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

Abstract

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 improvement in the 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.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefit and priority of U.S. Provisional Application No. 63 / 338,164, filed 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 methods 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 methods. The polymerization can be carried out in the presence of a catalyst system such as a catalyst system using Ziegler - Natta catalysts, chromium - based catalysts, or metallocene catalysts. Furthermore, since precatalysts (neutral, non-activated complexes) are often stored for several weeks before use, the precatalysts 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 from implementation at temperatures above 120 °C are particularly a challenge for catalyst development. At such high reactor temperatures, both high catalyst activity and high molecular weight capabilities decrease 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 stringent 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 challenging.

[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 regarding the general state of the art of 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 content of which is incorporated herein by reference.

[0004] Further information regarding the complexes 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

Mode for Carrying Out the Invention

[0006] 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 improvement in the 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 the present disclosure, the numbering scheme for the groups of the periodic table is used as described in Chemical and Engineering News, v.63(5), pg. 27 (1985). Thus, a "Group 4 metal" refers to an element 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 methylaluminoxane, 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.

[0007] 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 coordinate 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, is often considered to generate 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" 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.

[0008] "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, such as 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.

[0009] 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 heteroatom is inserted within the hydrocarbyl ring, or is replaced by at least one non-hydrogen group such as).

[0010] 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, or a hydrocarbyl radical substituted by (where at least one heteroatom is inserted within the hydrocarbyl ring), or a hydrocarbyl radical in which at least one heteroatom is inserted within 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:

[0011] [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 (capable of forming a cyclic or polycyclic hydrocarbyl ring structure or combinations 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.

[0012] 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.

[0013] 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.

[0014] 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, butyldimethylsilyl, butyldimethygermyl, dimethyloctylsilyl, dimethyloctylgermyl, etc. The terms "dihydrocarbylamino" and "dihydrocarbylphosphino" mean a nitrogen group or a phosphorus group bonded to two hydrocarbyl groups. Examples of suitable dihydrocarbylamino groups and dihydrocarbylphosphino groups can include dimethylamino, dimethylphosphino, diethylamino, diethylphosphino, and all isomers of dipropylamino, dipropylphosphino, dibutylamino, dibutylphosphino, etc.

[0015] The term "substituted adamantyl" means an adamantyl 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 can be straight-chain, branched, or cyclic. The alkyl group can 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. The term "aryl" or "aryl group" means an aromatic ring and its substituted variants, for example, phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Similarly, heteroaryl means an aryl group in which the 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 ring, a heterocyclic substituent having properties and structures (substantially planar) similar to those of an aromatic heterocyclic ligand but not according to the definition of aromatic. Similarly, the term aromatic also refers to a substituted aromatic.

[0016] 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 an 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 an 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 six ring atoms and tetrahydrofuran has five ring atoms.

[0017] A heterocyclic ring is a ring having a heteroatom within the ring structure, as opposed to a ring substituted by a heteroatom in which the hydrogen on the 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.

[0018] 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 may be linear, branched or cyclic, and in the case of a cyclic one, it may be aromatic or non-aromatic, C 1 -C 100 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., adamantyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or tricontyl, and aryl groups such as phenyl, benzyl and naphthyl.

[0019] The terms "adamantyl" and "adamantanyl" may be used interchangeably. 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. 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 more. "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 points of differential scanning calorimetry (DSC).

[0020] 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 counter ion 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.

[0021] 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. "An anionic ligand" refers to a negatively charged ligand that donates one or more pairs of electrons to a metal ion. "A 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.

[0022] Transition metal complex In at least one embodiment, the catalyst compound represented by formula (I) is as follows.

Chemical formula

[0023] In at least one embodiment, the catalyst compound represented by formula (II) is as follows. [Chemical formula] (II) (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, A' and A" are each independently Si or Ge, and R a , R b , R c , R d , R e and R f are each independently a C 1 -C 40 hydrocarbyl or a C 1 -C 40 substituted hydrocarbyl, or one or more of R a and R b , R a and R c , R band R c 、R d and R e 、R d and R f or R e and R f One or more of them may combine to form one or more of a substituted hydrocarbyl ring or an unsubstituted hydrocarbyl ring. R 1 、R 3 、R 4 、R 5 、R 6 and R 8 Each is independently hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 120 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 3 and R 4 or R 5 and R 6 One or more of them may combine to 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 is independently hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 120 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 them may combine to 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 、R15 and R 16 each independently is hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 120 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 combine to 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 120 substituted hydrocarbyl, a heteroatom or a 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 combine to 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 combine together to form a bidentate Lewis base, The X group may bond to the L group to form a monoanionic bidentate group, Any two X groups may combine together to form a dianionic ligand group).

[0024] For example, M in formula (I) or (II) can be a metal of Group 3, Group 4 or Group 5. For example, M can be a Group 4 metal. The Group 4 metals can include zirconium, titanium and hafnium. In at least one embodiment, M is zirconium or hafnium.

[0025] Each of L in formula (I) or (II) 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 of 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) or (II) is 2, and each of X is independently chloro, benzyl or methyl.

[0026] R in formula (I) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 can each be independently selected from hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 120 substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen or phosphino, 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 7or R 7 and R 8 One or more of which may combine to 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.

[0027] R of formula (II) 1 、R 3 、R 4 、R 5 、R 6 、R 8 Each may independently be selected from hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 120 substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen or phosphino, or one or more of R 3 and R 4 or one or more of R 5 and R 6 may combine to 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.

[0028] In at least one embodiment, one or more of R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 1 、R 3 、R 4 、R 5 、R 6 、R 8One or more of them are independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, substituted phenyl, biphenyl or their isomers (these may be halogenated (e.g., perfluoropropyl, perfluorobutyl, perfluoroethyl, perfluoromethyl)), substituted hydrocarbyl radicals and all isomers of substituted hydrocarbyl radicals (including trimethylsilylpropyl, trimethylsilylmethyl, trimethylsilylethyl, phenyl), or all isomers of hydrocarbyl-substituted phenyls (including methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, dipropylphenyl, tripropylphenyl, dimethylethylphenyl, dimethylpropylphenyl, dimethylbutylphenyl or dipropylmethylphenyl).

[0029] For example, R in formula (I) or (II) 4 and R 5 are independently C 1 -C 20 alkyl can be, 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, heteroatoms or heteroatom-containing groups. For example, R 4 and R 5 can be independently 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 5can be aryl or (2) R 5 is C 1 -C 20 can be alkyl (e.g., R 5 can be tert-butyl) and R 4 is either aryl or can be. Alternatively, R 4 and / or R 5 can independently be a heteroatom, e.g., R 4 and R 5 can be a halogen atom (e.g., Br, Cl, F, or I). Alternatively, R 4 and / or R 5 can independently be a silyl group, e.g., 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., adamantyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, 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 independently C 1 -C 40Hydrocarbyl, C 1 -C 40 is a substituted hydrocarbyl, more preferably, R 4 and R 5 are 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 C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, 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). 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] R 1 of formula (I) or (II), R 3 , R6 , 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, 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 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 is hydrogen. Alternatively, the R 1 , R 3 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19Each can independently be hydrogen, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy or trimethylsilyl.

[0033] R in formula (I) 1 , R 2 , R 3 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 or R 16 at least one of which independently contains a silyl group or a germyl group of form A (R a )(R b )(R c ), 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, such as methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., n-pentyl, iso-pentyl, iso-amyl, neopentyl, cyclopentyl), hexyl (e.g., n-hexyl, iso-hexyl, cyclohexyl), heptyl (e.g., n-heptyl, iso-heptyl and norbornyl), octyl (e.g., n-octyl, isooctyl, cyclooctyl), nonyl (e.g., n-nonyl, iso-nonyl), decyl (e.g., n-decyl, iso-decyl, cyclodecyl, adamantyl), undecyl (e.g., n-undecyl, iso-undecyl), dodecyl (e.g., n-dodecyl, iso-dodecyl, cyclododecyl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, triacontyl and all their isomers, or R a and R b, R a and R c or R b and R c One or more of which may combine to form one or more of a substituted hydrocarbyl ring or an unsubstituted hydrocarbyl ring. In some embodiments, the silyl or germyl group of Form A (R a )(R b )(R c ) is selected from trimethylsilyl, triethylsilyl, tri(n-propyl)silyl, tri(n-butyl)silyl or tri(n-hexyl)silyl.

[0034] In some embodiments, R 1 , R 2 , R 3 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 or R 16 of Formula (I) is independently a silyl or germyl group of Form A (R a )(R b )(R c ).

[0035] In some embodiments, R 1 , R 2 , R 3 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 or R 16 of Formula (I) is independently a C in which at least one hydrogen atom of the hydrocarbyl is substituted by a silyl or germyl group of Form A (R a )(R b )(R c )1 -C 120 is a substituted hydrocarbyl.

[0036] In at least one embodiment, the catalyst compound is

Chemical formula

[0037] In at least one embodiment, one or more different catalyst compounds are present in the catalyst system. One or more different 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.

[0038] Further exemplary embodiments of the industrial progress of the present invention include the following. R 4 and R 5 are adamantyl, and R 2 and R 7 are independently a silyl group or a germyl group of form A(R a )(R b )(R c )(wherein A is Si or Ge), a composition of formula (I). R 4 and R 5 are adamantyl, and R 2 and R 7 are independently a silyl group of form A(R a )(R b )(R c )(wherein A is Si and A(R a )(R b )(R c ) contains at least 7 carbons), a composition of formula (I). R 4 and R 5 are adamantyl, and R 2 and R 7 are independently of form A(R a )(R b )(R c )(wherein A is Si and A(Ra )(R b )(R c ) contains at least 7 carbons, and at least one of R a , R b and R c is an aliphatic (C 3 -C 40 ) hydrocarbyl or a (C 2 -C 40 ) heterohydrocarbyl containing a linear carbon chain of at least 3 carbons with the end bonded to A), a composition of (I). R 4 and R 5 are adamantyl, and R 2 and R 7 are independently of the form A(R a )(R b )(R c ) (wherein A is Si, and A(R a )(R b )(R c ) contains at least 7 carbons, and at least one of R a , R b and R c is an aliphatic (C 3 -C 40 ) hydrocarbyl or a (C 2 -C 40 ) heterohydrocarbyl containing a linear carbon chain of at least 4 carbons with the end bonded to A), a composition of formula (I). R 4 and R 5 are adamantyl, and R 2 and R 7 are independently of the form A(R a )(R b )(R c ) (wherein A is Si, and A(R a )(R b )(R c ) contains at least 7 carbons, and at least two of R a , R b and R c are aliphatic (C 3 -C 40 ) hydrocarbyl or a (C 2 -C40 )A silyl group of formula (I) which is a hetero hydrocarbyl containing a linear carbon chain of at least 3 carbons with the terminus bonded to A. R 4 and R 5 are adamantyl, and R 18 is of form A (R a )(R b )(R c )(wherein A is Si or Ge), a composition of formula (I) containing a silyl group or a germyl group. R 4 and R 5 are adamantyl, and R 18 is of form A (R a )(R b )(R c )(wherein A is Si or Ge, and at least one of R a , R b and R c is an aliphatic (C 3 -C 40 ) hydrocarbyl or a (C 2 -C 40 ) hetero hydrocarbyl containing a linear carbon chain of at least 3 carbons with the terminus bonded to A), a composition of formula (I) containing a silyl group or a germyl group.

[0039] Further exemplary embodiments of the industrial progress of the present invention include the following. R 4 and R 5 are adamantyl, A' and A" are Si, A'(R a )(R b )(R c ) contains at least 7 carbons, and A"(R e )(R f )(R g ) contains at least 7 carbons, a composition of formula (II). R 4 and R 5 are adamantyl, A' and A" are Si, A'(R a )(R b )(R c ) contains at least 7 carbons, and R a , R b and Rc at least one of which is an aliphatic (C 3 -C 40 ) hydrocarbyl or (C 2 -C 40 ) heterohydrocarbyl, containing a linear carbon chain of at least 3 carbons with the end bonded to A’, and A”(R e )(R f )(R g ) contains at least 7 carbons, and at least one of R d , R e and R f is an aliphatic (C 3 -C 40 ) hydrocarbyl or (C 2 -C 40 ) heterohydrocarbyl, containing a linear carbon chain of at least 3 carbons with the end bonded to A”, of the composition of formula (II). R 4 and R 5 are adamantyl, A’ and A” are Si, A’(R a )(R b )(R c ) contains at least 7 carbons, and at least one of R a , R b and R c is an aliphatic (C 3 -C 40 ) hydrocarbyl or (C 2 -C 40 ) heterohydrocarbyl, containing a linear carbon chain of at least 4 carbons with the end bonded to A’, and A”(R e )(R f )(R g ) contains at least 7 carbons, and at least one of R d , R e and R f is an aliphatic (C 3 -C 40 ) hydrocarbyl or (C 2 -C 40 ) heterohydrocarbyl, containing a linear carbon chain of at least 4 carbons with the end bonded to A”, of the composition of formula (II). R 4 and R 5is adamantyl, A' and A" are Si, A'(R a )(R b )(R c ) contains at least 7 carbons, and at least two of R a , R b and R c are independently an aliphatic (C 3 -C 40 ) hydrocarbyl or a (C 2 -C 40 ) heterohydrocarbyl containing a linear carbon chain of at least 3 carbons with the terminus bonded to A', and A"(R e )(R f )(R g ) contains at least 7 carbons, and at least two of R d , R e and R f are independently an aliphatic (C 3 -C 40 ) hydrocarbyl or a (C 2 -C 40 ) heterohydrocarbyl containing a linear carbon chain of at least 3 carbons with the terminus bonded to A", a composition of formula (II).

[0040] An exemplary embodiment of the industrial progress of the present invention is also a homogeneous solution containing an aliphatic hydrocarbon solvent and a complex of formula (I) or (II), 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, the presence of the silyl or germyl group of the form A(R a )(R b )(R c ) in formula (I) or (II) is thought to help dissolve these complexes in the aliphatic solvent.

[0041] 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) or (II) to polymerize propylene and one or more optional C 3 -C 40 -olefins to form a propylene-based polymer, including the method. 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) or (II) to polymerize ethylene and one or more optional C 4 -C 40 -olefins to form a propylene-based or ethylene-based polymer, including the method.

[0042] Activators and optional scavengers, co-activators and chain transfer agents U.S. Patent Application No. 16 / 788,088 (Publication No. US2020 / 0254431) describes an activator, an optional scavenger, an optional co-activator, and an optional chain transfer agent that can be used by the industrial progress of the present invention. In particular, useful activators also include 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], which are described in PCT Application No. 2020 / 044865 (Publication No. WO2021 / 086467), U.S. Patent Application No. 16 / 394,174 (published as US2019 / 0330394) and PCT Application No. 2019 / 029056 (published as WO2019 / 210026).

[0043] 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 also 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.

[0044] 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, toluene-free hydrocarbon-soluble aluminoxanes and modified aluminoxanes including trimethylaluminum "free" aluminoxane may be used.

[0045] Furthermore, one of ordinary skill in the art can select suitable known activators and optional scavengers or co-activators or chain transfer agents for their 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.

[0046] Solvent The catalytic components of the present invention can be used together with aromatic solvents such as toluene. Preferably, in the polymerization process, when the catalytic components are used, they do not exist. Solvents useful for dissolving the catalyst compound and the activator compound, or for combining the catalyst compound and the activator together, 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.

[0047] Preferably, the aliphatic hydrocarbon solvent is C 4 ~C 10 linear, branched, or cyclic alkanes, or alternatively, C 5 ~C 8 selected from 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 not containing all aromatic solvents such as toluene, it means that the solvent is substantially free of aromatic solvents (e.g., present at 0 mol%, or alternatively, less than 1 mol%), preferably the polymerization reaction and / or the resulting polymer do not contain "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.

[0048] 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.

[0049] 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, as described in, for example, WO2015 / 123177 and WO2020 / 092587.

[0050] 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

[0051] General Considerations Regarding Synthesis The following chemicals 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 (n-BuLi), tert-butyllithium (t-BuLi). Room temperature is 23 °C unless otherwise specified.

[0052] Complexes 1 and 2 (shown below) were prepared as described in U.S. Patent Application Publication No. 2020 / 0255553. [Chemical Formula] All reagents were purchased from commercial suppliers (Sigma Aldrich, Fisher Scientific, Strem Chemical or Oakwood Chemical) and used as received unless otherwise specified. Solvents were purged with N 2 and dehydrated over 3 Å molecular sieves. All chemical manipulations 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 prior to use. Deuterated solvents were purchased from Cambridge Isotope Laboratories, degassed and dehydrated over molecular sieves prior to use. 1 H NMR spectroscopic data were acquired at 250 MHz, 400 MHz or 500 MHz using solutions prepared by dissolving approximately 10 mg of the sample in either C 6 D 6 , CD 2 Cl 2 , CDCl 3 , D 8 -toluene or other deuterated solvents. The chemical shifts (δ) shown are relative to the residual protium in the deuterated solvents 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.

[0053] Synthesis of Ligands and Catalysts 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. Evaporating the filtrate to near dryness gave 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%.

[0054] Adamantyl aryl precursor 2-(1-Adamantyl)-4-bromophenol

Chemical formula

[0055] 1-(5-Bromo-2-(methoxymethoxy)phenyl)adamantane [Chemistry] To a solution of 2-(1-adamantyl)-4-bromophenol (15.0 g, 48.8 mmol) in diethyl ether (80 mL) was added sodium hydride (1.37 g, 51 mmol) at ambient temperature. The reaction mixture was stirred for 3 h and then concentrated to dryness. The crude product was diluted with pentane (50 mL). The resulting mixture was stirred for 30 min and then filtered to give the aryloxide sodium intermediate as a white solid.

[0056] To a solution of the aryloxide sodium intermediate in THF (50 mL) was added methoxymethyl bromide (5.33 g, 43 mmol). The reaction mixture was stirred for 3 h and then concentrated to remove most of the THF. The crude product was diluted with dichloromethane (30 mL) and washed with water. The aqueous phase was separated and extracted with additional dichloromethane. The organic extracts were combined, dried over MgSO 4 and filtered and concentrated to dryness to give the product as a yellow solid (12.8 g, 75%). 1 H NMR (400 MHz, CDCl 3 ) δ 7.34 (s, 1H), 7.26 (d, J = 8.8 Hz, 1H), 7.00 (d, J = 8.6 Hz, 1H), 5.22 (s, 2H), 3.53 (d, J = 1.2 Hz, 3H), 2.10 (s, 9H), 1.79 (s, 6H).

[0057] 2-(2-(1-adamantyl)-4-bromophenoxy)tetrahydro-2H-pyran [Chemistry] A solution of 2-(1-adamantyl)-4-bromophenol (3.30 g, 10.7 mmol) and 3,4-dihydro-2H-pyran (2.71 g, 32.2 mmol) in dichloromethane (10 mL) was added with p-toluenesulfonic acid monohydrate (20.4 mg, 0.1 mmol) at 0 °C. The reaction mixture was stirred at 0 °C for 45 minutes. The reaction was poured into 1 M aqueous NaOH (10 mL), and the resulting mixture was extracted with dichloromethane (2 × 10 mL). The combined organic extracts were dehydrated with MgSO 4 and then evaporated to dryness. The residue was stirred in methanol for 2 hours. The product was isolated as a yellow solid by filtration (3.60 g, 86%). 1 H NMR (400 MHz, CDCl 3 ) δ 7.30 (d, J = 2.1 Hz, 1H), 7.23 (d, J = 8.7 Hz, 1H), 7.05 (d, J = 8.7 Hz, 1H), 5.43 (s, 1H), 3.86 (t, J = 9.6 Hz, 1H), 3.65 (d, J = 12.0 Hz, 1H), 2.09 (br, 9H), 1.97 - 1.89 (m, 2H), 1.84 - 1.36 (m, 10H).

[0058] (3-(1-Adamantyl)-4-(methoxymethoxy)phenyl)trimethylsilane

Chemical Structure

[0059] (3-(1 - Adamantyl)-4-(methoxymethoxy)-5-(4,4,5,5 - tetramethyl - 1,3,2 - dioxaborolan - 2 - yl)phenyl)trimethylsilane

Chemical formula

[0060] (5-(1-Adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)trimethylsilane

Chemical Structure

[0061] (4-(1-Adamantyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinin-2-yl)trimethylsilane

Chemical formula

[0062] 2’,2’’’-(Pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(trimethylsilyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0063] (3-(1-Adamantyl)-4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)triethylsilane

Chem.

[0064] (5-(1-Adamantyl)-2'-bromo-6-((tetrahydro-2H-pyran-2-yl)oxy)-[1,1'-biphenyl]-3-yl)triethylsilane

Chem.

[0065] 2’,2’’’-(Pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(triethylsilyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0066] (3-(1-Adamantyl)-4-(methoxymethoxy)phenyl)tripropylsilane

Chemical formula

[0067] (5-(1-Adamantyl)-2’-bromo-6-(methoxymethoxy)-[1,1’-biphenyl]-3-yl)tripropylsilane

Chemical formula

[0068] (4-(1-Adamantyl)-6-isopropoxy-benzo[c][1,2]benzoxaborinin-2-yl)tripropylsilane

Chemical Structure

[0069] Isopropanol (20 mL) was added to the residue and the resulting solution was refluxed for 16 hours. After the reaction was cooled to ambient temperature, the reaction was concentrated to dryness. The product was washed with cold isopropanol and isolated as a white solid (1.46 g, 81%). 1 H NMR (500 MHz, CDCl 3 ) δ 8.31 - 8.12 (m, 2H), 8.06 (d, J = 6.9 Hz, 1H), 7.69 (dt, J = 28.4, 7.8 Hz, 1H), 7.50 - 7.35 (m, 2H), 5.25 (q, J = 6.2 Hz, 1H in B), 4.03 (q, J = 6.0 Hz, 1H in A), 2.36 - 2.10 (m, 9H), 1.85 (br, 6H), 1.49 - 1.34 (m, 9H), 1.22 (d, J = 6.1 Hz, 3H), 1.00 (td, J = 7.3, 1.8 Hz, 9H), 0.89 - 0.78 (m, 6H).

[0070] 2’,2’’’-(Pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tripropylsilyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0071] (3-(1-Adamantyl)-4-(methoxymethoxy)phenyl)tributylsilane

Chemical formula

[0072] (5-(1-Adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)tributylsilane

Chemical Structure

[0073] (4-(1-adamantyl)-6-hydroxy-benzo[c][1,2]benzoxaborinin-2-yl)tributylsilane

Chemical Structure

[0074] Isopropanol (40 mL) was added to the residue and the resulting solution was refluxed for 3 hours. After the reaction was cooled to ambient temperature, the reaction was concentrated to dryness. The product was purified by flash chromatography on silica gel (impurities were eluted with 20% dichloromethane in hexane and then the product was eluted with 20% dichloromethane + 20% EtOAc in hexane). The product was isolated as a foamy solid (2.58 g, 58%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.33 - 8.14 (m, 2H), 8.08 (dd, J = 18.9, 7.5 Hz, 1H), 7.73 (dt, J = 15.3, 7.6 Hz, 1H), 7.48 - 7.40 (m, 2H), 4.57 (s, 1H), 2.35 - 2.11 (m, 6H), 2.08 (br, s, 3H), 1.87 - 1.74 (m, 6H), 1.41 - 1.29 (m, 12H), 0.93 - 0.81 (m, 15H).

[0075] 2’,2’’’-(Pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tributylsilyl)-[1,1’-biphenyl]-2-ol)

Chemical formula

[0076] (3-(1-Adamantyl)-4-(methoxymethoxy)phenyl)triisopropylsilane

Chemical formula

[0077] (3-(1-Adamantyl)-4-(methoxymethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)triisopropylsilane

Chemical Structure

[0078] (5-(1-Adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)triisopropylsilane

Chemical Structure

[0079] (4-(1-Adamantyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinin-2-yl)triisopropylsilane

Chemical formula

[0080] 2’,2’’’-(Pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(triisopropylsilyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0081] (3-(1-Adamantyl)-4-(methoxymethoxy)phenyl)(tert-butyl)diphenylsilane

Chemical Structure

[0082] (5-(1-Adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(tert-butyl)diphenylsilane

Chemical formula

[0083] The lithiated intermediate (1.14 g, 1.9 mmol) was dissolved in hexane. To the resulting solution was added dropwise 2-bromochlorobenzene (0.41 g, 2.1 mmol) in hexane (1 mL) at 60 °C. The reaction was stirred at 60 °C for 1 hour and then filtered through celite. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (10% dichloromethane in hexane) to give the product as a foamy solid (1.20 g, 93%). 1 H NMR (400 MHz, CDCl 3) δ 7.70 - 7.58 (m, 5H), 7.54 (d, J = 1.8 Hz, 1H), 7.44 - 7.32 (m, 8H), 7.31 (d, J = 1.7 Hz, 1H), 7.19 (td, J = 7.7, 1.9 Hz, 1H), 4.60 (d, J = 4.7 Hz, 1H), 4.43 (d, J = 4.7 Hz, 1H), 3.25 (s, 3H), 2.14 - 2.04 (m, 9H), 1.77 (br, 6H), 1.19 (s, 9H).

[0084] (4-(1-Adamantyl)-6-isopropoxy-benzo[c][1,2]benzoxaborinin-2-yl)(tert-butyl)diphenylsilane

Chemical Structure

[0085] Isopropanol (20 mL) was added to the residue and the resulting solution was refluxed for 2 hours. After the reaction was cooled to ambient temperature, the reaction was concentrated. The product was slowly precipitated from a solution below -20 °C and collected by filtration as a white solid (0.85 g, 78%). 1 H NMR (400 MHz, CDCl 3) δ 8.20 (s, 1H), 8.04 (d, J = 7.5 Hz, 1H), 7.85 (dd, J = 17.6, 8.2 Hz, 1H), 7.66 - 7.61 (m, 4H), 7.61 - 7.49 (m, 2H), 7.46 - 7.31 (m, 7H), 5.35 - 5.13 (m, 1H in B), 4.03 (td, J = 6.3, 4.1 Hz, 1H in A), 2.25 - 2.18 (m, 6H), 2.11 (br, 3H), 1.81 (br, 6H), 1.41 (d, J = 6.1 Hz, 3H), 1.26 - 1.18 (m, 12H).

[0086] 2’,2’’’-(Pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-((tert-butyl)diphenylsilyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0087] (3-(1-Adamantyl)-4-(methoxymethoxy)phenyl)(tert-butyl)dimethylsilane [Chemical Structure] To a dry THF (300 mL) solution of 13.0 g (37.0 mmol) of 1-(5-bromo-2-(methoxymethoxy)phenyl)adamantane was added dropwise 42.0 mL (75.8 mmol) of 1.8 M t-BuLi in pentane over 30 minutes at -80 °C. The reaction mixture was stirred at this temperature for 1 hour and then 6.69 g (44.4 mmol) of tert-butylchlorodimethylsilane was added. The resulting solution was stirred at room temperature for 1 hour and then poured into 300 mL of water. The resulting mixture was extracted with dichloromethane (3 × 100 mL). The combined organic extracts were dried over Na 2 SO 4 and then evaporated to dryness. The residue was recrystallized from n-hexane. Yield 11.5 g (80%) of a pale yellow solid. 1 1H NMR (CDCl 3, 400 MHz): δ7.48 (d, J = 1.6 Hz, 1H), 7.40 (dd, J = 8.1, 1.6 Hz, 1H), 7.18 (d, J = 8.1 Hz, 1H), 5.33 (s, 2H), 3.61 (s, 3H), 2.22 - 2.27 (m, 6H), 2.18 (br.s, 3H), 1.85 - 1.93 (m, 6H), 0.98 (s, 9H), 0.36 (s, 6H). 13 C NMR (CDCl 3 , 100 MHz): δ157.1, 137.1, 133.4, 132.7, 129.2, 113.5, 94.0, 56.2, 40.7, 37.13, 37.06, 29.1, 26.5, 16.9, -6.0.

[0088] (3-(1-Adamantyl)-4-(methoxymethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)(tert-butyl)dimethylsilane

Chemical Structure

[0089] (5-(1-Adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(tert-butyl)dimethylsilane

Chemical Structure

[0090] (4-(1 - Adamantyl)-6 - isopropoxy - 6H - dibenzo[c,e][1,2]oxaborinin - 2 - yl)(tert - butyl)dimethylsilane

Chemical Structure

[0091] 2’,2’’’-(Pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyldimethylsilyl)-[1,1’-biphenyl]-2-ol) [Chemical formula] To a solution of 5.87 g (12.1 mmol) of (4-(1-adamantyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinin-2-yl)(tert-butyl)dimethylsilane in 1,4-dioxane (30 mL) were successively added 1.32 g (5.56 mmol) of 2,6-dibromopyridine, 11.8 g (36.2 mmol) of cesium carbonate and 15 mL of water. The resulting mixture was purged with argon for 10 minutes and then 703 mg (0.61 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 resulting mixture 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). Yield 4.21 g (84%) of a mixture of two isomers as a white powder. 1 1H NMR (CDCl 3, 400 MHz): δ 8.25 (s, 2H in A), 7.36 - 7.56 (m, 9H), 7.20 (d, J = 1.3 Hz, 2H in A), 7.03 (d, J = 1.4 Hz, 2H in B), 6.97 (d, J = 7.8 Hz, 2H in A), 6.94 (d, J = 7.8 Hz, 2H in B), 6.72 (d, J = 1.4 Hz, 2H in A), 6.70 (d, J = 1.3 Hz, 2H in B), 1.83 - 2.04 (m, 18H), 1.63 - 1.72 (m, 12H), 0.75 (s, 18H in B), 0.61 (s, 18H in A), 0.15 (s, 12H in B), 0.05 (s, 6H in A), 0.04 (s, 6H in A). 13 C NMR (CDCl 3 , 100 MHz) δ 157.7, 153.3, 139.3, 137.3, 137.0, 135.4, 132.2, 132.0, 131.1, 129.8, 129.0, 127.9, 127.2, 122.6, 40.5, 37.0, 36.8, 29.1, 26.3, 16.7, -6.1, -6.3.

[0092] (3-(1-Adamantyl)-4-(methoxymethoxy)phenyl)(butyl)dimethylsilane

Chemical Structure

[0093] (5-(1-Adamantyl)-2’-bromo-6-(methoxymethoxy)-[1,1’-biphenyl]-3-yl)(butyl)dimethylsilane [Chemical formula] To a solution of (3-(1-adamantyl)-4-(methoxymethoxy)phenyl)(butyl)dimethylsilane (1.70 g, 4.4 mmol) in diethyl ether (10 mL) was added n-BuLi (1.6 M in hexane, 2.8 mL, 4.4 mmol) at ambient temperature. The solution was stirred for 1 h and then concentrated to dryness. The lithiated intermediate was dissolved in hexane. To the resulting solution was added dropwise 2-bromochlorobenzene (0.88 g, 4.6 mmol) in hexane (1 mL) at 60 °C. The reaction was stirred at 60 °C for 1 h and then filtered through Celite. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (10% dichloromethane in hexane) to give the product as a foamy solid (1.94 g, 81%). 1 H NMR (400 MHz, CDCl 3) δ 7.68 (dd, J = 8.0, 1.2 Hz, 1H), 7.45 (d, J = 1.7 Hz, 1H), 7.40 (dd, J = 7.6, 1.9 Hz, 1H), 7.35 (td, J = 7.4, 1.2 Hz, 1H), 7.23 - 7.20 (m, 1H), 7.19 (d, J = 1.7 Hz, 1H), 4.48 (dd, J = 43.0, 4.7 Hz, 2H), 3.23 (s, 3H), 2.28 - 2.04 (m, 9H), 1.79 (br, 6H), 1.39 - 1.28 (m, 4H), 0.93 - 0.82 (m, 3H), 0.79 - 0.66 (m, 2H), 0.25 (d, J = 4.2 Hz, 6H).

[0094] (4-(1-Adamantyl)-6-isopropoxy-benzo[c][1,2]benzoxaborinin-2-yl)(butyl)dimethylsilane

Chemical Structure

[0095] Isopropanol (20 mL) was added to the residue, and the resulting solution was refluxed for 4 h. After the reaction mixture was cooled to ambient temperature, it was concentrated. The crude product was slowly precipitated as a white solid from the solution at < -20 °C. The pure product (1.32 g, 76%) was isolated by filtration. 1 H NMR (400 MHz, CDCl 3 ) δ 8.27 - 8.15 (m, 2H), 8.06 (d, J = 7.4 Hz, 1H), 7.68 (dddd, J = 22.7, 8.4, 7.2, 1.6 Hz, 1H), 7.52 - 7.37 (m, 2H), 5.25 (p, J = 6.1 Hz, 1H in B), 4.04 (pd, J = 6.1, 4.2 Hz, 1H in A), 2.36 - 2.07 (m, 9H), 1.85 (br, 6H), 1.41 (d, J = 6.1 Hz, 3H), 1.40 - 1.31 (m, 4H), 1.22 (d, J = 6.1 Hz, 3H), 0.94 - 0.85 (m, 3H), 0.85 - 0.75 (m, 2H), 0.33 (s, 6H).

[0096] 2’,2’’’-(Pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(butyldimethylsilyl)-[1,1’-biphenyl]-2-ol) [Chemical formula] (4-(1-Adamantyl)-6-isopropoxy-benzo[c][1,2]benzoxaborinin-2-yl)(butyl)dimethylsilane (1.21 g, 2.50 mmol) in THF (8 mL) was successively added with 2,6-dibromopyridine (0.29 g, 1.25 mmol), potassium carbonate (1.03 g, 7.5 mmol), Buchwald RuPhos precatalyst (Strem, CAS 1028206-60-1, 9.1 mg, 0.01 mmol) and water (2 mL). The mixture was stirred at 90 °C for 16 h, then cooled to ambient temperature and diluted with water (5 mL). The resulting mixture was extracted with dichloromethane (2 × 10 mL). The combined organic extracts were dehydrated with MgSO 4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel (impurities were eluted with 20% dichloromethane in hexane and then the product was eluted with 30% dichloromethane + 10% EtOAc in hexane). The product was isolated as a mixture of two isomers (0.89 g, 78%) as a foamy solid. 1 H NMR (400 MHz, CDCl 3 ) δ 8.13 (s, 2H in A), 7.54 - 7.34 (m, 9H), 7.21 (s, 2H), 7.09 (d, J = 1.5 Hz, 2H in B), 7.06 - 6.96 (m, 2H), 6.86 (s, 2H in B), 6.72 (d, J = 1.5 Hz, 2H in A), 2.06 - 1.75 (m, 18H), 1.73 - 1.57 (m, 12H), 1.36 - 1.20 (m, 8H in A), 1.18 - 1.09 (qd, J = 8.3, 5.8 Hz, 8H in B), 0.84 (t, J = 7.2 Hz, 6H), 0.68 - 0.59 (m, 4H in B), 0.53 (td, J = 7.8, 5.9 Hz, 4H in A), 0.13 (s, 12H in B), 0.00 (d, J = 6.0 Hz, 12H in A).

[0097] (3-(1-Adamantyl)-4-(methoxymethoxy)phenyl)(octyl)dimethylsilane

Chem.

[0098] (5-(1-Adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(octyl)dimethylsilane

Chem.

[0099] (4-(1-adamantyl)-6-hydroxy-benzo[c][1,2]benzoxaborinin-2-yl)(octyl)dimethylsilane

Chemical Structure

[0100] Isopropanol (20 mL) was added to the residue and the resulting solution was refluxed for 2 hours. After the reaction was cooled to ambient temperature, the reaction was concentrated to dryness. The product was purified by flash chromatography on silica gel (impurities were eluted with 20% dichloromethane in hexane and then the product was eluted with 20% dichloromethane + 20% EtOAc in hexane). The product was isolated as a foamy solid (0.90 g, 58%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.36 - 8.17 (m, 2H), 8.08 (dd, J = 13.4, 7.4 Hz, 1H), 7.73 (dt, J = 14.8, 7.7 Hz, 1H), 7.51 - 7.38 (m, 2H), 4.51 (s, 1H), 2.30-2.06 (m, 9H), 1.87-1.74 (m, 6H), 1.44 - 1.12 (m, 12H), 0.95 - 0.68 (m, 5H), 0.33 (d, J = 5.9 Hz, 6H).

[0101] 2’,2’’’-(Pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(octyldimethylsilyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0102] (3-(1-Adamantyl)-4-(methoxymethoxy)phenyl)(3,3-dimethylbutyl)dimethylsilane

Chemical formula

[0103] (5-(1-Adamantyl)-2’-bromo-6-(methoxymethoxy)-[1,1’-biphenyl]-3-yl)(3,3-dimethylbutyl)dimethylsilane

Chemical Structure

[0104] (4-(1-Adamantyl)-6-isopropoxy-benzo[c][1,2]benzoxaborinin-2-yl)(3,3-dimethylbutyl)dimethylsilane

Chemical Structure

[0105] Isopropanol (20 mL) was added to the residue and the resulting solution was refluxed for 16 hours. After the reaction was cooled to ambient temperature, the reaction was concentrated and cooled to below -20 °C for 1 hour. The product was collected by filtration and washed with a small amount of cold isopropanol to isolate a white solid (1.54 g, 70%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.27 - 8.16 (m, 2H), 8.06 (d, J = 7.7 Hz, 1H), 7.68 (dtd, J = 23.3, 8.2, 7.7, 1.5 Hz, 1H), 7.53 - 7.37 (m, 2H), 5.25 (p, J = 6.2 Hz, 1H in B), 4.03 (p, J = 6.1 Hz, 1H in A), 2.37 - 2.07 (m, 9H), 1.84 (d, J = 3.3 Hz, 6H), 1.41 (d, J = 6.1 Hz, 3H), 1.27 - 1.13 (m, 5H), 0.87 (s, 9H), 0.79 - 0.67 (m, 2H), 0.32 (s, 6H).

[0106] 2’,2’’’-(Pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-((3,3-dimethylbutyl)dimethylsilyl)-[1,1’-biphenyl]-2-ol)

Chemical formula

[0107] (3-(1-Adamantyl)-4-(methoxymethoxy)phenyl)(2,4,4-trimethylpentyl)dimethylsilane [Chemical formula] To a solution of 1-(5-bromo-2-(methoxymethoxy)phenyl)adamantane (2.08 g, 5.9 mmol) in THF (5 mL) was added dropwise t-BuLi (1.7 M in pentane, 7.0 mL, 12.0 mmol) over 10 minutes at -60 °C. The reaction mixture was stirred at -60 °C for 1 hour and then (2,4,4-trimethylpentyl)-dimethylchlorosilane (1.27 g, 6.1 mmol) was added. The solution was stirred at -60 °C for 30 minutes and then at ambient temperature for 1 hour. The reaction was poured into water (10 mL) and the resulting mixture was extracted with dichloromethane (2 × 10 mL). The combined organic extracts were dried over MgSO 4 and then evaporated to dryness. The residue was purified by flash chromatography on silica gel (10% dichloromethane in hexane) to give the product as a foamy solid (1.61 g, 61%). 1 H NMR (400 MHz, CDCl 3) δ 7.37 (d, J = 1.6 Hz, 1H), 7.29 (dd, J = 8.1, 1.6 Hz, 1H), 7.07 (d, J = 8.1 Hz, 1H), 5.23 (s, 2H), 3.51 (s, 3H), 2.36 - 1.97 (m, 9H), 1.78 (br, 6H), 1.23 (dd, J = 14.0, 4.3 Hz, 1H), 1.11 (dd, J = 13.9, 6.4 Hz, 1H), 1.00 - 0.78 (m, 14H), 0.69 (dd, J = 14.7, 8.8 Hz, 1H), 0.27 (d, J = 3.0 Hz, 6H).

[0108] (5-(1-Adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(2,4,4-trimethylpentyl)dimethylsilane [Chemical formula] (3-(1-Adamantyl)-4-(methoxymethoxy)phenyl)(2,4,4-trimethylpentyl)dimethylsilane (1.60 g, 3.6 mmol) in diethyl ether (10 mL) was added n-BuLi (1.6 M in hexane, 2.3 mL, 3.6 mmol) at ambient temperature. The solution was stirred for 1 hour and then concentrated to dryness. The lithiated intermediate was dissolved in hexane. To the resulting solution was added dropwise 2-bromochlorobenzene (0.70 g, 3.6 mmol) in hexane (1 mL) at 60 °C. The reaction was stirred at 60 °C for 1 hour and then filtered through Celite. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (10% dichloromethane in hexane) to give the product as a foamy solid (1.95 g, 90%). 1 H NMR (400 MHz, CDCl 3) δ 7.68 (dd, J = 8.0, 1.1 Hz, 1H), 7.46 (d, J = 1.7 Hz, 1H), 7.42 - 7.31 (m, 2H), 7.24 - 7.15 (m, 2H), 4.52 (dd, J = 4.6, 1.4 Hz, 1H), 4.43 (d, J = 4.7 Hz, 1H), 3.22 (s, 3H), 2.26 - 2.04 (m, 9H), 1.79 (br, 6H), 1.21 (dt, J = 14.0, 3.9 Hz, 1H), 1.09 (ddd, J = 13.9, 6.5, 3.6 Hz, 1H), 0.97 (d, J = 6.6 Hz, 1H), 0.91 (d, J = 6.5 Hz, 3H), 0.89 - 0.82 (m, 1H), 0.81 (d, J = 2.1 Hz, 9H), 0.70 (dd, J = 14.7, 8.6 Hz, 1H), 0.29 (dd, J = 3.9, 2.7 Hz, 6H).

[0109] (4-(1-Adamantyl)-6-hydroxy-benzo[c][1,2]benzoxaborinin-2-yl)(2,4,4-trimethylpentyl)dimethylsilane [Chemical formula] (5-(1-Adamantyl)-2'-bromo-6-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)(2,4,4-trimethylpentyl)dimethylsilane (1.95 g, 3.3 mmol) in THF (5 mL) was added dropwise with stirring at -60 °C to BuLi (2.5 M, 1.40 mL, 3.6 mmol) in hexane over 10 minutes. The reaction mixture was stirred at -60 °C for 1 hour and then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.91 g, 4.9 mmol) was added. The resulting suspension was stirred at ambient temperature for 1 hour and then poured into 5 mL of water. The resulting mixture was extracted with dichloromethane (3 × 5 mL). The combined organic extracts were dried over MgSO n and then evaporated to dryness. 4 ​

[0110] Isopropanol (20 mL) was added to the residue, and the resulting solution was refluxed for 6 h. After cooling the reaction mixture to ambient temperature, the reaction mixture was concentrated to dryness. The product was purified by flash chromatography on silica gel (impurities were eluted with 20% dichloromethane in hexane, and then the product was eluted with 20% dichloromethane + 10% EtOAc in hexane). The product was isolated as a foamy solid (0.53 g, 33%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.41 - 8.19 (m, 2H), 8.12 (ddd, J = 17.0, 7.5, 1.5 Hz, 1H), 7.80 - 7.70 (m, 1H), 7.56 - 7.37 (m, 2H), 4.74 (s, 1H), 2.30 (d, J = 2.9 Hz, 4H), 2.20 - 2.08 (m, 5H), 1.95 - 1.70 (m, 6H), 1.31 - 1.27 (m, 1H), 1.18 (ddd, J = 13.9, 6.4, 2.9 Hz, 1H), 1.00 (d, J = 6.6 Hz, 1H), 0.96 (dd, J = 6.6, 2.8 Hz, 3H), 0.94 - 0.74 (m, 11H), 0.41 (dd, J = 6.1, 5.1 Hz, 6H).

[0111] 2’,2’’’-(Pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-((2,4,4-trimethylpentyl)dimethylsilyl)-[1,1’-biphenyl]-2-ol)

Chemical Structure

[0112] Preparation of transition metal complex Complex 3

Chemical formula

[0113] To a suspension of 97 mg (0.301 mmol) of hafnium tetrachloride in dry toluene (20 mL) was added 436 μL (1.26 mmol) of 2.9 M MeMgBr in diethyl ether at 0 °C in one portion via syringe. To the resulting suspension was added in one portion and immediately 250 mg (0.301 mmol) of 2’,2’’’-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(trimethylsilyl)-[1,1’-biphenyl]-2-ol). The reaction mixture was stirred at room temperature for 4 h and then almost evaporated to dryness. The resulting solid was extracted with 2 × 20 mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane. The resulting precipitate was filtered off, washed twice with 5 mL of n-hexane and then dried in vacuo. Yield 266 mg (85%) of a white-beige solid. Elemental analysis C 57 H 69 HfNSi 2 O 2 Calculated for: C, 66.16; H, 6.72; N, 1.35. Found: C 66.47; H, 6.99; N 1.20. 1 H NMR (C 6 D 6 , 400 MHz): δ 7.75 (d, J = 1.7 Hz, 2H), 7.28 (d, J = 1.7 Hz, 2H), 6.95 - 7.19 (m, 8H), 6.32 - 6.39 (m, 3H), 2.51 - 2.58 (m, 6H), 2.37 - 2.44 (m, 6H), 2.18 (br.s, 6H), 1.95 - 2.02 (m, 6H), 1.80 - 1.87 (m, 6H), 0.30 (s, 18H), -0.11 (s, 6H). 13 C NMR (C 6 D 6, 100 MHz) δ 162.9, 157.8, 143.5, 139.8, 138.8, 134.4, 133.9, 133.6, 132.9, 132.5, 131.7, 131.4, 128.5, 128.3, 125.0, 51.8, 41.9, 38.3, 37.8, 30.0, -0.11.

[0114] Complex 4 [Chemical formula] ZrCl in toluene (about 8 mL) cooled to 0 °C 4 (Et 2 O) 2 (63 mg, 0.165 mmol) and 2′,2′′′-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(triethylsilyl)-[1,1′-biphenyl]-2-ol) (375 mg, 0.150 mmol), MeMgBr (3.0 M, 0.24 mL, 0.721 mmol) was added dropwise. The reaction mixture was stirred at ambient temperature for 90 minutes, stored at -40 °C overnight, and then almost evaporated to dryness. The resulting solid was extracted with pentane (about 9 mL) and toluene (about 1 mL). The extract was filtered through celite on a glass fiber plug. The resulting filtrate was concentrated under vacuum to give an oily residue, which was triturated with pentane several times to finally give a light yellowish-brown foam (127 mg). The foam was dissolved in pentane and the minimum amount of toluene. The resulting solution was stored at -40 °C to give colorless crystals, which were isolated by decantation and dried under vacuum. Yield 65.2 mg (42%). 1 H NMR (C 6 D 6, 400 MHz): δ 7.73 (s, 2H), 7.21 (d, J = 8.7 Hz, 4H), 7.06 (dt, J = 18.9, 7.4 Hz, 4H), 6.92 (d, J = 7.3 Hz, 2H), 6.55 - 6.50 (m, 1H), 6.42 (d, J = 7.6 Hz, 2H), 2.58 (d, J = 12.1 Hz, 6H), 2.44 (d, J = 12.3 Hz, 6H), 2.18 (s, 6H), 1.98 (d, J = 12.0 Hz, 6H), 1.83 (d, J = 12.2 Hz, 6H), 1.05 (t, J = 7.8 Hz, 18H), 0.83 (q, J = 7.6 Hz, 12H), 0.14 (s, 6H).

[0115] Complex 5

Chem.

[0116] Complex 6

Chem.

[0117] ZrCl in toluene (ca. 6 mL) cooled to -40 °C 4 (Et 2 O) 2 (143 mg, 0.375 mmol) and 2’,2’’’-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tributylsilyl)-[1,1’-biphenyl]-2-ol) (375 mg, 0.347 mmol), MeMgBr (3.0 M, 0.52 mL, 1.56 mmol) was added dropwise. The reaction mixture was stirred at ambient temperature for 25 min and then almost evaporated to dryness. The resulting residue was triturated with pentane three times and then concentrated in vacuo to give a beige solid. The solid was extracted with pentane and the combined extracts were filtered through celite. Next, the filtrate (already containing some microcrystalline material) was stored at -40 °C and slowly evaporated. After several days, the brown supernatant was removed and the remaining solid was washed with cold pentane (3 × 0.5 mL) and then dried in vacuo to give the product as a white microcrystalline solid (136 mg, 33%). The supernatant and the pentane washings were combined and concentrated in vacuo to give a brown foam (223 mg). Total recovered mass: 359 mg, 86%. 1 H NMR (C 6 D 6 , 400 MHz): δ 7.78 (d, J = 1.8 Hz, 2H), 7.32 - 7.21 (m, 4H), 7.07 (dtd, J = 21.1, 7.4, 1.5 Hz, 4H), 6.95 (dd, J = 7.5, 1.6 Hz, 2H), 6.75 - 6.67 (m, 1H), 6.50 (d, J = 7.8 Hz, 2H), 2.68 - 2.39 (m, 12H), 2.17 (d, J = 5.1 Hz, 6H), 2.04 - 1.73 (m, 12H), 1.56 - 1.31 (m, 24H), 1.10 - 0.70 (m, 30H), 0.14 (s, 6H).

[0118] Complex 7 [Chemical]

[0119] To a suspension of 701 mg (3.01 mmol) of zirconium tetrachloride in dry toluene (350 mL) was added at -30 °C in one portion via syringe 4.36 mL (12.6 mmol, 2.9 M) of MeMgBr in diethyl ether. To the resulting suspension was added in one portion immediately 3.00 g (3.01 mmol) of 2′,2′′′-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(triisopropylsilyl)-[1,1′-biphenyl]-2-ol). The reaction mixture was stirred at room temperature for 3 h and then almost evaporated to dryness. The resulting solid was extracted with 2 × 100 mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 10 mL of n-hexane. The resulting precipitate was filtered off, washed twice with 10 mL of n-hexane and then dried in vacuo. Yield 3.24 g (96%) of a light beige solid. Elemental analysis C 69 H 93 ZrSi 2 NO 2 Calculated for: C, 74.27; H, 8.40; N, 1.26. Found: C 74.41; H, 8.58; N 1.10. 1 H NMR (C 6 D 6, 400 MHz): δ 7.69 (d, J = 1.5 Hz, 2H), 7.23 (dd, J = 7.6, 1.2 Hz, 2H), 6.99 - 7.14 (m, 6H), 6.94 (dd, J = 7.5, 1.3 Hz, 2H), 6.71 (t, J = 7.7 Hz, 1H), 6.54 (d, J = 7.8 Hz, 2H), 2.54 - 2.63 (m, 6H), 2.40 - 2.49 (m, 6H), 2.18 (br.s, 6H), 1.94 - 2.03 (m, 6H), 1.77 - 1.86 (m, 6H), 1.29 - 1.44 (m, 6H), 1.16 (d, J = 8.0 Hz, 24H), 1.14 (d, J = 7.7 Hz, 12H), 0.15 (s, 6H). 13 C NMR (C 6 D 6 , 100 MHz): δ 162.1, 158.5, 143.6, 137.9, 136.3, 134.6, 133.6, 133.4, 133.1, 131.7, 131.1, 124.5, 122.3, 43.7, 42.2, 38.4, 37.8, 30.0, 19.3, 11.6.

[0120] Complex 8

Chem.

[0121] Complex 9 [Chemical formula] To a suspension of 766 mg (3.28 mmol) of zirconium tetrachloride in dry toluene (350 mL) was added in one portion via syringe 2.9 M MeMgBr in 4.80 mL (13.8 mmol) of diethyl ether at -30 °C. To the resulting suspension was added in one portion immediately 3.00 g (3.28 mmol) of 2′,2′′′-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyldimethylsilyl)-[1,1′-biphenyl]-2-ol). The reaction mixture was stirred at room temperature for 3 h and then almost evaporated to dryness. The resulting solid was extracted with 2 × 100 mL of toluene and the combined organic extracts were filtered through a thin pad of Celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 10 mL of n-hexane. The resulting precipitate was filtered off, washed twice with 10 mL of n-hexane and then dried in vacuo. Yield 3.14 g (93%) of a light beige solid. Elemental analysis C 63 H 81 ZrSi 2 NO 2 Calculated for: C, 73.34; H, 7.91; N, 1.36. Found: C 73.25; H, 7.98; N 1.32. 1 H NMR (C 6 D 6, 400 MHz): δ 7.72 (d, J = 1.6 Hz, 2H), 7.21 - 7.24 (m, 4H), 6.99 - 7.10 (m, 4H), 6.96 (dd, J = 7.5, 1.8 Hz, 2H), 6.52 (dd, J = 8.3, 7.2 Hz, 1H), 6.39 (d, J = 7.6 Hz, 2H), 2.53 - 2.62 (m, 6H), 2.39 - 2.48 (m, 6H), 2.17 (br.s, 6H), 1.93 - 2.02 (m, 6H), 1.78 - 1.87 (m, 6H), 0.99 (s, 18H), 0.29 (s, 6H), 0.27 (s, 6H), 0.13 (s, 6H). 13 C NMR (C 6 D 6 , 100 MHz): δ 162.3, 158.3, 143.5, 139.6, 137.9, 135.4, 133.9, 133.6, 133.0, 131.7, 131.2, 125.8, 124.5, 43.7, 42.1, 38.4, 37.8, 30.0, 27.3, 17.7, -5.3, -5.5.

[0122] Complex 10

Chem.

[0123] ZrCl in toluene (about 3 mL) cooled to -40 °C 4 (Et 2 O) 2(80 mg, 0.210 mmol) and 2′,2′′′-(pyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(n-butyldimethylsilyl)-[1,1′-biphenyl]-2-ol) (180 mg, 0.197 mmol) were added dropwise with MeMgBr (3.0 M, 0.30 mL, 0.900 mmol). The reaction mixture was stirred at ambient temperature for 80 minutes and then almost evaporated to dryness. The resulting solid was extracted with pentane, and the combined extracts were filtered through celite. The filtrate (ca. 2 mL) was stored at ambient temperature and slowly evaporated. After several days, evaporation of the pentane gave a solid, which was washed with cold pentane on a plastic frit funnel and then dried under vacuum to give the product as an off-white powder (75.8 mg, 37%).

[0124] Complex 11

Chemical Structure

[0125] ZrCl in toluene (ca. 3 mL) cooled to -40 °C 4 (Et 2 O) 2 (55 mg, 0.144 mmol) and 2′,2′′′-(pyridine-2,6-diyl)bis(3-(1-adamantanyl)-5-(dimethyl(octyl)silyl)-[1,1′-biphenyl]-2-ol) (141 mg, 0.137 mmol) were added dropwise with MeMgBr (3.0 M, 0.2 mL, 0.600 mmol). The reaction mixture was stirred at ambient temperature for 30 minutes and then almost evaporated to dryness. The resulting solid was extracted with pentane. The extract was filtered through celite on a glass fiber plug. Concentration of the resulting filtrate under vacuum gave a light yellowish brown foam. Yield 54.2 mg (34.5%).

[0126] Complex 12

Chemical Structure

[0127] Complex 13

Chemical formula

[0128] Solubility of the complex General considerations: The solubility studies for Complexes 2, 6, and 9 were carried out using the recrystallized materials. The solubility studies for all other complexes were carried out using the synthesized materials. Complex 2 was co-crystallized with 1.4 equivalents of methylcyclohexane. Complex 9 was co-crystallized with 0.52 equivalents of isohexane. The solvents used were purged with nitrogen (30 - 60 min) and dried over 3 Å molecular sieves. Unless otherwise specified, all measurements were carried out at ambient temperature (20 - 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.

[0129] Method 1. A tared vial was charged with a small amount of the complex (the actual mass recorded including any residual solvents noted above, typically 5 - 30 mg). 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.

[0130] Method 2. The measured amount (the actual mass recorded including any residual solvents as noted above) of the complex 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 the total solvent added to achieve the homogeneous solution and the higher boundary value of the solubility calculated using the total 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 the total solvent added. The equations used to calculate solubility are listed below. Solvents present in the complex are included in the mass and formula weight of the complex. Solubility (mM) = [10 6 * [(number of grams of complex) / (formula mass of complex (g / mol))] / [(total volume of solvent (mL))] or Solubility (mM) = [10 6 * [(number of grams of complex) / (formula mass of complex (g / mol))] / [(number of grams of solvent) / (density of solvent (g / mL))] Solubility (mass%) =

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

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

[0131]

Table 1

[0132] Polymerization Example Toluene (ExxonMobil Chemical - anhydrous, stored under N 2 at below) (98%) or isohexane (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 0.5 mmol / L. The polymerization-grade toluene and / or isohexane 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 filled with dried 3 Å molecular sieves (8 - 12 mesh; Aldrich Chemical Company), and two 500 cc columns in series filled with dried 5 Å molecular sieves (8 - 12 mesh; Aldrich Chemical Company).

[0133] Polymerization-grade propylene (C​​3 ) was further purified by passing the above polymerization grade propylene through a series of columns: a 2250 cc Oxiclear cylinder made by Labclear, then a 2250 cc column packed with 3 Å molecular sieves (8 - 12 mesh; Aldrich Chemical Company), then two 500 cc columns in series packed with 5 Å molecular sieves (8 - 12 mesh; Aldrich Chemical Company), then a 500 cc column packed with Selexsorb CD (BASF), and finally a 500 cc column packed with Selexsorb COS (BASF). 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 wt% 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 prior to introducing the activator and the pre - catalyst into the reactor. TNOA was typically used as a 5 mmol / L solution in toluene or isohexane.

[0134] Description and preparation of the reactor: The polymerization was carried out in an autoclave equipped with an external heater for temperature control, a glass insert (internal volume 22.5 mL), a septum inlet for regulating the supply of nitrogen and propylene, and a disposable PEEK mechanical stirrer (800 RPM) in an inert atmosphere (N 2 ) dry box. 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.

[0135] 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 process conditions. The reactor temperature was monitored and typically maintained within + / - 1 °C. Polymerization was terminated by adding a compressed dry air gas mixture of 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 is reported as the quench time (s). The reported yield includes the total mass of the polymer and residual catalyst. Catalyst activity is reported as 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 along with further physical property evaluations in Table 3.

[0136] Polymer Characterization Regarding the analytical tests, 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%, 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 - 0.9 mg / mL, including a BHT concentration such that there was 1.25 mg of BHT per 1 mL of TCB. The sample was cooled to 135 °C for testing.

[0137] 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 5000 and 3,390,000). Alternatively, 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 a 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.

[0138] Differential scanning calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting points of the polymers. The samples were pre-annealed at 220° C. for 15 minutes and then cooled at room temperature overnight. The samples were then heated to 220° C. at a rate of 100° C. / min and then cooled at a rate of 50° C. / min. Melting points were collected during the heating period. The results are reported under the heading Tm (° C.) in Table 2.

[0139] 13 C NMR spectroscopy was used to characterize some of the polypropylene polymer samples produced in the experiments collected in Table 2. This data is collected in Table 3. Unless otherwise indicated, 13 d Polymer samples for C NMR spectroscopy 2 - Dissolved in 1,1,2,2-tetrachloroethane, 150MHz 13 Samples were recorded at 125° C. using an NMR spectrometer using C NMR frequencies. Polymer resonance peaks are referenced to mmmm=21.8 ppm. Calculations involved in the characterization of polymers by NMR follow the work of FA Bovey in "Polymer Conformation and Configuration" Academic Press, New York 1969 and J. Randall in "Polymer Sequence Determination, Carbon-13 NMR Method", Academic Press, New York, 1977.

[0140] Steric defects measured as "steric defects / 10,000 monomer units" are calculated from the sum of the intensities of the mmrr, mmrm+rrmr, and rmrm resonance peaks multiplied by 5000. The intensities used in this calculation are normalized to the total number of monomers in the sample. The methods for measuring 2,1-position defects / 10,000 monomers and 1,3-position defects / 10,000 monomers follow standard methods. Additional references include Grassi, A. et.al. Macromolecules, 1988, v)21, pp. 617-622 and Busico et.al. Macromolecules, 1994, v)27, pp. 7538-7543. Average meso length = 10000 / [(steric defects / 10,000 C) + (2,1-position defects / 10,000 C) + (1,3-position defects / 10,000 C)].

[0141] The polymerization results are collected in Tables 2 and 3. "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) for identifying the pre-catalyst 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.

[0142] The 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, and 4.1 ml of total solvent, and the quench value is 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 was used, both the pre-catalyst and the activator solution were present in toluene. When activator B was used, both the pre-catalyst and the activator solution were present in isohexane. A small amount of methylcyclohexane (MCH) was derived from activator B supplied by the manufacturer as a 10 wt% solution in methylcyclohexane.

[0143]

Table 2

Table 3

[0144] 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, e.g., 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 recited values, taking into account experimental error and variations that would be expected by one of ordinary skill in the art. Any value in a table can be presented with an additional + / - 10% around the endpoints of the range that defines their individual measured values or characteristics.

[0145] All documents described herein, including any priority documents and / or test procedures, are incorporated herein by reference to the extent they are not inconsistent with this specification. As will be 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.

[0146] 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,[[]] 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 、 R 7 and R 8 are each, independently, hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 120 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of 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 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 120 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 120 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 120 substituted hydrocarbyl, a heteroatom or a 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 bonded together to form a bidentate Lewis base,[[]] The X group may be bonded to the L group to form a monoanionic bidentate group,[[]] Any two X groups may be bonded together to form a dianionic ligand group,[[]] However, R 1 R 2 R 3 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 and R 16 at least one of which is a silyl group or a germyl group containing a moiety 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 of a substituted hydrocarbyl ring or an unsubstituted hydrocarbyl ring))

2. The catalyst compound according to claim 1, represented by formula (II). [Chemical Formula 2] (II) (In the formula,[[]] A' and A" are each, independently, Si or Ge, and R a , R b , R c , R d , R e and R f 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 , R b and R c , R d and R e , R d and R f or R e and R f may together form one or more of a substituted hydrocarbyl ring or an unsubstituted hydrocarbyl ring)

3. R 2 and R 7 are silyl groups or germyl groups of form A (R a )(R b )(R c )(wherein A is Si or Ge, preferably Si, and A(R a )(R b )(R c ) may contain at least 7 carbons), preferably independently containing silyl groups, the catalyst compound according to claim 1.

4. R 2 and R 7 each has the form A(R a )(R b )(R c )(wherein A is Si, and A(R a )(R b )(R c ) contains at least 7 carbons, and at least one, preferably two, of R a , R b and R c are aliphatic (C 3 -C 40 ) hydrocarbyl or (C 2 -C 40 ) heterohydrocarbyl, each containing a linear carbon chain of at least 3, preferably 4, carbons with the terminal bonded to A), and the catalyst compound according to claim 1 containing a silyl group.

5. A' and A" are Si, and A'(R a )(R b )(R c ) contains at least 7 carbons, and A"(R e )(R f )(R g ) contains at least 7 carbons, the catalyst compound according to claim 2.

6. A' and A" are Si, and A'(R a )(R b )(R c ) contains at least 7 carbons, and at least one, preferably two, of R a , R b and R c are aliphatic (C 3 -C 40 ) hydrocarbyl or (C 2 -C 40 ) heterohydrocarbyl, containing a linear carbon chain of at least 3 carbons with the end bonded to A', and A"(R e )(R f )(R g ) contains at least 7 carbons, and at least one of R d , R e and R f is aliphatic (C 3 -C 40 ) hydrocarbyl or (C 2 -C 40 ) heterohydrocarbyl, containing a linear carbon chain of at least 3, preferably 4, carbons with the end bonded to A", the catalyst compound according to claim 2.

7. R 4 and R 5 is independently adamantyl or substituted adamantyl, the catalyst compound according to any one of claims 1 to 6.

8. The following: 【Chemical Formula 3】 The catalyst compound according to claim 1, which is one of.

9. 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 8.

10. A homogeneous solution comprising an aliphatic hydrocarbon solvent, and at least one catalyst compound according to claim 1 or 2, 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.

11. The homogeneous solution according to claim 10, wherein the aliphatic hydrocarbon solvent is isooctane, cyclohexane, methylcyclohexane, pentane, isopentane, heptane, isoparaffin solvent, non-aromatic cyclic solvent or a combination thereof.

12. A method for producing a propylene-based or ethylene-based polymer or copolymer, comprising, in one or more continuous stirred tank reactors or loop reactors in series or in parallel, a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30 ° C to 230 ° C, contacting propylene and / or ethylene and optionally a comonomer with the catalyst system according to claim 9 to polymerize propylene and / or ethylene and optionally a comonomer, and forming a propylene-based or ethylene-based polymer or copolymer. A method.

13. The method according to claim 12, wherein the catalyst system and the activator are supplied to the reactor individually.

14. The method according to claim 12, wherein the catalyst system and the activator are premixed before being fed into the reactor.

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