Substituted pyridine-2, 6-bis (phenylene phenolate) complexes with enhanced solubility useful as olefin polymerization catalyst components

Abstract

Exemplary embodiments of the present technical progress include pyridine-2, 6-bis (phenylene phenolate) complexes that can be used as catalyst components for olefin polymerization and have improved solubility in non-aromatic hydrocarbons, such as isohexane. Improved solubility of these complexes is achieved by modifying the ligand backbone at specific positions, which results in improved solubility, but does not adversely affect the performance of the complexes when used as catalysts for olefin polymerization.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 338,169, filed on May 4, 2022, the disclosure of which is incorporated herein by reference. Technical Field

[0002] The present disclosure relates to bis(arylphenolate) Lewis base transition metal complexes, catalyst systems comprising the bis(arylphenolate) Lewis base transition metal complexes, and polymerization processes for producing polyolefin polymers such as polyethylene-based polymers and polypropylene-based polymers. Background Art

[0003] Polyolefins, such as polyethylene, typically have comonomers, such as hexene, incorporated into the polyethylene backbone. These copolymers provide varying physical properties compared to polyethylene itself and are typically prepared in low pressure reactors using, for example, solution, slurry or gas phase polymerization processes. Polymerization can be carried out in the presence of catalyst systems such as those using Ziegler-Natta catalysts, chromium-based catalysts or metallocene catalysts.

[0004] In addition, the procatalyst (neutral, unactivated complex) should be thermally stable at ambient and above ambient temperatures because they are typically stored for weeks before use. The performance of a given catalyst is closely affected by reaction conditions such as monomer concentration and temperature. For example, solution processes that benefit from operating at temperatures above 120°C are particularly challenging for catalyst development. At such high reactor temperatures, it is generally difficult to maintain high catalyst activity and high molecular weight capabilities because these two properties decrease fairly consistently with increasing reactor temperature. Due to the need for a wide range of polyolefin products from high-density polyethylene (HDPE) to elastomers (e.g., thermoplastic elastomers (TPE), ethylene-propylene-diene (EPDM)), many different catalyst systems may be required because a single catalyst is unlikely to be able to meet all the needs for producing these various polyolefin products. The stringent set of requirements required to develop and produce new polyolefin products makes it a highly challenging endeavor to identify suitable catalysts for a given product and production process.

[0005] Aromatic solvents are commonly used to dissolve catalyst components in industrial olefin polymerization processes. However, replacing aromatic solvents with non-aromatic solvents such as isohexane is often challenging due to the poor solubility of catalyst components in non-aromatic solvents.

[0006] Further information on the general prior art of non-metallocene olefin polymerization catalysts can be found in Baier, MC (2014) “Post-metallocenes in the industrial production of poly-olefins,” Angew. Chem. Int. Ed., v. 53, pp. 9722-9744, the entire contents of which are hereby incorporated by reference.

[0007] For further information about the complex, see: Goryunov, GP et al. (2021) "Rigid postmetallocene catalysts for propylene polymerization: ligand design prevents the temperature-dependent loss of stereo-and regioselectivities," AC Catalysis, v. 11 (13), pp. 8079-8086; US 2020 / 0255556; US 2020 / 0255555; US 2020 / 0254431; and US 2020 / 0255553, the entire contents of each of which are hereby incorporated by reference. Summary of the invention SUMMARY OF THE INVENTION

[0008] The catalyst compound represented by formula (I): in: M is a Group 3, 4 or 5 metal; 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 not greater than 4; R 10 and R 14 Each of which is independently C4-C 40 Hydrocarbon or OR 20 , where R 20 It is C4-C 40 Hydrocarbon; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 9 , R 11 and R 12 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 11 and R 12 may be linked to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 13 , R 15 and R 16 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 15 and R 16 may be linked to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 Each of which is independently hydrogen, C 1- C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 or R 17 and R 19One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; Any two L groups can be linked together to form a bidentate Lewis base; The X group may be linked to the L group to form a monoanionic bidentate group; and Any two X groups may be linked together to form a dianionic ligand group.

[0009] A homogeneous solution comprising: an aliphatic hydrocarbon solvent; and at least one complex of formula (I), wherein the concentration of the complex is 0.20 wt % or greater (or 0.25 wt % or greater, or 0.30 wt % or greater, or 0.35 wt % or greater, or 0.40 wt % or greater, or 0.50 wt % or greater, or 1.0 wt % or greater, or 2.0 wt % or greater).

[0010] A method for producing a propylene-based polymer, comprising: polymerizing propylene by contacting propylene with a catalyst system prepared by formula (I) in one or more continuous stirred tank reactors or loop reactors connected in series or in parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to form a propylene-based polymer.

[0011] A method for producing an ethylene-based polymer, comprising: polymerizing ethylene by contacting ethylene with a catalyst system prepared by formula (I) in one or more continuous stirred tank reactors or loop reactors connected in series or in parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to form an ethylene-based polymer. DETAILED DESCRIPTION OF THE INVENTION

[0012] Exemplary embodiments of the present technological advances include pyridine-2,6-bis(phenylenephenolate) complexes that are useful as catalyst components for olefin polymerization and have improved solubility in non-aromatic hydrocarbons such as isohexane. The improved solubility of these complexes is achieved by modifying the ligand backbone at specific positions, which results in improved solubility, but does not adversely affect the performance of the complex when used as a catalyst for olefin polymerization.

[0013] For purposes of this disclosure, the new numbering scheme for the Periodic Table Groups is used as described in Chemical and Engineering News, v. 63(5), pg. 27, (1985). Thus, a "Group 4 metal" is an element selected from Group 4 of the Periodic Table, such as Hf, Ti, or Zr.

[0014] The following abbreviations may be used herein: Me is methyl, Et is ethyl, Ph is phenyl, tBu is tert-butyl, MAO is methylaluminoxane, NMR is nuclear magnetic resonance, t is time, s is seconds, h is hours, psi is pounds per square inch, psig is pounds per square inch, gauge pressure, equiv is equivalent, and RPM is revolutions per minute.

[0015] The specification describes transition metal complexes. The term complex is used to describe molecules in which an auxiliary ligand is coordinated to a central transition metal atom. The ligand is so large and stably bonded to the transition metal that it maintains its influence during catalyst application (e.g., polymerization). The ligand can be coordinated to the transition metal by covalent bonds and / or electron-donating coordination or intermediate bonds. An activator is generally used to activate transition metal complexes to exert their polymerization or oligomerization functions, without wishing to be bound by theory, and the activator is believed to produce cations due to the removal of anionic groups (commonly referred to as leaving groups) from transition metals.

[0016] The terms "substituent," "radical," "group," and "moiety" are used interchangeably.

[0017] "Conversion" is the amount of monomer converted to polymer product and is reported as mol% and is calculated based on polymer yield and the amount of monomer fed to the reactor.

[0018] "Catalyst activity" is a measure of how active a catalyst is and is reported as grams of product polymer (P) produced per mmol of catalyst (cat) used per hour (gP.mmolcat -1 .h -1 ).

[0019] The term "heteroatom" refers to any Group 13-17 element excluding carbon. Heteroatoms may include B, Si, Ge, Sn, N, P, As, O, S, Se, Te, F, Cl, Br, and I. The term "heteroatom" may include the above elements with hydrogen attached, such as BH, BH2, SiH2, OH, NH, NH2, etc. The term "substituted heteroatom" describes heteroatoms in which one or more of these hydrogen atoms are replaced by a hydrocarbyl or substituted hydrocarbyl(s).

[0020] Unless otherwise indicated (e.g., the definitions of "substituted hydrocarbyl," "substituted aromatic," etc.), the term "substituted" means that at least one hydrogen atom has been replaced by at least one non-hydrogen group, such as a hydrocarbyl, 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 or a halocarbyl, and two or more R* may be linked together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom has been inserted into the hydrocarbyl ring.

[0021] The term "substituted hydrocarbyl" refers to a hydrocarbyl group wherein at least one of the hydrogen atoms of the hydrocarbyl group has been 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, wherein each R* is independently a hydrocarbyl or a halocarbon group, and two or more R* may be linked together to form a substituted or unsubstituted fully saturated, partially unsaturated, substituted or unsubstituted hydrocarbyl group, or an aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom has been inserted into the hydrocarbyl ring. The term "hydrocarbyl-substituted phenyl" refers to a phenyl group having 1, 2, 3, 4, or 5 hydrogen groups replaced by hydrocarbyl or substituted hydrocarbyl groups. For example, a "hydrocarbyl-substituted phenyl group" may be represented by the following formula: Where R a , R b , R c , R d and R e Each of which can be independently selected from hydrogen, C1-C 40 Hydrocarbon or C1-C 40 Substituted hydrocarbon group, heteroatom or heteroatom-containing group (provided that R a , R b , R c , R d and R e At least one of them is not H), or R a , R b , R c , R d and R eTwo or more of these can be linked together to form C4-C 62 Cyclic or polycyclic hydrocarbon ring structures, or combinations thereof.

[0022] The term "substituted aromatic" refers to aromatic groups having one or more hydrogen radicals replaced with hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing groups.

[0023] The term "substituted phenyl" refers to a phenyl group having one or more hydrogen radicals replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0024] The term "substituted carbazole" refers to a carbazole group having one or more hydrogen groups replaced with a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

[0025] The term "substituted naphthyl" refers to a naphthyl group having one or more hydrogen groups replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0026] The term "substituted anthracenyl" refers to anthracenyl groups having one or more hydrogen groups replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0027] The term "substituted fluorenyl" refers to a fluorenyl group having one or more hydrogen radicals replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0028] The terms trihydrocarbylsilyl and trihydrocarbylgermyl refer to silyl or germyl groups combined with three hydrocarbyl groups. Examples of suitable trihydrocarbylsilyl and trihydrocarbylgermyl groups may include trimethylsilyl, trimethylgermyl, triethylsilyl, triethylgermyl, and all isomers of tripropylsilyl, tripropylgermyl, tributylsilyl, tributylgermyl, tripentylsilyl, tripentylgermyl, butyldimethylsilyl, butyldimethylgermyl, dimethyloctylsilyl, dimethyloctylgermyl, and the like.

[0029] The terms dihydrocarbylamino and dihydrocarbylphosphino refer to nitrogen or phosphorus groups bonded to two hydrocarbyl groups. Examples of suitable dihydrocarbylamino and dihydrocarbylphosphino groups may include dimethylamino, dimethylphosphino, diethylamino, diethylphosphino, and all isomers of dipropylamino, dipropylphosphino, dibutylamino, dibutylphosphino, etc.

[0030] The term "substituted adamantanyl" refers to an adamantyl group having one or more hydrogen groups replaced with a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

[0031] The terms "alkoxy" and "alkoxide" refer to an alkyl or aryl group bonded to an oxygen atom, such as an alkyl ether or aryl ether group attached to an oxygen atom, and may include groups in which the alkyl / aryl group is C1-C 10 The alkyl radicals may be straight chain, branched or cyclic alkyl radicals. The alkyl radicals may be saturated or unsaturated. Examples of suitable alkoxy radicals may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy.

[0032] The term "aryl" or "aryl group" refers to aromatic rings and substituted variants thereof, for example phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O or S. As used herein, the term "aromatic" also refers to quasi-aromatic heterocycles, which are heterocyclic substituents having similar properties and structure (almost planar) to aromatic heterocyclic ligands, but which do not fall within the definition of aromatic; likewise, the term aromatic also refers to substituted aromatic compounds.

[0033] The term "aralkyl" refers to an aryl group in which a hydrogen has been replaced with an alkyl or substituted alkyl group. For example, 3,5'-di-tert-butylphenylindenyl is an indene substituted with an aralkyl group. When an aralkyl group is a substituent on another group, it is bonded to that group via the aryl group.

[0034] The term "alkaryl" refers to an alkyl group in which a hydrogen has been replaced with an aryl or substituted aryl group. For example, phenethyl indenyl is an indene substituted with an ethyl group bonded to a phenyl group. When an alkaryl group is a substituent on another group, it is bonded to that group via an alkyl group.

[0035] The term "ring atoms" refers to atoms that are part of a cyclic ring structure. According to this definition, benzyl has 6 ring carbon atoms and tetrahydrofuran has 5 ring carbon atoms.

[0036] A heterocycle is a ring having heteroatoms in the ring structure, as opposed to a heteroatom-substituted ring in which hydrogens on a ring atom are replaced by heteroatoms. For example, tetrahydrofuran is a heterocycle and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles may include pyridine, imidazole, and thiazole.

[0037] The terms "hydrocarbyl radical", "hydrocarbyl group" or "hydrocarbyl" are used interchangeably and are defined to mean a group consisting only of hydrogen and carbon atoms. For example, a hydrocarbyl radical can be C1-C 100A group which may be linear, branched or cyclic and, when cyclic, may be aromatic or non-aromatic. Examples of such groups may 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., isopentyl, cyclopentyl), hexyl (e.g., cyclohexyl), octyl (e.g., cyclooctyl), nonyl, decyl (e.g., adamantyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or triacontyl, and aryl groups such as phenyl, benzyl and naphthyl.

[0038] As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, Mz is the z average molecular weight, wt% is the weight percentage, and mol% is the mole percentage. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are g / mol.

[0039] As used herein, unless otherwise indicated, "high molecular weight" is defined as a number average molecular weight (Mn) value of 100,000 g / mol or greater. "Low molecular weight" is defined as a Mn value of less than 100,000 g / mol.

[0040] Unless otherwise indicated, all melting points (Tm) are differential scanning calorimetry (DSC) second melts.

[0041] A "catalyst system" is a combination 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," "procatalyst compound," and "procatalyst complex" are used interchangeably. When "catalyst system" is used to describe such a pairing before activation, it refers to an unactivated catalyst complex (procatalyst) together with an activator and, optionally, a co-activator. When it is used to describe such a pairing after activation, it refers to an activated complex and an activator or other charge-balancing structural part. The transition metal compound can be neutral, as in a procatalyst, or a charged species with a counterion, as in an activated catalyst system. For the purposes of this disclosure and its claims, when a catalyst system is described as comprising a neutral stable form of a component, it will be understood by those skilled in the art that the ionic form of the component is a form that reacts with a monomer to produce a polymer. A polymerization catalyst system is a catalyst system that can polymerize a monomer into a polymer. In addition, the catalyst compounds and activators represented by the structural formulas herein are intended to cover catalyst compounds and activators in neutral and ionic forms.

[0042] In the description herein, the catalyst may be described as a catalyst, a catalyst precursor, a procatalyst compound, a catalyst compound, or a transition metal compound, and these terms are used interchangeably.

[0043] "Anionic ligands" are negatively charged ligands that donate one or more electron pairs to a metal ion. "Lewis bases" are neutrally charged ligands that donate one or more electron pairs 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 heterocyclic. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan. Bis(arylphenolate)Lewis base ligands are tridentate ligands that bind to a metal via two anion donors (phenolates) and one heterocyclic Lewis base donor (e.g., pyridyl). Bis(arylphenolate)heterocyclic ligands are tridentate ligands that bind to a metal via two anion donors (phenolates) and one heterocyclic Lewis base donor.

[0044] The term "continuous" refers to a system that operates without interruption or stopping. For example, a continuous process for making a polymer would be one in which the reactants are continuously introduced into one or more reactors and the polymer product is continuously withdrawn. Transition Metal Complexes

[0045] In at least one embodiment, the catalyst compound represented by formula (I) is as follows. in: M is a Group 3, 4 or 5 metal; 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 not greater than 4; R 10 and R 14 Each of which is independently C4-C 40 Hydrocarbon or OR 20 , where R 20 It is C4-C 40 Hydrocarbon; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 9 , R 11 and R 12 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 11 and R 12 may be linked to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 13 , R 15 and R 16 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 15 and R 16 may be linked to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 or R 17 and R 19 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; Any two L groups can be linked together to form a bidentate Lewis base; The X group may be linked to the L group to form a monoanionic bidentate group; and Any two X groups may be linked together to form a dianionic ligand group.

[0046] For example, M of formula (I) may be a Group 3, 4 or 5 metal, for example M may be a Group 4 metal. Group 4 metals may include zirconium, titanium and hafnium. In at least one embodiment, M is zirconium or hafnium.

[0047] Each L of formula (I) can be independently selected from ether, amine, phosphine, thioether, ester, such as Et2O, MeOtBu, Et3N, PhNMe2, MePh2N, tetrahydrofuran, methyl acetate and dimethyl sulfide, and each X can be independently selected from methyl, benzyl, trimethylsilyl, methyl (trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydride (hydrido), chloro (chloro), fluoro (fluoro), bromo (bromo), iodo (iodo), trifluoromethanesulfonate (trifluoromethanesulfonate), dimethylamino (dimethylamido), diethylamino (diethylamido), dipropylamino (dipropylamido) and diisopropylamino (diisopropylamido). In at least one embodiment, n of formula (I) is 2 and each X is independently chloro, benzyl or methyl.

[0048] R of formula (I) 1, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 Each of which can be independently selected from hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbyl, hydrocarbyloxy, trihydrocarbylsilyl, trihydrocarbylgermyl, dihydrocarbylamino, dihydrocarbylphosphino or halogen, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms.

[0049] In at least one embodiment, R of formula (I) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8One or more of the groups are independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, substituted phenyl, biphenyl or isomers thereof, which may be halogenated (e.g., perfluoropropyl, perfluorobutyl, perfluoroethyl, perfluoromethyl), substituted alkyl and all isomers of substituted alkyl, including trimethylsilylpropyl, trimethylsilylmethyl, trimethylsilylethyl, phenyl or all isomers of alkyl-substituted phenyl, including methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, diphenyl Propylphenyl, tripropylphenyl, dimethylethylphenyl, dimethylpropylphenyl, dimethylbutylphenyl or dipropylmethylphenyl, heteroatom-containing groups include trimethylsilyl, triethylsilyl, methoxy, ethoxy, cyclohexyloxy, trifluoromethyl, dimethylamino, diethylamino, dicyclohexylamino, and all isomers of tripropylsilyl, tributylsilyl, tripropylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, dimethyloctylsilyl, butyldimethylsilyl (e.g., tert-butyldimethylsilyl), propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, and the like.

[0050] For example, R of formula (I) 4 and R 5 Can be C1-C independently 20 Alkyl groups, such as R 4 and R 5 It can be tert-butyl or adamantyl. In at least one embodiment, R 4 and R 5 is independently selected from unsubstituted phenyl, substituted phenyl, unsubstituted carbazole, substituted carbazole, unsubstituted naphthyl, substituted naphthyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted fluorenyl or substituted fluorenyl, a heteroatom or a heteroatom-containing group, such as R 4 and R 5 may independently be unsubstituted phenyl or 3,5-di-tert-butylbenzyl. In addition, (1) R 4 Can be C1-C 20 Alkyl (e.g., R 4 may be tert-butyl) and R 5 It may be an aryl group, or (2) R 5 Can be C1-C 20 Alkyl (e.g., R 5 may be tert-butyl) and R 4 It can be an aromatic group. Alternatively, R 4 and / or R 5 can be independently a heteroatom, such as R 4 and R 5It may be a halogen atom (such as Br, Cl, F or I). 4 and / or R 5 can be independently silyl, for example R 4 and R 5 It can be a trialkylsilyl group or a triarylsilyl group, wherein the alkyl group is C1 to C 30 The alkyl group is C6 to C 1, C7 to C 1, C8 to C9, C9 to C10, C11 to C12, C12 to C13, C14 to C16, C15 to C17, C18 to C19, C19 to C20, C19 to C21, C11 to C22, C12 to C13, C14 to C16, C15 to C18, C19 to C21, C11 to C12, C11 to C13, C12 to C14, C13 to C16, C14 to C18, C15 to C19, C11 to C12, C11 to C13, C12 to C13, C13 to C14, C14 to C16 30 Aryl (eg, phenyl, benzyl, and naphthyl).

[0051] In some embodiments, R 4 and R 5 Independently C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon groups, more preferably, each R 4 and R 5 independently selected from tertiary hydrocarbon groups (e.g., tert-butyl, tert-pentyl, tert-hexyl, tert-heptyl, tert-octyl, tert-nonyl, tert-decyl, tert-undecyl, tert-dodecyl) and cyclic tertiary hydrocarbon groups (e.g., 1-methylcyclohexyl, 1-norbornyl, 1-adamantyl or substituted 1-adamantyl).

[0052] In some embodiments, R 4 and R 5 Independently C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon groups, more preferably, R 4 and R 5 Each of the groups is independently a non-aromatic cyclic alkyl group (e.g., cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, adamantyl, norbornyl or 1-methylcyclohexyl or substituted adamantyl), most preferably a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, 1-adamantyl, substituted 1-adamantyl or 1-norbornyl).

[0053] In some embodiments, R 4 and R 5 Independently for C3-C 30The heteroatom-containing groups include trimethylsilyl, triethylsilyl, and all isomers of tripropylsilyl, tributylsilyl, tripentylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, dimethyloctylsilyl, butyldimethylsilyl and the like.

[0054] R 4 and R 5 The nature of can be used to control the molecular weight of the polymer product. For example, when R 4 and R 5 When one or two of the R groups are tert-butyl groups, the catalyst compound can provide a high molecular weight polymer. 4 , R 5 or R 4 and R 5 When phenyl, the catalyst compound can provide a low molecular weight polymer.

[0055] In at least one embodiment, each R of formula (I) 2 and R 7 Independently C1-C 10 Alkyl groups, such as R 2 and R 7 and tert-butyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dimethylpentyl, tert-butyl, isopropyl or an isomer thereof.

[0056] In at least one embodiment, each R of formula (I) 2 and R 7 Independently for C3-C 30 Substituted hydrocarbon or C3-C 30 Groups containing heteroatoms, such as R 2 and R 7 and independently trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, trioctylsilyl, dimethyloctylsilyl, butyldimethylsilyl (including tert-butyldimethylsilyl), methyltrimethylsilyl or an isomer thereof.

[0057] R of formula (I) 1 , R 3 , R 6 , R 8 , R 9 , R 11 , R 12 , R 13 , R 15 , R 16 , R 17 , R 18 and R 19Each of can be independently hydrogen or C1-C 10 Alkyl groups, such as 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 can independently be hydrogen, methyl, ethyl, propyl or isopropyl. In at least one embodiment, R 1 , R 3 , R 6 , R 8 , R 9 , R 11 , R 12 , R 13 , R 15 , R 16 , R 17 , R 18 and R 19 is hydrogen. Alternatively, 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 Each of may independently be hydrogen, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy or trimethylsilyl.

[0058] R of formula (I) 10 and R 14 Each of which is independently C4-C 40 Hydrocarbon, such as C4-C 20alkyl, such as butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., n-pentyl, isopentyl, isopentyl, neopentyl, cyclopentyl), hexyl (e.g., n-hexyl, isohexyl, cyclohexyl), heptyl (e.g., n-heptyl, isoheptyl, and norbornyl), octyl (e.g., n-octyl, isooctyl, cyclooctyl), nonyl (e.g., n-nonyl, isononyl), decyl (e.g., n-decyl, isodecyl, cyclodecyl, adamantyl), undecyl (e.g., n-undecyl, isoundecyl), dodecyl (e.g., n-dodecyl, isododecyl, cyclododecyl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and all isomers thereof; or R of formula (I) 10 and R 14 Each of the 20 , where R 20 C4-C 40 Hydrocarbon, such as C4-C 20 Hydrocarbyl, such as butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., n-pentyl, isopentyl (iso-pentyl), isopentyl (iso-amyl), neopentyl, cyclopentyl), hexyl (e.g., n-hexyl, isohexyl, cyclohexyl), heptyl (e.g., n-heptyl, isoheptyl and norbornyl), octyl (e.g., n-octyl, isooctyl, cyclooctyl), nonyl (e.g., n-nonyl, isononyl), decyl (e.g., n-decyl, isodecyl, cyclodecyl, adamantyl), undecyl (e.g., n-undecyl, isoundecyl), dodecyl (e.g., n-dodecyl, isododecyl, cyclododecyl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and all isomers thereof. In some embodiments, R 10 It is C4-C 40 Hydrocarbon and R 14 Yes OR 20 , where R 20 It is C4-C 40 In some embodiments, R 14 It is C4-C 40 Hydrocarbon and R 10 Yes OR 20 , where R 20 It is C4-C 40 In some embodiments, R 10 and R 14 Independently C4-C 40 In some embodiments, R 10 and R 14 Independently OR 20 , where R 20 It is C4-C 40Hydrocarbon.

[0059] In some embodiments, R 10 and R 14 is selected from the group consisting of butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, eicosyloxy and isomers thereof. In at least one embodiment, R 10 and R 14 Selected from butoxy, hexyloxy, octyloxy and dodecyloxy.

[0060] In some embodiments of Formula (I), R 4 and R 5 It can be adamantyl or substituted adamantyl, R 2 and R 7 It can be a C1-C8 hydrocarbon group, and R 10 and R 14 Selected from butoxy, hexyloxy, octyloxy and dodecyloxy.

[0061] In some embodiments of Formula (I), R 4 and R 5 It can be adamantyl or substituted adamantyl, R 2 and R 7 can be tert-butyl or methyl, and R 10 and R 14 Selected from butoxy, hexyloxy, octyloxy and dodecyloxy.

[0062] In at least one embodiment, the catalyst compound is one or more of the following:

[0063] In at least one embodiment, one or more different catalyst compounds are present in the catalyst system. One or more different catalyst compounds may be present in the reaction zone where the method(s) described herein are performed. The same activator may be used for the transition metal compound, however, two different activators may be used in combination, such as a non-coordinating anion activator and an aluminoxane.

[0064] Other exemplary embodiments of the present technological advancement include the following. A composition of formula (I), wherein R 4 and R 5 is adamantyl, R 2 and R 7 It is C4-C 40 Hydrocarbyl, and R 10 and R 14 Yes OR 20, where R 20 It is C4-C 12 The composition of formula (I), wherein R 4 and R 5 is adamantyl, R 2 and R 7 is a C4-C8 hydrocarbon group, and R 10 and R 14 Yes OR 20 , where R 20 It is C4-C 12 The composition of formula (I), wherein R 4 and R 5 is adamantyl, R 2 and R 7 is tert-butyl, and R 10 and R 14 Yes OR 20 , where R 20 It is C4-C 12 The composition of formula (I), wherein R 2 , R 7 , R 10 and R 14 The substituent has a total carbon number of 12 carbon atoms or more, or 14 carbon atoms or more, or 16 carbon atoms or more, or 18 carbon atoms or more. The composition of formula (I), wherein R 2 , R 7 , R 10 and R 14 The substituent has a total carbon number of 12 carbon atoms or more, or 14 carbon atoms or more, or 16 carbon atoms or more, or 18 carbon atoms or more, and R 4 and R 5 is selected from tert-butyl, adamantyl and substituted adamantyl, wherein the upper limit may be 48 or 50. The composition of formula (I), wherein R 2 , R 7 , R 4 , R 5 , R 10 and R 14 The substituent has a total carbon number of 32 carbon atoms or more, or 34 carbon atoms or more, or 36 carbon atoms or more, where the upper limit may be 72 or up to 80.

[0065] An exemplary embodiment of the present technological advancement may also be a homogeneous solution comprising an aliphatic hydrocarbon solvent and a complex of formula (I), wherein the concentration of the complex is 0.15 wt % or more (or 0.20 wt % or more, or 0.25 wt % or more, or 0.30 wt % or more, or 0.35 wt % or more, or 0.40 wt % or more, or 0.50 wt % or more, or 1.0 wt % or more, or 2.0 wt % or more). Without wishing to be bound by theory, it is believed that R 10 and R 14 The substituents alone or in combination with R 4 and R 5 Substituents and / or R 2 and R 7 The combination of substituents contributes to the solubility of the complex of formula (I) in aliphatic solvents.

[0066] Another exemplary embodiment of the present technological advance includes a process for producing a propylene-based polymer, the process comprising: reacting propylene and one or more optional C3-C 40 Olefin polymerization, propylene and one or more optional C3-C 40 The olefin is contacted with a catalyst system comprising a composition of formula (I) in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to form a propylene-based polymer.

[0067] Another exemplary embodiment of the present technological advance includes a process for producing an ethylene-based polymer, the process comprising: reacting ethylene and one or more optional C4-C 40 Olefin polymerization, ethylene and one or more optional C4-C 40 The olefin is contacted with a catalyst system comprising a composition of formula (I) in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to form a propylene or ethylene-based polymer. Activators and optional scavengers, co-activators and chain transfer agents

[0068] U.S. Patent Application Serial No. 16 / 788,088 (published as US 2020 / 0254431) describes activators, optional scavengers, optional co-activators, and optional chain transfer agents that can be used with the present technology advancement. Particularly useful activators are also described in PCT Application No. PCT / US2020 / 044865 (published as WO 2021 / 086467), U.S. Patent Application Serial No. 16 / 394,174 (published as US 2019 / 0330394), and PCT Application No. PCT / US2019 / 29056 (published as WO 2019 / 210026), which describes non-aromatic hydrocarbon soluble activator compounds, such as [tetrakis (pentafluorophenyl) boric acid] N-methyl-4-nonadecyl-N-octadecylanilinium, [tetrakis (heptafluoronaphthyl) boric acid] N-methyl-4-nonadecyl-N-octadecylanilinium, [tetrakis (pentafluorophenyl) boric acid)] N-methyl-N-octadecyl-4-(octadecyloxy)anilinium, [tetrakis (heptafluoronaphthyl) boric acid] N-methyl-N-octadecyl-4-(octadecyloxy)anilinium, [tetrakis (pentafluorophenyl) boric acid] N,N-di(hydrogenated tallow (hydrogenated tallow) [tetrakis(heptafluoronaphthyl)borate]N,N-di(hydrogenated tallow)methylammonium[tetrakis(pentafluorophenyl)borate]N,N-di(octadecyl)methylammonium[tetrakis(heptafluoronaphthyl)borate], [tetrakis(pentafluorophenyl)borate]N,N-di(octadecyl)methylammonium[tetrakis(heptafluoronaphthyl)borate], [tetrakis(pentafluorophenyl)borate]N,N-di(hexadecyl)methylammonium[tetrakis(heptafluoronaphthyl)borate], [tetrakis(pentafluorophenyl)borate]N,N-di(hexadecyl)methylammonium[tetrakis(pentafluorophenyl)borate], and [tetrakis(heptafluoronaphthyl)borate]N-octadecyl-N-hexadecylmethylammonium[tetrakis(pentafluorophenyl)borate].

[0069] Although it is preferred to use an activator that is soluble in a non-aromatic hydrocarbon solvent, activators that are poorly soluble or insoluble in a non-aromatic hydrocarbon solvent may also be used. When used, these activators can be fed to the reactor via a slurry or as a solid. Particularly useful activators in this class include triphenylcarbon tetrakis(pentafluorophenyl)borate, , triphenylcarbon tetrakis(perfluoronaphthyl)borate , N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, etc.

[0070] Typical activator to catalyst ratios are about 1: 1 molar ratios. Alternative preferred ranges include 0.1: 1 to 100: 1, or 0.5: 1 to 200: 1, or 1: 1 to 500: 1, or 1: 1 to 1000: 1. Particularly useful ranges are 0.5: 1 to 10: 1, preferably 1: 1 to 1: 10.

[0071] 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. In addition, hydrocarbon-soluble aluminoxanes and modified aluminoxanes that do not contain toluene, including "trimethylaluminum-free" aluminoxanes, can be used.

[0072] In addition, one of ordinary skill in the art will be able to select suitable known activators (one or more) and optional scavengers or co-activators or chain transfer agents for their particular purpose without undue experimentation. Combinations of various activators may be used. Likewise, combinations of various optional scavengers or co-activators or chain transfer agents may be used. Solvents

[0073] Although the catalyst components of the present technology advancement can be used with aromatic solvents such as toluene, they are preferably absent when the catalyst components are used in the polymerization process. Solvents that can be used to dissolve the catalyst compound, the activator compound, or for combining the catalyst compound and the activator, and / or for introducing the catalyst system or any component thereof into the reactor, and / or for the polymerization process include, but are not limited to, aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, or combinations thereof; preferred solvents may include normal paraffins (e.g., Norpar available from ExxonMobil Chemical Company of Houston, TX). TM solvents), isoparaffin solvents (e.g., Isopar available from ExxonMobil Chemical Company of Houston TX), TM solvents), non-aromatic cyclic solvents (e.g., Nappar available from ExxonMobil Chemical Company of Houston, TX) TM solvent) and combinations thereof.

[0074] Preferably, the aliphatic hydrocarbon solvent is selected from C4 to C 10 Linear, branched or cyclic alkanes, or selected from C5 to C8 linear, branched or cyclic alkanes.

[0075] Preferably, the aliphatic hydrocarbon solvent is substantially free of all aromatic solvents. Preferably, the solvent is substantially free of toluene. Free of all aromatic solvents, such as toluene, means that the solvent is substantially free of aromatic solvents (e.g., present at 0 mol %, or present at less than 1 mol %), preferably, the polymerization reaction and / or the resulting polymer does not contain "detectable aromatic hydrocarbon solvents", such as toluene.

[0076] Preferred aliphatic hydrocarbon solvents include isohexane, cyclohexane, methylcyclohexane, pentane, isopentane, heptane, and combinations thereof, as well as commercially available solvent mixtures such as Nappar 6 TM and IsopareE TM However, one of ordinary skill in the art may select other suitable non-aromatic hydrocarbon solvents without undue experimentation.

[0077] Highly preferred aliphatic hydrocarbon solvents include isohexane, methylcyclohexane and commercially available solvent mixtures such as Nappa 6 TM and IsoparE TM .

[0078] For compound solubility testing, preferred solvents include isohexane and methylcyclohexane. Optional carrier material

[0079] In the embodiments herein, the catalyst system may include an inert support material. The support material may be a porous support material, for example, talc, and an inorganic oxide. U.S. Patent Application Serial No. 16 / 788,088 (Publication No. US2020 / 0254431) describes optional support materials that can be used with this technological advancement. In addition, one of ordinary skill in the art can select a suitable known support for its specific purpose without excessive experimentation. Aggregation methods

[0080] The present disclosure relates to a polymerization process wherein monomers (e.g., ethylene; propylene) and optionally one or more comonomers (e.g., C2 to C 20 α-olefins, C4 to C 40 Cyclic olefins, C5 to C 20 The catalyst system of the present invention is a catalyst system comprising an activator and at least one catalyst compound as described above. The catalyst compound and the activator can be combined in any order. The catalyst compound and the activator can be combined before contacting with the monomer. Alternatively, the catalyst compound and the activator can be introduced separately into a polymerization reactor, where they are subsequently reacted to form an active catalyst.

[0081] U.S. patent application Ser. No. 16 / 788,088 (Pub. No. US2020 / 0254431) describes monomers that can be used in the present technological advancement and describes polymerization methods that can be used in the present technological advancement.

[0082] Additionally, catalysts that are highly soluble in aliphatic hydrocarbon solvents can be used as trim catalysts in well-known polymerization processes, such as described in WO 2015 / 123177 and WO 2020 / 092587. blends and films

[0083] Polymers prepared using the present technological advances can be used to prepare blends and films as described in U.S. Patent Application Serial No. 16 / 788,088 (Publication No. US 2020 / 0254431) without undue experimentation. Example General considerations for synthesis

[0084] The following chemicals can be abbreviated with lowercase or uppercase letters: 1,2-dimethoxyethane (dme), diethyl ether (ether), tetrahydrofuran (thf), diatomaceous earth (Celite), methylcyclohexane (MeCy), 1,4-dimethoxyethane (dme), diethyl ether (ether), tetrahydrofuran (thf), diatomaceous earth (Celite), methylcyclohexane (MeCy), Alkane (di The room temperature was 23°C unless otherwise specified.

[0085] Complexes 1 (dimethylzirconium [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenolate)] and 2 (dimethylzirconium [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenolate)]) (shown below) and 2-(3-adamantan-1-yl)-5-methyl-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane were prepared as described in U.S. Pat. No. 5,599,937.

[0086] All other reagents were purchased from commercial suppliers (Sigma Aldrich, Fisher Scientific, Strem Chemical, or Oakwood Chemical) and used as received unless otherwise stated. The solvents were sparged with N2 and All chemical manipulations were performed under nitrogen atmosphere unless otherwise stated. Flash column chromatography was performed using silica gel from Sigma Aldrich (70 mesh - 230 mesh) using the specified solvent system. All anhydrous solvents were purchased from Fisher Chemical and degassed and dried over molecular sieves before use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and degassed and dried over molecular sieves before use. Solutions prepared by dissolving approximately 10 mg of sample in C6D6, CD2Cl2, CDCl3, D8-toluene or other deuterated solvents were used and obtained at 250 MHz, 400 MHz or 500 MHz. 1 H NMR spectral data. The chemical shifts (δ) presented are relative to the residual protium in the deuterated solvent at 7.15 ppm, 5.32 ppm, 7.24 ppm and 2.09 ppm for C6D6, CD2Cl2, CDCl3, D8-toluene, respectively. Synthesis of ligands and catalysts (or complexes)

[0087] ZrCl4(ether)2 Combine dichloromethane (100mL) and ZrCl4 (10.0g, 42.9mmol) to form a slurry. Add ether (9.54g, 129mmol) dropwise over 60 minutes. Stir the mixture for 1 hour. Allow the undissolved solid to settle, then decant the supernatant and filter through diatomaceous earth on a sintered disk. Evaporate the filtrate to near dryness to provide a slurry. Add isohexane (60mL) to the slurry and stir the mixture vigorously. The resulting off-white solid is collected on a glass frit, washed with isohexane, and dried under reduced pressure. Yield: 12.5g, 76.6%.

[0088] 1-Butoxy-3-iodobenzene 3-Iodophenol (15.0 g, 68.2 mmol) and 1-bromobutane (11.2 g, 81.8 mmol) were dissolved in DMF (50 mL). K2CO3 (28.5 g, 205 mmol) was added and the mixture was stirred at ambient temperature for 16 hours. The solution was diluted with water and extracted with 3 portions of diethyl ether. The combined organic fractions were rinsed with water and brine, dried over MgSO4, filtered and concentrated to give the product as a clear orange liquid. Yield: 15.0 g, 79.7%. 1 H NMR (400MHz, CDCl3, δ): 7.27 (m, 2H), 6.98 (t, J = 8.0Hz, 1H), 6.86 (m, 1H), 3.92 (t, J = 6.5Hz, 2H), 1.74 (m, 2H), 1.48 (m, 2H), 0.97 (t, J = 7.4Hz, 3H).

[0089] 1-Bromo-4-butoxy-2-iodobenzene 1-Butoxy-3-iodobenzene (15.0 g, 54.3 mmol) was dissolved in DMF (50 mL). NBS (10.6 g, 59.8 mmol) was added in several portions. The reaction was heated to 80 °C for 4 hours. After cooling to ambient temperature, the solution was diluted with water and extracted with 3 portions of diethyl ether. The combined organic fractions were rinsed with brine, dried over MgSO4, filtered and concentrated to give the crude product. The material was recrystallized in hot isohexane to give the product as a white crystalline solid. Yield: 15.6 g, 80.9%. 1 HNMR (400MHz, CDCl3, δ): 7.45 (d, J = 8.8 Hz, 1H), 7.38 (d, J = 2.9 Hz, 1H), 6.75 (dd, J = 8. 8, 2.9Hz, 1H), 3.90 (t, J = 6.4Hz, 2H), 1.73 (m, 2H), 1.47 (m, 2H), 0.97 (t, J = 7.4Hz, 3H).

[0090] 1-Iodo-3-(octyloxy)benzene 3-Iodophenol (8.00 g, 36.4 mmol) and 1-bromooctane (8.43 g, 43.6 mmol) were dissolved in DMF (50 mL). K2CO3 (15.2 g, 109 mmol) was added and the mixture was stirred at ambient temperature for 16 hours. The solution was diluted with water and extracted with 3 portions of diethyl ether. The combined organic fractions were washed with water and brine, dried over MgSO4, filtered and concentrated. The crude liquid was purified on SiO2 with 100% isohexane to give the product as a colorless oil. Yield: 10.7 g, 88.7%. 1 H NMR (400MHz, CDCl3, δ): 7.26 (m, 2H), 6.98 (t, J = 8.0Hz, 1H), 6.86 (d, J = 8.3Hz, 1H), 3.91 ( t,J=6.5Hz,2H),1.76(p,J=6.8Hz,2H),1.44(m,2H),1.29(m,8H),0.89(t,J=6.5Hz,3H).

[0091] 1-Bromo-2-iodo-4-(octyloxy)benzene 1-Iodo-3-(octyloxy)benzene (10.7 g, 32.3 mmol) was dissolved in DMF (75 mL). NBS (6.03 g, 33.9 mmol) was added in several portions. The reaction was heated to 80°C for 4 hours. After cooling to ambient temperature, the solution was diluted with water and extracted with 3 portions of diethyl ether. The combined organic fractions were washed with water and brine, dried over MgSO4, filtered and concentrated to give the product as a clear liquid. Yield: 10.9 g, 82.0%. 1 H NMR (400MHz, CDCl3, δ): 7.44 (d, J = 8.9 Hz, 1H), 7.38 (d, J = 2.8 Hz, 1H), 6.74 (dd, J = 8.9, 2.9 Hz, 1H) ,3.88(t,J=6.5Hz,2H),1.75(p,J=6.8Hz,2H),1.43(m,2H),1.29(m,10H),0.90(t,J=7.4Hz,3H).

[0092] 1-(Dodecyloxy)-3-iodobenzene 3-Iodophenol (8.00 g, 36.4 mmol) and 1-bromododecane (10.9 g, 43.6 mmol) were dissolved in DMF (50 mL). K2CO3 (13.3 g, 94.5 mmol) was added and the mixture was stirred at ambient temperature for 16 hours. The solution was diluted with water and extracted with 3 portions of diethyl ether. The combined organic fractions were washed with water and brine, dried over MgSO4, filtered and concentrated. The crude liquid was purified on SiO2 with 100% isohexane to give the product as a colorless oil. Yield: 7.34 g, 52.0%. 1 H NMR (400MHz, CDCl3, δ): 7.26 (m, 2H), 6.98 (t, J = 7.9Hz, 1H), 6.86 (d, J = 8.5Hz, 1H), 3.91 ( t,J=6.5Hz,2H),1.76(p,J=6.8Hz,2H),1.43(m,2H),1.27(m,16H),0.88(t,J=6.5Hz,3H).

[0093] 1-Bromo-4-(dodecyloxy)-2-iodobenzene 1-(Dodecyloxy)-3-iodobenzene (7.34 g, 18.9 mmol) was dissolved in DMF (75 mL). NBS (3.53 g, 19.9 mmol) was added in several portions. The reaction was heated to 80°C for 4 hours. After cooling to ambient temperature, the solution was diluted with water and extracted with 3 portions of diethyl ether. The combined organic fractions were washed with water and brine, dried over MgSO4, filtered and concentrated. The material was recrystallized from hot isohexane to give the product as a white crystalline solid. Yield: 5.75 g, 65.1%. 1 H NMR (400MHz, CDCl3, δ): 7.45 (d, J = 8.8 Hz, 1H), 7.38 ( d, J = 2.8 Hz, 1H), 6.75 ( dd, J = 8.9, 2.9 Hz, 1H) ,3.89(t,J=6.5Hz,2H),1.75(p,J=6.8Hz,2H),1.43(m,2H),1.26(m,18H),0.88(t,J=7.4Hz,3H).

[0094] 2-(Adamantane-1-yl)-4-(tert-butyl)phenol Dichloromethane (120 mL) was added to 4-(tert-butyl)phenol (20.0 g, 133 mmol) and 1-adamantanol (21.3 g, 140 mmol) in a 500 mL round bottom flask. It was stirred until all solids dissolved. Concentrated sulfuric acid (10.8 mL) was added dropwise to the clear solution over 20 minutes. The reactants were stirred at room temperature for 4 hours. Water (20 mL) was added and the mixture was adjusted to neutral pH using 2M sodium hydroxide. The organics were extracted with dichloromethane (3×50 mL), filtered, and dried over magnesium sulfate. The product was purified on SiO2 using 40-60% by volume ethyl acetate in isohexane. Yield: 20.9 g, 55.1%. 1 H NMR (400MHz, CDCl3): δ7.29 (d, 1H, J = 2.5Hz), 7.11 (dd, 1H, J = 8.2, 2.4Hz), 6.61 (d, 1H, J = 8.2H z),2.21-2.16(m,6H),2.15-2.10(m,3H),1.85-1.81(m,6H),1.34(s,9H).

[0095] 1-(5-(tert-butyl)-2-(methoxymethoxy)phenyl)adamantane Sodium hydride (2.29 g, 95.3 mmol) was gradually added to 2-(adamantan-1-yl)-4-(tert-butyl)phenol (20.9 g, 73.3 mmol) in tetrahydrofuran (100 mL). The reaction mixture was stirred overnight. Chloromethyl methyl ether (10.0 g, 125 mmol) was added to the stirred solution, and the reaction mixture was stirred for 4 hours. The reactants were quenched with water (25 mL), and the pH was adjusted to 8-10 using 1 M potassium hydroxide. The product was extracted with ether (3×25 mL), dried over MgSO4, and concentrated under reduced pressure. Yield: 22.6 g, 94.0%. 1 H NMR (400MHz, CDCl3): δ7.31 (d, 1H, J = 2.5Hz), 7.18 (dd, 1H, J = 8.5, 2.5Hz), 7.06 (d, 1H, J = 8.5H z),5.24(s,2H),3.55(s,3H),2.20-2.14(m,6H),2.14-2.08(m,3H),1.84-1.78(m,6H),1.34(s,9H).

[0096] (3-(adamantan-1-yl)-5-(tert-butyl)-2-(methoxymethoxy)phenyl)lithium Isohexane (100 mL) was added to 1-(5-(tert-butyl)-2-(methoxymethoxy)phenyl)adamantane (7.00 g, 23.1 mmol) to form a suspension. A hexane solution of butyllithium (2.60 M, 8.90 mL, 23.1 mmol) was added dropwise over 6 minutes. The mixture was stirred for 30 minutes, during which time a cloudy yellow solution was formed. The mixture was gravity filtered through diatomaceous earth to give a clear yellow solution. DME (2.41 mL, 23.1 mmol) was added and the mixture was stirred. A precipitate formed within 30 minutes. The mixture was stirred for several more hours, and then the volatiles were evaporated to near dryness. Isohexane (20 mL) was added and the suspension was cooled to 0°C. The solid was collected on a glass frit and washed with cold isohexane, then dried under reduced pressure. 1 H NMR data indicated that the product was crystallized with 0.5 molar equivalent of DME. Yield: 4.63 g, 52.7%. 1 H NMR (400MHz, C6D610%C4D4O): δ7.95 (d, 1H, J = 2.4Hz), 7.31 (d, 1H, J = 2.5Hz), 5.79 (s, 2H), 3. 22(s,3H),2.50(brs,6H),2.20(brs,3H),2.01-1.93(m,3H),1.92-1.84(m,3H),1.57(s,9H).

[0097] 2-(3-(adamantan-1-yl)-5-(tert-butyl)-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Ether (60 mL) was added to (3-(adamantan-1-yl)-5-(tert-butyl)-2-(methoxymethoxy)phenyl)lithium (4.63 g, 12.2 mmol, co-crystallized with 0.5 DME) and the mixture was cooled to -45 °C. 2-Isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.95 g, 15.9 mmol) in ether (3 mL) was quickly added to the stirring suspension. The mixture was allowed to slowly warm to ambient temperature over several hours and then stirred for an additional hour. The very cloudy, colorless mixture was transferred to a separatory funnel containing 60 mL of water. The mixture was shaken until the solids disappeared and the organics were separated. The organics were extracted with water until the aqueous layer was at neutral pH. The organics were dried with brine (15 mL) and then over MgSO4. Removal of volatiles afforded the product as a colorless foam. Yield: 4.95 g, 89.3%. 1 H NMR (400MHz, CDCl3): δ7.52 (d, 1H, J = 2.6Hz), 7.41 (d, 1H, J = 2.6Hz), 5.16 (s, 2H), 3.59 (s, 3H),2.19-2.13(m,6H),2.11-2.04(m,3H),1.83-1.71(m,6H),1.35(s,12H),1.31(s,9H).

[0098] 1-(2'-bromo-5'-butoxy-5-(tert-butyl)-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane A 250 mL round-bottom flask was charged with 2-(3-adamantan-1-yl)-5-(tert-butyl)-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.93 g, 10.8 mmol), 1-bromo-4-butoxy-2-iodobenzene (3.85 g, 10.8 mmol), Na2CO3 (2.87 g, 27.1 mmol), dihydrogen 2-thiophene (400 mg, 100% ethanol), and 1-bromo-4-butoxy-2-iodobenzene (3.85 g, 10.8 mmol). alkane (60mL) and water (30mL). The mixture was bubbled with nitrogen for 50 minutes, then solid Pd(PPh3)4 (0.627g, 0.542mmol) was added. The mixture was bubbled for another 40 minutes, then stirred rapidly and heated in an oil bath maintained at 100°C. After 20 hours, the volatiles were evaporated to near dryness, then ether (70mL) and water (70mL) were added. The organic matter was separated and extracted with water until neutral pH. The organic matter was dried over brine, then evaporated and dried under reduced pressure to obtain light yellow foam (6.78g). The crude material contains impurities (one or more) with low solubility in cold isohexane. Purification was completed by adding isohexane (50mL), cooling to -40°C for 1 hour and cold filtration. The stripping volatiles obtained a product of acceptable purity. 1 H NMR data indicated the presence of 0.3 molar equivalents of isohexane in the product. Yield: 6.24 g, 98.9%). 1 H NMR (400MHz, CDCl3): δ7.55(d,1H,J=8.8Hz),7.37(d,1H,J=2.5Hz),7.09(d,1H, J=2.5Hz),6.97(d,1H,J=3.1Hz),6.79(dd,1H,J=8.8,3.1Hz),4.53(dd,2H,J=45 .9,4.5Hz),3.97(t,2H,J=6.6Hz),3.28(s,3H),2.23-2.19(m,6H),2.15-2.09(m ,3H),1.86-1.75(m,8H),1.56-1.46(m,2H),1.35(s,9H),0.99(t,3H,J=7.4Hz).

[0099] (3'-(adamantan-1-yl)-5-butoxy-5'-(tert-butyl)-2'-(methoxymethoxy)-[1,1'-biphenyl]-2-yl)lithium Isohexane (50 mL) was added to 1-(2'-bromo-5'-butoxy-5-(tert-butyl)-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane (6.24 g, 10.7 mmol, with 0.3 equiv. isohexane) to form a clear solution. The mixture was cooled to -50 °C. The mixture became very cloudy upon cooling, which was probably due to the presence of some impurities. A solution of butyllithium in hexane (1.66 M, 6.79 mL, 11.3 mmol) was added dropwise over a few minutes. The mixture was allowed to slowly warm to ambient temperature. When the mixture was at -20 °C, the mixture was clear and orange. After reaching ambient temperature, a large amount of precipitate was formed. The solid was collected on a glass frit and washed thoroughly with isohexane to give a fine colorless solid, which was dried under reduced pressure. Due to the fineness of the solid, filtration was quite slow. Yield: 3.60 g, 69.5%. 1 H NMR (400MHz, C6D6+5% D8-THF): δ7.61-7.55(m,1H),7.51(d,1H,J=2.6Hz),7.47(d,1H,J=2.5Hz),7.30(d,1H,J=2.3Hz),7.04-6.94(m,1H),4.72(br s,2H),3.89(t,2H,J=6.4Hz),2.96(s,3H),2.48-2.36(m,6H),2.22-2.13(m,3H), 1.95-1.79(m,6H),1.69-1.60(m,2H),1.42-1.29(m,11H),0.80(t,3H,J=7.4Hz).

[0100] 2-(3'-(adamantan-1-yl)-5-butoxy-5'-(tert-butyl)-2'-(methoxymethoxy)-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Ether (70 mL) was added to (3'-(adamantan-1-yl)-5-butoxy-5'-(tert-butyl)-2'-(methoxymethoxy)-[1,1'-biphenyl]-2-yl)lithium (3.59 g, 7.44 mmol) to form a clear solution. The mixture was cooled to -45°C. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.80 g, 9.67 mmol) was then added in one portion. The mixture was slowly warmed in a cold bath for 1 hour. The cloudy solution was then removed from the cold bath and stirred for an additional hour. The mixture was poured into a separatory funnel and extracted with water until the aqueous layer was at a neutral pH. The organics were dried with brine and then MgSO4 and then filtered. The solvent was evaporated under reduced pressure to obtain the product as a foam.1 H NMR indicated acceptable purity. Yield: 4.18 g, 93.2%. 1 HNMR (400MHz, CDCl3): δ7.74 (dd, 1H, J = 7.9, 0.7Hz), 7.29 (d, 1H, J = 2.6Hz), 6.98 (d,1H,J=2.5Hz),6.91-6.88(m,2H),4.51(dd,2H,J=50.0,4.7Hz),4.00(t,2H,J =6.6Hz),3.27(s,3H),2.24-2.19(m,6H),2.14-2.09(m,3H),1.87-1.73(m,8H), 1.54-1.43(m,2H),1.32(s,9H),1.14(d,12H,J=15.2Hz),0.98(t,3H,J=7.4Hz).

[0101] 6',6"'-(pyridine-2,6-diyl)bis(3'-butoxy-3-(adamantan-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-phenol) A 250 mL round-bottom flask was charged with 2-(3′-(adamantan-1-yl)-5-butoxy-5′-(tert-butyl)-2′-(methoxymethoxy)-[1,1′-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.18 g, 6.94 mmol), 2,6-dibromopyridine (0.789 g, 3.33 mmol), Na2CO3 (1.84 g, 17.3 mmol), dichloromethane (0.34 g, 1.7 g), and 1,2-dibromopyridine (0.789 g, 3.33 mmol). Alkane (60mL) and water (30mL). The mixture was bubbled with nitrogen for 50 minutes, then solid Pd(PPh3)4 (0.401g, 0.347mmol) was added. The mixture was bubbled for another 40 minutes, then stirred rapidly and heated in an oil bath maintained at 100°C. After 14 hours, the volatiles were evaporated to near dryness, then ether (70mL) and water (70mL) were added. The organic matter was separated and extracted with water until neutral pH. The organic matter was dried over brine and then evaporated to a residue. Methanol (40mL), THF (40mL) and concentrated HCl (4mL) were added and the mixture was heated to 60°C. After 4.5 hours, the mixture was cooled to ambient temperature and the volatiles were evaporated. The residue was dissolved in ether (70mL) and water (30mL), and the mixture was transferred to a separatory funnel. The organic matter was separated and extracted with water until the pH of the washings was neutral. It was then dried with brine, then the organic matter was dried over MgSO4, and then filtered. Removal of volatiles gave the crude product as a yellow foam (3.57 g). The crude was purified on SiO2 using 0%-2.5% ethyl acetate in isohexane. Yield: 2.82 g, 90.1%. 1 HNMR (400MHz, CDCl3): δ8.51 (brs, 2H), 7.44 (d, 2H, J = 8.7Hz), 7.14-6.84 (m, 9H), 6.54 (d, 2H, J = 2.4Hz), 4.01 (t, 4H,J=6.4Hz),1.98-1.88(m,12H),1.86-1.76(m,6H),1.73-1.64(m,12H),1.58-1.48(m,4H),1.05-0.97(m,28H).

[0102] 1-(2′-bromo-5′-butoxy-2-(methoxymethoxy)-5-methyl-[1,1′-biphenyl]-3-yl)adamantane A 250 mL round-bottom flask was charged with 2-(3-(adamantan-1-yl)-2-(methoxymethoxy)-5-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.90 g, 9.46 mmol), 1-bromo-4-butoxy-2-iodobenzene (3.42 g, 9.65 mmol), Na2CO3 (2.51 g, 23.6 mmol), dichloromethane (0.25 g, 1.3 mmol), and 1-bromo-4-butoxy-2-iodobenzene (0.25 g, 1.3 mmol). alkane (30mL) and water (15mL). The mixture was bubbled with nitrogen for 50 minutes, then solid Pd(PPh3)4 (0.546g, 0.473mmol) was added. The mixture was bubbled for another 40 minutes, then rapidly stirred and heated in an oil bath maintained at 100°C. After 16 hours, the volatiles were evaporated to near dryness, then ether (70mL) and water (70mL) were added. The organics were separated and extracted with water until neutral pH. The organics were dried over brine and then evaporated to a yellow oil. The crude product was purified on SiO2 using 0-2% by volume ethyl acetate in isohexane. The product was isolated as a thick oil. Moderate purity. Yield: 4.68g, 96.4%. 1 H NMR (400MHz, CDCl3): δ7.54(d,1H,J=8.8Hz), 7.16(d,1H,J=2.2Hz), 6.93(d,1H, J=3.0Hz), 6.90(d,1H,J=2.3Hz), 6.79(dd,1H,J=8.8,3.1Hz), 4.53(dd,2H,J=20. 6,4.7Hz),3.96(t,2H,J=6.55Hz),3.27(s,3H),2.35(s,3H),2.21-2.18(m,6H), 2.15-2.09(m,3H),1.83-1.79(m,6H),1.56-1.44(m,2H),0.99(t,3H,J=7.38Hz).

[0103] (3′-(adamantan-1-yl)-5-butoxy-2′-(methoxymethoxy)-5′-methyl-[1,1′-biphenyl]-2-yl)lithium Isohexane (80 mL) was added to 1-(2'-bromo-5'-butoxy-2-(methoxymethoxy)-5-methyl-[1,1'-biphenyl]-3-yl)adamantane (4.66 g, 9.08 mmol) to form a clear solution. The mixture was cooled to -45 °C. A hexane solution of BuLi (1.66 M, 5.74 mL, 9.53 mmol) was added dropwise over a few minutes. The mixture became cloudy when BuLi was initially added, but no additional precipitate was formed as BuLi was continued to be added. The mixture was slowly warmed to 15 °C over a few hours, during which time a large amount of colorless precipitate was formed. The mixture was cooled to -45 °C again and maintained for about 30 minutes. The solid was then collected on a sintered tray, washed with cold isohexane (20 mL), and dried under reduced pressure. The product was isolated as a colorless microcrystalline solid. 1 H NMR spectroscopy indicated the presence of 0.5 equivalents of isohexane co-crystallized. Yield: 3.64 g, 82.3%. 1H NMR(400MHz,C6D6+10% D8-THF): δ7.81(d,1H,J=7.4Hz),7.26(d,1H,J=2.2Hz),7.24(d,1H,J=2.3 Hz),7.12(d,1H,J=2.2Hz),6.97(dd,1H,J=7.5,2.2Hz),4.72(s,2H),3.91 (t,2H,J=6.4Hz),2.92(s,3H),2.38-2.28(m,9H),2.15-2.07(m,3H),1.90 -1.74(m,6H),1.71-1.61(m,2H),1.46-1.34(m,2H),0.82(t,3H,J=7.5Hz).

[0104] 2-(3'-(adamantan-1-yl)-5-butoxy-2'-(methoxymethoxy)-5'-methyl-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Ether (70 mL) was added to (3'-(adamantan-1-yl)-5-butoxy-2'-(methoxymethoxy)-5'-methyl-[1,1'-biphenyl]-2-yl)lithium (3.64 g, 7.52 mmol) to form a colorless suspension. The mixture was cooled to -45°C. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.82 g, 9.78 mmol) was then added in one portion. The mixture was allowed to warm slowly in the cold bath. After stirring overnight, the mixture was poured into a separatory funnel and extracted with water until the aqueous layer was at neutral pH. The organics were dried over brine and then over MgSO4, then filtered and dried under reduced pressure to give a colorless foam. Yield: 4.34 g, 103%. 1 HNMR (400MHz, CDCl3): δ7.71 (d, 1H, J = 8.2Hz), 7.07 (d, 1H, J = 2.3Hz), 6.92-6.82 (m, 3H), 4.53-4.42 (m, 2H), 4.00 (t, 2H, J = 6.6Hz), 3.29 (s ,3H),2.3(s,3H),2.23-2.18(m,6H),2.14-2.08(m,3H),1.83-1.73(m,8H),1.55-1.44(m,2H),1.17(d,12H,J=18.3Hz),0.98(t,3H,J=7.4 Hz).

[0105] 6',6"'-(pyridine-2,6-diyl)bis(3'-butoxy-3-(adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenol) A 200 mL round-bottom flask was charged with 2-(3′-(adamantan-1-yl)-5-butoxy-2′-(methoxymethoxy)-5′-methyl-[1,1′-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.34 g, 7.74 mmol), 2,6-dibromopyridine (0.880 g, 3.72 mmol), Na2CO3 (2.05 g, 19.4 mmol), dihydrogen iodide (10% by volume, 1% by volume), and 2-(3′-(adamantan-1-yl)-5-butoxy-2′-(methoxymethoxy)-5′-methyl-[1,1′-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.34 g, 7.74 mmol). Alkane (60mL) and water (30mL). The mixture was bubbled with nitrogen for 60 minutes, then solid Pd(PPh3)4 (0.447g, 0.387mmol) was added. The mixture was bubbled for another 40 minutes, then stirred rapidly and heated in an oil bath maintained at 100°C. After 20 hours, the volatiles were evaporated to near dryness, then ether (80mL) and water (80mL) were added. The organic matter was separated and extracted with water until neutral pH. The organic matter was dried over brine and then evaporated to a residue. Methanol (40mL), THF (40mL) and concentrated HCl (4mL) were added and the mixture was heated to 60°C. After 4 hours, the mixture was cooled to ambient temperature and the volatiles were evaporated. The residue was dissolved in ether (80mL) and water (50mL), and the mixture was transferred to a separatory funnel. The organic matter was separated and extracted with water until the pH of the washings was neutral. It was then dried with brine, then dried over MgSO4, and then filtered. Volatiles were removed to give 3.68 g of an off-white solid coated with a small amount of orange oily residue. Methylcyclohexane (50 ml) was added and the resulting suspension was stirred for several hours. Undissolved material was collected on a glass frit, washed with methylcyclohexane (2×5 mL) and dried under reduced pressure to give a colorless solid (2.53 g). The methylcyclohexane filtrate and washings were loaded onto a SiO2 column and eluted with 0%-2.5% ethyl acetate in isohexane. Both batches appeared to be clean, but contained a small amount of co-crystallized ether (crop 1 contained 0.2 equivalents of ether, crop 2 contained 0.1 equivalents of ether). Yield: crop 1 (solid washed with MeCy): 2.53 g, 78.2% (with 0.2 equivalents of ether); crop 2 (MeCy filtrate purified on SiO2): 0.345 g, 10.8% (containing 0.1 equivalents of ether). 1H NMR (400MHz, CDCl3): δ8.02 (s, 1H), 7.50 (d, 1H, J = 8.5Hz), 7.44 (d, 1H, J = 8.5Hz), 7.42-7.34 (m, 1H), 7.05-6.96 (m, 2 H), 6.94-6.82 (m, 7H), 6.18 (d, 1H, J = 2.1Hz), 4.04-3.96 (m, 4H), 2.26 (s, 3H), 2.0-1.46 (m, 41H), 1.05-0.96 (m, 6H).

[0106] 1-(2′-bromo-5-(tert-butyl)-2-(methoxymethoxy)-5′-(octyloxy)-[1,1'-biphenyl]-3-yl)adamantane A 20 mL scintillation vial was charged with 2-(3-(adamantan-1-yl)-5-tert-butyl-2-(methoxymethoxy)-phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.00 g, 4.40 mmol), 1-bromo-2-iodo-4-(octyloxy)benzene (1.90 g, 4.62 mmol), K2CO3 (1.53 g, 11.0 mmol), dihydrogen 2-thiophene (1.00 g, 0.70 mmol), and 1-bromo-2-iodo-4-(octyloxy)benzene (1.90 g, 0.70 mmol). 10mL) and degassed water (10mL). Finally solid Pd(PPh3)4 (0.254g, 0.220mmol) was added and the reaction was heated to 100°C. After 36 hours, the reaction was cooled to ambient temperature. The solution was diluted with water and extracted with 3 portions of dichloromethane. The combined organic fractions were rinsed with brine, dried over MgSO4, filtered and concentrated. The crude product was purified on SiO2 with 10% by volume acetone in isohexane to give the desired product as a clear oil. Yield: 2.00g, 74.3%. 1 H NMR (400MHz, CDCl3): δ7.53(d,1H,J=8.7Hz),7.34(s,1H),7.06(s,1H),6.94(d ,1H,J=3.0Hz),6.77(dd,1H,J=8.8,3.1Hz),4.56(d,1H,J=4.5Hz),4.44(d,1H, J=4.5Hz),3.93(t,2H,J=6.7Hz),3.25(s,3H),2.18(brs,6H),2.14-2.05(m,3H ),1.84-1.72(m,8H),1.50-1.39(m,2H),1.38-1.21(m,17H),0.92-0.81(m,3H).

[0107] 2-(3′-(adamantan-1-yl)-2′-(methoxymethoxy)-5′-methyl-5-(octyloxy)-[1,1′-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Isohexane (75 mL) was added to 1-(2′-bromo-5-(tert-butyl)-2-(methoxymethoxy)-5′-(octyloxy)-[1,1′-biphenyl]-3-yl)adamantane (2.00 g, 3.27 mmol) to form a clear solution. The mixture was cooled to -45°C. A hexane solution of BuLi (2.50 M, 1.37 mL, 3.43 mmol) was added dropwise over several minutes. Upon initial addition of BuLi, the mixture became cloudy, but the precipitate quickly dissolved back into solution. The mixture was stirred at -45°C for 1 hour and then slowly warmed to ambient temperature over 1 hour. The mixture was cooled to -45°C again and maintained for about 30 minutes. 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.833 g, 4.48 mmol) was then added in one portion. The mixture was stirred at -45°C for 1 hour and then slowly warmed to ambient temperature over 1 hour to give a yellow slurry. The solution was diluted with water and extracted with 3 portions of ethyl acetate. The combined organic fractions were rinsed with brine, dried over MgSO4, filtered and concentrated. The crude product was purified on SiO2 with 5% by volume acetone in isohexane to give the desired product as a colorless foam. Yield: 1.10 g, 51%. 1 HNMR (400MHz, CDCl3): δ7.71 (d, 1H, J = 8.0Hz), 6.96 (s, 1H), 6.89-6.82 (m, 2H), 4.54 (d, 1H, J = 4.6Hz), 4.42 (d, 1H, J = 4.1Hz), 3.96 (t, 2H, J = 6.6Hz), 3.25(s,3H),2.19(brs,6H),2.09(brs,3H),1.86-1.71(m,8H),1.49-1.38 (m,2H),1.38-1.21(m,17H),1.13(s,6H),1.09(s,6H),0.91-0.81(m,3H).

[0108] 6',6"'-(pyridine-2,6-diyl)bis(3'-octyloxy-3-(adamantan-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-phenol) A 250 mL round-bottom flask was charged with 2-(3′-(adamantan-1-yl)-2′-(methoxymethoxy)-5′-methyl-5-(octyloxy)-[1,1′-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.10 g, 1.67 mmol), 2,6-dibromopyridine (0.188 g, 0.794 mmol), Na2CO3 (0.425 g, 3.97 mmol), dichloromethane (0.25 g, 0.70 mmol), and 1,2-dibromopyridine (0.188 g, 0.794 mmol). alkane (40mL) and degassed water (20mL). Finally, solid Pd(PPh3)4 (0.092g, 0.079mmol) was added and the reaction was heated to 100°C for 16 hours. After cooling to ambient temperature, the solution was diluted with water and extracted with 3 portions of ethyl acetate. The combined organic fractions were rinsed with brine, dried over MgSO4, filtered and concentrated. Methanol (30mL), THF (30mL) and concentrated HCl (2mL) were added and the mixture was heated to 60°C. After 4 hours, the solution was adjusted to pH=6 with saturated aqueous sodium bicarbonate solution, slightly concentrated to remove methanol, and extracted with 3 portions of ethyl acetate. The combined organic fractions were rinsed with water and brine, dried over MgSO4, filtered and concentrated. The crude product was purified on SiO2 with 5% by volume acetone in isohexane to give the desired product as a colorless foam. Yield: 0.150g, 18.0%. 1 H NMR, isomers integrated together as one (400 MHz, CDCl3): δ 8.49 (brs, 1H), 7.44-7.27 (m, 3H), 7.14-6.91 (m, 5H), 6.90-6.83 (3H), 6.51 (d, 1H, J = 2.4 Hz), 3.97 (t, 4H, J = 6.5 Hz), 2.03-1.84 (m, 15H), 1.84-1.73 (m, 6H), 1.73-1.57 (m, 11H), 1.52-1.41 (m, 4H), 1.41-1.25 (m, 18H), 1.04-0.81 (m, 24H).

[0109] 1-(2'-bromo-5-(tert-butyl)-5'-(dodecyloxy)-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane Potassium carbonate (2.30 g, 16.64 mmol) was added to a mixture of 2-(3-(1-adamantyl)-5-(tert-butyl)-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.00 g, 6.60 mmol) and 1-bromo-4-(dodecyloxy)-2-iodobenzene (3.70 g, 7.92 mmol) in distilled water. The mixture was stirred for 2 hours at 4 ℃ for 1 h. The mixture was stirred for 2 hours at 4 ℃ for 3 hours at 4 ℃ for 1 h. The mixture was stirred for 2 hours at 4 ℃ for 3 hours at 4 ℃ for 3 hours at 4 ℃ for 4 hours at 5 ℃ for 5 minutes at 8 ℃ for 8 hours at 5 ℃ for 2 hours at 8 ℃ for 3 hours at 5 ℃ for 4 hours at 8 ℃ for 5 hours at 8 ℃ for 2 hours at 5 ℃ for 3 hours at 8 ℃ for 4 hours at 8 ℃ for 5 hours at 8 ℃ for 2 hours at 5 ℃ for 4 hours at 8 ℃ for 2 hours at 8 ℃ for 3 hours at 8 ℃ for 4 hours at 8 ℃ for 5 hours at 8 ℃ for 2 hours at 8 ℃ for 4 hours at 8 ℃ for 2 hours at 8 ℃ for 3 ... 1 H NMR (400MHz, CDCl 3): δ7.56(d,1H,J=8.8Hz),7.37(d,1H,J=2.6Hz),7.09(d,1H,J=2.5Hz),6.98(d,1H ,J=3.0Hz),6.80(dd,1H,J=8.8,3.1Hz),4.59(d,1H,J=4.6Hz),4.48(d,1H,J=4.5Hz) ,3.96(t,2H,J=6.6Hz),3.28(s,3H),2.24-2.19(m,6H),2.16-2.10(m,3H),1.87-1.7 5(m,8H),1.51-1.41(m,2H),1.35(s,9H),1.32-1.25(m,16H),0.91(t,3H,J=7.4Hz).

[0110] 2-(3'-(adamantan-1-yl)-5'-(tert-butyl)-5-(dodecyloxy)-2'-(methoxymethoxy)-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Isohexane (70 mL) was added to 1-(2′-bromo-5-(tert-butyl)-5′-(dodecyloxy)-2-(methoxymethoxy)-[1,1′-biphenyl]-3-yl)adamantane (3.45 g, 5.17 mmol) to form a clear solution. The mixture was cooled to -45°C. A hexane solution of BuLi (2.60 M, 2.02 mL, 5.42 mmol) was added dropwise over one minute. The mixture was stirred for 80 minutes. The mixture was removed from the cold bath and allowed to warm to ambient temperature. The mixture was then cooled back to -45°C, and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.31 g, 7.05 mmol) was added in one portion. The mixture was stirred for 1 hour, then warmed to ambient temperature and stirred for an additional 45 minutes. The suspension was poured into a separatory funnel containing water (75 mL). The mixture was shaken thoroughly and the aqueous layer was removed. The organics were extracted with water until the wash was pH neutral. The organics were then dried over brine, MgSO4, and filtered. Removal of volatiles afforded a thick oil (3.61 g). Purification on SiO2 with 1-3% ethyl acetate in isohexane. Yield: 1.21 g, 32.8%. 1 H NMR (400MHz, CDCl 3): δ7.71(dd,1H,J=7.9,0.8Hz),7.27(d,1H,J=2.7Hz),6.96(d,1H,J=2.5Hz),6. 88-6.83(m,2H),4.54(d,1H,J=4.6Hz),4.42(d,1H,J=4.7Hz),3.96(t,2H,J=6.7H z),3.25(s,3H),2.23-2.16(m,6H),2.13-2.05(m,3H),1.85-1.71(m,8H),1.48-1 .38(m,2H),1.34-1.23(m,25H),1.13(s,6H),1.09(s,6H),0.88(t,3H,J=6.8Hz).

[0111] 6',6"'-(pyridine-2,6-diyl)bis(3'-dodecyloxy-3-(adamantan-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-phenol) A 200 mL round-bottom flask was charged with 2-(3′-(adamantan-1-yl)-5′-(tert-butyl)-5-(dodecyloxy)-2′-(methoxymethoxy)-[1,1′-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.21 g, 1.69 mmol), 2,6-dibromopyridine (0.193 g, 0.812 mmol), Na2CO3 (0.449 g, 4.23 mmol), dihydrogen iodide (0.20 g, 1.09 mmol), and 1,2-dihydrogen iodide (0.30 g, 1.08 mmol). Alkane (40mL) and water (20mL). The mixture was bubbled with nitrogen for 50 minutes, then solid Pd(PPh3)4 (0.0978g, 0.0846mmol) was added. The mixture was bubbled for another 40 minutes, then stirred rapidly and heated in an oil bath maintained at 100°C. After 21 hours, the volatiles were evaporated to near dryness, then ether (70mL) and water (70mL) were added. The organic matter was separated and extracted with water until neutral pH. The organic matter was dried over brine and then evaporated to a residue. Methanol (20mL), THF (20mL) and concentrated HCl (2mL) were added, and the mixture was heated to 60°C. After 4.5 hours, the mixture was cooled to ambient temperature and the volatiles were evaporated. The residue was dissolved in ether (75mL) and water (75mL), and the mixture was transferred to a separatory funnel. The organic matter was separated and extracted with water until the pH of the washings was neutral. It was then dried with brine, then the organic matter was dried over MgSO4, and then filtered. Removal of volatiles afforded the crude product. The crude product was purified on SiO2. Charged with methylcyclohexane and eluted with 0-2.5% ethyl acetate in isohexane. The product was isolated as a white foam. Yield: 0.776 g, 82.0%. 1 H NMR, isomers integrated together as one (400 MHz, CDCl3): δ 8.50 (br s, 1H), 7.45-7.27 (m, 3H), 7.14-6.91 (m, 5H), 6.90-6.83 (m, 3H), 6.51 (d, 1H, J = 2.4 Hz), 3.97 (t, 4H, J = 6.4 Hz), 2.22-1.84 (m, 18H), 1.84-1.58 (m, 18H), 1.40-1.15 (m, 38H), 1.03-0.82 (m, 20H). Preparation of transition metal complexes

[0112] Complex 3[6',6"'-(pyridine-2,6-diyl)bis(3'-butoxy-3-(adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenol)dimethylzirconium] Toluene (15 mL) was added to ZrCl4(ether)2 (0.167 g, 0.437 mmol) and 6',6"'-(pyridine-2,6-diyl)bis(3'-butoxy-3-(adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenol) (0.343 g, 0.397 mmol). The mixture was stirred for several minutes and then cooled to -20 °C. An ethereal solution of MeMgBr (3.28 M, 0.642 mL) was added in one portion. , 2.11 mmol). The mixture was allowed to warm to ambient temperature over 90 minutes and then stirred for an additional 15 minutes. The volatiles were removed under reduced pressure. The residue was extracted with methylcyclohexane (20 mL) and filtered through celite 503. The volatiles were evaporated to about 2 mL, warmed slightly, and then isohexane (3 mL) was added. The mixture was cooled to 0°C for 4 days. The off-white solid was collected, washed with cold isohexane (1 mL), and dried under reduced pressure. The product was co-crystallized with about 0.6 equivalents of isohexane (by 1 H NMR spectrum). Yield: 0.286 g, 70.1%. 1 H NMR (400MHz, C6D6): δ7.20 (d, 2H, J = 2.3Hz), 7.03 (d, 4H, J = 1.5Hz), 6.91 (t, 2H, J = 1.5 Hz),6.87(dd,2H,J=2.3,0.9Hz),6.59-6.50(m,3H),3.63-3.47(m,4H),2.57-2.47(m ,6H),2.43-2.33(m,6H),2.24(s,6H),2.21-2.21(m,6H),2.02-1.94(m,6H),1.84-1. 76(m,6H),1.52-1.39(m,4H),1.33-1.17(m,4H),0.78(t,6H,J=7.3Hz),0.23(s,6H).

[0113] Complex 4[6',6"'-(pyridine-2,6-diyl)bis(3'-butoxy-3-(adamantan-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-phenol)dimethylzirconium] Toluene (80 mL) was added to ZrCl4(ether)2 (1.25 g, 3.29 mmol) and 6',6"'-(pyridine-2,6-diyl)bis(3'-butoxy-3-(adamantan-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-phenol) (2.81 g, 2.99 mmol). The mixture was stirred for several minutes and then cooled to -20 °C. An ethereal solution of MeMgBr (3.28 M, 4.83 mL, 15.8 mmol) was added in one portion. The mixture was slowly warmed to ambient temperature over several hours and then The mixture was stirred for 30 minutes. The volatiles were removed under reduced pressure. The residue was extracted with methylcyclohexane (80mL) and filtered through diatomite 503. The volatiles were evaporated to near dryness and isohexane (10mL) was added. The mixture was cooled to 0 ° C overnight. The next day, the thin solid was suspended in the mixture. The solid was collected on a glass frit, washed with cold isohexane (5mL), and dried under reduced pressure (crops 1). The mother liquor was evaporated to about 4mL and HMDSO (10mL) was added. Grind this mixture to obtain a thin solid, which was collected on a glass frit and dried under reduced pressure (crops 2). 1 H NMR indicated that crop 1 had 0.5 equivalents of co-crystallized isohexane. 1 H NMR indicated that crop 2 had 0.5 equivalents of co-crystallized hmdso. Yield (crop 1): 1.94 g, 58.9% (containing 0.5 equivalents of isohex); (crop 2): 0.486 g, 14.3% (containing 0.5 equivalents of hmdso). 1 H NMR (400MHz, C6D6): δ7.57 (d, 2H, J = 2.6Hz), 7.16 (d, 2H, J = 2.6Hz), 7.02-6.9 1(m,6H),6.56-6.45(m,3H),3.61-3.44(m,4H),2.66-2.56(m,6H),2.53-2.42 (m,6H),2.25-2.17(m,6H),2.05-1.95(m,6H),1.86-1.77(m,6H),1.51-1.37 (m,4H),1.34(s,18H),1.28-1.16(m,4H),0.77(t,6H,J=7.4Hz),0.24(s,6H).

[0114] Complex 5[6',6"'-(pyridine-2,6-diyl)bis(3'-octyloxy-3-(adamantan-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-phenol)dimethylzirconium] Toluene (20 mL) was added to ZrCl4(ether)2 (0.0513 g, 0.135 mmol) and 6',6"'-(pyridine-2,6-diyl)bis(3'-octyloxy-3-(adamantan-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-phenol) (0.128 g, 0.122 mmol). The mixture was stirred for 1 min and then cooled to -20°C. An ethereal solution of MeMgBr (3.28 M, 0.198 mL, 0.649 mmol) was added in one portion. The mixture was allowed to warm to ambient temperature over several hours and then stirred for an additional 30 min. The volatiles were removed under reduced pressure. The residue was extracted with methylcyclohexane (6 mL) and filtered. Evaporated to near dryness and isohexane (1 mL) was added to form a solution. Attempts to crystallize the product from isohexane or HMDSO failed. The volatiles were evaporated and dried under reduced pressure to give an orange-brown foamy semisolid. 1 H NMR indicated the presence of about 0.7 equivalents of hmdso. Yield: 0.157 g, 99.8%. 1 H NMR (400MHz, C6D6): δ7.58(d,2H,J=2.6Hz),7.18(d,2H,J=2.5Hz),7.06- 6.95(m,6H),6.58-6.48(m,3H),3.66-3.48(m,4H),2.68-2.57(m,6H),2.5 3-2.44(m,6H),2.27-2.19(m,6H),2.07-1.97(m,6H),1.89-1.78(m,6H),1 .57-1.46(m,4H),1.40-1.12(m,38H),0.91(t,6H,J=7.0Hz),0.26(s,6H).

[0115] Complex 6[6',6"'-(pyridine-2,6-diyl)bis(3'-dodecyloxy-3-(adamantan-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-phenol)dimethylzirconium] Toluene (40 mL) was added to ZrCl4(ether)2 (0.251 g, 0.659 mmol) and 6',6"'-(pyridine-2,6-diyl)bis(3'-dodecyloxy-3-(adamantan-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-phenol) (0.769 g, 0.599 mmol). The mixture was stirred for 1 minute and then cooled to -20°C. An ethereal solution of MeMgBr (3.28 M, 0.968 mL, 3.18 mmol) was added in one portion. The mixture was allowed to warm to ambient temperature over several hours and then stirred for another 3 hours. Stir for 30 minutes. Then remove volatiles under reduced pressure to obtain a residue. The residue is extracted with toluene (12mL) and filtered through diatomaceous earth 503 on a sintered disk. Toluene is evaporated to dryness, then isohexane (3mL) is added to form a clear brown solution. The solution is cooled to 0°C overnight, but the solution remains completely homogeneous. The mixture is concentrated to 2mL and cooled to -20°C. No crystallization can be achieved after a few hours. The volatiles are then evaporated and the residue is dried under reduced pressure. Adding HMDSO (4ml) and grinding does not produce solids. The volatiles are evaporated, and the residue is dried under reduced pressure to obtain a sticky foam solid. 1 H NMR spectral data indicated the presence of 0.5 equivalents of hmdso. Yield: 0.845 g, 103%. 1 H NMR (400MHz, CD2Cl2): δ7.71(t,1H,J=7.8Hz),7.22(d,2H,J=2.6Hz),7.11(d,2H,J=7.8Hz),2.99(d,2H,J=8.4Hz),6.91-6.83(m,3H),6.80(d,2H, J=2.5Hz),4.00(t,4H,J=6.6Hz),2.31-2.21(m,6H),2.19-2.02(m,12H), 1.87-1.70(m,16H),1.49-1.20(m,54H),0.92-0.84(m,6H),-0.46(s,6H). Complex solubility

[0116] General Considerations: Solubility studies were performed using complexes isolated as crystalline or microcrystalline solids. Comparative complex 2 was co-crystallized with 1.4 equivalents of methylcyclohexane. Comparative complex 1 had no co-crystallization solvent. Complex 3, embodying the advance in the art, was co-crystallized with 0.6 equivalents of isohexane. Complex 4, embodying the advance in the art, was co-crystallized with 0.5 equivalents of isohexane. The solvents used were sparged with nitrogen (30-60 minutes) and dried over 3 angstrom molecular sieves. All measurements were performed at ambient temperature (20°C-25°C) unless otherwise stated.

[0117] General procedure: A small amount of complex (actual mass recorded, usually 5-30 mg) is loaded into a tared vial. Then, a small stirring bar (8 mm) is added. Then the solvent is added and the mixture is stirred rapidly (1000 rpm). If a homogeneous mixture is not formed within 30 minutes, additional solvent is added and the mixture is stirred for another 30 minutes. This process is repeated until a clear solution is obtained (no visible solids or turbidity) or the vial is full. When the mixture approaches a homogeneous phase (i.e., very little residual solid is observed), the volume of solvent addition is kept small (<1 mL) to minimize the excess of solvent required to reach a homogeneous phase. Then the stirring bar is removed and the mass of the mixture is measured. If a clear solution is formed, the solubility of the complex is calculated based on the mass of the complex and the amount of solvent added to obtain a homogeneous solution. If the mixture remains heterogeneous (visible solids or turbidity), the reported value is given as "less than" the calculated value. The formula for calculating solubility is as follows. The cocrystallization solvent is included in the mass and molecular weight of the complex. The density of isohexane used in the calculations was 0.672 g / mL, and the density of the complex was assumed to be 1.0 g / mL.

[0118] Solubility (wt%) =

[100] × [(weight of complex) / (weight of solution)] Solubility (mM) = [10 6 ]×[(grams of complex) / (molecular weight of complex, g / mol)] / [(grams of solvent) / (density of solvent, g / mL)] Table 1. Solubility of the complexes in isohexane at room temperature Complex Solubility in isohexane (wt%) Solubility in isohexane (mM) 1 <0.08 <0.6 2 0.081 0.52 3 0.168 1.10 4 2.55 15.7 Polymerization Example

[0119] Solutions of the procatalyst were prepared using toluene (ExxonMobil Chemical - anhydrous, stored under N2) (98%) or isohexane (ExxonMobil Chemical - polymerisation grade and purified as described below). Procatalyst solutions were typically 0.25 mmol / L.

[0120] Solvents, polymer grade toluene and / or isohexane, were supplied by ExxonMobil Chemical Co. and purified by passage through a series of columns: two 500 cc Oxyclear cartridges in series from Labclear (Oakland, Calif.), followed by dry Two 500 cc columns filled in series with molecular sieves (8-12 mesh; Aldrich Chemical Company) and dried Two 500 cc columns were connected in series and packed with molecular sieves (8-12 mesh; Aldrich Chemical Company).

[0121] Polymer grade propylene (C3) was used and further purified by passing it through a series of columns: a 2250cc Oxiclear cartridge from Labclear, followed by a column filled with molecular sieves (8-12 mesh, Aldrich Chemical Company), followed by a 2250 cc column filled with molecular sieves (8-12 mesh; Aldrich Chemical Company) in series, followed by a 500 cc column packed with Selexsorb CD (BASF), and finally a 500 cc column packed with Selexsorb COS (BASF).

[0122] Activation of the procatalyst was by dimethylanilinium tetrakisperfluorophenylborate (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.

[0123] Tri-n-octylaluminum (TnOAl or TNOA, neat, AkzoNobel) was also used as a scavenger before the activator and procatalyst were introduced into the reactor. TNOA was typically used as a 5 mmol / L solution in toluene or isohexane. Reactor Description and Preparation:

[0124] The polymerization was carried out in an inert atmosphere (N2) dry box using an autoclave equipped with an external heater for temperature control, a glass insert (internal volume of 22.5 mL), a septum inlet, a regulated supply of nitrogen and propylene, and a disposable PEEK mechanical stirrer (800 RPM). 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. Propylene Polymerization (PP):

[0125] The reactor is 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 scavenger (TNOA, 0.5 μmol) are added via a syringe. The reactor is then brought to process temperature (70°C or 100°C) while stirring at 800RPM. The activator solution, followed by the precatalyst solution, is injected into the reactor under process conditions via a syringe. The reactor temperature is monitored and typically maintained within + / -1°C. The polymerization is stopped by adding a mixture of about 50 psi compressed dry air gas to the autoclave for about 30 seconds. The polymerization is quenched based on a predetermined pressure loss (maximum quenching value) or up to 30 minutes. The reactor is cooled and vented. The polymer is isolated after removing the solvent in a vacuum. The actual quenching time (s) is reported as the quenching time (s). The reported yield includes the total weight of the polymer and the residual catalyst. The catalyst activity is reported as grams of polymer / mmol transition metal compound / hour reaction time (g / mmol·hr). Propylene homopolymerization examples are reported in Table 2 and additional characterizations are reported in Table 3. Polymer characterization

[0126] For analytical testing, polymer sample solutions were prepared by dissolving the polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity, obtained from Sigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%, obtained from Aldrich) at 165°C in a shaker oven for approximately 3 hours. Typical concentrations of polymer in solution were 0.1 to 0.9 mg / mL and BHT concentration was 1.25 mg BHT / mL TCB. Samples were cooled to 135°C for testing.

[0127] High temperature size exclusion chromatography was performed using an automated "Rapid 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 weight (weight average molecular weight (Mw), number average molecular weight (Mn)) and z average molecular weight (Mz)) and molecular weight distribution (MWD = Mw / Mn), which is sometimes also referred to as the polydispersity (PDI) of the polymer, are 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 SM-10: Mp (peak Mw) between 5,000 and 3,390,000 g / mol). Alternatively, the samples are measured using a Symyx Technology GPC equipped with a dual wavelength infrared detector and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) between 580 and 3,039,000). Samples were run using three Polymer Laboratories: PLgel 10 μm Mixed-B 300×7.5 mm columns in series with an eluent flow rate of 2.0 mL / min (135°C sample temperature, 165°C oven / column) (250 μl of polymer in TCB solution was injected into the system). No column spreading corrections were used. A 10 μm HPLC-MS / MS column, available from Symyx Technologies, was used. Numerical analysis was performed using the Automation Studio software available from Freeslate or the Automation Studio software available from Freeslate. The molecular weights obtained are relative to linear polystyrene standards. The molecular weight data are reported in Table 2 under the headings Mn, Mw, Mz and PDI as defined above.

[0128] 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 allowed to cool to 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 stage. The results are reported in Table 2 under the heading Tm (°C).

[0129] 13C NMR spectroscopy was used to characterize some of the polypropylene polymer samples prepared in the experiments collected in Table 2. This data is collected in Table 3. Unless otherwise stated, the data used for 13 C NMR spectroscopy of polymer samples dissolved in d2-1,1,2,2-tetrachloroethane and heated at 125 °C using 13 The samples were recorded on an NMR spectrometer with a C NMR frequency of 150 MHz. The polymer resonance peak reference mmmm = 21.8 ppm. The calculations involved in the characterization of polymers by NMR followed the works of FA Bovey, "Polymer Conformation and Configuration", Academic Press, New York 1969 and J. Randall, "Polymer Sequence Determination, Carbon-13 NMR Method", Academic Press, New York, 1977.

[0130] The stereo defects measured as "stereo defects / 10,000 monomer units" are calculated by multiplying the sum of the intensities of the mmrr, mmrm+rrmr and rmrm resonance peaks by 5,000. The intensity used in the calculation is normalized to the total number of monomers in the sample. The method for measuring 2,1-regio defects / 10,000 monomers and 1,3-regio defects / 10,000 monomers follows standard methods. Additional references include Macromolecules by Grassi, A. et al., 1988, v.21, pp.617-622 and Macromolecules by Busico et al., 1994, v.27, pp.7538-7543. Average meso run length = 10000 / [(stereo defect / 10000C)+(2,1-region defect / 10000C)+(1,3-region defect / 10000C)].

[0131] The polymerization results are collected in Table 2. "Ex#" represents the example number. Example numbers starting with "C" are comparative examples. "Cat ID" identifies the procatalyst used in the experiment. The corresponding number identifying the procatalyst (also called procatalyst, catalyst, complex or compound) is located in the synthetic experimental section. T (℃) is the polymerization temperature typically maintained within + / -1℃. "Yield" is the polymer yield and is not corrected for catalyst residues. "Quenching time (s)" is the actual duration of the polymerization batch in seconds. For propylene homopolymerization batches, the quenching value represents the maximum set pressure loss (conversion) of propylene during polymerization. Activity is reported in grams of polymer / mmol catalyst / hour.

[0132] Standard polymerization conditions included 0.015 μmol catalyst complex, 1.1 equivalents activator, 0.5 μmol TNOA scavenger, 1.0 ml propylene, 4.1 ml total solvent, quench value at 8 psi pressure loss, or a maximum reaction time of 30 minutes. Activator A was N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator and activator B was (hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate. When activator A was used, both the procatalyst and activator solutions were in toluene. When activator B was used, both the procatalyst and activator solutions were in isohexane. A small amount of methylcyclohexane (MCH) was generated by activator B, which was provided by the manufacturer as a 10 wt % solution in methylcyclohexane.

[0133] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It is understood that ranges including combinations of any two values, such as any lower limit value combined with any upper limit value, any combination of any two lower limits, and / or any combination of any two upper limits are contemplated unless otherwise stated. Certain lower limits, upper limits, and ranges may appear in one or more claims below. All numerical values ​​are "about" or "approximately" indicative values, and take into account experimental errors and deviations that would be expected by a person of ordinary skill in the art. Any value in the table may provide an endpoint defining a range of its corresponding measurement or property, with an additional + / - 10%.

[0134] All documents described herein, including any priority documents and / or test procedures are incorporated by reference in all jurisdictions not inconsistent with the present invention. It is apparent from the above overview and specific embodiments that, although the form of the present disclosure has been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Therefore, it is not desired that the present disclosure be limited in this manner.

[0135] While the present disclosure has been described in terms of a number of embodiments and examples, those skilled in the art, after reading this disclosure, will appreciate that other embodiments can be devised without departing from the scope and spirit of the present disclosure.

Claims

1. A catalyst compound represented by formula (I): in: M is a Group 3, 4 or 5 metal; 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 not greater than 4; R 10 and R 14 Each of which is independently C4-C 40 Hydrocarbon or OR 20 , where R 20 It is C4-C 40 Hydrocarbon; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 One or more pairs of R may be linked to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings or unsubstituted heterocyclic rings, each of which has 5, 6, 7 or 8 ring atoms; R 9 , R 11 and R 12 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 11 and R 12 may be linked to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 13 , R 15 and R 16 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 15 and R 16 may be linked to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 or R 17 and R 19 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; Any two L groups can be linked together to form a bidentate Lewis base; The X group may be linked to the L group to form a monoanionic bidentate group; and Any two X groups may be linked together to form a dianionic ligand group.

2. The catalyst compound of claim 1, wherein R 4 and R 5 are each independently adamantyl, R 2 and R 7 Each independently is C4-C 40 A hydrocarbon group, preferably a C4-C8 hydrocarbon group, more preferably a tert-butyl group, and R 10 and R 14 Each independently is OR 20 , where R 20 C4-C 12 Hydrocarbon.

3. The catalyst compound of claim 1 or 2, wherein R 2 , R 7 , R 10 and R 14 The substituent has a total carbon number of 12 carbon atoms or more, or 14 carbon atoms or more, or 16 carbon atoms or more, or 18 carbon atoms or more.

4. The catalyst compound of claim 1 or 2, wherein R 2 , R 7 , R 10 and R 14 The substituent has a total carbon number of 12 carbon atoms or more, or 14 carbon atoms or more, or 16 carbon atoms or more, or 18 carbon atoms or more, and R 4 and R 5 is selected from the group consisting of tert-butyl, adamantyl and substituted adamantyl.

5. The catalyst compound of claim 1 or 2, wherein R 2 , R 7 , R 4 , R 5 , R 10 and R 14 The substituent has a total carbon number of 32 carbon atoms or more, or 34 carbon atoms or more, or 36 carbon atoms or more.

6. The catalyst compound of claim 1, wherein the catalyst compound is one of the following:

7. The catalyst compound of claim 1, wherein R 10 and R 14 Each of the 20 , where R 20 It is C4-C 40 Hydrocarbon.

8. A catalyst system comprising an activator, preferably a non-aromatic hydrocarbon, and optionally a support material, and a catalyst compound according to any of the preceding claims.

9. A homogeneous solution comprising: an aliphatic hydrocarbon solvent; and At least one complex of formula (I), wherein the concentration of the complex is 0.15 wt % or greater (or 0.20 wt % or greater, or 0.25 wt % or greater, or 0.30 wt % or greater, or 0.35 wt % or greater, or 0.40 wt % or greater, or 0.5 wt % or greater, or 1.0 wt % or greater, or 2.0 wt % or greater).

10. The homogeneous solution of claim 9, wherein the aliphatic hydrocarbon solvent is isohexane, cyclohexane, methylcyclohexane, pentane, isopentane, heptane, an isoparaffin solvent, a non-aromatic cyclic solvent, or a combination thereof.

11. A method for producing a propylene-based polymer, comprising: Propylene is polymerized by contacting propylene with the catalyst system of claim 8 in one or more continuous stirred tank reactors or loop reactors connected in series or in parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to form a propylene-based polymer.

12. A method for producing an ethylene-based polymer comprising: Ethylene is polymerized by contacting ethylene with the catalyst system of claim 8 in one or more continuous stirred tank reactors or loop reactors connected in series or in parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to form an ethylene-based polymer.

13. The process of claim 11 or 12, wherein the catalyst compound and the activator are fed separately into the one or more reactors.

14. The process of claim 11 or 12, wherein the catalyst compound and the activator are premixed prior to feeding into the one or more reactors.

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