chemical formula] To a solution of 8.97 g (31.5 mmol) of 4-methyl-2-(3,5,7-trimethyladamantan-1-yl)phenol in dichloromethane (90 ml) was added dropwise 5.04 g (31.5 mmol) of bromine at room temperature. The resulting mixture was stirred at room temperature for 12 hours and then carefully poured into 200 ml of 5% NaHCO 3It was carefully poured in. The crude product was extracted with dichloromethane (3 × 50 mL), and the combined organic extracts were dehydrated with Na 2 SO 4 and then evaporated to dryness. Yield 11.4 g (99%) of a white solid. 1 1H NMR (CDCl 3 , 400 MHz): δ 7.17 (d, J = 2.0 Hz, 1H), 6.99 (d, J = 2.0 Hz, 1H), 5.65 (s, 1H), 2.28 (s, 3H), 1.67 (s. 6H), 1.10 - 1.21 (m, 6H), 0.91 (s, 9H). 13 13C NMR (CDCl 3 , 100 MHz): δ 148.1, 136.5, 130.3, 129.4, 127.3, 112.1, 50.3, 45.8, 39.9, 32.1, 30.5, 20.6.

[0140] 1-(3-Bromo-2-(methoxymethoxy)-5-methylphenyl)-3,5,7-trimethyladamantane [Chemical formula] To a solution of 11.4 g (31.4 mmol) of 2-bromo-4-methyl-6-(3,5,7-trimethyladamantan-1-yl)phenol in dry THF (100 mL) was added 1.06 g (34.9 mmol, 60 wt% in mineral oil) of sodium hydride at room temperature. Then, 2.65 mL (34.9 mmol) of chloromethyl methyl ether was added in one portion. The reaction mixture was heated at 60 °C for 24 h and then poured into 130 mL of cold water. The crude product was extracted with 3 × 20 mL of dichloromethane. The combined organic extracts were dehydrated with Na 2 SO 4 and then evaporated to dryness. Yield 11.9 g (91%) of a yellow solid. 1 1H NMR (CDCl 3, 400 MHz): δ 7.25 (d, J = 2.0 Hz, 1H), 7.06 (d, J = 2.0 Hz, 1H), 5.23 (s, 2H), 3.71 (s, 3H), 2.29 (s, 3H), 1.68 (s, 6H), 1.10 - 1.21 (m, 6H), 0.92 (s, 9H). 13 C NMR (CDCl 3 , 100 MHz): δ 151.3, 144.0, 134.4, 131.9, 127.4, 117.6, 99.9, 57.8, 50.2, 46.8, 40.3, 32.2, 30.6, 20.7.

[0141] 2-(2-(Methoxymethoxy)-5-methyl-3-(3,5,7-trimethyladamantan-1-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Chemical Structure

[0142] 1-(2'-Bromo-2-(methoxymethoxy)-5-methyl-[1,1'-biphenyl]-3-yl)-3,5,7-trimethyladamantane

Chemical Structure

[0143] 2-(2’-(Methoxymethoxy)-5’-methyl-3’-(3,5,7-trimethyladamantan-1-yl)-[1,1’-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Chemical Structure

[0144] 2’,2’’’-(4-(Pyrrolidin - 1 - yl)pyridine - 2,6 - diyl)bis(5 - methyl - 3-(3,5,7 - trimethyladamantan - 1 - yl)-[1,1’ - biphenyl]-2 - ol)

Chemical Structure

[0145] 2-(3,5-Dimethyladamantan-1-yl)-4-methylphenol

Chem.

[0146] 2-Bromo-6-(3,5-dimethyladamantan-1-yl)-4-methylphenol

Chem.

[0147] 1-(3-Bromo-5-methyl-2-(methoxymethoxy)phenyl)-3,5-dimethyladamantane

Chemical formula

[0148] 2-(3-(3,5-Dimethyladamantan-1-yl)-5-methyl-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Chemical Structure

[0149] 1-(2’-Bromo-2-(methoxymethoxy)-5-methyl-[1,1’-biphenyl]-3-yl)-3,5-dimethyladamantane

Chemical Structure

[0150] 2-(3’-(3,5-Dimethyladamantan-1-yl)-2’-(methoxymethoxy)-5’-methyl-[1,1’-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Chem.

[0151] 2’,2’’’-(4-(Pyrrolidin-1-yl)pyridine-2,6-diyl)bis(3-(3,5-dimethyladamantan-1-yl)-5-methyl-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0152] Preparation of Transition Metal Complex Complex 3 [Chem.] ZrCl in toluene (approx. mL) 4 (Et 2 O) 2 (50 mg, 0.131 mmol) and 2’,2’’’-(4-methylpyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol) (100 mg, 0.123 mmol) in a mixture, MeMgBr (3.0 M, 0.18 mL, 0.54 mmol) was added dropwise. The reaction mixture was stirred at ambient temperature for 2 hours and then evaporated to dryness. The resulting solid was extracted with pentane, and the combined extracts were filtered through celite on a glass fiber plug. The filtrate was concentrated under vacuum to give a brown foam. The crude product was recrystallized from pentane at -40 °C with slow evaporation. Yield 29.0 mg (product isolated containing 1 equivalent of pentane). 1 1H NMR (C 6 D 6, 400 MHz): δ 7.54 (d, J = 2.4 Hz, 2H), 7.25 - 6.96 (m, 10H), 6.21 (s, 2H), 2.73 - 2.38 (m, 12H), 2.19 (br, 6H), 2.06 - 1.77 (m, 12H), 1.32 (d, J = 1.3 Hz, 18H), 1.19 (s, 3H), 0.13 (s, 6H).

[0153] Complex 4 [Chemical formula] To a pre-cooled, stirred suspension of zirconium chloride (0.142 g, 0.609 mmol, 1 equiv) in toluene (2 mL), methylmagnesium bromide (0.82 mL, 3.0 M in diethyl ether, 2.5 mmol, 4.0 equiv) was added. Next, a pre-cooled solution of 2’,2’’’-(4-ethylpyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol) (0.502 g, 0.609 mmol) in toluene (3 mL) was added dropwise. The reaction mixture was stirred at room temperature for 3 h. The reaction mixture was concentrated under a nitrogen stream and then under high vacuum. The residue was stirred in hexane (20 mL) and heated to reflux. The mixture was filtered through Celite while warm. The filtrate was further extracted with refluxing hexane (2 × 20 mL). Concentration of the combined hexane filtrates under a nitrogen stream and then under high vacuum gave the product containing hexane (0.18 equiv) and toluene (0.96 equiv) as a yellowish brown - gray solid (0.424 g, 66% yield). 1 H NMR (C 6 D 6, 400 MHz): δ 7.54 (d, 2H, J = 2.6 Hz), 7.24 - 7.20 (m, 2H), 7.14 - 7.00 (m, 8H), 6.39 (s, 2H), 2.65 - 2.54 (m, 6H), 2.49 - 2.40 (m, 6H), 2.24 - 2.15 (m, 6H), 2.06 - 1.96 (m, 6H), 1.89 - 1.80 (m, 6H), 1.68 (q, 2H, J = 7.6 Hz), 1.33 (s, 18H), 0.48 (t, 3H, J = 7.6 Hz), 0.14 (s, 6H).

[0154] Complex 5

Chemical formula

[0155] Complex 6

Chem.

[0156] Complex 7

Chem.

[0157] Complex 8

Chem.

[0158] Complex 9 [Chemical formula] To a mixture of ZrCl 4 (Et 2 O) 2 (60 mg, 0.157 mmol) and 2′,2′′′-(4-((trihexylsilyl)methyl)pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1′-biphenyl]-2-ol) (155 mg, 0.142 mmol) in toluene (ca. 4 mL) cooled to -40 °C was added dropwise MeMgBr (3.0 M, 0.22 mL, 0.66 mmol). The reaction mixture was stirred at ambient temperature for 14 h and then evaporated to dryness. The resulting solid was extracted with pentane (ca. 10 ml in total), and the combined extracts were filtered through celite on a glass fiber plug. Concentration of the filtrate under vacuum gave a brown foam. 1 H NMR (400 MHz, C 6 D 6 ) δ 7.57 (d, J = 2.6 Hz, 2H), 7.31 - 6.71 (m, 10H), 6.50 (s, 2H), 2.71 - 2.37 (m, 12H), 2.18 (s, 6H), 2.06 - 1.73 (m, 12H), 1.59 - 1.04 (m, 44H), 0.93 (t, J = 7.0 Hz, 9H), 0.61 (s, 3H), 0.27 (dd, J = 10.2, 6.4 Hz, 6H), 0.14 (s, 3H).

[0159] Complex 10

Chem.

[0160] Complex 11

Chem.

[0161] Complex 12 [Chemical formula] ZrCl in toluene (ca. 5 mL) cooled to -40 °C 4 (Et 2 O) 2 (53 mg, 0.139 mmol) and 2′,2′′′-(4-(3-butenyl)pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1′-biphenyl]-2-ol) (114 mg, 0.134 mmol) were added dropwise with MeMgBr (3.0 M, 0.2 mL, 0.6 mmol). The reaction mixture was stirred at ambient temperature for 1 hour and then evaporated to dryness. The resulting solid was extracted with n-hexane (ca. 10 mL x 2), and the combined extracts were filtered through a medium glass frit funnel. The filtrate was concentrated in vacuo to a brown solid. The resulting solid was dissolved in n-hexane (total ca. 10 mL) and filtered through a glass fiber plug. The resulting filtrate was concentrated in vacuo to give a brown solid (110.5 mg, 85%). 1 H NMR (400 MHz, C 6 D 6) δ 7.53 (d, J = 2.7 Hz, 2H), 7.25 - 7.00 (m, 10H), 6.28 (s, 2H), 5.18 (ddt, J = 17.1, 10.2, 6.7 Hz, 1H), 4.74 (d, J = 9.5 Hz, 1H), 4.46 (d, J = 17.1, 1H), 2.65 - 2.31 (m, 12H), 2.19 (s, 6H), 2.08 - 1.79 (m, 12H), 1.76 - 1.51 (m, 2H), 1.33 (s, 18H), 0.88 (t, J = 6.9 Hz, 2H), 0.12 (s, 6H).

[0162] Complex 13

Chem.

[0163] Complex 14

Chem.

[0164] Complex 15 [Chemical formula] ZrCl in toluene (about 5 mL) cooled to -40 °C 4 (Et 2 O) 2(57 mg, 0.149 mmol) and 2’,2’’’-(4-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol) (135 mg, 0.135 mmol) were added dropwise with MeMgBr (3.0 M, 0.2 mL, 0.6 mmol). The reaction mixture was stirred at ambient temperature for 90 minutes and then evaporated to dryness. The resulting solid was extracted with pentane (total of about 20 mL), and the combined extracts were filtered through a plastic frit funnel. The filtrate was rinsed with additional pentane (2 × 10 mL). The combined filtrates were concentrated in vacuo to a solid, which was then redissolved in pentane (total of 10 mL) and filtered through Celite on a glass fiber plug. Concentration of the filtrate in vacuo gave a yellow-tan solid (132.4 mg). The solid was further purified by precipitation from pentane at -40 °C to give a white solid.

[0165] Complex 16: Synthesis of Dimethyld zirconium[2’,2’’’-(4-(tert-butyl)-thiopyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1’-biphenyl]-2-olate)] [Chemical formula] To a pre-cooled, stirred suspension of zirconium(IV) chloride (57 mg, 0.25 mmol, 1 equiv) in toluene (3 mL) was added methylmagnesium bromide (0.33 mL, 3.0 M in diethyl ether, 0.99 mmol, 4.1 equiv). Next, a pre-cooled solution of 2’,2’’’-(4-(tert-butyl)thiopyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol) (214 mg, 0.24 mmol) in toluene (5 mL) was added. The reaction was stirred at room temperature for 1 h. The reaction was concentrated under a nitrogen stream and then under high vacuum. The residue was extracted with pentane (10 mL, then 5 mL) and filtered through celite. The combined pentane extracts were cooled to -35 °C. The resulting precipitate was collected and concentrated under high vacuum to give the product containing toluene (0.39 equiv) as a white solid. (104 mg, 41% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ 7.55 (d, 2H, J = 2.6 Hz), 7.21 (d, 2H, J = 7.3 Hz), 7.12-6.99 (m, 8H), 6.95 (s, 2H), 2.59-2.51 (m, 6H), 2.45-2.37 (m, 6H), 2.22-2.16 (m, 6H), 2.03-1.94 (m, 6H), 1.89-1.80 (m, 6H), 1.33 (s, 18H), 0.86 (s, 9H), 0.11 (s, 6H).

[0166] Complex 17: Synthesis of Dimethyld zirconium[2’,2’’’-(4-(butylthio)pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1’-biphenyl]-2-olate]

Chemical Structure

[0167] Complex 18: Synthesis of Dimethyld zirconium[2’,2’’’-(4-(dodecylthio)-pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1’-biphenyl]-2-olate)]

Chemical Structure

[0168] Complex 19

Chem.

[0169] Complex 20: Synthesis of Dimethyldirconium [2’,2’’’-(4-(diisopropylaminomethyl)pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1’-biphenyl]-2-olate)] [Chemical formula] To a pre-cooled stirred suspension of zirconium tetrachloride (27 mg, 0.12 mmol, 1 equiv) in toluene (2 mL) was added methylmagnesium bromide (0.16 mL, 3.0 M in diethyl ether, 0.48 mmol, 4.2 equiv). Next, a pre-cooled solution of 2’,2’’’-(4-((diisopropylamino)methyl)-pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(tert-butyl)-[1,1’-biphenyl]-2-ol) (104 mg, 0.114 mmol) in toluene (2 mL) was added. The reaction was stirred at room temperature for 18.5 hours. The reaction was concentrated at 50 °C under a nitrogen stream and then under high vacuum. The residue was extracted with pentane (15 mL) and then with toluene (5 mL) and filtered through celite. The combined extracts were concentrated under a nitrogen stream and then under high vacuum. The residue was further extracted with hot hexane and filtered through celite. The filtrate was concentrated under a nitrogen stream and then under high vacuum to give the product containing hexane (2.63 equiv) and toluene (0.28 equiv) as a yellowish-brown to brown solid (71.2 mg, 48% yield). 1 H NMR (400 MHz, C6 D 6 ): δ 7.53 (d, 2H, J = 2.6 Hz), 7.26 - 7.23 (m, 2H), 7.14 - 7.09 (m, 8H), 6.93 (s, 2H), 2.97 - 2.80 (m, 2H), 2.60 - 2.50 (m, 8H), 2.47 - 2.38 (m, 6H), 2.24 - 2.16 (m, 6H), 2.05 - 1.95 (m, 6H), 1.89 - 1.81 (m, 6H), 1.34 (s, 18H), 0.63 (d, 6H, J = 6.7), 0.55 (d, 6H, J = 6.5 Hz), 0.14 (s, 6H).

[0170] Complex 21: Synthesis of Dimethyld zirconium [2’,2’’’-(4-[4-Methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl]pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1’-biphenyl]-2-olate)]

Chemical Structure

[0171] Complex 22

Chemical Structure

[0172] Hypothetical synthesis of complex 23

Chemical formula

[0173] Synthesis of complex 24: dimethyld zirconium [2’,2’’’-(4-(((1S,2R,5S)-2-isopropyl-5-methylcyclohexyl)oxy)pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1’-biphenyl]-2-olate)]

Chemical formula

[0174] Complex 25: Synthesis of Dimethyld zirconium[2’,2’’’-(4-ethoxypyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1’-biphenyl]-2-olate]

Chemical Structure

[0175] Hypothetical synthesis of complex 26

Chem.

[0176] Hypothetical synthesis of complex 27

Chemical formula

[0177] Hypothetical synthesis of complex 28

Chemical formula

[0178] Complex 29: Dimethylhafnium [2’,2’’’-(4-(pyrrolidin-1-yl)pyridine-2,6-diyl)bis(5-methyl-3-(3,5,7-trimethyladamantan-1-yl)-[1,1’-biphenyl]-2-olate)]

Chemical formula

[0179] Complex 30: Dimethylhafnium[2’,2’’’-(4-(pyrrolidin-1-yl)pyridine-2,6-diyl)bis(3-(3,5-dimethyladamantan-1-yl)-5-methyl-[1,1’-biphenyl]-2-olate)]

Chemical Structure

[0180] Complex solubility General considerations: The solubility study for complex 2 was carried out using the recrystallized material. The solubility study for all other complexes was carried out using the synthesized material. Complex 2 was co-crystallized with 1.4 equivalents of methylcyclohexane. Complex 3 was isolated containing 1 equivalent of pentane. Complex 4 was isolated containing 0.18 equivalents of hexane and 0.96 equivalents of toluene. Complex 6 was isolated containing 0.75 equivalents of pentane. Complex 8 was isolated containing 0.5 equivalents of pentane. Complex 14 was isolated containing 1 equivalent of isohexane. Complex 16 was isolated containing 0.39 equivalents of toluene. Complex 20 was isolated containing 2.63 equivalents of hexane and 0.28 equivalents of toluene. Complex 24 was isolated containing 0.69 equivalents of hexane. Complex 25 was isolated containing 1.14 equivalents of hexane. Nitrogen was bubbled through the solvents used (for 30 - 60 minutes) and dehydrated with 3 Å molecular sieves. Unless otherwise specified, all measurements were carried out at ambient temperature (20 °C - 25 °C). General procedure: Solubility was determined using either Method 1 or Method 2 below. For calculations, a value of 0.672 g / mL was used for the density of isohexane.

[0181] Method 1: A small amount of the complex (the actual mass recorded including any residual solvents as specified above, typically 5 - 30 mg) was loaded into a tared vial. Next, a small stir bar (8 mm) was added. Then, the solvent was added and the mixture was stirred rapidly (1000 rpm). If a homogeneous mixture was not formed within 30 minutes, additional solvent was added and the mixture was stirred for an additional 30 minutes. This process was repeated until either a clear solution (no visible solids or turbidity) was obtained or the vial was full. When the mixture approached homogeneity (i.e., little residual solid was observed), the amount of added solvent was maintained at a small amount (<1 mL) to minimize the excess over the solvent necessary to achieve homogeneity. Next, the stir bar was removed and the mass of the mixture was measured. If a clear solution was formed, the solubility of the complex was calculated as a single value based on the mass of the complex and the amount of solvent added to achieve the homogeneous solution. If the mixture was still in a heterogeneous state (visible solids or turbidity), the reported value was indicated as "less than" the calculated value.

[0182] Method 2: The measured amount of the complex (the actual mass recorded including any residual solvents as specified above) was added to a tared vial, and then a stir bar was added. Dry isohexane was added in small portions, and after each portion of isohexane, the resulting mixture was stirred. If a clear solution was formed, the solubility was reported as the range between the lower boundary value of the solubility calculated using all the solvent added to achieve the homogeneous solution and the higher boundary value of the solubility calculated using all the solvent measured before achieving the homogeneous solution. If the mixture was still in a heterogeneous (visible solids or turbidity) state, the solubility of the higher boundary value was calculated using all the solvent added. The equations used to calculate the solubility are listed below. The solvent present in the complex is included in the mass and formula weight of the complex. Solubility (mM) = [10 6 * [(grams of complex) / (formula mass of complex (g / mol))] / [(total volume of solvent (mL))] or Solubility (mM) = [10 6 * ​​[(Gram number of complex) / (formula mass of complex (g / mol))] / [(gram number of solvent) / (density of solvent (g / mL))] Solubility (mass %) =

[0100] * [(gram number of complex) / [(gram number of complex) + (total volume of solvent (mL)) * (density of solvent (g / mL))]] or Solubility (mass %) =

[0100] * [(mass of complex) / (mass of solution)].

[0183]

Table 1

[0184] Polymerization example Toluene (ExxonMobil Chemical - anhydrous, N 2 stored below) (98%) or isooctane (ExxonMobil Chemical - polymerization grade and purified as described below) was used to prepare a solution of the pre-catalyst. The pre-catalyst solution was typically 0.25 mmol / L. The polymerization grade toluene and / or isooctane used as the solvent was supplied by ExxonMobil Chemical Co. and purified by passing through a series of columns: two 500 cc Oxyclear cylinders in series made by Labclear (Oakland, Calif), then two 500 cc columns in series packed with dried 3 Å molecular sieves (8 - 12 mesh; Aldrich Chemical Company), and two 500 cc columns in series packed with dried 5 Å molecular sieves (8 - 12 mesh; Aldrich Chemical Company).

[0185] Polymerization grade propylene (C 3Using [[ID=]], a series of columns: a 2250 cc Oxiclear cylinder made by Labclear, then a 2250 cc column filled with 3 Å molecular sieves (8 - 12 mesh; Aldrich Chemical Company), then two 500 cc columns in series filled with 5 Å molecular sieves (8 - 12 mesh; Aldrich Chemical Company), then a 500 cc column filled with Selexsorb CD (BASF), and finally a 500 cc column filled with Selexsorb COS (BASF), the above - mentioned polymerization - grade propylene was further purified by passing it through these columns. The activation of the pre - catalyst was by either dimethylanilinium tetrakis(pentafluorophenyl)borate (Boulder Scientific or Albemarle Corp; Act ID = A), or (hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate (Boulder Scientific; Act ID = B) supplied as a 10 mass% solution in methylcyclohexane. The activator was typically used as a 0.25 mmol / L solution in toluene or isohexane. Tri - n - octylaluminum (TnOAl or TNOA, solvent - free, AkzoNobel) was also used as a scavenger before introducing the activator and the pre - catalyst into the reactor. TNOA was typically used as a 5 mmol / L solution in toluene or isohexane.

[0186] Description and preparation of the reactor: The polymerization was carried out using an autoclave equipped with an external heater for temperature control, a glass insert (C 2 and C 2 / C 8 In the case of, the internal volume of the reactor = 23.5 mL, and in the case of the implementation of C 3 ; 22.5 mL), with a septum inlet for regulating the supply of nitrogen, ethylene, and propylene, and equipped with a disposable PEEK mechanical stirrer (800 RPM), under an inert atmosphere (N 2It was carried out in a dry box of ). The autoclave was prepared by purging with dry nitrogen at 110 °C or 115 °C for 5 hours and then at 25 °C for 5 hours.

[0187] Propylene polymerization (PP): The reactor was prepared as described above, then heated to 40 °C, and then purged with propylene gas at atmospheric pressure. Toluene or isohexane, liquid propylene (1.0 mL), and a scavenger (TNOA, 0.5 μmol) were added by syringe. Next, while stirring at 800 RPM, the reactor was brought to the process temperature (70 °C or 100 °C). The activator solution and then the pre-catalyst solution were injected into the reactor by syringe under the process conditions. The reactor temperature was monitored and typically maintained within + / - 1 °C. Polymerization was terminated by adding a compressed dry air gas mixture at approximately 50 psi for approximately 30 seconds to the autoclave. Polymerization was quenched based on a predetermined pressure drop (maximum quench value) or for a maximum of 30 minutes. The reactor was cooled and vented. After removing the solvent in vacuo, the polymer was isolated. The actual quench time was reported as the quench time (s). The reported yield included the total mass of the polymer and the residual catalyst. Catalyst activity was reported as the grams of polymer per mmol of transition metal compound per hour of reaction time (g / mmol·h). Examples of propylene homopolymerization are reported in Table 2.

[0188] Polymer Characterization Regarding the analytical test, a solution of the polymer sample was prepared by dissolving the polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity, Sigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%, manufactured by Aldrich) in a shaker oven at 165 °C for approximately 3 hours. The typical concentration of the polymer in the solution was between 0.1 and 0.9 mg / mL, including a BHT concentration of 1.25 mg of BHT per 1 mL of TCB. The sample was cooled to 135 °C for the test.

[0189] High temperature size exclusion chromatography was performed using an automated "high speed GPC" system as described in U.S. Patent Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388, each of which is incorporated herein by reference. Molecular weights (weight average molecular weight (Mw), number average molecular weight (Mn) and z average molecular weight (Mz)), and sometimes also the molecular weight distribution (MWD = Mw / Mn), also referred to as the polydispersity index (PDI) of the polymer, were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector (ELSD) and calibrated using polystyrene standards (Polymer Laboratories: polystyrene calibration kit S-M-10: Mp (peak Mw) between 5,000 and 3,390,000). Alternatively, the samples were measured by gel permeation chromatography using a Symyx Technology GPC equipped with a dual wavelength infrared detector and calibrated using polystyrene standards (Polymer Laboratories: polystyrene calibration kit S-M-10: Mp (peak Mw) between 580 and 3,039,000). Samples (250 μL of polymer solution in TCB injected into the system) were run at an eluent flow rate of 2.0 mL / min (sample temperature 135 °C, oven / column 165 °C) using three Polymer Laboratories: PLgel 10 μm Mixed-B 300 × 7.5 mm columns in series. Column spreading correction was not used. Numerical analysis was performed using Epoch® software available from Symyx Technologies, or Automation Studio software available from Freeslate. The molecular weights obtained are relative to linear polystyrene standards. Molecular weight data are reported under the headings of Mn, Mw, Mz and PDI as defined above in Table 2.

[0190] Differential scanning calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point of the polymer. The samples were pre-annealed at 220 °C for 15 minutes and then cooled overnight at room temperature. Next, the samples were heated to 220 °C at a rate of 100 °C / min and then cooled at a rate of 50 °C / min. The melting point was collected during the heating period. The results are reported below the heading Tm (°C) in Table 2. The polymerization results are collected in Table 2 below. "Example number (Ex#)" represents the number of the example. Example numbers starting with "C" are comparative examples. "Cat ID" identifies the pre-catalyst used in this experiment. The corresponding numbers (also referred to as pre-catalysts, catalysts, complexes or compounds) identifying the pre-catalysts are in the synthesis experiment section. T (°C) is the polymerization temperature typically maintained within a range of + / - 1 °C. "Yield" is the polymer yield and is not corrected for catalyst residues. "Quench time" is the actual time in seconds for which the polymerization was carried out. In the case of propylene homopolymerization, the quench value indicates the maximum set pressure drop (conversion) of propylene during polymerization (in the case of PP). Activity is reported as grams of polymer per mmol of catalyst per hour.

[0191] Standard polymerization conditions include 0.015 μmol of catalyst complex, 1.1 equivalents of activator, 0.5 μmol of TNOA scavenger, 1.0 mL of propylene, 4.1 mL of total solvent, and the quench value is either a pressure drop of 8 psi or a maximum reaction time of 30 minutes. Activator A is N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator, and activator B is (hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate. When activator A is used, the pre-catalyst solution is present in either isohexane or toluene, and the activator solution is present in toluene. When activator B is used, both the pre-catalyst and activator solutions are present in isohexane. A small amount of methylcyclohexane is derived from activator B supplied by the manufacturer as a 10 wt% solution in methylcyclohexane.

[0192] [Table 2] JPEG2025517141000123.jpg249155 JPEG2025517141000124.jpg248156 JPEG2025517141000125.jpg250156 JPEG2025517141000126.jpg250156 JPEG2025517141000127.jpg250155 JPEG2025517141000128.jpg250156 JPEG2025517141000129.jpg249156 JPEG2025517141000130.jpg24869 The polymerization was also carried out in a continuous stirred tank reactor system. The 1-liter autoclave reactor was equipped with a stirrer, a pressure control device, and a water-cooling / steam-heating element by a temperature control device. This reactor was operated under liquid filling conditions at a reactor pressure above the bubble point pressure of the reactant mixture, maintaining the reactants in the liquid phase. Isohexane and propylene were pumped into the reactor by a Pulsa feed pump. The total liquid flow rate was controlled using a Coriolis mass flow controller (Quantim series made by Brooks). Ethylene was flowed as a gas under its own pressure by a Brooks flow controller. The feeds of ethylene and propylene were combined into one stream and then mixed with a stream of pre-cooled isohexane cooled to at least 0 °C. Next, this mixture was fed to the reactor from a single line. A solution of tri(n-octyl)aluminum was added to the above combined solvent and monomer stream immediately before they entered the reactor. The catalyst solution was fed to the reactor from an individual line using an ISCO syringe pump. Isohexane (used as a solvent) and monomers (e.g., propylene and ethylene) were purified over beds of alumina and molecular sieves. Toluene and isohexane used to prepare the catalyst solution were purified by the same technique.

[0193] The polymer produced in the reactor exited through a backpressure control valve that reduced the pressure to atmospheric pressure. As a result, the unconverted monomers in the solution were vigorously flowed into the vapor phase exhausted from the top of the vapor-liquid separator. To recover the polymer, the liquid phase mainly containing the polymer and the solvent was collected. The collected sample was first air-dried in a hood to evaporate most of the solvent, and then dried in a vacuum oven at a temperature of about 90 °C for about 12 hours. The sample dried in the vacuum oven was weighed to obtain the yield. All reactions were carried out at a pressure of about 2.4 MPa / g unless otherwise specified.

[0194] The conditions of the detailed polymerization method and the physical properties of the produced polymer are listed in Table C 1 below. N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate was used as the activator for all polymerizations. The catalyst solution was prepared by combining the catalyst with the activator in toluene. Examples G01 - G06 are propylene-ethylene copolymers made from catalyst 6. Examples G07 - G11 are propylene-ethylene copolymers made from catalyst 15. Examples G12 - G13 are propylene-ethylene copolymers made from catalyst 14.

[0195] The ethylene content was determined using FTIR in accordance with ASTM D3900.

[0196] The peak melting point Tm (also referred to as the melting point), the peak crystallization temperature Tc (also referred to as the crystallization temperature), the glass transition temperature (Tg), and the heat of fusion (ΔHf or Hf) were determined using differential scanning calorimetry (DSC) manufactured by TA Instruments (model Q200) in accordance with the procedure of ASTM D3418-03.

[0197] MFR is the melt flow rate (g / 10 min) measured at a temperature of 230 °C and a mass of 2.16 kg in accordance with ASTM D1238. HL MFR is the melt flow rate (g / 10 min) measured at a temperature of 230 °C and a mass of 21.6 kg in accordance with ASTM D1238.

Table 3

Table 4

Table 5

[0198] Certain embodiments and features are described using a set of numerical upper limits and a series of numerical lower limits. It should be understood that any combination of two values, for example, any combination of a lower value and a higher value, including any combination of two lower values and / or any combination of two higher values, is contemplated unless specifically indicated otherwise. Certain lower limits, upper limits, and ranges can be found in one or more of the following claims. All numerical values are “about” or “substantially” their indicated values, taking into account experimental error and variations that would be expected by one of ordinary skill in the art. Any value in the table can be presented with an additional + / - 10% around the endpoints of the ranges that define their individual measured values or characteristics.

[0199] All documents described herein, including any priority documents and / or test procedures, are incorporated herein by reference to the extent not inconsistent with this specification. As is apparent from the foregoing general description and the specific embodiments, while the forms of the present disclosure have been illustrated and described, various changes can be made without departing from the spirit and scope of the present disclosure. Accordingly, the present disclosure is not intended to be limited thereby.

[0200] Although the present disclosure has been described with respect to several embodiments and examples, those of ordinary skill in the art having the benefit of the present disclosure understand that other embodiments can be devised that do not depart from the scope and spirit of the present disclosure.

Claims

1. A catalyst compound represented by formula (I). 【Chemical 1】 (I) (In the formula,[[]]END] M is a metal of Group 3, 4 or 5,[[]]END] L is a Lewis base,[[]]END] X is an anionic ligand,[[]]END] n is 1, 2 or 3,[[]]END] m is 0, 1 or 2,[[]]END] n + m is 4 or less,[[]]END] R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 are each, independently, hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 、R 2 and R 3 、R 3 and R 4 、R 5 and R 6 、R 6 and R 7 or R 7 and R 8 one or more of which may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring or an unsubstituted heterocyclic ring, each having 5, 6, 7 or 8 ring atoms, R 9 、 R 10 、 R 11 and R 12 each independently is hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 9 and R 10 、 R 10 and R 11 or R 11 and R 12 may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring or an unsubstituted heterocyclic ring, each having 5, 6, 7 or 8 ring atoms, R 13 、R 14 、R 15 and R 16 each independently is hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 13 and R 14 、R 14 and R 15 or R 15 and R 16 one or more of which may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring or an unsubstituted heterocyclic ring, each having 5, 6, 7 or 8 ring atoms, R 17 、R 18 and R 19 each independently is hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 17 and R 18 , R 18 and R 19 or R 17 and R 19 may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring or an unsubstituted heterocyclic ring, each having 5, 6, 7 or 8 ring atoms, Any two L groups may be bonded together to form a bidentate Lewis base,[[]]END] The X group may be bonded to the L group to form a monoanionic bidentate group,[[]]END] Any two X groups may be bonded together to form a dianionic coordination group,[[]]END] However, R 17 , R 18 and R 19 at least one of which contains at least two or more saturated or unsaturated carbon atoms)

2. R 18 or R 19 is C 2 -C 40 hydrocarbyl, C 2 -C 40 substituted hydrocarbyl or a C 2 -C 40 heteroatom-containing group, the catalyst compound according to claim 1.

3. R 18 or R 19 The catalyst compound according to claim 1, wherein R or R is a linear chain having at least three non-hydrogen atoms in length and having a terminal bonded to pyridine.

4. C 2 -C 40 The hydrocarbyl is selected from ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, tricontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl and isomers thereof, and the catalyst compound according to claim 2.

5. C 2 -C 40 The catalyst compound according to claim 4, wherein the hydrocarbyl is selected from ethyl, propyl, butyl, butenyl, hexynyl, butylphenyl and their isomers.

6. C 2 -C 40 The catalyst compound according to claim 2, wherein the substituted hydrocarbyl is selected from hydrocarbylene trihydrocarbylsilane, hydrocarbylene trihydrocarbylgermane, (dihydrocarbylamino)hydrocarbylene, (dihydrocarbylphosphino)hydrocarbylene, (hydrocarbyloxy)hydrocarbylene, and (hydrocarbylthio)hydrocarbylene.

7. C 2 -C 40 The catalyst compound according to claim 6, wherein the substituted hydrocarbyl is selected from methylenedimethylbutylsilane, methylenetriethylsilane, methylenetrihexylsilane, (dipropylamino)methylene, 1,5-diazabicyclo[3.2.1]octan-8-yl, 4-methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl, (tolyloxy)methylene, and isomers thereof.

8. C containing one or more heteroatoms 2 -C 40 The catalyst compound according to claim 2, wherein the heteroatom-containing group is selected from hydrocarbyloxy, hydrocarbylthio, trihydrocarbylsilyl, trihydrocarbylgermyl, dihydrocarbylamino, and dihydrocarbylphosphino.

9. C containing one or more heteroatoms 2 -C 40 The catalyst compound according to claim 8, wherein the heteroatom-containing group is selected from ethylthio, butylthio, dodecylthio, ethoxy, butoxy, phenoxy-4-(2,4,4-trimethylpentan-2-yl), (1R,2S,5R)-2-isopropyl-5-methylcyclohexan-1-oxy, pyrrolidinyl, dimethylbutylsilyl and isomers thereof.

10. R 4 and R 5 The catalyst compound according to claim 1, wherein R and R are adamantanyl or substituted adamantanyl.

11. R 4 and R 5 are adamantanyl or substituted adamantanyl, and R 18 is of formula A(R a )(R b )(R c )(wherein A is Si or Ge, and R a , R b and R c are each independently C 1 -C 40 hydrocarbyl or C 1 -C 40 substituted hydrocarbyl, or one or more of R a and R b , R a and R c or R b and R c may together form one or more substituted hydrocarbyl rings or unsubstituted hydrocarbyl rings), a silyl group or a germyl group containing the catalyst compound according to claim 1.

12. The following: [Chemical Formula 2] 【Chem.】 【Chem.】 【Chem.】 The catalyst compound according to claim 1, which is one of the following.[[]]END]

13. A catalyst system comprising an activator, preferably a non-aromatic hydrocarbon, and optionally a support material, and the catalyst compound according to any one of claims 1 to 12.[[]]END]

14. A homogeneous solution,[[]]END] comprising an aliphatic hydrocarbon solvent,[[]]END] and at least one catalyst compound according to one of claims 1 to 12, wherein the concentration of the at least one catalyst compound is 0.20% by mass or more (alternatively 0.25% by mass or more, alternatively 0.30% by mass or more, alternatively 0.35% by mass or more, alternatively 0.40% by mass or more, alternatively 0.50% by mass or more, alternatively 1.0% by mass or more, alternatively 2.0% by mass or more). A homogeneous solution.[[]]END]

15. The homogeneous solution according to claim 14, wherein the aliphatic hydrocarbon solvent is isohexane, cyclohexane, methylcyclohexane, pentane, isopentane, heptane, an isoparaffin solvent, a non-aromatic cyclic solvent, or a combination thereof.[[]]END]

16. A method for producing a propylene-based or ethylene-based polymer or copolymer, in one or more continuous stirred tank reactors or loop reactors in series or parallel, at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30 °C to 230 °C, contacting propylene, ethylene, or ethylene and 1-octene with the catalyst system according to claim 13 to polymerize propylene, ethylene, or ethylene and 1-octene to form a propylene-based or ethylene-based polymer or copolymer. A method comprising the step of.[[]]END]

17. The method according to claim 16, wherein the catalyst system and the activator are supplied to the reactor individually.[[]]END]

18. The method according to claim 16, wherein the catalyst system and the activator are premixed before being fed into the reactor.

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