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

Abstract

Exemplary embodiments of the industrial advances of the present invention include pyridine-2,6-bis(phenylenephenolate) complexes that are useful as catalyst components for olefin polymerization and have improved solubility in non-aromatic hydrocarbons (e.g., isohexane). The improved solubility of these complexes was achieved through modifications of the ligand framework at specific positions that resulted in improved solubility, but did not adversely affect the performance of the complexes when used as catalysts for olefin polymerization.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 338,169, filed May 4, 2022, the disclosure of which is incorporated herein by reference. The present disclosure relates to bis(arylphenolate) Lewis base transition metal complexes, catalyst systems including bis(arylphenolate) Lewis base transition metal complexes, and polymerization methods for producing polyolefin polymers, such as polyethylene- and polypropylene-based polymers. [Background technology]

[0002] Polyolefins such as polyethylene typically have a comonomer, such as hexene, incorporated into the polyethylene backbone. These copolymers provide different physical properties compared to polyethylene alone and are typically produced in low pressure reactors using, for example, solution, slurry or gas phase polymerization processes. The polymerization can be carried out in the presence of a catalyst system, such as a catalyst system using a Ziegler-Natta catalyst, a chromium-based catalyst or a metallocene catalyst. Furthermore, since the precatalyst (neutral unactivated complex) is often stored for several weeks before use, the precatalyst should be thermally stable at ambient temperature or above. 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 often difficult to maintain high catalyst activity and high molecular weight capability, as both attributes decrease very consistently with increasing reactor temperature. For a wide range of desired polyolefin products, ranging from high density polyethylene (HDPE) to elastomers (e.g., thermoplastic elastomers (TPE); ethylene-propylene-diene (EPDM)), a large number of different catalyst systems may be required, since a single catalyst is unlikely to be able to address all the needs for the production of these various polyolefin products. The stringent set of requirements necessary for the development and production of new polyolefin products makes the effort to identify a suitable catalyst for a given product and production process very challenging.

[0003] Aromatic solvents are typically used to dissolve catalyst components in industrial olefin polymerization processes, but replacing aromatic solvents with non-aromatic solvents such as isohexane is challenging because the catalyst components usually have poor solubility in non-aromatic solvents. Further information regarding the general state of the art regarding nonmetallocene 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 incorporated herein by reference. Further information regarding the complexes can be found in Goryunov, GP et al. (2021) "Rigid Postmetallocene Catalysts for Propylene Polymerization: Ligand Design Prevents the Temperature-Dependent Loss of Stereo- and Regioselectivities," ACS Catalysis, v.11(13), pp. 8079-8086; US2020 / 0255556; US2020 / 0255555; US2020 / 0254431; and US2020 / 0255553, each of which is incorporated by reference in its entirety. Summary of the Invention

[0004] A catalyst compound represented by formula (I): [ka] (I) (In the formula, 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 equal to or less than 4, R 10 and R 14 are each independently 40 Hydrocarbyl or OR 20 and R 20 is C4-C 40 is a hydrocarbyl; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 Or R 7 and R 8 may be joined together to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 9 , R 11 and R 12 are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 11 and R 12 may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 13 , R 15 and R 16 are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 15 and R 16 may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 Or R 17 and R 19 may be joined together to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; any two L groups may be linked together to form a bidentate Lewis base; The X group may be attached to the L group to form a monoanionic bidentate group; Any two X groups may be linked together to form a dianionic coordinating group.

[0005] an aliphatic hydrocarbon solvent; and at least one complex of formula (I), wherein the concentration of the complex is 0.20% by weight or more (alternatively 0.25% by weight or more, alternatively 0.30% by weight or more, alternatively 0.35% by weight or more, alternatively 0.40% by weight or more, alternatively 0.50% by weight or more, alternatively 1.0% by weight or more, alternatively 2.0% by weight or more). A method for producing a propylene-based polymer comprising the step of polymerizing propylene 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. by contacting the propylene with a catalyst system made from formula (I) to form a propylene-based polymer. A process for producing an ethylene-based polymer comprising the step of polymerizing ethylene 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. by contacting the ethylene with a catalyst system made from formula (I) to form a propylene-based polymer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] Exemplary embodiments of the industrial advances of the present invention include pyridine-2,6-bis(phenylenephenolate) complexes that are useful as catalyst components for olefin polymerization and have improved solubility in non-aromatic hydrocarbons (e.g., isohexane). The improved solubility of these complexes was achieved through modifications of the ligand framework at specific positions that resulted in improved solubility, but did not adversely affect the performance of the complexes when used as catalysts for olefin polymerization. For purposes of this disclosure, the numbering scheme for the Periodic Table Groups will be used as set forth in Chemical and Engineering News, v.63(5), pg. 27 (1985). Thus, a "Group 4 metal" refers to an element in Group 4 of the Periodic Table, e.g., Hf, Ti, or Zr. The following abbreviations may be used herein: Me is methyl, Et is ethyl, Ph is phenyl, tBu is tertiary butyl, MAO is methylalumoxane, NMR is nuclear magnetic resonance, t is hour, s is seconds, h is hours, psi is pounds per square inch, psig is pounds per square inch gauge, equiv is equivalent, and RPM is revolutions per minute.

[0007] This specification describes transition metal complexes. The term complex is used to describe molecules in which ancillary ligands are coordinated to a central transition metal atom. The ligands are bulky and stably bound to the transition metal so as to maintain their influence during the use of the catalyst, such as polymerization. The ligands can be coordinated to the transition metal by covalent and / or electron donating coordination or intermediate bonds. Transition metal complexes are generally activated to perform their polymerization or oligomerization functions using an activator, which, without being bound by theory, is believed to generate a cation as a result of removal of an anionic group, often referred to as a leaving group, from the transition metal. The terms "substituents," "radicals," "groups," and "moieties" may be used interchangeably. "Conversion" refers to the amount of monomer that is converted to polymer product, reported as mol %, and calculated based on the polymer yield and the amount of monomer fed to the reactor.

[0008] "Catalytic activity" is a measure of how active a catalyst is and is expressed as grams of product polymer (P) produced per millimole of catalyst (cat) per hour (gP.mmolcat -1 .h -1 ) The term "heteroatom" refers to any of the Groups 13-17 elements, except carbon. Heteroatoms can include B, Si, Ge, Sn, N, P, As, O, S, Se, Te, F, Cl, Br, and I. The term "heteroatom" can include the elements listed above with a hydrogen atom attached thereto, such as BH, BH2, SiH2, OH, NH, NH2. The term "substituted heteroatom" describes a heteroatom where one or more of these hydrogen atoms have been replaced by a hydrocarbyl or substituted hydrocarbyl group.

[0009] Unless otherwise indicated (e.g., in the definitions of "substituted hydrocarbyl," "substituted aromatic," etc.), the term "substituted" means that at least one hydrogen atom has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group, such as -NR * 2, -OR * , -SeR * , -TeR * , -PR * 2, -AsR * 2, -SbR * 2, -SR * , -BR * 2, -SiR * 3. -GeR * 3. -SnR * 3. -PbR * 3, R * are each independently a hydrocarbyl radical or a halocarbyl radical, and two or more R *means that the ring is replaced by at least one non-hydrogen group such as aryl, arylsulfates, arylalkyl ...

[0010] The term “substituted hydrocarbyl” refers to a hydrocarbyl radical in which at least one hydrogen atom has been replaced with at least one heteroatom (e.g., a halogen, such as Br, Cl, F, or I) or 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, R * are each independently a hydrocarbyl radical or a halocarbyl radical, and two or more R * means a hydrocarbyl radical replaced by a heteroatom which may be joined together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or a hydrocarbyl radical in which at least one heteroatom is inserted within the hydrocarbyl ring. The term "hydrocarbyl-substituted phenyl" means a phenyl group in which one, two, three, four or five hydrogen radicals have been replaced by a hydrocarbyl or substituted hydrocarbyl group. For example, a "hydrocarbyl-substituted phenyl" group can be represented by the formula:

[0011] [ka] (R a , R b , R c , R d and R eare hydrogen, C1-C 40 Hydrocarbyl or C1-C 40 Substituted hydrocarbyl, heteroatom or heteroatom-containing group (wherein R a , R b , R c , R d and R e at least one of R a , R b , R c , R d and R e Two or more of these together form C4-C 62 may form cyclic or polycyclic hydrocarbyl ring structures or combinations thereof It can be expressed as: The term "substituted aromatic" means an aromatic group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group. The term "substituted phenyl" means a phenyl group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group. The term "substituted carbazole" refers to a carbazolyl group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group. The term "substituted naphthyl" means a naphthyl group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group. The term "substituted anthracenyl" refers to an anthracenyl group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group. The term "substituted fluorenyl" refers to a fluorenyl group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0012] The terms trihydrocarbylsilyl and trihydrocarbylgermyl refer to a silyl or germyl group bonded to three hydrocarbyl groups. Examples of suitable trihydrocarbylsilyl and trihydrocarbylgermyl groups include trimethylsilyl, trimethylgermyl, triethylsilyl, triethylgermyl, and all isomers of tripropylsilyl, tripropylgermyl, tributylsilyl, tributylgermyl, tripentylsilyl, tripentylgermyl, butyldimethylsilyl, butyldimethylgermyl, dimethyloctylsilyl, dimethyloctylgermyl, and the like. The terms dihydrocarbylamino and dihydrocarbylphosphino refer to a nitrogen or phosphorus group 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, and the like.

[0013] The term "substituted adamantanyl" refers to an adamantanyl group in which one or more hydrogen radicals have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group. The terms "alkoxy" and "alkoxide" refer to an alkyl or aryl group bonded to an oxygen atom, e.g., an alkyl ether group or an aryl ether group / radical bonded to an oxygen atom, wherein the alkyl / aryl group is a C1-C 10 The alkyl groups may include those that are hydrocarbyl (also referred to as hydrocarbyloxy groups). The alkyl groups may be linear, branched or cyclic. The alkyl groups may be saturated or unsaturated. Examples of suitable alkoxy radicals may include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, phenoxy. The term "aryl" or "aryl group" refers to aromatic rings and substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Similarly, heteroaryl refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) is replaced by a heteroatom such as N, O or S. As used herein, the term "aromatic" also refers to pseudoheteroaromatic rings, which are heterocyclic substituents with similar properties and structure (nearly planar) to aromatic heterocyclic ligands, but which are not according to the definition of aromatic. Similarly, the term aromatic also refers to substituted aromatics.

[0014] The term "arylalkyl" refers to an aryl group in which a hydrogen is replaced by an alkyl group or a substituted alkyl group. For example, 3,5'-di-tert-butyl-phenylindenyl is an indene substituted by an arylalkyl group. When an arylalkyl group is a substituent on another group, the arylalkyl group is bonded to the other group through the aryl. The term "alkylaryl" refers to an alkyl group in which a hydrogen has been replaced by an aryl group or a substituted aryl group. For example, phenethylindenyl is an indene substituted with an ethyl group attached to a benzene group. When an alkylaryl group is a substituent on another group, the alkylaryl group is attached to the other group via the alkyl. The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has 6 ring atoms and a tetrahydrofuran has 5 ring atoms.

[0015] A heterocycle is a ring that has a heteroatom in the ring structure, as opposed to a heteroatom-substituted ring, in which a hydrogen atom on a ring atom is replaced by a heteroatom. For example, tetrahydrofuran is a heterocycle, and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles can include pyridine, imidazole, and thiazole. The terms "hydrocarbyl radical", "hydrocarbyl group" or "hydrocarbyl" may be used interchangeably and are defined to mean a group consisting solely of hydrogen and carbon atoms. For example, a hydrocarbyl may be linear, branched or cyclic, and if cyclic, may be aromatic or non-aromatic, C1-C 100 Examples of such radicals include, but are not limited to, alkyl groups such as methyl, ethyl, propyl (e.g., n-propyl, isopropyl, cyclopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., iso-amyl, cyclopentyl), hexyl (e.g., cyclohexyl), octyl (e.g., cyclooctyl), nonyl, decyl (e.g., adamantanyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, or tricontyl, and aryl groups such as phenyl, benzyl, and naphthyl.

[0016] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol. Unless otherwise indicated, as used herein, "high molecular weight" is defined as a number average molecular weight (Mn) value of 100,000 g / mol or greater. "Low molecular weight" is defined as a Mn value of less than 100,000 g / mol. Unless otherwise stated, all melting points (Tm) are second run melting points of differential scanning calorimetry (DSC).

[0017] 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", "pre-catalyst compound" and "pre-catalyst complex" are used interchangeably. When "catalyst system" is used to describe such a pair prior to activation, "catalyst system" refers to the unactivated catalyst complex (pre-catalyst) together with an activator, and optionally together with a co-activator. When "catalyst system" is used to describe such a pair after activation, "catalyst system" refers to the activated complex and the activator or other charge-balancing moiety. The transition metal compound may be neutral, as in a pre-catalyst, or may be a charged species with a counterion, as in an activated catalyst system. For purposes of this disclosure and claims thereto, when a catalyst system is described as including neutral stable forms of the components, it is well understood by those skilled in the art that the ionic forms of the components are the forms that react with monomers to produce polymers. A polymerization catalyst system is a catalyst system capable of polymerizing monomers into polymers. Additionally, the catalyst compounds and activators represented by formulas herein are intended to encompass both the neutral and ionic forms of the catalyst compounds and activators.

[0018] In the description herein, the catalyst may be described as a catalyst, a catalyst precursor, a pre-catalyst compound, a catalyst compound, or a transition metal compound, and these terms are used interchangeably. An "anionic ligand" is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A "Lewis base" is a neutrally charged ligand that donates one or more pairs of electrons to a metal ion. Examples of Lewis bases include diethyl ether, trimethylamine, pyridine, tetrahydrofuran, dimethylsulfide, and triphenylphosphine. The term "heterocyclic Lewis base" refers to a Lewis base that is also a heterocycle. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan. Bis(arylphenolate) Lewis base ligands are tridentate ligands that bind to metals via two anionic donors (phenolates) and one heterocyclic Lewis base donor (e.g., a pyridinyl group). Bis(arylphenolate) heterocyclic ligands are tridentate ligands that bind to metals via two anionic donors (phenolates) and one heterocyclic Lewis base donor. The term "continuously" refers to a system that operates without interruption or cessation. For example, a continuous process for producing a polymer is one in which reactants are continuously introduced into one or more reactors and polymer product is continuously removed.

[0019] Transition metal complexes In at least one embodiment, the catalyst compound represented by formula (I) is as follows: [ka] (I) (In the formula, 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 equal to or less than 4, R 10 and R 14 are each independently 40 Hydrocarbyl or OR 20 and R 20is C4-C 40 is a hydrocarbyl; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 Or R 7 and R 8 may be joined together to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 9 , R 11 and R 12 are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 11 and R 12 may be joined together to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 13 , R 15 and R 16 are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 15 and R 16may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 Or R 17 and R 19 may be joined together to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; any two L groups may be linked together to form a bidentate Lewis base; The X group may be attached to the L group to form a monoanionic bidentate group; Any two X groups may be linked together to form a dianionic coordinating group.

[0020] For example, M in formula (I) can be a metal of Group 3, Group 4, or Group 5, e.g., M can be a Group 4 metal. Group 4 metals can include zirconium, titanium, and hafnium. In at least one embodiment, M is zirconium or hafnium. Each L in formula (I) can be independently selected from ether, amine, phosphine, thioether, ester, (e.g., Et2O, MeOtBu, etc.), Et3N, PhNMe2, MePh2N, tetrahydrofuran, methyl acetate, and dimethylsulfide, and each X can be independently selected from methyl, benzyl, trimethylsilyl, methyl(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydride, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamide, diethylamide, dipropylamide, and diisopropylamide. In at least one embodiment, n in formula (I) is 2, and each X is independently chloro, benzyl, or methyl.

[0021] R in formula (I) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 or R may be independently selected from substituted hydrocarbyl, hydrocarbyloxy, trihydrocarbylsilyl, trihydrocarbylgermyl, dihydrocarbylamino, dihydrocarbylphosphino, or halogen; 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 Or R 7 and R 8 may be joined to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms.

[0022] In at least one embodiment, R of formula (I)1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 one or more of the following may be selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, substituted phenyl, biphenyl or their isomers, which may be halogenated (e.g., perfluoropropyl, perfluorobutyl, perfluoroethyl, perfluoromethyl), substituted hydrocarbyl radicals, and all isomers of substituted hydrocarbyl radicals, including trimethylsilylpropyl, trimethylsilylmethyl, trimethylsilylethyl, phenyl, or all isomers of hydrocarbyl substituted phenyl, including methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, and heteroatom-containing groups including trimethylsilyl, triethylsilyl, methoxy, ethoxy, cyclohexyloxy, trifluoromethyl, dimethylamino, diethylamino, dicyclohexylamino, and all isomers of tripropylsilyl, tributylsilyl, tripropylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, dimethyloctylsilyl, butyldimethylsilyl (e.g., t-butyldimethylsilyl), propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, and the like.

[0023] For example, R in formula (I) 4 and R 5 are independent, C1-C 20 It can be alkyl, e.g., R 4 and R 5can be tert-butyl or adamantanyl. In at least one embodiment, R 4 and R 5 are independently selected from unsubstituted phenyl, substituted phenyl, unsubstituted carbazole, substituted carbazole, unsubstituted naphthyl, substituted naphthyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted fluorenyl or substituted fluorenyl, a heteroatom or a heteroatom-containing group, e.g., R 4 and R 5 can be independently unsubstituted phenyl or 3,5-di-tert-butylbenzyl. 4 is C1-C 20 can be alkyl (e.g., R 4 can be tert-butyl), R 5 can be aryl, or (2) R 5 is C1-C 20 can be alkyl (e.g., R 5 can be tert-butyl) and R 4 Alternatively, R can be aryl. 4 and / or R 5 can independently be a heteroatom, for example, R 4 and R 5 can be a halogen atom (e.g., Br, Cl, F or I). Alternatively, R 4 and / or R 5 can independently be a silyl group, e.g., R 4 and R 5 can be a trialkylsilyl group or a triarylsilyl group, where alkyl is C1-C 30alkyl (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl, cyclopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., iso-amyl, cyclopentyl), hexyl (e.g., cyclohexyl), octyl (e.g., cyclooctyl), nonyl, decyl (e.g., adamantanyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, or tricontyl); aryl is C6-C 30 Aryl (eg, phenyl, benzyl and naphthyl).

[0024] In some embodiments, R 4 and R 5 are independent, C1-C 40 Hydrocarbyl, C1-C 40 More preferably, R 4 and R 5 are each independently selected from tertiary hydrocarbyl groups (e.g., tert-butyl, tert-pentyl, tert-hexyl, tert-heptyl, tert-octyl, tert-nonyl, tert-decyl, tert-undecyl, tert-dodecyl) and cyclic tertiary hydrocarbyl groups (e.g., 1-methylcyclohexyl, 1-norbornyl, 1-adamantanyl, or substituted 1-adamantanyl). In some embodiments, R 4 and R 5 are independent, C1-C 40 Hydrocarbyl, C1-C 40 More preferably, R 4 and R 5is each independently a non-aromatic cyclic alkyl group (e.g., cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, adamantanyl, norbornyl, or 1-methylcyclohexyl or substituted adamantanyl), most preferably a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, 1-adamantanyl, substituted 1-adamantanyl, or 1-norbornyl).

[0025] In some embodiments, R 4 and R 5 are independently C3-C silyl groups, including trimethylsilyl, triethylsilyl, and all isomers of tripropylsilyl, tributylsilyl, tripentylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, dimethyloctylsilyl, butyldimethylsilyl, etc. 30 It is a heteroatom-containing group. R 4 and R 5 The molecular weight of the polymer product can be controlled by using the values ​​of R 4 and R 5 When one or both of R are tert-butyl, the catalyst compound can provide high molecular weight polymers. 4 , R 5 , or R 4 and R 5 When is phenyl, the catalyst compound can give low molecular weight polymers. In at least one embodiment, R of formula (I) 2 and R 7 are each independently 10 is alkyl, e.g., R 2 and R 7 are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dimethyl-pentyl, tert-butyl, isopropyl or an isomer thereof.

[0026] In at least one embodiment, R of formula (I) 2 and R 7 are each independently30 Substituted hydrocarbyl or C3-C 30 Heteroatom-containing groups, such as R 2 and R 7 are independently trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, trioctylsilyl, dimethyloctylsilyl, butyldimethylsilyl (including t-butyldimethylsilyl), methyltrimethylsilyl, or an isomer thereof. R in formula (I) 1 , R 3 , R 6 , R 8 , R 9 , R 11 , R 12 , R 13 , R 15 , R 16 , R 17 , R 18 and R 19 each independently represents hydrogen or C 10 It can be alkyl, e.g., 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 be independently hydrogen, methyl, ethyl, propyl, or isopropyl. In at least one embodiment, R 1 , R 3 , R 6 , R 8 , R 9 , R 11 , R 12 , R 13 , R 15 , R 16 , R 17 , R 18 and R 19 is hydrogen. Alternatively, R in formula (I) 1 , R 3 , R 6 , R 8 , R9 , R 11 , R 12 , R 13 , R 15 , R 16 , R 17 , R 18 and R 19 Each may independently be hydrogen, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, or trimethylsilyl.

[0027] R in formula (I) 10 and R 14 are each independently 40 Hydrocarbyl, e.g., C4-C 20 Alkyl, for example, butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., n-pentyl, iso-pentyl, iso-amyl, neopentyl, cyclopentyl), hexyl (e.g., n-hexyl, iso-hexyl, cyclohexyl), heptyl (e.g., n-heptyl, iso-heptyl and norbornyl), octyl (e.g., n-octyl, isooctyl, cyclooctyl). , nonyl (e.g., n-nonyl, iso-nonyl), decyl (e.g., n-decyl, iso-decyl, cyclodecyl, adamantanyl), undecyl (e.g., n-undecyl, iso-undecyl), dodecyl (e.g., n-dodecyl, iso-dodecyl, cyclododecyl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and all isomers thereof, or R of formula (I) 10 and R 14 are each independently OR 20 and R 20 is C4-C 40 Hydrocarbyl, e.g., C4-C 20Hydrocarbyls, for example, butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., n-pentyl, iso-pentyl, iso-amyl, neopentyl, cyclopentyl), hexyl (e.g., n-hexyl, iso-hexyl, cyclohexyl), heptyl (e.g., n-heptyl, iso-heptyl, and norbornyl), octyl (e.g., n-octyl, isooctyl, cyclobutyl), In some embodiments, R is an aryl group selected from the group consisting of octyl, nonyl (e.g., n-nonyl, iso-nonyl), decyl (e.g., n-decyl, iso-decyl, cyclodecyl, adamantanyl), undecyl (e.g., n-undecyl, iso-undecyl), dodecyl (e.g., n-dodecyl, iso-dodecyl, cyclododecyl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, and all isomers thereof. 10 is C4-C 40 is hydrocarbyl, R 14 OR 20 and R 20 is C4-C 40 In some embodiments, R 14 is C4-C 40 is hydrocarbyl, R 10 OR 20 and R 20 is C4-C 40 In some embodiments, R 10 and R 14 is independently 40 In some embodiments, R 10 and R 14 are, independently, OR 20 and R 20 is C4-C 40 It is a hydrocarbyl.

[0028] In some embodiments, R 10 and R 14is selected from butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy, tetradecoxy, pentadecoxy, hexadecoxy, heptadecoxy, octadecoxy, nonadecoxy, icosoxy, and isomers thereof. 10 and R 14 is selected from butoxy, hexoxy, octoxy and dodecoxy. In some embodiments of Formula (I), R 4 and R 5 can be adamantanyl or substituted adamantanyl; R 2 and R 7 can be C1-C8 hydrocarbyl, R 10 and R 14 is selected from butoxy, hexoxy, octoxy and dodecoxy. In some embodiments of Formula (I), R 4 and R 5 can be adamantanyl or substituted adamantanyl; R 2 and R 7 can be tert-butyl or methyl, R 10 and R 14 is selected from butoxy, hexoxy, octoxy and dodecoxy.

[0029] In at least one embodiment, the catalyst compound is [ka] One or more of the following:

[0030] In at least one embodiment, one or more different catalyst compounds are present in the catalyst system. One or more different catalyst compounds can be present in the reaction zone in which the process described herein is carried out. The same activator can be used for the transition metal compound, but two different activators, such as a non-coordinating anion activator and an alumoxane, can be used in combination. Further exemplary embodiments of the present invention include the following: 4 and R 5 is adamantanyl, and R 2 and R 7 But, C4-C 40 is hydrocarbyl, R 10 and R 14 But, OR 20 and R 20 But, C4-C 12 The composition of formula (I) is hydrocarbyl. 4 and R 5 is adamantanyl, and R 2 and R 7 is a C4-C8 hydrocarbyl; R 10 and R 14 But, OR 20 and R 20 But, C4-C 12 The composition of formula (I) is hydrocarbyl. 4 and R 5 is adamantanyl, and R 2 and R 7 is tert-butyl, and R 10 and R 14 But, OR 20 and R 20 But, C4-C 12 The composition of formula (I) is hydrocarbyl. 2 , R 7 , R 10 and R 14 The composition of formula (I), wherein the substituents have a total number of carbon atoms that is 12 carbon atoms or more, alternatively 14 carbon atoms or more, alternatively 16 carbon atoms or more, alternatively 18 carbon atoms or more. 2 , R 7 , R 10 and R 14 the substituents have a total number of carbon atoms that is 12 carbon atoms or more, alternatively 14 carbon atoms or more, alternatively 16 carbon atoms or more, alternatively 18 carbon atoms or more; and R 4 and R 5The composition of formula (I) wherein R is selected from tert-butyl, adamantanyl, and substituted adamantanyl, and the upper limit can be 48 or 50. 2 , R 7 , R 4 , R 5 , R 10 and R 14 The composition of formula (I), wherein the substituents have a total number of carbon atoms that is 32 carbon atoms or more, alternatively 34 carbon atoms or more, alternatively 36 carbon atoms or more, and the upper limit can be 72 or up to 80.

[0031] An exemplary embodiment of the present invention can also be a homogeneous solution, comprising an aliphatic hydrocarbon solvent and a complex of formula (I) at a concentration of 0.15% by weight or more (alternatively 0.20% by weight or more, alternatively 0.25% by weight or more, alternatively 0.30% by weight or more, alternatively 0.35% by weight or more, alternatively 0.40% by weight or more, alternatively 0.50% by weight or more, alternatively 1.0% by weight or more, alternatively 2.0% by weight or more). Without intending to be bound by theory, it is believed that R 10 and R 14 The substituents may be alone or as R 4 and R 5 Substituents and / or R 2 and R 7 In combination with the substituents, it is believed that the solubility of the complexes of formula (I) in aliphatic solvents is aided. Another exemplary embodiment of the industrial advancement of the present invention is a process for producing a propylene-based polymer, comprising reacting propylene and one or more optional C3-C olefins 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. 40 Propylene and one or more optional C3-C olefins are produced by contacting the olefins with a catalyst system comprising the composition of formula (I). 40 The method includes a step of polymerizing olefins to form a propylene-based polymer. Another exemplary embodiment of the industrial advancement of the present invention is a process for producing an ethylene-based polymer comprising reacting ethylene and one or more optional C4-C olefins 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. 40 Ethylene and one or more optional C4-C olefins are produced by contacting the olefins with a catalyst system comprising a composition of formula (I). 40 The method includes a process comprising the step of polymerizing olefins to form a propylene-based or ethylene-based polymer.

[0032] Activators and optional scavengers, co-activators and chain transfer agents US Patent Application No. 16 / 788,088 (Publication No. US2020 / 0254431) describes activators, optional scavengers, optional co-activators and optional chain transfer agents that can be used according to the industrial advancement of the present invention. In particular, useful activators are also non-aromatic hydrocarbon-soluble activator compounds, such as N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(pentafluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(heptafluoronaphthalenyl)borate], N-methyl-N-octadecyl-4-(octadecyloxy)anilinium [tetrakis(pentafluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(pentafluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(pentafluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(pentafluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(pentafluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecyl-4-(octadecyloxy) ... late], N-methyl-N-octadecyl-4-(octadecyloxy)anilinium [tetrakis(heptafluoronaphthalenyl)borate], N,N-di(hydrogenated tallow)methylammonium [tetrakis(pentafluorophenyl)borate], N,N-di(hydrogenated tallow)methylammonium [tetrakis(heptafluoronaphthalenyl)borate], N,N-di(octadecyl)methylammonium [tetrakis(pentafluorophenyl)borate] )borate], N,N-di(octadecyl)methylammonium [tetrakis(heptafluoronaphthalenyl)borate], N,N-di(hexadecyl)methylammonium [tetrakis(pentafluorophenyl)borate], N,N-di(hexadecyl)methylammonium [tetrakis(heptafluoronaphthalenyl)borate], N-octadecyl-N-hexadecylmethylammonium [tetrakis(pentafluorophenyl)borate No. PCT / US2020 / 044865 (publication no. WO2021 / 086467), U.S. Patent Application No. 16 / 394,174 (published as US2019 / 0330394), and PCT Application No. PCT / US2019 / 29056 (published as WO2019 / 210026), which describe N-octadecyl-N-hexadecylmethylammonium [tetrakis(heptafluoronaphthalenyl)borate] and N-octadecyl-N-hexadecylmethylammonium [tetrakis(heptafluoronaphthalenyl)borate].

[0033] It is preferred to use an activator that is soluble in non-aromatic hydrocarbon solvents, but activators that are poorly soluble or insoluble in non-aromatic hydrocarbon solvents can be used. If used, these activators can be fed to the reactor by slurry or as a solid. Particularly useful activators in this class include triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, and the like. A typical activator to catalyst ratio is about 1:1 molar ratio. Alternative preferred ranges include 0.1:1 to 100:1, alternatively 0.5:1 to 200:1, alternatively 1:1 to 500:1, alternatively 1:1 to 1000:1. A particularly useful range is 0.5:1 to 10:1, preferably 1:1 to 1:10. Particularly useful optional scavengers or coactivators or chain transfer agents include, for example, trialkylaluminums, such as triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and dialkylzincs, such as diethylzinc. Additionally, toluene-free hydrocarbon-soluble alumoxanes and modified alumoxanes may be used, including trimethylaluminum "free" alumoxanes. Moreover, one skilled in the art can select suitable known activators and optional scavengers or co-activators or chain transfer agents for his or her particular purpose without undue experimentation. Combinations of multiple activators can be used. Similarly, combinations of multiple optional scavengers or co-activators or chain transfer agents may be used.

[0034] solvent Although it is possible to use the catalyst components of the present industrial advancement with aromatic solvents such as toluene, preferably the catalyst components are not present when the catalyst components are used in a polymerization process. Solvents useful for dissolving the catalyst compound, activator compound, or for combining the catalyst compound and activator, and / or for introducing the catalyst system or any of its components into the reactor, and / or for use in a polymerization process include aliphatic hydrocarbon solvents, including, but not limited to, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, or combinations thereof. Preferred solvents can include normal paraffins (e.g., Norpar™ solvents available from ExxonMobil Chemical Company, Houston, TX), isoparaffinic solvents (e.g., Isopar™ solvents available from ExxonMobil Chemical Company, Houston, TX), non-aromatic cyclic solvents (e.g., Nappar™ solvents available from ExxonMobil Chemical Company, Houston, TX), and combinations thereof.

[0035] Preferably, the aliphatic hydrocarbon solvent is a C4-C 10 It is selected from linear, branched or cyclic alkanes, alternatively C5 to C8 linear, branched or cyclic alkanes. Preferably, the aliphatic hydrocarbon solvent is substantially free of all aromatic solvents. Preferably, the solvent is substantially free of toluene. By free of all aromatic solvents such as toluene, it is meant that the solvent is substantially free of aromatic solvents (e.g., present at zero mol%, alternatively present at less than 1 mol%), and preferably the polymerization reaction and / or the resulting polymer does not contain "detectable aromatic hydrocarbon solvents" such as toluene. Preferred aliphatic hydrocarbon solvents include isohexane, cyclohexane, methylcyclohexane, pentane, isopentane, heptane, and combinations thereof, as well as commercially available solvent mixtures such as Nappar6™ and IsoparE™, however, one of ordinary skill in the art can select other suitable non-aromatic hydrocarbon solvents without undue experimentation. Highly preferred aliphatic hydrocarbon solvents include isohexane, methylcyclohexane, and commercially available solvent mixtures such as Nappar 6™ and Isopar E™. For testing the solubility of compounds, preferred solvents include isohexane and methylcyclohexane.

[0036] Optional Support Material In an embodiment of the present specification, the catalyst system may include an inert support material. The support material can be a porous support material, such as talc and inorganic oxides. U.S. Patent Application No. 16 / 788,088 (Publication No. US2020 / 0254431) describes optional support materials that can be used according to the industrial advancement of the present invention. Furthermore, a person skilled in the art can select a suitable known support for his or her particular purpose without undue experimentation. Polymerization method The present disclosure relates to a polymerizable composition comprising a monomer (e.g., ethylene; propylene) and, optionally, one or more comonomers (e.g., C2-C 20 Alpha Olefins, C4-C 40 Cyclic olefins, C5-C 20 The present invention relates to a polymerization process in which a non-conjugated diene (non-conjugated diene) is contacted with a catalyst system comprising an activator and at least one catalyst compound as described above. The catalyst compound and activator may be combined in any order. The catalyst compound and activator may be combined prior to contacting with the monomer. Alternatively, the catalyst compound and activator may be introduced separately into the polymerization reactor, in which case they are subsequently reacted to form the active catalyst. U.S. Patent Application No. 16 / 788,088 (Publication No. US2020 / 0254431) describes monomers that can be used in accordance with the industrial advancement of the present invention and describes polymerization methods that can be used in accordance with the industrial advancement of the present invention. Additionally, catalysts that are highly soluble in aliphatic hydrocarbon solvents may be used as trim catalysts in known polymerization processes, for example, as described in WO2015 / 123177 and WO2020 / 092587.

[0037] Blends and Films The polymers produced by the industrial advances of the present invention can be used to make the blends and films described in U.S. Patent Application No. 16 / 788,088 (Application No. US2020 / 0254431) without undue experimentation. EXAMPLES

[0038] General Synthesis Considerations The following chemicals may be abbreviated as shown, either in lowercase or by their initial letters: 1,2-dimethoxyethane (dme), ethyl ether (ether), tetrahydrofuran (thf), diatomaceous earth (celite), methylcyclohexane (MeCy), 1,4-dioxane (dioxane), hexamethyldisiloxane (hmdso), N,N-dimethylformamide (DMF), N-bromosuccinimide (NBS), n-butyllithium (BuLi). Room temperature is 23°C unless otherwise noted. Complex 1 dimethylzirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-olate)] and complex 2 dimethylzirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)] (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. Patent Application Publication No. 2020 / 0255553.

[0039] [ka] All other reagents were purchased from commercial suppliers (Sigma Aldrich, Fisher Scientific, Strem Chemical, or Oakwood Chemical) and used as received unless otherwise stated. Solvents were flushed with N2 and dried over 3 Å molecular sieves. All chemical manipulations were carried out in a nitrogen environment unless otherwise stated. Flash column chromatography was performed on Sigma Aldrich silica gel 60 Å (70 mesh to 230 mesh) using the solvent system indicated. All anhydrous solvents were purchased from Fisher Chemical and were degassed and dried over molecular sieves before use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and were degassed and dried over molecular sieves before use. 1H NMR spectroscopic data were acquired at 250 MHz, 400 MHz, or 500 MHz using solutions prepared by dissolving approximately 10 mg of sample in either C6D6, CD2Cl2, CDCl3, D8-toluene, or other deuterated solvents. Chemical shifts (δ) shown are relative to 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.

[0040] Synthesis of ligands and catalysts (or complexes) ZrCl4 (Ether) 2. Dichloromethane (100 mL) and ZrCl4 (10.0 g, 42.9 mmol) were combined to form a slurry. Ether (9.54 g, 129 mmol) was added dropwise over 60 min. The mixture was stirred for 1 h. Undissolved solids were allowed to settle, then the supernatant was decanted and filtered through Celite on a fritted disk. The filtrate was evaporated to near dryness to give a slurry. To the slurry was added isohexane (60 mL) and the mixture was stirred thoroughly. The resulting off-white solid was collected on the frit, washed with isohexane, and dried under reduced pressure. Yield: 12.5 g, 76.6%.

[0041] 1-Butoxy-3-iodobenzene [ka] 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 h. The solution was diluted with water and extracted with three 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%. 1H NMR (400 MHz, CDCl3, δ): 7.27 (m, 2H), 6.98 (t, J = 8.0 Hz, 1H), 6.86 (m, 1H), 3.92 (t, J = 6.5 Hz, 2H), 1.74 (m, 2H), 1.48 (m, 2H), 0.97 (t, J = 7.4 Hz, 3H).

[0042] 1-Bromo-4-butoxy-2-iodobenzene [ka] 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 small portions. The reaction was heated to 80° C. for 4 h. After cooling to ambient temperature, the solution was diluted with water and extracted with three portions of diethyl ether. The combined organic fractions were rinsed with brine, dried over MgSO4, filtered and concentrated to give the crude product. This material was recrystallized in hot isohexane to give the product as a white crystalline solid. Yield: 15.6 g, 80.9%. 1 H NMR (400 MHz, CDCl3, δ): 7.45 (d, J = 8.8 Hz, 1H), 7.38 (d, J = 2.9 Hz, 1H), 6.75 (dd, J = 8.8, 2.9 Hz, 1H), 3.90 (t, J = 6.4 Hz, 2H), 1.73 (m, 2H), 1.47 (m, 2H), 0.97 (t, J = 7.4 Hz, 3H).

[0043] 1-Iodo-3-(octyloxy)benzene [ka] 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 h. The solution was diluted with water and extracted with three portions of diethyl ether. The combined organic fractions were rinsed with water and brine, dried over MgSO4, filtered and concentrated. The crude liquid was purified over SiO2 using 100% isohexane to give the product as a colorless oil. Yield: 10.7 g, 88.7%. 1 H NMR (400 MHz, CDCl3, δ): 7.26 (m, 2H), 6.98 (t, J = 8.0 Hz, 1H), 6.86 (d, J = 8.3 Hz, 1H), 3.91 (t, J = 6.5 Hz, 2H), 1.76 (p, J = 6.8 Hz, 2H), 1.44 (m, 2H), 1.29 (m, 8H), 0.89 (t, J = 6.5 Hz, 3H).

[0044] 1-Bromo-2-iodo-4-(octyloxy)benzene [ka] 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 small portions. The reaction was heated to 80° C. for 4 h. After cooling to ambient temperature, the solution was diluted with water and extracted with three 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 liquid. Yield: 10.9 g, 82.0%. 1H NMR (400 MHz, 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 = 6.5 Hz, 2H), 1.75 (p, J = 6.8 Hz, 2H), 1.43 (m, 2H), 1.29 (m, 10H), 0.90 (t, J = 7.4 Hz, 3H).

[0045] 1-(dodecyloxy)-3-iodobenzene [ka] 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 h. The solution was diluted with water and extracted with three portions of diethyl ether. The combined organic fractions were rinsed with water and brine, dried over MgSO4, filtered and concentrated. The crude liquid was purified on SiO2 using 100% isohexane to give the product as a colorless oil. Yield: 7.34 g, 52.0%. 1 H NMR (400 MHz, CDCl3, δ): 7.26 (m, 2H), 6.98 (t, J = 7.9 Hz, 1H), 6.86 (d, J = 8.5 Hz, 1H), 3.91 (t, J = 6.5 Hz, 2H), 1.76 (p, J = 6.8 Hz, 2H), 1.43 (m, 2H), 1.27 (m, 16H), 0.88 (t, J = 6.5 Hz, 3H).

[0046] 1-Bromo-4-(dodecyloxy)-2-iodobenzene [ka] 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 small portions. The reaction was heated to 80° C. for 4 h. After cooling to ambient temperature, the solution was diluted with water and extracted with three portions of diethyl ether. The combined organic fractions were rinsed with water and brine, dried over MgSO4, filtered and concentrated. The material was recrystallized in hot isohexane to give the product as a white crystalline solid. Yield: 5.75 g, 65.1%. 1 H NMR (400 MHz, 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 = 6.5 Hz, 2H), 1.75 (p, J = 6.8 Hz, 2H), 1.43 (m, 2H), 1.26 (m, 18H), 0.88 (t, J = 7.4 Hz, 3H).

[0047] 2-(adamantan-1-yl)-4-(tert-butyl)phenol [ka] In a 500 mL round bottom flask, 4-(tert-butyl)phenol (20.0 g, 133 mmol) and 1-adamantanol (21.3 g, 140 mmol) were added to dichloromethane (120 mL). This was stirred until all solids were dissolved. To this clear solution, concentrated sulfuric acid (10.8 mL) was added dropwise over 20 min. The reaction was stirred at room temperature for 4 h. Water (20 mL) was added and the mixture was brought to neutral pH using 2 M sodium hydroxide. The organics were extracted with dichloromethane (3x50 mL), filtered and dried over magnesium sulfate. The product was purified on SiO2 using 40-60 vol% ethyl acetate in isohexane. Yield: 20.9 g, 55.1%. 1H NMR (400MHz, CDCl3): δ7.29 (d, 1H, J = 2.5 Hz), 7.11 (dd, 1H, J = 8.2, 2.4 Hz), 6.61 (d, 1H, J = 8.2 Hz), 2.21-2.16 (m, 6H), 2.15-2.10 (m, 3H), 1.85-1.81 (m, 6H), 1.34 (s, 9H).

[0048] 1-(5-(tert-butyl)-2-(methoxymethoxy)phenyl)adamantane [ka] To 2-(adamantan-1-yl)-4-(tert-butyl)phenol (20.9 g, 73.3 mmol) in tetrahydrofuran (100 mL) was added sodium hydride (2.29 g, 95.3 mmol) in small portions. The mixture was stirred overnight. To the stirred solution was added chloromethyl methyl ether (10.0 g, 125 mmol) and the reaction mixture was stirred for 4 h. The reaction was quenched with water (25 mL) and the pH was adjusted to 8-10 using 1 M potassium hydroxide. The product was extracted with ethyl ether (3x25 mL), dried over MgSO4 and concentrated under reduced pressure. Yield: 22.6 g, 94.0%. 1 H NMR (400MHz, CDCl3): δ 7.31 (d, 1H, J = 2.5 Hz), 7.18 (dd, 1H, J = 8.5, 2.5 Hz), 7.06 (d, 1H, J = 8.5 Hz), 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).

[0049] (3-(adamantan-1-yl)-5-(tert-butyl)-2-(methoxymethoxy)phenyl)lithium [ka] To 1-(5-(tert-butyl)-2-(methoxymethoxy)phenyl)adamantane (7.00 g, 23.1 mmol) was added isohexane (100 mL) forming a suspension. Butyllithium in hexane (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 formed. The mixture was gravity filtered through celite 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 a few 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 frit, washed with cold isohexane and then dried under reduced pressure. 1 H-NMR data showed that the product crystallized with 0.5 molar equivalents of DME. Yield: 4.63 g, 52.7%. 1 H NMR (400 MHz, C6D6 with 10%C4D4O): δ 7.95 (d, 1H, J = 2.4 Hz), 7.31 (d, 1H, J = 2.5 Hz), 5.79 (s, 2H), 3.22 (s, 3H), 2.50 (br s, 6H), 2.20 (br s, 3H), 2.01-1.93 (m, 3H), 1.92-1.84 (m, 3H), 1.57 (s, 9H).

[0050] 2-(3-(adamantan-1-yl)-5-(tert-butyl)-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ka] To (3-(adamantan-1-yl)-5-(tert-butyl)-2-(methoxymethoxy)phenyl)lithium (4.63 g, 12.2 mmol, co-crystallized with 0.5 DME) was added ether (60 mL) and the mixture was cooled to -45°C. To the stirred suspension was added 2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.95 g, 15.9 mmol) in ether (3 mL) quickly. The mixture was allowed to warm slowly 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 no solids were visible and the organics were separated. The organics were extracted with water until the pH of the aqueous layer was neutral. The organics were dried with brine (15 mL) and then dried over MgSO4. Removal of the volatiles afforded the product as a colorless foam. Yield: 4.95g, 89.3%. 1 H NMR (400 MHz, CDCl3): δ 7.52 (d, 1H, J = 2.6 Hz), 7.41 (d, 1H, J = 2.6 Hz), 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).

[0051] 1-(2'-Bromo-5'-butoxy-5-(tert-butyl)-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane [ka] 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), dioxane (60 mL) and water (30 mL). The mixture was sparged with nitrogen for 50 min and then solid Pd(PPh3)4 (0.627 g, 0.542 mmol) was added. The mixture was sparged for an additional 40 min and then rapidly stirred and heated in an oil bath maintained at 100 °C. After 20 hours, the volatiles were evaporated to near dryness then ether (70 mL) and water (70 mL) were added. The organics were separated and extracted with water until pH was neutral. The organics were dried with brine then evaporated and dried under reduced pressure to give a pale yellow foam (6.78 g). The crude material contains impurities that are poorly soluble in cold isohexane. Purification was achieved by adding isohexane (50 mL), cooling to -40°C for 1 hour and cold filtering. Stripping of the volatiles gave the product of acceptable purity. 1 H-NMR data showed 0.3 molar equivalents of isohexane present in the product. Yield: 6.24 g, 98.9%. 1 H NMR (400MHz, CDCl3): δ 7.55 (d, 1H, J = 8.8 Hz), 7.37 (d, 1H, J = 2.5 Hz), 7.09 (d, 1H, J = 2.5 Hz), 6.97 (d, 1H, J = 3.1 Hz), 6.79 (dd, 1H, J = 8.8, 3.1 Hz), 4.53 (dd, 2H, J = 45.9, 4.5Hz), 3.97 (t, 2H, J = 6.6 Hz), 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 = 7.4 Hz).

[0052] (3'-(adamantan-1-yl)-5-butoxy-5'-(tert-butyl)-2'-(methoxymethoxy)-[1,1'-biphenyl]-2-yl)lithium [ka] To 1-(2'-bromo-5'-butoxy-5-(tert-butyl)-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane (6.24 g, 10.7 mmol, containing 0.3 equivalents of isohexane) was added isohexane (50 mL), forming a clear solution. The mixture was cooled to -50°C. The mixture became very cloudy upon cooling, likely due to the presence of an impurity. Butyllithium in hexane (1.66 M, 6.79 mL, 11.3 mmol) was added dropwise over several minutes. The mixture was allowed to warm slowly to ambient temperature. When the mixture reached -20°C, it became clear and turned orange in color. Upon reaching ambient temperature, a copious precipitate formed. The solid was collected on a frit and washed thoroughly with isohexane to give a fine, colorless solid, which was dried under reduced pressure. The filtration was fairly slow due to the fineness of the solids. Yield: 3.60 g, 69.5%. 1 H NMR (400MHz, C6D6+ 5% D8-THF): δ 7.61-7.55 (m, 1H), 7.51 (d, 1H, J = 2.6 Hz), 7.47 (d, 1H, J = 2.5 Hz), 7.30 (d, 1H, J = 2.3 Hz), 7.04-6.94 (m, 1H), 4.72 (br s, 2H), 3.89 (t, 2H, J = 6.4 Hz), 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 = 7.4 Hz).

[0053] 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 [ka] To (3'-(adamantan-1-yl)-5-butoxy-5'-(tert-butyl)-2'-(methoxymethoxy)-[1,1'-biphenyl]-2-yl)lithium (3.59 g, 7.44 mmol) was added ether (70 mL) 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 allowed to warm slowly in a cold bath for 1 h. The cloudy solution was then removed from the ice bath and stirred for an additional 1 h. The mixture was poured into a separatory funnel and extracted with water until the pH of the aqueous layer was neutral. The organics were dried with brine, then MgSO4, and then filtered. The solvent was evaporated under reduced pressure to give the product as a foam. 1 H-NMR indicates acceptable purity. Yield: 4.18 g, 93.2%. 1 H NMR (400MHz, CDCl3): δ 7.74 (dd, 1H, J = 7.9, 0.7 Hz), 7.29 (d, 1H, J = 2.6 Hz), 6.98 (d, 1H, J = 2.5 Hz), 6.91-6.88 (m, 2H), 4.51 (dd, 2H, J = 50.0, 4.7 Hz), 4.00 (t, 2H, J = 6.6 Hz), 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 = 15.2 Hz), 0.98 (t, 3H, J = 7.4 Hz).

[0054] 6',6'''-(pyridine-2,6-diyl)bis(3'-butoxy-3-(adamant-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-ol) [ka] 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), dioxane (60 mL) and water (30 mL). The mixture was sparged with nitrogen for 50 min and then solid Pd(PPh3)4 (0.401 g, 0.347 mmol) was added. The mixture was sparged for an additional 40 min and then rapidly stirred and heated in an oil bath maintained at 100 °C. After 14 h, the volatiles were evaporated to near dryness, then ether (70 mL) and water (70 mL) were added. The organics were separated and extracted with water until pH was neutral. The organics were dried with brine and then evaporated to a residue. Methanol (40 mL), thf (40 mL) and concentrated HCl (4 mL) were added and the mixture was heated to 60° C. After 4.5 h, the mixture was cooled to ambient temperature and the volatiles were evaporated. The residue was dissolved in ether (70 mL) and water (30 mL) and the mixture was transferred to a separatory funnel. The organics were separated and extracted with water until pH of the washings was neutral. The organics were then dried with brine, then dried over MgSO4 and then filtered. Removal of the 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: 2.82g, 90.1%. 1H NMR (400MHz, CDCl3): δ 8.51 (br s, 2H), 7.44 (d, 2H, J = 8.7 Hz), 7.14-6.84 (m, 9H), 6.54 (d, 2H, J = 2.4 Hz), 4.01 (t, 4H, J = 6.4 Hz), 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).

[0055] 1-(2'-Bromo-5'-butoxy-2-(methoxymethoxy)-5-methyl-[1,1'-biphenyl]-3-yl)adamantane [ka] 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), dioxane (30 mL) and water (15 mL). The mixture was sparged with nitrogen for 50 min and then solid Pd(PPh3)4 (0.546 g, 0.473 mmol) was added. The mixture was sparged for an additional 40 min and then rapidly stirred and heated in an oil bath maintained at 100 °C. After 16 h, the volatiles were evaporated to near dryness then ether (70 mL) and water (70 mL) were added. The organics were separated and extracted with water until pH was neutral. The organics were dried with brine then evaporated to a yellow oil. The crude product was purified on SiO2 using 0% to 2% by volume of ethyl acetate in isohexane. The product was isolated as a thick oil. Moderate purity. Yield: 4.68 g, 96.4%. 1H NMR (400MHz, CDCl3): δ 7.54 (d, 1H, J = 8.8 Hz), 7.16 (d, 1H, J = 2.2Hz), 6.93 (d, 1H, J = 3.0 Hz), 6.90 (d, 1H, J = 2.3 Hz), 6.79 (dd, 1H, J = 8.8, 3.1 Hz), 4.53 (dd, 2H, J = 20.6, 4.7 Hz), 3.96 (t, 2H, J = 6.55 Hz), 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 = 7.38 Hz)

[0056] (3'-(adamantan-1-yl)-5-butoxy-2'-(methoxymethoxy)-5'-methyl-[1,1'-biphenyl]-2-yl)lithium [ka] To 1-(2'-bromo-5'-butoxy-2-(methoxymethoxy)-5-methyl-[1,1'-biphenyl]-3-yl)adamantane (4.66 g, 9.08 mmol) was added isohexane (80 mL) forming a clear solution. The mixture was cooled to -45°C. A solution of BuLi in hexane (1.66 M, 5.74 mL, 9.53 mmol) was added dropwise over several minutes. Upon initial addition of BuLi the mixture became cloudy, but no further precipitate formed as the addition of BuLi continued. The mixture was allowed to warm slowly to 15°C over several hours, during which time a large amount of colorless precipitate formed. The mixture was again cooled to -45°C for approximately 30 minutes. The solid was then collected on a fritted disk, washed with cold isohexane (20 mL) and dried under reduced pressure. The product was isolated as a colorless microcrystalline solid. 1 H-NMR spectroscopy showed the presence of 0.5 equivalents of co-crystallized isohexane. Yield: 3.64 g, 82.3%. 1H NMR (400MHz, C6D6+ 10% D8-THF): δ 7.81 (d, 1H, J = 7.4 Hz), 7.26 (d, 1H, J = 2.2 Hz), 7.24 (d, 1H, J = 2.3 Hz), 7.12 (d, 1H, J = 2.2 Hz), 6.97 (dd, 1H, J = 7.5, 2.2 Hz), 4.72 (s, 2H), 3.91 (t, 2H, J = 6.4 Hz), 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 = 7.5 Hz).

[0057] 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 [ka] To (3'-(adamantan-1-yl)-5-butoxy-2'-(methoxymethoxy)-5'-methyl-[1,1'-biphenyl]-2-yl)lithium (3.64 g, 7.52 mmol) was added ether (70 mL) forming 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 a cold bath. The mixture was stirred overnight, then poured into a separatory funnel and extracted with water until the pH of the aqueous layer was neutral. The organics were dried with brine, then MgSO4, then filtered and dried under vacuum to give a colorless foam. Yield: 4.34 g, 103%. 1H NMR (400MHz, CDCl3): δ 7.71 (d, 1H, J = 8.2 Hz), 7.07 (d, 1H, J = 2.3 Hz), 6.92-6.82 (m, 3H), 4.53-4.42 (m, 2H), 4.00 (t, 2H, J = 6.6 Hz), 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 = 18.3 Hz), 0.98 (t, 3H, J = 7.4 Hz).

[0058] 6',6'''-(Pyridine-2,6-diyl)bis(3'-butoxy-3-(adamant-1-yl)-5-methyl-[1,1'-biphenyl]-2-ol) [ka] 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), dioxane (60 mL) and water (30 mL). The mixture was sparged with nitrogen for 60 min and then solid Pd(PPh3)4 (0.447 g, 0.387 mmol) was added. The mixture was sparged for an additional 40 min and then rapidly stirred and heated in an oil bath maintained at 100 °C. After 20 hours, the volatiles were evaporated to near dryness, then ether (80 mL) and water (80 mL) were added. The organics were separated and extracted with water until pH was neutral. The organics were dried with brine and then evaporated to a residue. Methanol (40 mL), thf (40 mL) and concentrated HCl (4 mL) 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 (80 mL) and water (50 mL) and the mixture was transferred to a separatory funnel. The organics were separated and extracted with water until pH of the washings was neutral. The organics were then dried with brine, then dried over MgSO4 and then filtered. Removal of the volatiles gave 3.68 g of an off-white solid covered by a slightly orange colored oily residue. Methylcyclohexane (50 mL) was added and the resulting suspension was stirred for several hours. The undissolved material was collected on a frit, washed with methylcyclohexane (2 x 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 using 0% to 2.5% ethyl acetate in isohexane. Both batches appeared clear but contained small amounts of co-crystallized ether (crop 1 had 0.2 equiv. ether, crop 2 had 0.1 equiv. ether). Yields: crop 1 (solid washed with MeCy): 2.53 g, 78.2% (contained 0.2 equiv. ether).Crop 2 (MeCy filtrate purified over SiO2): 0.345 g, 10.8% (contains 0.1 equivalents of ether). 1 H NMR (400MHz, CDCl3): δ 8.02 (s, 1H), 7.50 (d, 1H, J = 8.5 Hz), 7.44 (d, 1H, J = 8.5 Hz), 7.42-7.34 (m, 1H), 7.05-6.96 (m, 2H), 6.94-6.82 (m, 7H), 6.18 (d, 1H, J = 2.1 Hz), 4.04-3.96 (m, 4H), 2.26 (s, 3H), 2.0-1.46 (m, 41H), 1.05-0.96 (m, 6H).

[0059] 1-(2'-bromo-5-(tert-butyl)-2-(methoxymethoxy)-5'-(octyloxy)-[1,1'-biphenyl]-3-yl)adamantane [ka] 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), dioxane (10 mL) and degassed water (10 mL). Solid Pd(PPh3)4 (0.254 g, 0.220 mmol) was finally added and the reaction was heated to 100° C. After 36 h, the reaction was cooled to ambient temperature. The solution was diluted with water and extracted with three portions of dichloromethane. The combined organic fractions were rinsed with brine, dried over MgSO4, filtered and concentrated. The crude product was purified on SiO2 using 10% by volume of acetone in isohexane to give the desired product as a clear oil. Yield: 2.00 g, 74.3%. 1H NMR (400 MHz, CDCl3): δ 7.53 (d, 1H, J = 8.7 Hz), 7.34 (s, 1H), 7.06 (s, 1H), 6.94 (d, 1H, J = 3.0 Hz), 6.77 (dd, 1H, J = 8.8, 3.1 Hz), 4.56 (d, 1H, J = 4.5 Hz), 4.44 (d, 1H, J = 4.5 Hz), 3.93 (t, 2H, J = 6.7 Hz), 3.25 (s, 3H), 2.18 (br s, 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).

[0060] 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 [ka] To 1-(2'-bromo-5-(tert-butyl)-2-(methoxymethoxy)-5'-(octyloxy)-[1,1'-biphenyl]-3-yl)adamantane (2.00 g, 3.27 mmol) was added isohexane (75 mL) forming a clear solution. The mixture was cooled to -45°C. A solution of BuLi in hexane (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 h and then slowly warmed to ambient temperature over 1 h. The mixture was cooled again to -45°C for approximately 30 min. 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 h and then slowly warmed to ambient temperature over 1 h, which produced a yellow slurry. The solution was diluted with water and extracted with three 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 using 5% by volume acetone in isohexane to give the desired product as a colorless foam. Yield: 1.10 g, 51%. 1 H NMR (400 MHz, CDCl3): δ 7.71 (d, 1H, J = 8.0 Hz), 6.96 (s, 1H), 6.89-6.82 (m, 2H), 4.54 (d, 1H, J = 4.6 Hz), 4.42 (d, 1H, J = 4.1 Hz), 3.96 (t, 2H, J = 6.6 Hz), 3.25 (s, 3H), 2.19 (br s, 6H), 2.09 (br s, 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).

[0061] 6',6'''-(pyridine-2,6-diyl)bis(3'-octyloxy-3-(adamant-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-ol) [ka] 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), dioxane (40 mL) and degassed water (20 mL). Solid Pd(PPh3)4 (0.092 g, 0.079 mmol) was finally 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 three portions of ethyl acetate. The combined organic fractions were rinsed with brine, dried over MgSO4, filtered and concentrated. Methanol (30 mL), thf (30 mL) and concentrated HCl (2 mL) were added and the mixture was heated to 60° C. After 4 h, the solution was brought to pH=6 with saturated aqueous sodium bicarbonate, concentrated slightly to remove methanol and extracted with three 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 using 5% acetone by volume in isohexane to give the desired product as a colorless foam. Yield: 0.150 g, 18.0%. 1H NMR, isomers integrated together as a single species (400 MHz, CDCl3): δ 8.49 (br s, 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).

[0062] 1-(2'-Bromo-5-(tert-butyl)-5'-(dodecyloxy)-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane [ka] To a solution of 2-(3-(1-adamantanyl)-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 dioxane (44 mL) was added potassium carbonate (2.30 g, 16.64 mmol). To the stirred suspension was added water (17 mL). The mixture was sparged with nitrogen for 60 minutes after which tetrakis(triphenylphosphine)palladium(0) (0.38 g, 0.33 mmol) was added. The reaction was heated to 100° C. and stirred for 2 days. The reaction mixture was brought to room temperature and dichloromethane (50 mL) and water (100 mL) were added. The organics were separated and the aqueous layer was extracted with dichloromethane (2 x 50 mL). The combined organic fractions were dried (MgSO4), filtered and concentrated in vacuo. The product was purified on SiO2 using 40% to 60% by volume of dichloromethane in isohexane. Yield: 3.602 g, 81.7%. 1H NMR (400MHz, CDCl3): δ 7.56 (d, 1H, J = 8.8 Hz), 7.37 (d, 1H, J = 2.6 Hz), 7.09 (d, 1H, J = 2.5 Hz), 6.98 (d, 1H, J = 3.0 Hz), 6.80 (dd, 1H, J = 8.8, 3.1 Hz), 4.59 (d, 1H, J = 4.6 Hz), 4.48 (d, 1H, J = 4.5 Hz), 3.96 (t, 2H, J = 6.6 Hz), 3.28 (s, 3H), 2.24-2.19 (m, 6H), 2.16-2.10 (m, 3H), 1.87-1.75 (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).

[0063] 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 [ka] To 1-(2'-bromo-5-(tert-butyl)-5'-(dodecyloxy)-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane (3.45 g, 5.17 mmol) was added isohexane (70 mL) to form a clear solution. The mixture was cooled to -45°C. A solution of BuLi in hexane (2.60 M, 2.02 mL, 5.42 mmol) was added dropwise over 1 min. The mixture was stirred for 80 min. 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 h, then allowed to warm to ambient temperature and stirred for an additional 45 min. The suspension was poured into a separatory funnel containing water (75 mL). The mixture was shaken thoroughly and then the aqueous layer was removed. The organics were extracted with water until the pH of the washings was neutral. The organics were then dried over brine, MgSO4 and filtered. The volatiles were removed to give a thick oil (3.61 g). Purified on SiO2 using 1-3% ethyl acetate in isohexane. Yield: 1.21 g, 32.8%. 1 H NMR (400MHz, CDCl3): δ 7.71 (dd, 1H, J = 7.9, 0.8 Hz), 7.27 (d, 1H, J = 2.7 Hz), 6.96 (d, 1H, J = 2.5 Hz), 6.88-6.83 (m, 2H), 4.54 (d, 1H, J = 4.6 Hz), 4.42 (d, 1H, J = 4.7 Hz), 3.96 (t, 2H, J =6.7 Hz), 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 = 6.8 Hz).

[0064] 6',6'''-(Pyridine-2,6-diyl)bis(3'-dodecyloxy-3-(adamant-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-ol) [ka] 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), dioxane (40 mL) and water (20 mL). The mixture was sparged with nitrogen for 50 min and then solid Pd(PPh3)4 (0.0978 g, 0.0846 mmol) was added. The mixture was sparged for an additional 40 min and then rapidly stirred and heated in an oil bath maintained at 100 °C. After 21 h, the volatiles were evaporated to near dryness, then ether (70 mL) and water (70 mL) were added. The organics were separated and extracted with water until pH was neutral. The organics were dried with brine and then evaporated to a residue. Methanol (20 mL), thf (20 mL) and concentrated HCl (2 mL) were added and the mixture was heated to 60° C. After 4.5 h, the mixture was cooled to ambient temperature and the volatiles were evaporated. The residue was dissolved in ether (75 mL) and water (75 mL) and the mixture was transferred to a separatory funnel. The organics were separated and extracted with water until pH of the washings was neutral. The organics were then dried with brine, then dried over MgSO4 and then filtered. The volatiles were removed to give the crude product. The crude product was purified on SiO2. Methylcyclohexane was loaded and eluted with 0-2.5% ethyl acetate in isohexane. The product was isolated as a white foam. Yield: 0.776 g, 82.0%. 1H NMR, isomers integrated together as a single species (400MHz, 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).

[0065] Preparation of transition metal complexes Complex 3 Dimethylzirconium [6',6''-(pyridine-2,6-diyl)bis(3'-butoxy-3-(adamant-1-yl)-5-methyl-[1,1'-biphenyl]-2-olate)] [ka] Toluene (15 mL) was added to ZrCl4(ether)2 (0.167 g, 0.437 mmol) and 6',6'''-(pyridin-2,6-diyl)bis(3'-butoxy-3-(adamant-1-yl)-5-methyl-[1,1'-biphenyl]-2-ol) (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, 2.11 mmol) was added in one portion. 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 approximately 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 obtained by eluting with approximately 0.6 equivalents of isohexane ( 1 H-NMR spectroscopy. Yield: 0.286 g, 70.1%. 1H NMR (400MHz, C6D6): δ 7.20 (d, 2H, J = 2.3 Hz), 7.03 (d, 4H, J = 1.5 Hz), 6.91 (t, 2H, J = 1.5 Hz), 6.87 (dd, 2H, J = 2.3, 0.9 Hz), 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 = 7.3 Hz), 0.23 (s, 6H).

[0066] Complex 4 Dimethylzirconium [6',6''-(pyridine-2,6-diyl)bis(3'-butoxy-3-(adamant-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-olate)] [ka] Toluene (80 mL) was added to ZrCl4(ether)2 (1.25 g, 3.29 mmol) and 6',6'''-(pyridin-2,6-diyl)bis(3'-butoxy-3-(adamant-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-ol) (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 allowed to warm slowly to ambient temperature over several hours and then stirred for an additional 30 minutes. The volatiles were removed under reduced pressure. The residue was extracted with methylcyclohexane (80 mL) and filtered through Celite 503. The volatiles were evaporated to near dryness and isohexane (10 mL) was added. The mixture was cooled to 0°C overnight. The next day a fine solid was suspended in the mixture. The solid was collected on a frit, washed with cold isohexane (5 mL) and dried under reduced pressure (crop 1). The mother liquor was evaporated to approximately 4 mL and hmdso (10 mL) was added. Trituration of the mixture gave a fine solid which was collected on a frit and dried under reduced pressure (crop 2). 1 H-NMR shows that crop 1 has 0.5 equivalents of isohexane co-crystallized. 1 H-NMR shows that crop 2 has 0.5 equivalents of co-crystallized hmdso. Yield (crop 1): 1.94 g, 58.9% (including 0.5 equivalents of isohexane); (crop 2): 0.486 g, 14.3% (including 0.5 equivalents of hmdso). 1H NMR (400MHz, C6D6): δ 7.57 (d, 2H, J = 2.6 Hz), 7.16 (d, 2H, J = 2.6 Hz), 7.02-6.91 (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 = 7.4 Hz), 0.24 (s, 6H).

[0067] Complex 5: Dimethylzirconium [6',6''-(pyridine-2,6-diyl)bis(3'-octyloxy-3-(adamant-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-olate)] [ka] 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-(adamant-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-ol) (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 either isohexane or hmdso were unsuccessful. Evaporation of the volatiles and drying under reduced pressure gave an orange-brown foamy semi-solid. 1H-NMR indicates that there is about 0.7 equivalents of hmdso present. Yield: 0.157 g, 99.8%. 1 H NMR (400MHz, C6D6): δ 7.58 (d, 2H, J = 2.6 Hz), 7.18 (d, 2H, J = 2.5 Hz), 7.06-6.95 (m, 6H), 6.58-6.48 (m, 3H), 3.66-3.48 (m, 4H), 2.68-2.57 (m, 6H), 2.53-2.44 (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 = 7.0 Hz), 0.26 (s, 6H).

[0068] Complex 6: Dimethylzirconium [6',6''-(pyridine-2,6-diyl)bis(3'-dodecyloxy-3-(adamant-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-olate)] [ka] To ZrCl4(ether)2 (0.251 g, 0.659 mmol) and 6',6'''-(pyridin-2,6-diyl)bis(3'-dodecyloxy-3-(adamant-1-yl)-5-tert-butyl-[1,1'-biphenyl]-2-ol) (0.769 g, 0.599 mmol) was added toluene (40 mL). The mixture was stirred for 1 min 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 an additional 30 min. The volatiles were then removed under reduced pressure to give a residue. The residue was extracted with toluene (12 mL) and filtered through Celite 503 on a fritted disk. The toluene was evaporated to dryness and then isohexane (3 mL) was added, forming a clear brown solution. The solution was cooled to 0° C. overnight and remained completely homogenous. The mixture was concentrated to 2 mL and cooled to −20° C. After several hours, no crystallization had occurred. The volatiles were then evaporated and the residue dried under vacuum. HMDSO (4 mL) was added and triturated, but no solids were formed. The volatiles were evaporated and the residue dried under vacuum to give a thick foamy solid. 1 H-NMR spectroscopic data indicates that 0.5 equivalents of hmdso are present. Yield: 0.845 g, 103%. 1 H NMR (400MHz, CD2Cl2): δ 7.71 (t, 1H, J = 7.8 Hz), 7.22 (d, 2H, J = 2.6 Hz), 7.11 (d, 2H, J = 7.8 Hz), 2.99 (d, 2H, J = 8.4 Hz), 6.91-6.83 (m, 3H), 6.80 (d, 2H, J = 2.5 Hz), 4.00 (t, 4H, J = 6.6 Hz), 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).

[0069] Solubility of the complex 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 has no co-crystallization solvent. Complex 3 embodying the industrial advancement of the present invention was co-crystallized with 0.6 equivalents of isohexane. Complex 4 embodying the industrial advancement of the present invention was co-crystallized with 0.5 equivalents of isohexane. Solvents used were sparged with nitrogen (30-60 minutes) and dehydrated over 3 Angstrom molecular sieves. All measurements were performed at ambient temperature (20°C-25°C) unless otherwise stated. General procedure: A tared vial was charged with a small amount of complex (actual mass recorded, typically 5-30 mg). A small stir bar (8 mm) was then added. Solvent was then added and the mixture was stirred rapidly (1000 rpm). If a homogeneous mixture did not form within 30 minutes, more solvent was added and the mixture was stirred for an additional 30 minutes. This process was repeated until either a clear solution was obtained (no visible solids or turbidity) or the vial was full. If the mixture approached homogeneity (i.e., little residual solids were observed), the amount of added solvent was kept small (<1 mL) to minimize the excess of solvent required to achieve homogeneity. The stir bar was then removed and the mixture was weighed. If a clear solution formed, the solubility of the complex was calculated based on the mass of the complex and the amount of solvent added to achieve a homogeneous solution. If the mixture is still inhomogeneous (visible solids or turbidity), the reported value is stated as "less than" the calculated value. The formulas used to calculate solubility are listed below. The co-crystallized solvent is included in the mass and formula 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. Solubility (mass%) =

[0100] * [(mass of complex) / (mass of solution)] Solubility (mM)=[10 6 ] * [(grams of complex) / (formula mass of complex (g / mol))] / [(grams of solvent) / (density of solvent (g / mL))]

[0070] [Table 1]

[0071] Polymerization Example Toluene (ExxonMobil Chemical - anhydrous, stored under N2) (98%) or isohexane (ExxonMobil Chemical - polymerization grade and purified as described below) was used to make solutions of the pre-catalyst. The pre-catalyst solution was typically 0.25 mmol / L. The solvent, polymerization grade toluene and / or isohexane, was supplied by ExxonMobil Chemical Co. and was purified by passage through a series of columns: two 500 cc Oxyclear cylinders in series manufactured by Labclear (Oakland, Calif), followed by two 500 cc columns in series packed with dry 3 Å molecular sieves (8-12 mesh; Aldrich Chemical Company), and two 500 cc columns in series packed with dry 5 Å molecular sieves (8-12 mesh; Aldrich Chemical Company).

[0072] Polymerization grade propylene (C3) was used and further purified by passing it through a series of columns: a 2250 cc Oxiclear cylinder from Labclear, then a 2250 cc column packed with 3 Å molecular sieves (8-12 mesh; Aldrich Chemical Company), then two 500 cc columns in series packed with 5 Å molecular sieves (8-12 mesh; Aldrich Chemical Company), then a 500 cc column packed with Selexsorb CD (BASF), and finally a 500 cc column packed with Selexsorb COS (BASF). Activation of the precatalyst was with either 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. Activators were typically used as 0.25 mmol / L solutions in toluene or isohexane. Tri-n-octylaluminum (TnOAl or TNOA, neat, AkzoNobel) was also used as an activator and scavenger prior to introducing the precatalyst into the reactor. TNOA was typically used as a 5 mmol / L solution in toluene or isohexane.

[0073] Reactor description and preparation: Polymerizations were carried out in a drybox under inert atmosphere (N2) using an autoclave equipped with an external heater for temperature control, a glass insert (internal volume 22.5 mL), septum inlets to regulate the nitrogen and propylene feed rates, 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, then at 25°C for 5 hours. Propylene Polymerization (PP): The reactor was prepared as described above, then heated to 40° C., then purged with propylene gas at atmospheric pressure. Toluene or isohexane, liquid propylene (1.0 mL), and scavenger (TNOA, 0.5 μmol) were added via syringe. The reactor was then brought to process temperature (70° C. or 100° C.) with stirring at 800 RPM. The activator solution, followed by the pre-catalyst solution, was injected into the reactor at process conditions via syringe. The reactor temperature was monitored and typically maintained within + / - 1° C. The polymerization was stopped by adding approximately 50 psi compressed dry air gas mixture to the autoclave for approximately 30 seconds. The polymerization was quenched based on a pre-determined pressure drop (maximum quench value) or for a maximum of 30 minutes. The reactor was cooled and vented. The polymer was isolated after the solvent was removed in vacuum. The actual quench time is reported as quench time (s). The reported yields include the total mass of polymer and residual catalyst. Catalyst activities are reported as grams of polymer per mmol of transition metal compound per hour of reaction time (g / mmol·hr). Examples of propylene homopolymerization are reported in Table 2, with further characterization in Table 3.

[0074] Polymer characterization For analytical testing, solutions of polymer samples were prepared by dissolving the polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity, Sigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%, Aldrich) in a shaker oven at 165°C for approximately 3 hours. Typical concentrations of polymer in solution were between 0.1-0.9 mg / mL, with a BHT concentration of 1.25 mg BHT per mL of TCB. Samples were cooled to 135°C for testing.

[0075] High temperature size exclusion chromatography was performed using an automated "Fast GPC" system as described in U.S. Patent Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388, each of which is incorporated herein by reference. Molecular weights (weight average molecular weight (Mw), number average molecular weight (Mn) and z-average molecular weight (Mz)) and molecular weight distributions (MWD=Mw / Mn), sometimes also referred to as the polydispersity index (PDI) of the polymers, were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector (ELSD) and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene calibration kit SM-10: Mp (peak Mw) between 5,000 and 3,390,000). Alternatively, samples were measured by gel permeation chromatography using a Symyx Technology GPC equipped with a dual wavelength infrared detector and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene calibration kit SM-10: Mp (peak Mw) between 580 and 3,039,000). Samples (250 μL of polymer solution in TCB was injected into the system) 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 (sample temperature 135° C., oven / column 165° C.). No column broadening correction was used. Numerical analysis was performed using Epoch® software available from Symyx Technologies or Automation Studio software available from Freeslate. Molecular weights obtained are relative to linear polystyrene standards. Molecular weight data are reported in Table 2 under the headings Mn, Mw, Mz and PDI as defined above.

[0076] Differential scanning calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting points of the polymers. The samples were pre-annealed at 220° C. for 15 minutes and then cooled at room temperature overnight. The samples were then heated to 220° C. at a rate of 100° C. / min and then cooled at a rate of 50° C. / min. Melting points were collected during the heating period. The results are reported under the heading Tm (° C.) in Table 2. 13 C NMR spectroscopy was used to characterize some of the polypropylene polymer samples produced in the experiments collected in Table 2. This data is collected in Table 3. Unless otherwise indicated, 13 Polymer samples for C NMR spectroscopy were dissolved in d2-1,1,2,2-tetrachloroethane and analyzed by a 150 MHz spectrometer. 13 Samples were recorded at 125° C. using an NMR spectrometer using C NMR frequencies. Polymer resonance peaks are referenced to mmmm=21.8 ppm. Calculations involved in the characterization of polymers by NMR follow the work of F. A. Bovey in "Polymer Conformation and Configuration" Academic Press, New York 1969 and J. Randall in "Polymer Sequence Determination, Carbon-13 NMR Method", Academic Press, New York, 1977.

[0077] Steric defects, measured as "steric defects / 10,000 monomer units", are calculated from the sum of the intensities of the mmrr, mmrm+rrmr and rmrm resonance peaks multiplied by 5,000. The intensities used in this calculation are normalized to the total number of monomers in the sample. Methods for measuring 2,1 regiodefects / 10,000 monomers and 1,3 regiodefects / 10,000 monomers follow standard methods. Additional references include Grassi, A. et.al. Macromolecules, 1988, v.21, pp. 617-622 and Busico et.al. Macromolecules, 1994, v.27, pp. 7538-7543. The average mesolan length = 10000 / [(steric defects / 10000 C) + (2,1-positional defects / 10000 C) + (1,3-positional defects / 10000 C)]. The polymerization results are collected in Table 2. "Example number (Ex#)" represents the example number. Example numbers beginning with "C" are comparative examples. "Cat ID" identifies the pre-catalyst used in this experiment. The corresponding numbers identifying the pre-catalyst (also called pre-catalyst, catalyst, complex or compound) are found in the synthetic experiment section. T (°C) is the polymerization temperature, which was typically maintained within + / - 1°C. "Yield" is the polymer yield, not corrected for catalyst residues. "Quench time" is the actual time the polymerization was carried out in seconds. For propylene homopolymerization runs, the quench value indicates the maximum set pressure drop (conversion) of propylene during the polymerization. Activity is reported in grams of polymer per mmol of catalyst per hour.

[0078] Standard polymerization conditions included 0.015 μmol catalyst complex, 1.1 equivalents of activator, 0.5 μmol TNOA scavenger, 1.0 ml propylene, 4.1 ml total solvent, with a quench value of 8 psi pressure drop 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 precatalyst and activator solutions were in toluene. When activator B was used, both the precatalyst and activator solutions were in isohexane. The small amount of methylcyclohexane came from activator B, which was supplied by the manufacturer as a 10 wt. % solution in methylcyclohexane (MCH).

[0079] [Table 2] JPEG2025515174000036.jpg244157 JPEG2025515174000037.jpg244147 [Table 3] Certain embodiments and features are described using a set of numerical upper limits and a set of numerical lower limits. It should be understood that ranges including any combination of two values, such as any combination of a lower value with any combination of a higher value, any combination of two lower values, and / or any combination of two higher values, are contemplated unless otherwise indicated. Certain lower limits, upper limits, and ranges can be found in one or more claims below. All numerical values ​​are "about" or "approximately" their stated values, taking into account experimental error and variation that would be expected by one of ordinary skill in the art. Any values ​​in the table can be presented with an additional + / - 10% as the endpoints of the ranges defining their respective measurements or properties.

[0080] All documents cited herein, including any priority documents and / or test procedures, are incorporated herein by reference to the extent that they are not inconsistent with the present specification. As is apparent from the above general description and specific embodiments, the present disclosure has been illustrated and described in its various forms, but various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, the present disclosure is not intended to be limited thereby.

[0081] While this disclosure has been described with respect to certain embodiments and examples, those skilled in the art, having the benefit of this disclosure, will understand that other embodiments may be devised that do not depart from the scope and spirit of the present disclosure.

Claims

1. A catalyst compound represented by formula (I): 【Chemistry 1】 (I) (In the formula, 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 4 or less, R 10 and R 14 are each independently 4 -C 40 Hydrocarbyl or OR 20 and R 20 is C 4 -C 40 is a hydrocarbyl; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 Or R 7 and R 8 may be joined together to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 9 , R 11 and R 12 are each independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 11 and R 12 may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 13 , R 15 and R 16 are each independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 15 and R 16 may together form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 are each independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 Or R 17 and R 19 may be joined together to form one or more of a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; any two L groups may be joined together to form a bidentate Lewis base; The X group may be attached to the L group to form a monoanionic bidentate group; Any two X groups may be linked together to form a dianionic coordinating group.

2. R 4 and R 5 are each independently adamantanyl; R 2 and R 7 However, each independently, C 4 -C 40 Hydrocarbyl, preferably C 4 -C 8 hydrocarbyl, more preferably tert-butyl; R 10 and R 14 are each independently OR 20 and R 20 But, C 4 -C 12 10. The catalyst compound of claim 1 which is a hydrocarbyl.

3. R 2 , R 7 , R 10 and R 14 3. The catalyst compound of claim 1 or 2, wherein the substituents have a total number of carbon atoms that is 12 carbon atoms or more, alternatively 14 carbon atoms or more, alternatively 16 carbon atoms or more, alternatively 18 carbon atoms or more.

4. R 2 , R 7 , R 10 and R 14 the substituents have a total number of carbon atoms that is 12 carbon atoms or more, alternatively 14 carbon atoms or more, alternatively 16 carbon atoms or more, alternatively 18 carbon atoms or more; R 4 and R 5 3. The catalyst compound according to claim 1 or 2, wherein is selected from tert-butyl, adamantanyl and substituted adamantanyl.

5. R 2 , R 7 , R 4 , R 5 , R 10 and R 14 3. The catalyst compound of claim 1 or 2, wherein the substituents have a total number of carbon atoms that is 32 carbon atoms or more, alternatively 34 carbon atoms or more, alternatively 36 carbon atoms or more.

6. below: 【Chemistry 2】 2. The catalyst compound of claim 1, wherein the catalyst compound is one of:

7. R 10 and R 14 are each independently OR 20 and R 20 But, C 4 -C 40 10. The catalyst compound of claim 1 which is a hydrocarbyl.

8. A catalyst system comprising an activator, preferably a non-aromatic hydrocarbon, and optionally a support material, and a catalyst compound according to any one of claims 1 to 7.

9. A homogeneous solution, an aliphatic hydrocarbon solvent; at least one complex of formula (I), wherein the concentration of the complex is 0.15% by weight or more (alternatively 0.20% by weight or more, alternatively 0.25% by weight or more, alternatively 0.30% by weight or more, alternatively 0.35% by weight or more, alternatively 0.40% by weight or more, alternatively 0.5% by weight or more, alternatively 1.0% by weight or more, alternatively 2.0% by weight or more).

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

11. 10. A method for producing a propylene-based polymer, comprising the step of polymerizing propylene 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. by contacting propylene with the catalyst system of claim 8 to form a propylene-based polymer.

12. 10. A method for producing an ethylene-based polymer, comprising the step of polymerizing ethylene 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. by contacting ethylene with the catalyst system of claim 8 to form an ethylene-based polymer.

13. 13. The process according to claim 11 or 12, wherein the catalyst compound and the activator are fed separately to the reactor.

14. 13. The process of claim 11 or 12, wherein the catalyst compound and the activator are premixed before being fed to the reactor.

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