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

Abstract

Exemplary embodiments of the present technical progress include pyridine-2, 6-bis (phenylene phenolate) complexes that can be used as catalyst components for olefin polymerization and have enhanced solubility in non-aromatic hydrocarbons (e.g., isohexane). The improved solubility of these complexes is achieved by modification of leaving groups, which typically results in improved solubility, without adversely affecting the performance of the complexes when used as catalysts for olefin polymerization.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 338,173, filed May 4, 2022, the disclosure of which is incorporated herein by reference. Technical Field

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

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

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

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

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

[0007] Further information about the complex 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", AC Catalysis, v.11(13), pp.8079-8086; US2020 / 0255556; US2020 / 0255555; US2020 / 0254431 and US2020 / 0255553, the entire contents of each of which are hereby incorporated by reference. Summary of the invention SUMMARY OF THE INVENTION

[0008] The catalyst compound represented by formula (I): in: M is a Group 3, 4 or 5 metal; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon, C 1 -C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R7 and R 8 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon, C 1 -C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or any two or more adjacent R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 may be linked to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon, C 1 -C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 or R 17 and R 19 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; L is a Lewis base; each X is independently a hydrocarbyl ligand or a substituted hydrocarbyl ligand, wherein at least one X is a non-aromatic hydrocarbyl ligand containing nine or more carbon atoms, or a substituted hydrocarbyl ligand containing at least five or more carbon atoms, or when n is 2, two X together can be a hydrocarbyl or substituted hydrocarbyl containing four or more carbon atoms and forming a 5-membered cyclic ring structure with M; n is 1, 2, or 3; m is 0, 1, or 2; n+m is not greater than 4; Any two L groups may be linked together to form a bidentate Lewis base; and The X group may be linked to the L group to form a monoanionic bidentate group.

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

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

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

[0012] Exemplary embodiments of the present technological advances include pyridine-2,6-bis(phenylenephenolate) complexes that are useful as catalyst components for olefin polymerization and have enhanced solubility in non-aromatic hydrocarbons (e.g., isohexane). The improved solubility of these complexes is achieved by modification of the leaving group (which generally results in improved solubility) without adversely affecting the performance of the complex when used as a catalyst for olefin polymerization.

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

[0014] The following abbreviations may be used herein: Me is methyl, Et is ethyl, Ph is phenyl, tBu is tert-butyl, Tf is trifluoromethanesulfonate (-SO 2 CF 3), Ad is adamantyl, MAO is methylaluminoxane, NMR is nuclear magnetic resonance, t is time, s is second, h is hour, psi is pounds per square inch, psig is pounds per square inch, gauge pressure, equiv. is equivalent, and RPM is revolutions per minute.

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

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

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

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

[0019] The term "heteroatom" refers to any element of Groups 13-17 excluding carbon. Heteroatoms may include B, Si, Ge, Sn, N, P, As, O, S, Se, Te, F, Cl, Br, and I. The term "heteroatom" may include the above elements with hydrogen attached, for example, BH, BH 2 、SiH 2 , OH, NH, NH 2 etc. The term "substituted heteroatom" describes heteroatoms in which one or more of the hydrogen atoms are replaced by a hydrocarbyl or substituted hydrocarbyl group(s).

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

[0021] The term "substituted hydrocarbyl" refers to a hydrocarbyl group wherein at least one of the hydrogen atoms of the hydrocarbyl group has been replaced by at least one heteroatom (e.g., a halogen such as Br, Cl, F, or I) or a heteroatom-containing group (e.g., a functional group such as -NR*). 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 、-SR*、-BR* 2 、-SiR* 3 , -GeR* 3 、-SnR* 3 , -PbR* 3 , wherein each R* is independently a hydrocarbyl or a halogenated carbonyl, and two or more R* may be linked together to form a substituted or unsubstituted fully saturated, partially unsaturated, substituted or unsubstituted hydrocarbyl, or an aromatic cyclic or polycyclic ring structure) substituted, or wherein at least one heteroatom has been inserted into the hydrocarbyl ring. The term "hydrocarbyl-substituted phenyl" refers to a phenyl having 1, 2, 3, 4 or 5 hydrogen groups replaced by a hydrocarbyl or substituted hydrocarbyl. For example, a "hydrocarbyl-substituted phenyl" may be represented by the formula: Where R a , R b , R c , R d and R e Each of which can be independently selected from hydrogen, C 1 -C 40 Hydrocarbon or C 1 -C 40 Substituted hydrocarbon group, heteroatom or heteroatom-containing group (provided that R a , R b , R c , R d and R e At least one of them is not H), or R a, R b , R c , R d and R e Two or more of these can be linked together to form C 4 -C 62 Cyclic or polycyclic hydrocarbon ring structures, or combinations thereof.

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

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

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

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

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

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

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

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

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

[0031] The terms "alkoxy" and "alkoxide" refer to an alkyl or aryl group bonded to an oxygen atom, such as an alkyl ether or aryl ether group attached to an oxygen atom, and may include groups in which the alkyl / aryl group is C 1 -C 10 The alkyl radicals may be straight chain, branched or cyclic alkyl radicals. The alkyl radicals may be saturated or unsaturated. Examples of suitable alkoxy radicals may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy.

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

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

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

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

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

[0037] The terms "hydrocarbyl radical", "hydrocarbyl group" or "hydrocarbyl" are used interchangeably and are defined to mean a group consisting solely of hydrogen and carbon atoms. For example, a hydrocarbyl radical may be C 1 -C 100 A group which may be linear, branched or cyclic and, when cyclic, may be aromatic or non-aromatic. Examples of such groups may include, but are not limited to, alkyl groups such as methyl, ethyl, propyl (e.g., n-propyl, isopropyl, cyclopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., isopentyl, cyclopentyl), hexyl (e.g., cyclohexyl), octyl (e.g., cyclooctyl), nonyl, decyl (e.g., adamantyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or triacontyl, and aryl groups such as phenyl, benzyl and naphthyl.

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

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

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

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

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

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

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

[0045] In at least one embodiment, the catalyst compound represented by formula (I) is as follows. in: M is a Group 3, 4 or 5 metal; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon, C 1 -C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon, C 1 -C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or any two or more adjacent R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 may be linked to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon, C1 -C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 or R 17 and R 19 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; L is a Lewis base; each X is independently a hydrocarbyl ligand or a substituted hydrocarbyl ligand, wherein at least one X is a non-aromatic hydrocarbyl ligand containing nine or more carbon atoms, or a substituted hydrocarbyl ligand containing at least five or more carbon atoms, or when n is 2, two X together can be a hydrocarbyl or substituted hydrocarbyl containing four or more carbon atoms and forming a 5-membered cyclic ring structure with M; n is 1, 2, or 3; m is 0, 1, or 2; n+m is not greater than 4; Any two L groups may be linked together to form a bidentate Lewis base; and The X group may be linked to the L group to form a monoanionic bidentate group.

[0046] When n is 2, the two X together can be represented by the following formula Ia, Ib, Ic or Id, wherein R 20 , R 20 '、R 21 , R 21 '、R 22 , R 22 '、R 23 , R 23 ' are independently hydrogen or C 1 -C 20 A hydrocarbon group in which the dashed line represents the bond to the metal atom M.

[0047] For example, M of formula (I) may be a Group 3, 4 or 5 metal, for example M may be a Group 4 metal. Group 4 metals may include zirconium, titanium and hafnium. In at least one embodiment, M is zirconium or hafnium.

[0048] Each L of formula (I) may be independently selected from ethers, amines, phosphines, thioethers, esters, such as Et 2 O、MeOtBu、Et 3 N. PhNMe 2 、MePh 2 N, tetrahydrofuran, methyl acetate and dimethyl sulfide.

[0049] R of formula (I) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 Each of which can be independently selected from hydrogen, C 1 -C 40 Hydrocarbon, C 1 -C 40 substituted hydrocarbyl, hydrocarbyloxy, trihydrocarbylsilyl, trihydrocarbylgermyl, dihydrocarbylamino, dihydrocarbylphosphino or halogen, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms.

[0050] In at least one embodiment, R of formula (I) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8One or more of the groups are independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, substituted phenyl, biphenyl or isomers thereof, which may be halogenated (e.g., perfluoropropyl, perfluorobutyl, perfluoroethyl, perfluoromethyl), substituted alkyl and all isomers of substituted alkyl, including trimethylsilylpropyl, trimethylsilylmethyl, trimethylsilylethyl, phenyl or all isomers of alkyl-substituted phenyl, including methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, diphenyl Propylphenyl, tripropylphenyl, dimethylethylphenyl, dimethylpropylphenyl, dimethylbutylphenyl or dipropylmethylphenyl, heteroatom-containing groups include trimethylsilyl, triethylsilyl, methoxy, ethoxy, cyclohexyloxy, trifluoromethyl, dimethylamino, diethylamino, dicyclohexylamino and all isomers of tripropylsilyl, tributylsilyl, tripentylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, dimethyloctylsilyl, butyldimethylsilyl (e.g., tert-butyldimethylsilyl), propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.

[0051] For example, R of formula (I) 4 and R 5 Can be independently C 1 -C 20 Alkyl groups, such as R 4 and R 5 It can be tert-butyl or adamantyl. In at least one embodiment, R 4 and R 5 is independently selected from unsubstituted phenyl, substituted phenyl, unsubstituted carbazole, substituted carbazole, unsubstituted naphthyl, substituted naphthyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted fluorenyl or substituted fluorenyl, a heteroatom or a heteroatom-containing group, such as R 4 and R 5 may independently be unsubstituted phenyl or 3,5-di-tert-butylbenzyl. In addition, (1) R 4 Can be C 1 -C 20 Alkyl (e.g., R 4 may be tert-butyl) and R 5 It may be an aryl group, or (2) R 5 Can be C 1 -C 20 Alkyl (e.g., R 5 may be tert-butyl) and R 4 It can be an aromatic group. Alternatively, R 4 and / or R 5 can be independently heteroatoms, such as R4 and R 5 It may be a halogen atom (such as Br, Cl, F or I). 4 and / or R 5 can be independently silyl, for example R 4 and R 5 It can be a trialkylsilyl group or a triarylsilyl group, wherein the alkyl group is C 1 To C 30 The alkyl group is C alkyl (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl, cyclopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., isopentyl, cyclopentyl), hexyl (e.g., cyclohexyl), octyl (e.g., cyclooctyl), nonyl, decyl (e.g., adamantyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, or triacontyl, and the aryl group is C 6 To C 30 Aryl (e.g., phenyl, benzyl, and naphthyl). Typically, R 4 and R 5 It may be triethylsilyl.

[0052] In some embodiments, R 4 and R 5 Independently for C 1 -C 40 Hydrocarbon, C 1 -C 40 Substituted hydrocarbon groups, more preferably, each R 4 and R 5 independently selected from tertiary hydrocarbon groups (e.g., tert-butyl, tert-pentyl, tert-hexyl, tert-heptyl, tert-octyl, tert-nonyl, tert-decyl, tert-undecyl, tert-dodecyl) and cyclic tertiary hydrocarbon groups (e.g., 1-methylcyclohexyl, 1-norbornyl, 1-adamantyl or substituted 1-adamantyl).

[0053] In some embodiments, R 4 and R 5 Independently for C 1 -C 40 Hydrocarbon, C 1 -C 40 Substituted hydrocarbon groups, more preferably, R 4 and R 5Each of the groups is independently a non-aromatic cyclic alkyl group (e.g., cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, adamantyl, norbornyl or 1-methylcyclohexyl or substituted adamantyl), most preferably a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, 1-adamantyl, substituted 1-adamantyl or 1-norbornyl).

[0054] In some embodiments, R 4 and R 5 Independently for C 3 -C 30 The heteroatom-containing groups include trimethylsilyl, triethylsilyl, and all isomers of tripropylsilyl, tributylsilyl, tripentylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, dimethyloctylsilyl, butyldimethylsilyl and the like.

[0055] R 4 and R 5 The nature of can be used to control the molecular weight of the polymer product. For example, when R 4 and R 5 When one or two of the R groups are tert-butyl groups, the catalyst compound can provide a high molecular weight polymer. 4 , R 5 or R 4 and R 5 When phenyl, the catalyst compound can provide a low molecular weight polymer.

[0056] In at least one embodiment, each R of formula (I) 2 and R 7 Independently for C 1 -C 10 Alkyl groups, such as R 2 and R 7 and tert-butyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dimethylpentyl, tert-butyl, isopropyl or an isomer thereof.

[0057] In at least one embodiment, each R of formula (I) 2 and R 7 Independently for C 3 -C 30 Substituted hydrocarbon or C 3 -C 30 Groups containing heteroatoms, such as R 2 and R 7and independently trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, trioctylsilyl, dimethyloctylsilyl, butyldimethylsilyl (including tert-butyldimethylsilyl), methyltrimethylsilyl or an isomer thereof.

[0058] R of formula (I) 1 , R 3 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 Each of which can independently be hydrogen or C 1 -C 10 Alkyl groups, such as R 1 , R 3 , R 6 , R 8 , R 9 , R 11 , R 12 , R 13 , R 15 , R 16 , R 17 , R 18 and R 19 can be independently hydrogen, methyl, ethyl, propyl or isopropyl. In at least one embodiment, R 1 , R 3 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 is hydrogen. Alternatively, R 1 , R 3 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R14 , R 15 , R 16 , R 17 , R 18 and R 19 Each of may independently be hydrogen, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy or trimethylsilyl.

[0059] Each X may independently be a hydrocarbyl ligand or a substituted hydrocarbyl ligand, wherein at least one X is C 9 -C 40 Non-aromatic hydrocarbon ligands, or C 9 -C 20 Non-aromatic hydrocarbon ligands, or C 10 -C 20 Non-aromatic hydrocarbon ligands, or C 12 -C 20 Non-aromatic hydrocarbon-based ligands.

[0060] Each X may independently be a hydrocarbyl ligand or a substituted hydrocarbyl ligand, wherein at least one X is C 9 -C 40 Non-aromatic hydrocarbon ligands, or C 9 -C 20 Non-aromatic hydrocarbon ligands, or C 10 -C 20 Non-aromatic hydrocarbon ligands, or C 12 -C 20 Non-aromatic hydrocarbon ligands, and other X is C 1 -C 40 Hydrocarbyl ligand or substituted hydrocarbyl ligand, or C 1 -C 20 A hydrocarbyl ligand or a substituted hydrocarbyl ligand.

[0061] Each X may independently be a hydrocarbyl ligand or a substituted hydrocarbyl ligand, wherein at least one X is C 9 -C 40 non-aromatic hydrocarbon ligand, and other X is C 1 -C 40 Hydrocarbon ligands.

[0062] Each X may independently be a hydrocarbyl ligand, wherein at least one X is C 9 -C 40 non-aromatic hydrocarbon ligand, and other X is C 1 -C 40 Non-aromatic hydrocarbon-based ligands.

[0063] Each X may independently be a hydrocarbyl ligand, wherein at least one X is C 9 -C 20 non-aromatic hydrocarbon ligand, and other X is C1 -C 20 Non-aromatic hydrocarbon-based ligands.

[0064] X's preferred C 9 -C 20 Non-aromatic hydrocarbon-based ligands include all isomers of nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl, such as n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2,2-dimethylhept-1-yl, 2,2-dimethyloct-1-yl, 2,2-dimethylnon-1-yl, 2,2-dimethyldec-1-yl, 3,7-dimethyloct-1-yl, 2-ethyldec-1-yl, 9-methylundec-1-yl, 2-hexyldec-1-yl, 3,7,11-trimethyldodec-1-yl, and the like.

[0065] X's preferred C 1 -C 20 Non-aromatic hydrocarbon-based ligands include methyl, ethyl, and all isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl. alkyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2,2-dimethylhept-1-yl, 2,2-dimethyloct-1-yl, 2,2-dimethylnon-1-yl, 2,2-dimethyldec-1-yl, 3,7-dimethyloct-1-yl, 2-ethyldec-1-yl, 9-methylundec-1-yl, 2-hexyldec-1-yl, 3,7,11-trimethyldodec-1-yl, and the like.

[0066] Each X may independently be a hydrocarbyl ligand, wherein at least one X is C 10 -C 20 non-aromatic hydrocarbon ligand, and other X is C 1 -C 20 Hydrocarbon ligands.

[0067] Each X may independently be a hydrocarbyl ligand, wherein at least one X is C 12 -C 20 non-aromatic hydrocarbon ligand, and other X is C 1 -C 20 Hydrocarbon ligands.

[0068] Each X may independently be a hydrocarbyl ligand or a substituted hydrocarbyl ligand, wherein at least one X is C 5 -C 40 Substituted hydrocarbon ligands, or C 5 -C 30 Substituted hydrocarbon ligands, or C 7 -C 30 Substituted hydrocarbon ligands, or C 10 -C 30 Substituted hydrocarbon ligands, or C 12 -C 30 Substituted hydrocarbyl ligands.

[0069] Each X may independently be a hydrocarbyl ligand or a substituted hydrocarbyl ligand, wherein at least one X is C 5 -C 30 Substituted hydrocarbyl ligands.

[0070] X's preferred C 5 -C 30 Substituted hydrocarbyl ligands include those selected from SiR 30 3 ,GeR 30 3 , OR 30 , SR 30 NR 30 2 Those containing heteroatom groups, wherein each R 30 Independently for C 1 -C 10 Hydrocarbyl, preferably selected from C 1 -C 10 Alkyl, C 7 -C 10 Alkyl aryl or C 7 -C 10 Arylalkyl, for example, (1,1-dimethylethoxy)oct-8-yl, [(trimethylsilyl)oxy]dec-10-yl, [tert-butyldimethylsilyl)oxy]hex-6-yl, [tert-butyldimethylsilyl)oxy]oct-8-yl, 4-(cyclohexylthio)benzyl, trimethylsilyleth-2-yl, trimethylsilylprop-3-yl, (triethylsilyl)methyl, and the like.

[0071] X's preferred C 7 -C 30 Substituted hydrocarbyl ligands include those selected from SiR 30 3 ,GeR 30 3 , OR 30 , SR 30 NR30 2 Those containing heteroatom groups, wherein each R 30 Independently for C 1 -C 10 Hydrocarbyl, preferably selected from C 1 -C 10 Alkyl, C 7 -C 10 Alkyl or C 7 -C 10 Aralkyl groups such as (1,1-dimethylethoxy)oct-8-yl, [(trimethylsilyl)oxy]dec-10-yl, [tert-butyldimethylsilyl)oxy]hex-6-yl, [tert-butyldimethylsilyl)oxy]oct-8-yl, 4-(cyclohexylthio)benzyl, 4-(cyclopentylthio)benzyl, 4-(cycloheptylthio)benzyl, 4-(cyclopentyloxy)benzyl, 4-(cyclohexyloxy)benzyl, 4-(cycloheptyloxy)benzyl, triethylsilyleth-2-yl, trimethylsilylbut-4-yl, (triethylsilyl)methyl and the like.

[0072] Each X may independently be a hydrocarbyl ligand or a substituted hydrocarbyl ligand, wherein at least one X is C 10 -C 30 Substituted hydrocarbyl ligands.

[0073] X's preferred C 10 -C 30 Substituted hydrocarbyl ligands include those selected from SiR 30 3 ,GeR 30 3 , OR 30 , SR 30 NR 30 2 Those containing heteroatom groups, wherein each R 30 Independently for C 1 -C 10 Hydrocarbyl, preferably selected from C 1 -C 10 Alkyl, C 7 -C 10 Alkyl or C 7 -C 10Aralkyl groups such as (1,1-dimethylethoxy)oct-8-yl, [(trimethylsilyl)oxy]dec-10-yl, [tert-butyldimethylsilyl)oxy]hex-6-yl, [tert-butyldimethylsilyl)oxy]oct-8-yl, 4-(cyclohexylthio)benzyl, 4-(cyclopentylthio)benzyl, 4-(cycloheptylthio)benzyl, 4-(cyclopentyloxy)benzyl, 4-(cyclohexyloxy)benzyl, 4-(cycloheptyloxy)benzyl, tripropylsilyleth-2-yl, trimethylsilyloct-8-yl, (tripropylsilyl)methyl and the like.

[0074] m may be 0, n may be 2, and the two Xs together may be C to form a 5-membered cyclic ring structure with M. 4 -C 40 A hydrocarbon group or a substituted hydrocarbon group.

[0075] m may be 0, n may be 2, and two X may be represented by Formula Ic, wherein R 20 , R 20’ , R 21 , R 22 , R 23 , R 23 ' can independently be hydrogen or C 1 -C 20 Hydrocarbon.

[0076] m may be 0, n may be 2, and two X may be represented by Formula Ic, wherein R 20 , R 20’ , R 23 , R 23 ' may be hydrogen, and each R 21 and R 22 can independently be hydrogen or a hydrocarbon group.

[0077] m may be 0, n may be 2, and two X may be represented by Formula Ic, wherein R 20 , R 20’ , R 23 , R 23 ' may be hydrogen, and R 21 and R 22 One of them may be hydrogen and the other may be hydrogen or a hydrocarbon group, or hydrogen or a C 1 -C 20 Hydrocarbyl, or hydrogen or C 1 -C 10 Hydrocarbon.

[0078] R 21 or R 22Preferred hydrocarbon radicals include methyl, ethyl, and all isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl, for example methyl, ethyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 3-methylbutan-2-yl, cyclopentyl, n-hexyl, isohexyl, 1-methylpent-1-yl, cyclohexyl, n-heptyl, 4-methylpent-3-en-1-yl, 1-methylhex-1-yl, n-octyl, 1-methylhept-1-yl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 4,8-dimethylnona-3,7-dien-1-yl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, etc.

[0079] m may be 0, n may be 2, and two X may be represented by Formula Ic, wherein R 20 , R 20’ , R 23 , R 23 ' may be hydrogen, and R 21 and R 22 One of them can be hydrogen and the other can be C 1 -C 10 Hydrocarbon.

[0080] m may be 0, n may be 2, and two X may be represented by Formula Ic, wherein R 20 , R 20’ , R 23 , R 23 ' may be hydrogen, and R 21 and R 22 One of the radicals may be hydrogen and the other is selected from hydrogen, methyl, ethyl, and all isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

[0081] m may be 0, n may be 2, and two X may be represented by Formula Ic, wherein R 20 , R 20’ , R 23 , R 23 ' may be hydrogen, and R 21 and R 22 One of the may be hydrogen and the other is selected from hydrogen, methyl or 4-methylpent-3-en-1-yl.

[0082] In formula (I), R 4 and R 5 It can be adamantyl, R 2 and R 7 Can be C 4 -C40 Hydrocarbon or C 6 -C 30 In the heteroatom-containing group, m may be 0, n may be 2, and two Xs may be represented by Formula Ic.

[0083] In formula (I), R 4 and R 5 It can be adamantyl, R 2 and R 7 Can be C 4 -C 8 Hydrocarbon or C 6 -C 20 In the heteroatom-containing group, m may be 0, n may be 2, and two Xs may be represented by Formula Ic.

[0084] In formula (I), R 4 and R 5 It can be adamantyl, R 2 and R 7 It may be tert-butyl, 1,1-dimethylpropyl, n-octyl or tert-butyldimethylsilyl, m may be 0, n may be 2, and two Xs may be represented by Formula Ic.

[0085] In formula (I), R 4 and R 5 It can be adamantyl, R 2 and R 7 Can be C 4 -C 40 Hydrocarbon or C 6 -C 30 containing a heteroatom group, m may be 0, n may be 2, two Xs may be represented by Formula Ic, and R 20 , R 20’ , R 23 , R 23’ may be hydrogen, and each R 21 and R 22 It may be hydrogen or a hydrocarbon group.

[0086] In formula (I), R 4 and R 5 It can be adamantyl, R 2 and R 7 Can be C 4 -C 8 Hydrocarbon or C 6 -C 20 containing a heteroatom group, m may be 0, n may be 2, two Xs may be represented by Formula Ic, and R 20 , R 20’ , R 23 , R 23’ may be hydrogen, and each R 21and R 22 It may be hydrogen or a hydrocarbon group.

[0087] In formula (I), R 4 and R 5 It can be adamantyl, R 2 and R 7 may be tert-butyl, 1,1-dimethylpropyl, n-octyl or tert-butyldimethylsilyl, m may be 0, n may be 2, two Xs may be represented by Formula Ic, and R 20 , R 20’ , R 23 , R 23’ may be hydrogen, and each R 21 and R 22 It may be hydrogen or a hydrocarbon group.

[0088] In any of the above exemplary embodiments of Formula (I), R 21 and R 22 One of them can be hydrogen and the other can be C 1 -C 20 Hydrocarbon.

[0089] In any of the above exemplary embodiments of Formula (I), R 21 and R 22 One of them can be hydrogen and the other can be C 1 -C 10 Hydrocarbon.

[0090] In any of the above exemplary embodiments of Formula (I), R 21 and R 22 One of the may be hydrogen and the other may be hydrogen, methyl or 4-methylpent-3-en-1-yl.

[0091] In any of the above exemplary embodiments of Formula (I), R 21 and R 22 One of the radicals may be hydrogen and the other may be methyl.

[0092] In any of the above exemplary embodiments of Formula (I), R 21 and R 22 One of the may be hydrogen and the other may be 4-methylpent-3-en-1-yl.

[0093] In any of the above exemplary embodiments of Formula (I), R 21 and R 22 All may be hydrogen.

[0094] In at least one embodiment, the catalyst compound is one or more of the following:

[0095] In at least one embodiment, one or more different catalyst compounds are present in the catalyst system. One or more different catalyst compounds may be present in the reaction zone where the method(s) described herein are performed. The same activator may be used for the transition metal compound, however, two different activators may be used in combination, such as a non-coordinating anion activator and an aluminoxane.

[0096] An exemplary embodiment of the present technical advancement may also be a homogeneous solution comprising an aliphatic hydrocarbon solvent and a complex of formula (I), wherein the concentration of the complex is 0.20 wt % or more (or 0.25 wt % or more, or 0.30 wt % or more, or 0.35 wt % or more, or 0.40 wt % or more, or 0.50 wt % or more, or 1.0 wt % or more, or 2.0 wt % or more). Without wishing to be bound by theory, it is believed that when n is 2 and two Xs are taken together as represented by formula Ic, the solubility of the complex of formula (I) in the aliphatic solvent is improved. By selecting R 4 and R 5 Substituents and / or R 2 and R 7 Substituents can further improve solubility in aliphatic solvents. For example, the combination of two Xs together is represented by Formula Ic, as in 2-methylbut-2-ene-1,4-diyl, and R 2 and R 7 The choice of substituent as octyl in complex 13 greatly improves the solubility of the complex in isohexane.

[0097] Another exemplary embodiment of the present technological advance includes a method for producing a propylene-based polymer, the method comprising: reacting propylene and one or more optional C 3 -C 40 Olefin polymerization, propylene and one or more optional C 3 -C 40 The olefin is contacted with a catalyst system comprising a composition of formula (I) in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to form a propylene-based polymer.

[0098] Another exemplary embodiment of the present technological advance includes a method for producing an ethylene-based polymer, the method comprising: reacting ethylene and one or more optional C 4 -C 40 Olefin polymerization, ethylene and one or more optional C 4 -C 40The olefin is contacted with a catalyst system comprising a composition of formula (I) in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to form a propylene-based or ethylene-based polymer. Activators and optional scavengers, co-activators and chain transfer agents

[0099] U.S. Patent Application Serial No. 16 / 788,088 (published as US2020 / 0254431) describes activators, optional scavengers, optional co-activators, and optional chain transfer agents that can be used with the present technology advancement. Particularly useful activators are also described in PCT Application No. PCT / US2020 / 044865 (published as WO 2021 / 086467), U.S. Patent Application Serial No. 16 / 394,174 (published as US2019 / 0330394), and PCT Application No. PCT / US2019 / 029056 (published as WO 2019 / 210026), which describes non-aromatic hydrocarbon soluble activator compounds, such as [tetrakis(pentafluorophenyl)boric acid] N-methyl-4-nonadecyl-N-octadecylanilinium, [tetrakis(heptafluoronaphthyl)boric acid] N-methyl-4-nonadecyl-N-octadecylanilinium, [tetrakis(pentafluorophenyl)boric acid)] N-methyl-N-octadecyl-4-(octadecyloxy)anilinium, [tetrakis(heptafluoronaphthyl)boric acid] N-methyl-N-octadecyl-4-(octadecyloxy)anilinium, [tetrakis(pentafluorophenyl)boric acid] N,N-di( Hydrogenated tallow) methylammonium, [tetrakis(heptafluoronaphthyl)borate] N,N-di(hydrogenated tallow) methylammonium, [tetrakis(pentafluorophenyl)borate] N,N-di(octadecyl)methylammonium [tetrakis(heptafluoronaphthyl)borate], [tetrakis(pentafluorophenyl)borate] N,N-di(octadecyl)methylammonium [tetrakis(heptafluoronaphthyl)borate], [tetrakis(pentafluorophenyl)borate] N,N-di(hexadecyl)methylammonium [tetrakis(heptafluoronaphthyl)borate], [tetrakis(pentafluorophenyl)borate] N,N-di(hexadecyl)methylammonium [tetrakis(pentafluorophenyl)borate] N-octadecyl-N-hexadecylmethylammonium [tetrakis(pentafluorophenyl)borate] and [tetrakis(heptafluoronaphthyl)borate] N-octadecyl-N-hexadecylmethylammonium.

[0100] Although it is preferred to use an activator that is soluble in a non-aromatic hydrocarbon solvent, activators that are poorly soluble or insoluble in a non-aromatic hydrocarbon solvent may also be used. When used, these activators can be fed to the reactor via a slurry or as a solid. Particularly useful activators in this class include triphenylcarbon tetrakis(pentafluorophenyl)borate, Triphenylcarbon tetrakis(perfluoronaphthyl)borate N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, etc.

[0101] Typical activator to catalyst ratios are about 1:1 molar ratios. Alternative preferred ranges include 0.1:1-100:1, or 0.5:1-200:1, or 1:1-500:1, or 1:1-1000:1. Particularly useful ranges are 0.5:1 to 10:1, preferably 1:1 to 1:10.

[0102] Particularly useful optional scavengers or co-activators or chain transfer agents include, for example, trialkylaluminums such as triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and dialkylzincs such as diethylzinc. In addition, hydrocarbon-soluble aluminoxanes and modified aluminoxanes that do not contain toluene, including "trimethylaluminum-free" aluminoxanes, can be used.

[0103] In addition, one of ordinary skill in the art will be able to select suitable known activators (one or more) and optional scavengers or co-activators or chain transfer agents for their particular purpose without undue experimentation. Combinations of various activators may be used. Likewise, combinations of various optional scavengers or co-activators or chain transfer agents may be used. Solvents

[0104] Although the catalyst components of the present technology advancement can be used with aromatic solvents such as toluene, they are preferably absent when the catalyst components are used in the polymerization process. Solvents that can be used to dissolve the catalyst compound, the activator compound, or to combine the catalyst compound and the activator, and / or to introduce the catalyst system or any component thereof into the reactor, and / or to be used in the polymerization process include, but are not limited to, aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, or combinations thereof; preferred solvents may include normal paraffins (e.g., Norpar available from ExxonMobil Chemical Company of Houston, TX); TM solvents), isoparaffin solvents (e.g., Isopar available from ExxonMobil Chemical Company of Houston TX), TM solvents), non-aromatic cyclic solvents (e.g., Nappar available from ExxonMobil Chemical Company of Houston, TX) TM solvent) and combinations thereof.

[0105] Preferably, the aliphatic hydrocarbon solvent is selected from C 4 To C 10 Linear, branched or cyclic alkanes, or selected from C 5 To C 8 Linear, branched or cyclic alkanes.

[0106] Preferably, the aliphatic hydrocarbon solvent is substantially free of all aromatic solvents. Preferably, the solvent is substantially free of toluene. Free of all aromatic solvents, such as toluene, means that the solvent is substantially free of aromatic solvents (e.g., present at 0 mol %, or present at less than 1 mol %), preferably, the polymerization reaction and / or the resulting polymer does not contain "detectable aromatic hydrocarbon solvents", such as toluene.

[0107] Preferred aliphatic hydrocarbon solvents include isohexane, cyclohexane, methylcyclohexane, pentane, isopentane, heptane, and combinations thereof, as well as commercially available solvent mixtures such as Nappar 6 TM and IsoparE TM However, one of ordinary skill in the art may select other suitable non-aromatic hydrocarbon solvents without undue experimentation.

[0108] Highly preferred aliphatic hydrocarbon solvents include isohexane, methylcyclohexane and commercially available solvent mixtures such as Nappa 6 TM and IsoparE TM .

[0109] For compound solubility testing, preferred solvents include isohexane and methylcyclohexane. Optional carrier material

[0110] In the embodiments herein, the catalyst system may include an inert support material. The support material may be a porous support material, for example, talc and an inorganic oxide. U.S. Patent Application Serial No. 16 / 788,088 (Publication No. US2020 / 0254431) describes optional support materials that can be used with this technological advancement. In addition, one of ordinary skill in the art can select a suitable known support for its specific purpose without excessive experimentation. Aggregation methods

[0111] The present disclosure relates to a polymerization process in which a monomer (e.g., ethylene; propylene) and optionally one or more comonomers (e.g., C 2 To C 20 α-olefins, C 4 To C 40 Cycloolefins, C 5 To C 20 The catalyst system of the present invention is a catalyst system comprising an activator and at least one catalyst compound as described above. The catalyst compound and the activator can be combined in any order. The catalyst compound and the activator can be combined before contacting with the monomer. Alternatively, the catalyst compound and the activator can be introduced separately into a polymerization reactor, where they are subsequently reacted to form an active catalyst.

[0112] U.S. patent application Ser. No. 16 / 788,088 (Pub. No. US2020 / 0254431) describes monomers that can be used in the present technological advancement and describes polymerization methods that can be used in the present technological advancement.

[0113] Additionally, catalysts that are highly soluble in aliphatic hydrocarbon solvents can be used as trim catalysts in well-known polymerization processes, such as described in WO2015 / 123177 and WO20 / 092587. blends and films

[0114] Polymers prepared using this technological advance can be used to prepare blends and films as described in U.S. Patent Application Serial No. 16 / 788,088 (Publication No. US2020 / 0254431) without undue experimentation. Example General considerations for synthesis

[0115] 2-Bromoiodobenzene (Millipore Sigma), cesium carbonate (Millipore Sigma), 2,6-dibromopyridine (Millipore Sigma), diisobutylaluminum hydride (Millipore Sigma), ethyl isobutyrate (Fisher Scientific), hexane (Millipore Sigma), ethylaluminum dichloride (Millipore Sigma), hydrochloric acid (Fisher Scientific), iodine (Millipore Sigma), isoprene (Millipore Sigma), 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Millipore Sigma), lithium diisopropylamide (Millipore Sigma), iodooctane (Fisher Scientific), magnesium powder (Strem Chemicals), methanesulfonyl chloride (Millipore Sigma), methanol (Millipore Sigma), methylmagnesium bromide (Millipore Sigma), 1-methyl-2-pyrrolidone (Millipore Sigma), Pd / C (5 wt% Pd) (Millipore Sigma), potassium carbonate (Strem Chemicals), sodium bicarbonate (Fisher Scientific), sodium bromide (Millipore Sigma), sodium chloride (Fisher Scientific), sodium sulfate (Fisher Scientific), sodium thiosulfate (Millipore Sigma), tetrakis(triphenylphosphine)palladium(0) (Millipore Sigma), tert-amylphenol (MilliporeSigma), triethylamine (Millipore Sigma), and zirconium(IV) chloride (Strem Chemicals) were used as received. Celite (Millipore Sigma) and molecular sieves (Fisher Scientific) were used after drying at 250°C under high vacuum for >2 days. 6 -benzene (Cambridge Isotope Laboratories), dichloromethane (MilliporeSigma), d 2- Dichloromethane (Cambridge Isotope Laboratories), diethyl ether (Millipore Sigma), 1,2-dimethoxyethane (Millipore Sigma), pentane (Millipore Sigma), tetrahydrofuran (MilliporeSigma), toluene (Millipore Sigma) were sparged with nitrogen for >30 min and activated before use. isohexane was obtained in-house and dried over 100 molecular sieves before use. All other reagents were purchased from commercial suppliers (Millipore Sigma, Fisher Scientific, Strem Chemical, or Oakwood Chemical) and used as received unless otherwise noted.

[0116] Magnesium-butadiene, tetrahydrofuran adduct was prepared as described in [Organometallics 1982, v.1, pp.388-396]. A 0.5 M solution of n-heptylmagnesium chloride in THF was synthesized from n-heptyl chloride (Sigma-Aldrich) and magnesium turnings in THF via a common synthetic protocol for Grignard reagent synthesis. 2-(1-adamantyl)-4-(tert-butyl)phenol was prepared as described in Org.Lett.2015, v.17, pg.2242. Lithium diisopropylamide (LDA) was prepared as described in Org.Synth.1986, v.64, pg.68. 2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) and [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)dimethylzirconium (complex 14) were prepared as described in U.S. patent application US2020 / 0255553. [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-phenol)dimethylzirconium (complex 8) was prepared as described in co-pending U.S. Provisional Application No. 63 / 338164.

[0117] Use 1-10% solution in deuterated solvent and record with at least 400 MHz spectrometer (e.g. Bruker Avance NEO 400 MHz spectrometer) 1 H and 13 C{ 1 H} NMR spectrum. 1 H and13 The chemical shifts of C are referenced to the residual deuterated solvent 1 H or 13 C resonance.

[0118] All reactions were carried out in a nitrogen-filled dry box unless otherwise specified. The room temperature was 25°C unless otherwise specified.

[0119] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)]zirconium dichloride (complex 1) To a pre-cooled stirred suspension of tetrakis(dimethylamino)zirconium(IV) (0.937 g, 3.50 mmol, 1 eq) in 1,2-dimethoxyethane (10 mL) was added zirconium(IV) chloride (0.812 g, 3.48 mmol) and additional 1,2-dimethoxyethane (1 mL). The reaction was stirred at room temperature for 19.5 hours. Stirring was stopped and the reaction contents were allowed to settle. The supernatant was collected and concentrated under a stream of nitrogen. The resulting solid was washed with pentane (10 mL). The pentane washed solid was concentrated under high vacuum to give bis(dimethylamido)zirconium dichloride, 1,2-dimethoxyethane adduct (1.94 g, 81% yield) as a white solid. 1 H NMR (400MHz, CD 2 Cl 2 ):δ3.94(s,4H),3.63(s,6H),3.11(s,12H). To a stirred solution of bis(dimethylamido)zirconium dichloride, 1,2-dimethoxyethane adduct (0.178 g, 0.524 mmol, 1 equiv) in toluene (20 mL) was slowly added a solution of 2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (0.417 g, 0.524 mmol) in toluene (20 mL). The reaction was stirred and heated to 70°C for 15 hours. While cooling, the reaction was concentrated under a stream of nitrogen. The residue was then concentrated at 70°C under high vacuum to give the product as a white solid (0.441 g, 88% yield). 1 H NMR (400MHz, CD 2 Cl 2): δ7.86(t,1H,J=7.8Hz), 7.65(td,2H,J=7.6,1.4Hz), 7.46(td,2H,J=7.6,1.3Hz), 7.35(dd,2H,J=7.8,1.2Hz), 7.27(d,2H,J=7.8Hz),7.25-7.20(m,4H),6.91(d,2H,J=2.5Hz),2.18-2.08(m,6H),2.09-1.97(m,12H),1.86(br d,6H,J=12.0Hz), 1.71(br d,6H,J=12.0Hz), 1.25(s,18H).

[0120] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)](2-butene-1,4-diyl)zirconium (complex 2) To a stirred suspension of magnesium-butadiene, tetrahydrofuran adduct (0.048 g, 0.22 mmol, 5.0 equiv) in diethyl ether (5 mL) was added a solution of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol)]zirconium dichloride (complex 1) (0.041 g, 0.043 mmol) in diethyl ether (5 mL). The reaction was stirred at 35 °C for 24 h. 5-nitropropene (2mL) was added to 4-nitropropene (2mL) and the mixture was filtered. The mixture was stirred for 2 hours at 40 ℃ for 3 hours. The reaction was filtered on diatomite. The filtrate was concentrated under a nitrogen stream and then concentrated under high vacuum to obtain an orange solid (0.023g, 57% yield). The solid was mixed with pentane (2mL) and the mixture was filtered. Under a nitrogen stream, the filtrate was then concentrated under high vacuum. The residue was mixed with hexane (2mL) and heated to reflux until the solid residue was completely dissolved. The solution was then slowly cooled to room temperature to produce small yellow crystals for structural confirmation by X-ray diffraction. 1 HNMR (400MHz, C 6 D 6 ): δ7.39(d,2H,J=2.6Hz),7.26-7.17(m,5H),7.14-7.08(m,3H),7.03(d,2H,J= 2.6Hz),6.58(s,2H),5.65-5.51(brs,2H),2.67-1.54(brm,34H),1.30(s,18H).

[0121] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)](2-methyl-2-butene-1,4-diyl)zirconium (complex 3) To a stirred suspension of activated magnesium powder (0.007 g, 0.3 mmol, 5.6 equiv) in diethyl ether (2 mL) was added a solution of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol)]zirconium dichloride (complex 1) (0.049 g, 0.051 mmol) in tetrahydrofuran (5 mL). Then, isoprene (0.05 mL, 0.5 mmol, 9.8 equiv) was added. The reaction was stirred at room temperature for 24 hours. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with hexanes (10 mL) and filtered on celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give an orange solid (0.036 g, 73% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ7.42(d,1H,J=2.7Hz),7.38-7.33(m,2H),7.27-7.17(m,4H),7.14-7.06(m,3H),7.05(d, 1H,J=2.6Hz),7.00(d,1H,J=2.5Hz),6.64-6.51(m,3H),5.50(t,1H,J=11.7Hz),2.93(t,1H, J=10.4Hz),2.5(d,1H,J=8.8Hz),2.29-2.15(m,6H),2.15-2.08(m,9H),2.05-1.96(m,3H),1 .91-1.73(m,15H),1.33(s,9H),1.27(s,9H),1.09(d,1H,J=9.9Hz),1.01(t,1H,J=11.3Hz).

[0122] Synthesis of 2,2-Dimethyldecanoic acid ethyl ester (A) At -78 ° C, ethyl isobutyrate (11.8 mL, 87.9 mmol) was added dropwise to a stirred solution of lithium diisopropylamide (9.93 g, 92.7 mmol, 1.06 equiv) in tetrahydrofuran (90 mL) within 5 minutes. The reactant was stirred at -78 ° C for 100 minutes. Then, iodooctane (16.3 mL, 90.5 mmol, 1.03 equiv) was added. The reactant was slowly warmed to room temperature and stirred overnight. The reactant was transferred to a fume hood and quenched with water (10 mL). Then, additional water (100 mL) and diethyl ether (100 mL) were added to the reactant. The contents were poured into a separatory funnel, and the organic layer was extracted. The aqueous phase was further extracted with diethyl ether (2×50 mL). The combined organic extracts were washed with brine, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated in vacuo to give a crude product. The crude material was purified by silica gel column chromatography (100% isohexane then 5% diethyl ether in isohexane) to give the product as a clear colourless oil (17.8 g, 88% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ3.99 (q, 2H, J = 7.1Hz), 1.59-1.52 (m, 2H), 1.36-1.22 (m, 12H), 1.21 (s, 6H), 0.97 (t, 3H, J = 7.1Hz), 0.90 (t, 3H, J = 6.9Hz).

[0123] Synthesis of 2,2-dimethyldecanol (B) To a precooled, stirred solution of ethyl 2,2-dimethyldecanoate (A) (17.8 g, 77.9 mmol) in dichloromethane (450 mL) was added diisobutylaluminum hydride (29.0 mL, 163 mmol, 2.09 equiv). The reaction was stirred at room temperature for 18.5 hours. The reaction was transferred to a fume hood, quenched with wet methanol (100 mL), and diluted with brine (100 mL). The resulting mixture was filtered through a plastic sintered funnel and further extracted from the filtered solid with diethyl ether (50 mL). Additional diethyl ether (100 mL) was added to the filtrate. The filtrate was poured into a separatory funnel and the organic layer was collected. The aqueous phase was further extracted with diethyl ether (2×100 mL). The combined organic extracts were dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated in vacuo. The gained crude product is filtered on the thick pad of silica (15-20cm is thick) that is filled with pentane, and the first fraction is extracted with pentane (300mL).In a separate flask, the remaining material on the 20% diethyl ether (500mL) extraction silica gel in pentane is used.Concentrate the second fraction in a vacuum and obtain a little product (11.0g).The first fraction contains iodooctane pollutant (1:0.14 product: iodooctane), and is therefore further purified via silica gel column chromatography.The pure fraction of this post is merged with the pure second fraction filtered from silica, and product is obtained, which is a clear colorless oil (12.88g, 88% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ3.10 (d, 2H, J = 5.7Hz), 1.38-1.15 (m, 14H), 0.95-0.89 (m, 3H), 0.82 (s, 6H), 0.65 (t, 1H, J = 5.7Hz).

[0124] Synthesis of 2,2-Dimethyldecyl Methanesulfonate (C) Methanesulfonyl chloride (2.2 mL, 28 mmol, 1.1 equiv) was added to a stirred solution of 2,2-dimethyldecanol (B) (4.71 g, 25.3 mmol) and triethylamine (5.3 mL, 38 mmol, 1.5 equiv) in dichloromethane (150 mL) over the course of about 30 seconds. The reactant (light orange solution) was stirred at room temperature for 19 hours. The reactant was transferred to a fume hood and poured into ice water in a separatory funnel. The mixture was shaken, and the organic layer was collected. The aqueous layer was further extracted with dichloromethane (100 mL). The combined dichloromethane extracts were washed with aqueous hydrochloric acid (50 mL, 1 M), then with saturated aqueous sodium bicarbonate (50 mL), and then with brine. The organic extract was dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo to give the product as an orange-brown oil (5.32 g, 79% yield). 1H NMR (400 MHz, C 6 D 6 ): δ3.65(s,2H),2.36-2.21(m,3H),1.42-1.00(m,14H),0.95-0.86(m,3H),0.74(s,6H).

[0125] Synthesis of 1-Bromo-2,2-Dimethyldecane (D) A mixture of methanesulfonic acid 2,2-dimethyldecyl ester (C) (1.00 g, 3.80 mmol) and anhydrous sodium bromide (1.17 g, 11.4 mmol, 3 equivalents) was stirred under high vacuum for 1 hour. Then, 1-methyl-2-pyrrolidone (8 mL) was added to the mixture. The resulting solution was stirred and heated to 140 ° C for 2 hours. The reactants were cooled to room temperature. The reactants were then transferred to a fume hood and distributed between water (100 mL) and pentane (50 mL). The water layer was drained and the pentane extracts were washed with sodium thiosulfate aqueous solution (50 mL). The pentane extracts were collected, dried over anhydrous potassium carbonate and filtered. The filtrate was concentrated in vacuo to give the product as an orange oil (0.728 g, 76% yield). 1 HNMR (400MHz, C 6 D 6 ): δ2.98(s,2H),1.38-1.14(m,12H),1.13-1.00(m,2H),0.93(t,3H,J=6.9Hz),0.82(s,6H).

[0126] Synthesis of 2,2-Dimethyldecylmagnesium bromide (E) To a gray suspension of magnesium powder (0.390 g, 16.0 mmol, 2 eq.) in diethyl ether (20 mL) was added iodine (0.102 g, 0.05 eq.). The reaction was stirred until the brown suspension returned to a gray suspension. Then, 1-bromo-2,2-dimethyldecane (D) (2.00 g, 8.02 mmol) was added. The reaction was stirred at room temperature for 5 hours. The resulting suspension was filtered on diatomaceous earth. The filtrate was titrated to show a concentration of 0.13 M. 1 H NMR also revealed the formation of 9,9,12,12-tetramethyleicosane (see procedure below). The solution was used as is without further characterization.

[0127] Synthesis of 9,9,12,12-Tetramethyleicosane(F) To a stirred suspension of magnesium powder (0.360 g, 14.8 mmol, 19.1 equiv) in diethyl ether (50 mL) was quickly added a solution of 1-bromo-2,2-dimethyldecane (D) (0.193 g, 0.774 mmol) in diethyl ether (10 mL). The reaction was stirred overnight at room temperature. The reaction was filtered on celite. A sample of the filtrate was titrated with iodine in tetrahydrofuran / lithium chloride, and no color disappeared, confirming the absence of activated Grignard material. 1 H NMR (400 MHz, C 6 D 6 ): δ1.37-1.21(m,16H),0.96-0.87(m,9H).

[0128] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)]methyl-(2,2-dimethyldecyl)zirconium (complex 4) To a stirred solution of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)]zirconium dichloride (complex 1) (0.070 g, 0.073 mmol) in diethyl ether was added methylmagnesium bromide (0.02 mL, 3.0 M in diethyl ether, 0.07 mmol, 0.8 eq). The reaction was stirred and heated at reflux for 2 h. Then, 2,2-dimethyldecylmagnesium bromide (E) in diethyl ether (0.56 mL, 0.13 M in diethyl ether, 0.073 mmol, 1 eq) and toluene were added. (5mL). The reaction was stirred and heated to 90°C for 66 hours. Then, additional methylmagnesium bromide was added and the reaction was heated to 105°C for 1.5 hours. The reaction was concentrated under a nitrogen stream. The resulting residue was extracted with pentane (5mL) and filtered on diatomaceous earth. The filtrate was then concentrated under a nitrogen stream under high vacuum. The resulting residue was dissolved in pentane (2mL) and cooled to -35°C. The resulting mixture was filtered on diatomaceous earth. The filtrate was concentrated under a nitrogen stream and then concentrated under high vacuum to obtain a product containing 9,9,12,12-tetramethyleicosane (1.42 equivalents) as an impurity. 1 H NMR (400 MHz, C 6 D 6): δ7.59(d,1H,J=2.6Hz),7.55(d,1H,J=2.7Hz),7.43(dd,1H,J=7.7,1.1Hz),7.31(td,1H,J=7.6,1.3Hz),7.21 (dd,2H,J=7.7,1.4Hz),7.12-6.99(m,5H),6.86(dd,1H,J=7.5,1.6Hz),6.46-6.40(m,2H),6.29(dd,1H,J=6.4,2 .5Hz),2.70-2.61(m,3H),2.58-2.52(m,3H),2.51-2.45(m,3H),2.39-2.32(m,3H),2.29-2.22(m,6H),2.12-2. 03(m,6H),1.94-1.82(m,6H),1.73(d,1H,J=12.6Hz),1.40-0.84(m,41H),0.04(s,3H),-1.01(d,1H,J=12.7Hz).

[0129] Synthesis of 2-(adamantan-1-yl)-4-(tert-amyl)phenol (G) To a solution of 39.5 g (241 mmol) of tert-amylphenol in 240 mL of dichloromethane was added 36.7 g (241 mmol) of adamantane-1-ol. Next, 14.5 ml of sulfuric acid was added dropwise to the resulting solution over 30 minutes. The resulting suspension was stirred at room temperature for 30 minutes and then carefully poured into 300 ml of crushed ice containing 50 ml of saturated aqueous ammonia. The resulting mixture was extracted with dichloromethane (3×100 ml) and eluted with 5% NaHCO 3 The combined organic extracts were washed and concentrated in Na 2 SO 4 The residue was recrystallized from n-hexane to give 43.2 g (60%) of a white solid. 1 H NMR (CDCl 3 ,400MHz): δ7.21(d,J=2.3Hz,1H),7.03(dd,J=8.2,2.3Hz,1H),6.58(d,J=8.2Hz,1H),4.60(s,1H),2.13-2 .19(m,6H),2.12(br.s,3H),1.79-1.85(m,6H),1.64(q,J=7.5Hz,2H),1.29(s,6H),0.73(t,J=7.5Hz,3H). 13 C NMR (CDCl 3,100MHz): δ151.8,141.4,135.4,124.6,123.9,116.1,40.6,37.5,37.1,37.0,36.8,29.1,28.6,9.2.

[0130] Synthesis of 2-(adamantan-1-yl)-6-bromo-4-(tert-amyl)phenol (H) To a solution of 43.9 g (147 mmol) of 2-(adamantan-1-yl)-4-(tert-amyl)phenol (G) in 400 ml of chloroform was added dropwise 7.53 ml (147 mmol) of bromine in 200 ml of chloroform at room temperature for 30 minutes. The resulting mixture was diluted with 400 ml of water. The resulting mixture was extracted with dichloromethane (3×100 ml) and 5% NaHCO 3 The combined organic extracts were washed and concentrated in Na 2 SO 4 The mixture was dried over medium and then evaporated to dryness to yield 55.4 g (almost quantitative) of a white solid. 1 H NMR (CDCl 3 ,400MHz): δ7.28(d,J=2.2Hz,1H),7.14(d,J=2.2Hz,1H),5.67(s,1H),2.13-2.17(m,6H),2. 11(br.s,3H),1.78-1.84(m,6H),1.62(q,J=7.5Hz,2H),1.27(s,6H),0.72(t,J=7.5Hz,3H). 13 C NMR (CDCl 3 ,100MHz): δ147.9,142.1,136.9,126.7,124.2,112.2,40.3,37.63,37.60,37.0,36.9,29.0,28.5,9.2.

[0131] Synthesis of 1-(3-bromo-2-(methoxymethoxy)-5-(tert-pentyl)phenyl)adamantane (I) To a solution of 55.4 g (147 mmol) of 2-(adamantan-1-yl)-6-bromo-4-(tert-amyl)phenol (H) in 700 mL of THF was added portionwise 6.35 g (159 mmol, 60 wt % in mineral oil) of sodium hydride at room temperature. To the resulting suspension was added dropwise 12.1 mL (159 mmol) of methoxymethyl chloride for 10 minutes at room temperature. The resulting mixture was stirred overnight and then poured into 1000 mL of water. The resulting mixture was extracted with dichloromethane (3×300 mL) and hydrated with 5% NaHCO 3 The combined organic extracts were washed and concentrated in Na 2 SO 4 The mixture was dried over medium and then evaporated to dryness to yield 61.8 g (quantitative) of a white solid. 1 H NMR (CDCl 3 ,400MHz): δ7.32(d,J=2.4Hz,1H),7.17(d,J=2.4Hz,1H),5.22(s,2H),3.70(s,3H),2.04- 2.14(m,9H),1.72-1.80(m,6H),1.58(q,J=7.4Hz,2H),1.23(s,6H),0.68(t,J=7.4Hz,3H). 13 C NMR (CDCl 3 ,100MHz): δ150.7,146.0,144.3,129.1,124.4,117.5,99.5,57.8,41.4,38.0,37.8,36.9,36.8,29.1,28.3,9.1.

[0132] Synthesis of 2-(3-(adamantan-1-yl)-2-(methoxymethoxy)-5-(tert-pentyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (J) To a solution of 61.8 g (147 mmol) of 1-(3-bromo-2-(methoxymethoxy)-5-(tert-pentyl)phenyl)adamantane (I) in 1,000 ml of dry THF was added dropwise 70.1 ml (176 mmol) of 2.5 M 2-(methoxymethoxy)-5-(tert-pentyl)phenyl)adamantane (I) at -80°C. n BuLi for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 45.3 ml (220 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The obtained suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The resulting mixture was extracted with dichloromethane (3×300 ml) and the combined organic extracts were concentrated in Na 2 SO4 The mixture was dried on ice and then evaporated to dryness to yield 69.2 g (equivalent) of a colorless viscous oil. 1 H NMR (CDCl 3 ,400MHz): δ7.45(d,J=2.6Hz,1H),7.33(d,J=2.6Hz,1H),5.16(s,2H),3.58(s,3H),2.13-2.18(m,6H),2. 07(br.s,3H),1.73-1.83(m,6H),1.62(q,J=7.4Hz,2H),1.35(s,12H),1.27(s,6H),0.69(t,J=7.4Hz,3H). 13 C NMR (CDCl 3 ,100MHz): δ159.6,143.0,140.4,131.3,128.0,100.9,83.5,57.7,41.3,37.6,37.3,37.1,36.9,29.2,28.4,24.8,9.2.

[0133] Synthesis of 1-(2'-bromo-2-(methoxymethoxy)-5-(tert-pentyl)-[1,1'-biphenyl]-3-yl)adamantane (K) Then, 34.5 g (73.5 mmol) of 2-(3-(adamantan-1-yl)-2-(methoxymethoxy)-5-(tert-pentyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (J) was added to 200 ml of 1,4-dioxaborolane. 20.9 g (73.5 mmol) of 2-bromoiodobenzene, 60.1 g (184 mmol) of cesium carbonate and 100 ml of water were added to the solution in oxane. The obtained mixture was purged with argon for 10 minutes, and then 4.25 g (3.69 mmol) of Pd(PPh 3 ) 4 The mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 100 ml of water. The resulting mixture was extracted with dichloromethane (3 x 100 ml) and the combined organic extracts were concentrated in Na 2 SO 4 The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane = 10:1, volume). 19.7 g (54%) of a white solid were obtained. 1 H NMR (CDCl 3,400MHz): δ7.68(d,J=7.8Hz,1H),7.42(dd,J=7.6,1.5Hz,1H),7.35(t,J=7.1Hz,1H), 7.29(d,J=2.3Hz,1H),7.20(dt,J=7.9,1.5Hz,1H),7.02(d,J=2.3Hz,1H),4.54-4.55( m,1H),4.41-4.42(m,1H),3.21(s,3H),2.17-2.21(m,6H),2.11(br.s,3H),1.75-1.86 (m,6H),1.64(dq,J=7.5,3.0Hz,2H),1.31(s,3H),1.28(s,3H),0.73(t,J=7.5Hz,3H). 13 C NMR (CDCl 3 ,100MHz): δ151.2,143.5,142.0,141.6,133.8,132.9,132.4,128.5,127.4,12 7.0,124.5,124.3,98.8,57.1,41.4,37.8,37.5,37.0,29.2,28.43,28.38,9.2.

[0134] Synthesis of 4-(adamantan-1-yl)-6-isopropoxy-2-(tert-pentyl)-6H-dibenzo[c,e][1,2]oxaborinine (L) To a solution of 19.7 g (39.6 mmol) of 1-(2'-bromo-2-(methoxymethoxy)-5-(tert-pentyl)-[1,1'-biphenyl]-3-yl)adamantane (K) in 300 ml of dry THF was added dropwise 19.0 ml (47.5 mmol) of 2.5 M 2-(methoxymethoxy)-5-(tert-pentyl)-[1,1'-biphenyl]-3-yl)adamantane (K) at -80°C. n BuLi for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 12.1 ml (59.3 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The obtained suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The resulting mixture was extracted with dichloromethane (3×300 ml) and the combined organic extracts were concentrated in Na 2 SO 4 The mixture was dried over 400 °C and then evaporated to dryness. 120 ml of isopropanol were added to the residue and the resulting solution was refluxed for 2 hours. After cooling to room temperature, the precipitate formed was filtered off on a glass frit (G4), washed with 10 ml of cold isopropanol and dried in vacuo. 13.6 g (77%) of a white solid were obtained. 1H NMR (CDCl 3 ,400MHz): δ8.19(d,J=8.3Hz,1H),8.09(d,J=6.5Hz,1H),8.01(d,J=2.0Hz,1H) ,7.67(dt,J=7.6,1.5Hz,1H),7.43(t,J=7.3Hz,1H),7.37(d,J=2.2Hz,1H),5.2 7(sept,J=6.1Hz,1H),2.28-2.38(m,6H),2.18(br.s,3H),1.83-1.93(m,6H),1 .74(q,J=7.4Hz,2H),1.43(d,J=6.1Hz,6H),1.40(s,6H),0.76(t,J=7.4Hz,3H). 13 CNMR (CDCl 3 ,100MHz): δ148.2,142.2,141.0,138.8,133.1,126.5,124.6,122.1,118.8,65.7,40.8,37.9,37.4,37.2,37.0,29.2,28.7,24.7,9.3.

[0135] Synthesis of 2',2"'-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-phenol)(M) Then, 13.6 g (30.6 mmol) of 4-(adamantan-1-yl)-6-isopropoxy-2-(tert-pentyl)-6H-dibenzo[c,e][1,2]oxaborinane (L) was added to 80 ml of 1,4-dihydro- 3.55 g (15.0 mmol) of 2,6-dibromopyridine, 24.4 g (76.6 mmol) of cesium carbonate and 38 ml of water were added to the solution in oxane. The obtained mixture was purged with argon for 10 minutes, and then 1.77 g (1.55 mmol) of Pd(PPh 3 ) 4 The mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 50 ml of water. The resulting mixture was extracted with dichloromethane (3 x 50 ml) and the combined organic extracts were concentrated in Na 2 SO 4 The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate = 10:1, volume). 10.5 g (85%) of a mixture of two isomers were obtained as a glassy solid. 1 H NMR (CDCl3 , 400 MHz): δ8.00 (s, 2H in A), 7.39-7.59 (m, 9H in A and B), 7.06 (d, J = 2.1 Hz, 2H in A and B), 7.01 (d, J = 7.6 Hz, 2H in B), 6.99 (d, J = 7.8 Hz, 2H in A), 6.88 (d, J = 2.1 Hz, 2H in B), 6.55 (d, J = 2.1 Hz, 2H in A), 6.36 (s, 2H in B), 1.91-2.0 8 (m, 18H in A and B), 1.71 (br.s, 2H in 1A and B), 1.49 (dq, J = 7.6, 2.5 Hz, 4H in B), 1.26-1.45 (m, 4H in A), 1.18 (s, 6H in B), 1.17 (s, 6H in B), 1.06 (s, 6H in A), 1.03 (s, 6H in A), 0.57 (t, J = 7.5 Hz, 6H in B), 0.42 (t, J = 7.5 Hz, 6H in A). 13 C NMR (CDCl 3 , 100 MHz, signals belonging to the minor isomers are marked with *): δ 157.8, 149.9, 149.1*, 140.1*, 140.0*, 139.9, 139.5, 137.8, 137.2, 137.1*, 136.8, 136.1*, 131.8, 130.9, 130.5*, 129.6, 129.0*, 128.9, 128 .5*,127.9*,127.7,126.8,126.3*,123.6,122.5,122.1*,40.5,40.4*,37.3*,37.2,37.0,36.99*,36.92*,36.87,29.12,29.09*,28.49,28.44,28.41*,28.3,9.12*,9.07.

[0136] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-amyl)-[1,1'-biphenyl]-2-phenol)dimethylzirconium (complex 5) To a suspension of 707 mg (3.03 mmol) zirconium tetrachloride in 350 ml dry toluene at -30 °C was added 4.71 mL (13.5 mmol) 2.9 M MeMgBr in diethyl ether in one portion via syringe. To the resulting suspension were immediately added 2.50 g (3.03 mmol) of 2',2"'-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-phenol) (M) in one portion. The reaction mixture was stirred at room temperature for 3 hours and then evaporated to near dryness. The solid obtained was extracted with 2 x 100 mL of toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 10 mL of n-hexane; the precipitate obtained was filtered off (G3), washed twice with 10 ml of n-hexane and then dried in vacuo. This yielded 2.66 g (93%) of a beige solid. C 61 H 73 ZrNO 2 Anal. Calcd.: C, 77.66; H, 7.80; N, 1.48. Found: C 77.88; H, 8.01; N 1.26. 1 H NMR (C 6 D 6 ,400MHz): δ7.48(d,J=2.4Hz,2H),7.20(dd,J=7.2,1.1Hz,2H),6.95-7.13(m,8 H),6.54(dd,J=8.3,7.2Hz,1H),6.41(d,J=7.9Hz,2H),2.52-2.61(m,6H),2.38- 2.47(m,6H),2.19(br.s,6H),1.95-2.04(m,6H),1.80-1.89(m,6H),1.64(dq,J =7.5, 2.3Hz, 4H), 1.31 (s, 6H), 1.29 (s, 6H), 0.76 (t, J = 7.5Hz, 6H), 0.12 (s, 6H). 13 CNMR(C 6 D 6 ,100MHz): δ159.1,158.3,143.8,139.4,138.7,138.0,133.6,133.3,133.1,131.5,131.2 ,127.9,126.5,125.1,124.5,42.9,42.0,38.5,38.0,37.91,37.85,30.0,29.3,29.2,9.9.

[0137] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-amyl)-[1,1'-biphenyl]-2-phenol)]dimethylzirconium (complex 6) To a stirred solution of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-phenol)]dimethylzirconium (complex 5) (0.236 g, 0.250 mmol) in toluene (15 mL) was added ethylaluminum dichloride solution (0.55 mL, 1.01 M in hexanes, 0.56 mmol, 2.2 equiv). The reaction was stirred and heated to 60 °C for 3 hours. While cooling, the reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was stirred in hexanes (10 mL) and filtered on a plastic sintered funnel. The filtered solid was further washed with hexanes (5 mL). The solid was collected and concentrated under high vacuum to give the product as a light grey solid (0.226 g, 91% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ7.50-7.44(m,2H),7.26-7.13(m,6H),7.09-7.02(m,2H),7.01-6.94(m,2H),6.52-6.46(m,1H),6.42-6.33(m,2H),2.52-2. 40(m,6H),2.40-2.28(m,6H),2.23-2.03(m,12H),1.88-1.77(m,6H),1.67-1.55(m,4H),1.31-1.20(m,12H),0.79-0.70(m,6H).

[0138] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-phenol)](2-methylbut-2-ene-1,4-diyl)zirconium (complex 7) To a stirred suspension of activated magnesium powder (0.015 g, 0.62 mmol, 6.1 equiv) in diethyl ether (3 mL) was added a solution of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-ol)]zirconium dichloride (complex 6) (0.099 g, 0.10 mmol) in tetrahydrofuran (3 mL). Then, isoprene (0.08 mL, 0.8 mmol, 8 equiv) was added. The reaction was stirred at room temperature for 2.5 hours. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with hexanes (15 mL) and filtered over celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give the product as an orange solid with hexanes (0.42 equiv) (0.049 g, 48% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ7.38-7.32(m,2H),7.27(d,1H,J=2.6Hz),7.26-7.08(m,7H),6.95(d,1H,J=2.6Hz),6.91(d,1H,J=2.5Hz), 6.73-6.57(m,3H),5.49(t,1H,J=11.7Hz),2.93(t,1H,J=10.6Hz),2.61(d,1H,J=8.6Hz),2.30-2.15(m,6H),2 .15-2.06(m,9H),2.04-1.95(m,3H),1.92-1.74(m,15H),1.66-1.52(m,4H),1.30(s,3H),1.28(s,3H),1.26(s , 3H), 1.23 (s, 3H), 1.09 (d, 1H, J = 9.1Hz), 1.02 (t, 1H, J = 11.3Hz), 0.74 (t, 3H, J = 7.4Hz), 0.66 (t, 3H, J = 7.4Hz).

[0139] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-phenol)]zirconium dichloride (complex 9) To a stirred solution of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-phenolato)]dimethylzirconium (complex 8) (0.272 g, 0.264 mmol) in toluene (15 mL) was added ethylaluminum dichloride solution (0.58 mL, 1.01 M in hexanes, 0.59 mmol, 2.2 equiv). The reaction was stirred and heated to 60 °C for 5 hours. While cooling, the reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was stirred in hexanes (10 mL) and filtered on a plastic sintered funnel. The filtered solid was further washed with hexanes (5 mL). The solid was collected and concentrated under high vacuum to give the product as a light grey solid (0.262 g, 92% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ7.74-7.69(m,2H),7.28-7.12(m,8H),7.08-7.03(m,2H),6.49-6.43(m,1H),6.39-6.30(m,2H),2.53-2.41(m,6H) ,2.41-2.31(m,6H),2.21-2.12(m,6H),2.11-2.00(m,6H),1.86-1.73(m,6H),1.01-0.95(m,18H),0.30-0.21(m,12H).

[0140] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-phenol)](2-methylbut-2-ene-1,4-diyl)zirconium (complex 10) To a stirred suspension of activated magnesium powder (0.012 g, 0.49 mmol, 5.3 equiv) in diethyl ether (3 mL) was added a solution of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-phenol)]zirconium dichloride (complex 9) (0.100 g, 0.093 mmol) in tetrahydrofuran (3 mL). Then, Isoprene (0.07 mL, 0.7 mmol, 7.5 equiv) was added. The reaction was stirred at room temperature for 2 hours. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was washed in hexanes (10 mL), stirred and filtered over celite. The hexane washed solids were then extracted with toluene (5 mL). The toluene extracts were concentrated under a stream of nitrogen and then under high vacuum to give the product as a brown solid (0.068 g, 68% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ7.58(d,1H,J=1.8Hz),7.50(d,1H,J=1.8Hz),7.33(d,1H,J=6.7Hz),7.25-6.99(m,9H),6.70-6. 64(m,1H),6.63-6.56(m,2H),5.49(t,1H,J=11.7Hz),2.92(t,1H,J=10.7Hz),2.59(d,1H,J=9.1Hz) ,2.31-2.16(m,6H),2.15-2.04(m,9H),2.03-1.95(m,3H),1.91-1.69(m,15H),1.13(d,1H,J=8.9Hz ),1.09-1.03(m,1H),0.97(s,9H),0.91(s,9H),0.29(s,3H),0.27(s,3H),0.26(s,3H),0.23(s,3H).

[0141] Synthesis of 1-(2-(methoxymethoxy)-5-octylphenyl)adamantane(N) To a solution of 17.1 g (56.9 mmol) of 3-(adamantan-1-yl)-4-(methoxymethoxy)benzaldehyde in 100 mL of THF was added dropwise 240 ml (120 mmol) of 0.5 M n-heptylmagnesium chloride in THF at 0°C for 20 minutes. The resulting suspension was stirred at room temperature for 12 hours and then poured into 300 ml of water. The resulting mixture was extracted with dichloromethane (3 x 200 ml) and the combined organic extracts were concentrated in Na 2 SO 4The mixture was dried on 400 mL of 4% paraffin and then evaporated to dryness. The residue was transferred to a hydrogenation reactor and then dissolved in a mixture of 75 ml of methanol and 75 ml of THF. 4.0 g of Pd / C (5 wt % Pd) was added to the resulting solution and the reactor was pressurized to 270 psi with hydrogen. The reaction mixture was stirred overnight at room temperature under constant pressure and then the pressure was released. The reaction mixture was filtered through a pad of diatomaceous earth 503 and the resulting filtrate was evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane = 10: 1 → 4: 1, volume). 16.1 g (73%) of yellow oil was produced. 1 H NMR (CDCl 3 ,400MHz): δ7.09(d,J=2.1Hz,1H),7.06(d,J=8.3Hz,1H),6.99(dd,J=8.3,2.1Hz,1H),5.24(s,2H),3.56( s,3H),2.56-2.60(m,2H),2.16-2.19(m,6H),2.12(br.s,3H),1.81-1.85(m,6H),1.59-1.68(m,2H),1.25 -1.40(m,10H),0.93(t,J=7.1Hz,3H). 13 C NMR (CDCl3, 100MHz): δ154.5,138.2,135.7,126.8,126.3,114.3,94.4,56.0,40.7,37.1,36.9,35.6,31.9,31.8,29.5,29.3,29.1,22.7,14.1.

[0142] Synthesis of 2-(3-(adamantan-1-yl)-2-(methoxymethoxy)-5-octylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(O) To a solution of 16.0 g (41.6 mmol) of 1-(2-(methoxymethoxy)-5-octylphenyl)adamantane (N) in 250 ml of diethyl ether was added dropwise 25.0 ml (62.4 mmol) of 2.5 M 2-(methoxymethoxy)-5-octylphenyl)adamantane (N) at 0°C. n BuLi for 20 minutes. The reaction mixture was stirred at room temperature for 12 hours and then cooled to -80 °C, followed by the addition of 17.0 ml (83.2 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The obtained suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The resulting mixture was extracted with dichloromethane (3 × 200 ml) and the combined organic extracts were concentrated in Na2 SO 4 The mixture was dried on ice and then evaporated to dryness to yield 20.6 g (97%) of a colorless oil. 1 H NMR (CDCl 3 ,400MHz): δ7.36(d,J=2.3Hz,1H),7.20(d,J=2.3Hz,1H),5.17(s,2H),3.61(s,3H),2.53-2.57(m,2H),2.15-2.20(m, 6H), 2.09 (br.s, 3H), 1.74-1.84 (m, 6H), 1.55-1.64 (m, 2H), 1.37 (s, 12H), 1.24-1.38 (m, 10H), 0.90 (t, J = 7.1Hz, 3H). 13 CNMR (CDCl 3 ,100MHz): δ159.5,140.8,136.5,133.5,130.1,100.6,83.2,57.4,40.9,36.7,35.2,31.5,31.4,29.2,29.1,28.9,28.8,24.4,22.3,13.7.

[0143] Synthesis of 1-(2'-bromo-2-(methoxymethoxy)-5-octyl-[1,1'-biphenyl]-3-yl)adamantane(P) Then, 20.5 g (40.3 mmol) of 2-(3-(adamantan-1-yl)-2-(methoxymethoxy)-5-octylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (O) in 100 ml of 1,4-dioxaborolane was added. 13.7 g (48.3 mmol) of 2-bromoiodobenzene, 33.0 g (100 mmol) of cesium carbonate and 50 ml of water were added to the solution in oxane. The obtained mixture was purged with argon for 10 minutes, and then 2.31 g (2.00 mmol) of Pd(PPh 3 ) 4 The mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 100 ml of water. The resulting mixture was extracted with dichloromethane (3 x 100 ml) and the combined organic extracts were concentrated in Na 2 SO 4 The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane = 10:1, volume). 14.5 g (67%) of a colorless oil were obtained. 1 H NMR (CDCl 3,400MHz): δ7.69(d,J=8.0Hz,1H),7.40(d,J=7.6Hz,1H),7.36(t,J=7.6Hz,1H),7.2 1(dt,J=8.0,1.8Hz,1H),7.16(d,J=1.8Hz,1H),6.91(d,J=1.8Hz,1H),4.53-4.54(m, 1H),4.45-4.46(m,1H),3.22(s,3H),2.58-2.62(m,2H),2.19-2.21(m,6H),2.12(br. s,3H),1.78-1.84(m,6H),1.60-1.69(m,2H),1.25-1.37(m,10H),0.90-0.92(m,3H). 13 CNMR(CDCl3,100MHz): δ151.2,142.4,140.9,136.9,134.1,132.5,131.9,128.9,128.2,126.72,12 6.69,123.8,98.5,56.7,40.9,36.9,36.6,35.3,31.5,31.1,29.08,29.06,28.9,28.8,22.4,13.8.

[0144] Synthesis of 2-(3'-(adamantan-1-yl)-2'-(methoxymethoxy)-5'-octyl-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Q) To a solution of 14.5 g (26.9 mmol) of 1-(2'-bromo-2-(methoxymethoxy)-5-octyl-[1,1'-biphenyl]-3-yl)adamantane (P) in 200 ml of dry THF was added dropwise 11.4 ml (28.3 mmol) of 2.5 M 2-(methoxymethoxy)-5-octyl-[1,1'-biphenyl]-3-yl)-adamantane (P) at -80°C. n BuLi for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 8.50 ml (40.4 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The obtained suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The resulting mixture was extracted with dichloromethane (3×100 ml) and the combined organic extracts were concentrated in Na 2 SO 4 The mixture was dried over medium and then evaporated to dryness to yield 15.8 g (99%) of a colorless glassy solid. 1 H NMR (CDCl 3,400MHz): δ7.75(d,J=7.4Hz,1H),7.42(dt,J=7.4,1.4Hz,1H),7.36(d,J=7.6Hz,1H),7.32(dt,J=7.3,1.3Hz,1H),7. 06(d,J=2.1Hz,1H),6.83(d,J=2.1Hz,1H),4.49-4.50(m,1H),4.40-4.41(m,1H),3.25(s,3H),2.53-2.57(m,2H),2.19 -2.22(m,6H),2.11(br.s,3H),1.76-1.84(m,6H),1.58-1.67(m,2H),1.25-1.38(m,10H),1.19(s,6H),1.14(s,6H),0.89(t,J=6.8Hz,3H). 13 C NMR (CDCl 3 ,100MHz): δ151.6,146.0,141.8,136.7,136.6,134.3,130.3,129.8,129.6,126.04,125.99,98.7,83.4 ,67.9,57.2,41.5,37.3,37.1,35.7,31.9,31.5,29.51,29.46,29.3,29.2,25.6,25.0,24.3,22.7,14.1.

[0145] Synthesis of 2',2"'-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(n-octyl)-[1,1'-biphenyl]-2-phenol)(R) Then, 15.8 g (26.9 mmol) of 2-(3'-(adamantan-1-yl)-2'-(methoxymethoxy)-5'-octyl-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Q) was added to 80 ml of 1,4-dioxaborolane. 2.93 g (12.4 mmol) of 2,6-dibromopyridine, 26.0 g (80.7 mmol) of cesium carbonate and 30 ml of water were added to the solution in oxane. The obtained mixture was purged with argon for 10 minutes, and then 1.55 g (1.34 mmol) of Pd(PPh 3 ) 4 The mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The resulting mixture was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were concentrated in Na 2 SO4 The mixture was dried over 400 °C and then evaporated to dryness. 100 ml of THF, 100 ml of methanol and 5 ml of 12N HCl were then added to the resulting oil. The reaction mixture was stirred at 60 °C overnight and then poured into 300 ml of water. The resulting mixture was extracted with dichloromethane (3×350 ml) and 5% NaHCO 3 The combined organic extracts were washed and concentrated in Na 2 SO 4 The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate = 10:1, volume). 4.60 g (41%) of a mixture of two isomers was obtained as a colorless glassy solid. 1 H NMR (CDCl 3 , 400 MHz): δ7.75 (s, 2H in A), 7.34-7.54 (m, 9H), 7.04 (s, 2H in B), 6.99 (d, J = 7.8 Hz, 2H in B), 6.98 (d, J = 7.8 Hz, 2H in A), 6.90 (d, J = 1.8 Hz, 2H in B), 6.84 (d, J = 7.8 Hz, 2H in A), 6.25 (d, J = 1.8 Hz, 2H in A), 2.46-2.50 (m, 4H in B), 2.18-2.27 (m, 4H in A), 1.78-1.98 (m, 16H), 1.52-1.71 (m, 18H), 1.11-1.36 (m, 20H), 0.85-0.91 (m, 6H). 13 C NMR (CDCl 3 , 100 MHz, signals attributed to the minor isomers are marked with *): δ 157.94, 157.88*, 150.3, 149.7*, 139.6, 138.8*, 137.9, 137.6, 137.5*, 137.3*, 136.8*, 133.9*, 133.6, 132.3*, 131.6, 130.4, 130.2*, 129.7*, 129.3*, 128. 8,128.5,128.2*,127.8*,127.7,126.2*,125.9,122.3,122.1*,40.4,40.2*,37.0,36.9*,36.7,36.6*,35.4*,35.2,31.9,31.6*,29.51,29.49*,29.29*,29.28,29.12,29.02*,22.7,14.1.

[0146] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(octyl)-[1,1'-biphenyl]-2-phenol)]dimethylzirconium (complex 11) To a suspension of 551 mg (2.37 mmol) of zirconium tetrachloride in 300 ml of dry toluene at 30° C., 3.73 ml (10.7 mmol) of 2.9 M MeMgBr in diethyl ether were added in one portion via syringe. To the resulting suspension were immediately added in one portion 2.50 g (3.03 mmol) of 2′,2″′-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(n-octyl)-[1,1′-biphenyl]-2-phenol) (R). The reaction mixture was stirred at room temperature for 3 hours and then evaporated to near dryness. The solid obtained was extracted with 2×100 ml of toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 10 mL of n-hexane; the precipitate obtained was filtered off (G3), washed twice with 10 ml of n-hexane and then dried in vacuo. 2.22 g (91%) of a beige solid were obtained. C 67 H 85 ZrNO 2 Anal. Calcd.: C, 78.31; H, 8.34; N, 1.36. Found: C 78.51; H, 8.60; N 1.27. 1 H NMR (C 6 D 6 ,400MHz): δ7.30(d,J=2.1Hz,2H),7.23(dd,J=6.1,2.1,Hz,2H),7.08-7.15(m,4H),7.02(dd,J= 6.1,2.1Hz,2H),6.85(d,J=2.1Hz,2H),6.55(dd,J=8.4,7.1Hz,1H),6.44(d,J=8.1Hz,2H),2.61( t,J=7.6Hz,4H),2.49-2.58(m,6H),2.33-2.44(m,6H),2.18(br.s,6H),1.95-2.03(m,6H),1.79- 1.88(m,6H),1.68(quint,J=7.6Hz,4H),1.22-1.38(m,20H),0.90(t,J=7.1Hz,6H),0.11(s,6H). 13 C NMR (C 6 D 6,100MHz): δ159.5,158.3,143.6,139.5,138.6,133.7,133.2,132.5,131.5,131.2,128. 0,127.8,124.5,42.9,42.0,38.3,37.9,36.5,32.7,32.65,30.3,30.1,30.0,23.5,14.7.

[0147] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(octyl)-[1,1'-biphenyl]-2-phenol)]zirconium dichloride (complex 12) To a stirred solution of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(octyl)-[1,1'-biphenyl]-2-phenolato)]dimethylzirconium (complex 11) (0.246 g, 0.239 mmol) in toluene (15 mL) was added ethylaluminum dichloride solution (0.52 mL, 1.01 M in hexanes, 0.53 mmol, 2.2 equiv). The reaction was stirred and heated to 60 °C for 3 hours. While cooling, the reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was stirred in hexanes (10 mL) and filtered on a plastic sintered funnel. The filtered solid was further washed with hexanes (5 mL). The solid was collected and concentrated under high vacuum to give the product as a light grey solid (0.223 g, 87% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ7.30-7.18(m,8H),7.13-7.07(m,2H),6.88-6.79(m,2H),6.54-6.47(m,1H),6.46-6.32(m,2H),2.61-2.53(m,4H),2.48-2. 36(m,6H),2.36-2.24(m,6H),2.24-2.03(m,12H),1.87-1.74(m,6H),1.72-1.58(m,4H),1.47-1.07(m,20H),0.95-0.84(m,6H).

[0148] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(octyl)-[1,1'-biphenyl]-2-phenol)](2-methylbut-2-ene-1,4-diyl)zirconium (complex 13) To a stirred suspension of activated magnesium powder (0.015 g, 0.62 mmol, 6.7 equiv) in diethyl ether (3 mL) was added a solution of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(octyl)-[1,1'-biphenyl]-2-ol)]zirconium dichloride (0.098 g, 0.092 mmol) in tetrahydrofuran (3 mL). Then, isoprene (0.07 mL, 0.7 mmol, 7.6 equiv) was added. The reaction was stirred at room temperature for 2 hours. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in hexanes (15 mL) and then filtered over celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give the product as an orange foam (0.058 g, 59% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ7.38(dd,1H,J=7.3,1.5Hz),7.26(td,1H,J=7.4,1.5Hz),7.23-7.08(m,8H),6.85(d,1H,J=2.3 Hz),6.80(d,1H,J=2.2Hz),6.68-6.64(m,2H),6.62-6.58(m,1H),5.51(t,1H,J=11.5Hz),2.94(t, 1H,J=10.5Hz),2.66-2.50(m,4H),2.27-2.03(m,15H),2.03-1.93(m,3H),1.91-1.72(m,15H),1.7 2-1.56(m,5H),1.40-1.16(m,20H),1.12-1.07(m,1H),1.02(t,1H,J=11.3Hz),0.92-0.86(m,6H).

[0149] 2-(2-(1-adamantyl)-4-tert-butylphenoxy)tetrahydro-2H-pyran(S) To a solution of 2-(1-adamantyl)-4-(tert-butyl)phenol (38.0 g, 133 mmol) and 3,4-dihydro-2H-pyran (22.5 g, 267 mmol) in dichloromethane (300 mL) at -10 ° C, p-toluenesulfonic acid monohydrate (203 mg, 1.07 mmol) was added. The reaction mixture was slowly warmed to ambient temperature and stirred while monitoring the reaction by thin layer chromatography (TLC). After the starting material was completely converted (indicated by TLC, about 5 minutes at ambient temperature), sodium tert-butoxide (128 mg, 1.33 mmol) was added immediately. The resulting mixture was filtered through a silica gel plug and then washed with a 1:1 dichloromethane:hexane solution. The combined filtrate was concentrated to give the product as a white solid (46.30 g, 94%). 1 H NMR (400 MHz, CDCl 3 )δ7.26(s,1H),7.17-7.08(m,2H),5.46(s,1H),3.92(t,J=10.8Hz,1H),3.65(d,J=1 1.8Hz,1H),2.28-2.00(m,10H),1.99-1.84(m,2H),1.84-1.56(m,9H),1.30(s,9H).

[0150] (3-(1-adamantyl)-5-(tert-butyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)lithium etherate (T) To a solution of 2-(2-(1-adamantyl)-4-tert-butylphenoxy)tetrahydro-2H-pyran (S) (46.3 g, 126 mmol) in diethyl ether (100 mL) was added n-butyl lithium (1.6 M, 82.4 mL, 132 mmol) in hexanes at ambient temperature. The solution was stirred for 1 hour and then concentrated to dryness. The crude product was slurried in pentane (30 mL) and stirred for 30 minutes. The product was isolated by filtration as a white solid (40.0 g, 71%). 1 H NMR (400 MHz, THF-d 8 )δ7.73(s,1H),6.86(s,1H),6.59(br,1H),3.91(t,J=11.7Hz,1H),3.55-3.43(m,1H),2. 27(q,J=12.4Hz,7H), 2.04(d,J=18.1Hz,5H), 1.80(td,J=23.8,13.1Hz,9H), 1.32(s,9H).

[0151] 2-((3-(1-adamantyl)-2'-bromo-5-(tert-butyl)-[1,1'-biphenyl]-2-yl)oxy)tetrahydro-2H-pyran (U) (3-(1-adamantyl)-5-(tert-butyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)lithium etherate (T) (20.1 g, 44.8 mmol) was dissolved in THF (100 mL) and hexane (100 mL). 2-Bromochlorobenzene (9.44 g, 49.4 mmol) in hexane (50 mL) was added dropwise to the resulting solution at 60°C. The reaction was stirred at 60°C for 1 hour. After the reaction was cooled to room temperature, water (100 mL) was added and the resulting mixture was stirred for 10 minutes. After separation of the two phases, the aqueous phase was extracted with diethyl ether. In MgSO 4 The organic extracts combined were dried on 4% paraffin and then concentrated under vacuum. The product was then precipitated from a minimum of pentane as a white solid which was collected by filtration. The remaining additional product in the filtrate was purified by flash chromatography on silica gel (30% dichloromethane in hexane). The overall yield was 87% (20.5 g). 1 H NMR (400MHz, chloroform-d) δ7.68 (dd, J=30.1, 8.0Hz, 1H), 7.53-7.13 (m, 4H), 7.01 (dd, J=59.7, 2.3Hz, 1H), 4.31 (dd, J=8.1, 2.3Hz, 1H), 3.79 (dd, J=39.7, 12.0Hz,1H),2.99(dt,J=97.6,11.2Hz,1H),2.26(dt,J=22.7,12.8Hz,6H ),2.11(s,3H),1.86-1.50(m,8H),1.47-1.23(m,12H),1.20-1.01(m,1H).

[0152] 4-(1-Adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (V) To a solution of 2-((3-(1-adamantyl)-2'-bromo-5-(tert-butyl)-[1,1'-biphenyl]-2-yl)oxy)tetrahydro-2H-pyran (U) (23.5 g, 44.9 mmol) in THF (200 mL) was added n-butyllithium (1.6 M, 33.4 mL, 53.5 mmol) in hexanes at -78 °C over 20 minutes. The reaction mixture was stirred at -78 °C for 1 hour, then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (11.8 g, 63.1 mmol) was added. The resulting suspension was stirred at ambient temperature for 1 hour, then poured into 100 mL of water. The resulting mixture was extracted with hexanes (100 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2 x 50 mL). The combined organic extracts were concentrated in MgSO 4 The mixture was dried over 40 °C and then evaporated to dryness. To the resulting residue was added isopropanol (150 mL) and the resulting solution was refluxed for 16 hours. After the reaction was cooled to ambient temperature, the reactant was concentrated and cooled to -20 °C for 1 hour to give the product as a white solid (16.6 g, 80%), which was separated by filtration. 1 H NMR (400 MHz, CDCl 3 )δ8.17(d,J=8.2Hz,1H),8.09-8.02(m,2H),7.65(t,J=8.0Hz,1H),7.45-7.40(m,2H), 5.24(p,J=6.1Hz,1H),2.30(br,6H),2.16(br,3H),1.84(br,6H),1.43-1.39(m,15H).

[0153] 2,6-Dibromo-4-ethylpyridine(W) A solution of 2,6-dibromo-4-methylpyridine (3.00 g, 12.0 mmol) in THF (5 mL) and a solution of freshly prepared LDA (1.28 g, 12.0 mmol) in THF (3 mL) were cooled separately in a cooling bath at -55 °C for 10 minutes. The cooled LDA solution was then slowly added to the solution of 2,6-dibromo-4-methylpyridine, which was stirred at -55 °C for 1 hour. Iodomethane (1.70 g, 12.0 mmol) was then added to the reaction mixture, which was stirred at ambient temperature for 2 hours. The reactant was then quenched with water and diluted with hexane. After separation of the two phases, the aqueous phase was extracted with dichloromethane (2 × 10 mL). In MgSO 4The combined organic extracts were dried over Celite® and then concentrated to dryness. Purification by flash chromatography on silica gel (30% dichloromethane in hexanes) gave the product in 67% yield (2.11 g). 1 H NMR (400 MHz, CDCl 3 )δ7.29(s,1H),2.61(q,J=7.6Hz,2H),1.24(td,J=7.7,1.2Hz,3H.

[0154] 2',2"'-(4-ethylpyridine-2,6-diyl)bis(3-(1-adamantyl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)(X) 4-(1-adamantyl)-2-(tert-butyl)-6-isopropoxy-6H-dibenzo[c,e][1,2]oxaborinane (V) (2.10 g, 4.91 mmol) was added to 1,4-dihydro- 2,6-bromo-4-ethylpyridine (W) (0.65 g, 2.45 mmol), potassium carbonate (2.03 g, 14.7 mmol), Buchwald RuPhos Palladacycle Gen I precatalyst (Strem, CAS 1028206-60-1, 27.0 mg, 0.04 mmol) and water (6 mL) were added to a solution in 1% MgSO (12 mL). This mixture was stirred at 100 °C for 16 hours, then cooled to ambient temperature and diluted with water (30 mL). The resulting mixture was diluted with hexane (20 mL). After separation of the two phases, the aqueous phase was extracted with dichloromethane (2 x 50 mL). In MgSO 4 The combined organic extracts were dried on 4% celite and then concentrated to dryness. The product was purified by flash chromatography on silica gel (eluting impurities with 15% dichloromethane in hexane, then eluting the product with 25% dichloromethane + 2% acetone in hexane). The product was isolated (1.59 g, 79%) as a mixture of two isomers. 1 H NMR (400 MHz, CDCl 3 )δ8.29(s, 2H in A),7.54-7.32(m, 8H),7.07-7.01(m, 2H),6.88(s, 2H in B),6.77(s, 2H in B),6.72(s, 2H in A),6.63(s, 2H in B),6.50(s, 2H in A),2.33(q, J=7.5Hz, 2H),2.06-1.77(m, 18H),1.62(br, 12H),1.13(s, 18H in B),0.95(s, 18H in A),0.88-0.79(m, 3H).

[0155] Synthesis of [2',2"'-(4-ethylpyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)]methylzirconium (complex 15) To a pre-cooled stirred suspension of zirconium chloride (0.142 g, 0.609 mmol, 1 eq) in toluene (2 mL) was added methylmagnesium bromide (0.82 mL, 3.0 M in diethyl ether, 2.5 mmol, 4.0 eq). Then, a pre-cooled solution of 2',2"'-(4-ethylpyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (X) (0.502 g, 0.609 mmol) in toluene (3 mL) was added dropwise. The reaction was stirred at room temperature for 3 hours. The reaction was concentrated under a nitrogen stream and then under high vacuum. The residue was stirred in hexanes (20 mL) and heated to reflux. The mixture was filtered over celite while hot. The filtered solid was further extracted with refluxing hexanes (2×20 mL). The combined hexane filtrates were concentrated under a nitrogen stream and then under high vacuum to give the product as a brown-grey solid containing hexanes (0.18 equiv.) and toluene (0.96 equiv.) (0.424 g, 66% yield). 1 H NMR (C 6 D 6 ,400MHz): δ7.54(d,2H,J=2.6Hz),7.24-7.20(m,2H),7.14-7.00(m,8H),6.39(s,2H),2.65-2.54(m,6H),2.49-2.40(m,6H),2. 24-2.15(m,6H),2.06-1.96(m,6H),1.89-1.80(m,6H),1.68(q,2H,J=7.6Hz),1.33(s,18H),0.48(t,3H,J=7.6Hz),0.14(s,6H).

[0156] Synthesis of [2',2"'-(4-ethylpyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)]zirconium dichloride (complex 16) To a stirred solution of [2',2"'-(4-ethylpyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenolato)]zirconium dimethyl (complex 15) (0.180 g, 0.191 mmol) in toluene (5 mL) was added ethylaluminum dichloride (0.42 mL, 1.01 M in hexanes, 0.42 mmol, 2.2 equiv). The reaction was stirred and heated to 60 °C for 2 hours. The reaction was concentrated under a stream of nitrogen while cooling. The residue was stirred in pentane (10 mL) and filtered. The filtered solid was further washed with additional pentane (5 mL). The filtered solid was collected and concentrated under high vacuum to give the product as a grey solid (0.147 g, 78% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ7.51(d,2H,J=2.6Hz),7.27-7.17(m,7H),7.15-6.99(m,3H),6.39(s,2H),2.51-2.42(m,6H),2.38-2.29(m,6H), 2.23-2.15(m,6H),2.13-2.05(m,6H),1.88-1.78(m,6H),1.64(q,2H,J=7.5Hz),1.29(s,18H),0.44(t,3H,J=7.5Hz).

[0157] Synthesis of [2',2"'-(4-ethylpyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)](2-methylbut-2-ene-1,4-diyl)zirconium (complex 17) To a stirred suspension of activated magnesium powder (0.018 g, 0.74 mmol, 5 eq) in diethyl ether (7 mL) was added a solution of [2',2"'-(4-ethylpyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol)]zirconium dichloride (complex 16) (0.147 g, 0.149 mmol) in tetrahydrofuran (3 mL). Then, isoprene (0.10 mL, 1.0 mmol, 6.7 eq) was added. The reaction was stirred at room temperature for 2 hr. The reaction mixture was stirred for 3 hours at room temperature. Additional isoprene (0.10 mL, 1.0 mmol, 6.7 equiv) was then added. The reaction mixture was stirred for another 2 hours at room temperature. Additional isoprene (0.10 mL, 1.0 mmol, 6.7 equiv) was then added. The reaction mixture was stirred for 3 days at room temperature. The reaction mixture was concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in hexanes (15 mL) and then filtered over celite. The filtrate was concentrated under a stream of nitrogen and then under high vacuum to give the product as an orange solid (0.027 g, 18% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ7.46(d,2H,J=7.6Hz),7.40(s,1H),7.30(s,1H),7.31-7.25(m,2H),7.25-7.20(m,4H),7.07-7 .00(m,2H),6.61(s,1H),6.53(s,1H),5.57-5.47(m,1H),2.96(t,1H,J=10.4Hz),2.63(d,1H,J=8.6 Hz),2.30-2.22(m,3H),2.22-2.16(m,3H),2.16-2.09(m,9H),2.05-1.98(m,3H),1.91-1.76(m,17 H), 1.32 (s, 9H), 1.26 (s, 9H), 1.06 (d, 1H, J = 12.2Hz), 0.88 (t, 1H, J = 6.5Hz), 0.56 (t, 3H, J = 7.5Hz).

[0158] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)](2-(4-methylpent-3-enyl)-but-2-ene-1,4-diyl)zirconium (complex 18) To a stirred suspension of activated magnesium powder (7 mg, 0.29 mmol, 2.5 equiv) in diethyl ether (3 mL) was added a solution of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol)dichlorozirconium (complex 1) (0.111 g, 0.116 mmol) in tetrahydrofuran (10 mL). Then, myrcene (0.02 mL, The mixture was stirred for 4 days at room temperature under nitrogen gas flow, and then concentrated under high vacuum. The residue was extracted with hexane and then filtered on diatomite. The filtrate was placed in a refrigerator and kept for 1 week, and then solid precipitation was obtained. The mixture was filtered on diatomite, and the filtrate was collected and concentrated under nitrogen gas flow, and then concentrated under high vacuum to obtain the product, which was a brown glassy solid (0.087g, 73% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ7.42(d,1H,J=2.7Hz),7.39-7.32(m,2H),7.29-7.21(m,3H),7.19-7.16(m,1H),7.13-7.06(m,3H),7.05(d,1H,J =2.6Hz),7.01(d,1H,J=2.5Hz),6.63-6.50(m,3H),5.59(t,1H,J=11.6Hz),5.41-5.34(m,1H),2.94(t,1H,J=10.6Hz ),2.71(d,1H,J=9.1Hz),2.48-2.37(m,2H),2.29-2.22(m,3H),2.22-2.16(m,3H),2.15-2.08(m,9H),2.04-1.96(m, 3H),1.95-1.74(m,14H),1.61(d,3H,J=1.4Hz),1.53(d,3H,J=1.2Hz),1.33(s,9H),1.26(s,9H),1.10-0.98(m,2H).

[0159] Synthesis of 4-cyclohexylthiobenzaldehyde (Y) To a stirred suspension of potassium carbonate (3.90 g, 28.2 mmol, 1.01 equiv.) in dimethyl sulfoxide (12 mL) was added cyclohexanethiol (3.5 mL, 29 mmol, 1.0 equiv.). Then, 4-fluorobenzaldehyde (3.0 mL, 28 mmol) was added. The reactants were stirred and heated to 95 ° C for 4 hours. The reactants were cooled to room temperature. Then, the reactants were poured onto water (100 mL) and the reaction residue was washed into water with dichloromethane (75 mL). The resulting mixture was poured into a separatory funnel and the organic phase was extracted. The aqueous phase was further extracted with dichloromethane (2×75 mL). The combined organic extracts were washed with brine (100 mL), dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated in vacuo to give the product as an orange-yellow liquid containing residual dichloromethane (0.16 eq.) and dimethyl sulfoxide (0.02 eq.) (6.20 g, 94% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ9.62(s,1H),7.44-7.39(m,2H),7.11-7.05(m,2H),2.98(tt,1H,J=10.5,3.7 Hz),1.89-1.77(m,2H),1.57-1.46(m,2H),1.41-1.20(m,3H),1.13-0.94(m,3H).

[0160] Synthesis of 4-cyclohexylthiobenzyl alcohol (Z) Sodium borohydride (1.10 g, 29.0 mmol, 1.10 equivalents) was added in small portions to a stirred solution of 4-cyclohexylthiobenzaldehyde (Y) (6.20 g, 26.3 mmol) in ethanol (75 mL) cooled in an ice bath. The reactants were stirred at room temperature for 5 hours. The reactants were poured onto a mixture of pentane (100 mL) and hydrochloric acid (100 mL, 4 M, aqueous solution). The mixture was poured into a separatory funnel. The organic layer was collected and the aqueous phase was further extracted with additional pentane (2 × 50 mL). The combined pentane extracts were washed with brine (100 mL), dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated in vacuo to give a light yellow oil. The oil was purified by silica gel column chromatography to give the product as a clear colorless oil (3.94 g, 67% yield). 1 H NMR (400 MHz, C 6 D 6): δ7.41(d,2H,J=8.2Hz), 7.05(d,2H,J=8.5Hz), 4.24(d,2H,J=5.5Hz), 2.98(tt,1H,J=1 0.6,3.7Hz),2.00-1.89(m,2H),1.63-1.52(m,2H),1.44-1.29(m,3H),1.15-0.98(m,3H).

[0161] Synthesis of 4-cyclohexylthiobenzyl bromide (AA) Phosphorus tribromide (1.9 mL, 20 mmol, 1.1 equivalents) was added to a stirred solution of 4-cyclohexylthiobenzyl alcohol (Z) (3.94 g, 17.7 mmol) in diethyl ether cooled in an ice-water bath. The reaction was stirred and allowed to warm to room temperature for 4 hours. The reaction was then poured onto cold water (200 mL). Then, pentane (100 mL) was added to the water and the mixture was poured into a separatory funnel. The organic layer was collected and the aqueous phase was further extracted with additional pentane (100 mL). The combined pentane extracts were washed with water (100 mL), dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated in vacuo to obtain the product (3.73 g, 73% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ7.19(d,2H,J=8.3Hz), 6.91(d,2H,J=8.3Hz), 3.96(s,2H), 2.95(tt,1H,J=10.6, 3.7Hz),1.95-1.79(m,2H),1.63-1.46(m,2H),1.43-1.22(m,3H),1.15-0.96(m,3H).

[0162] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)]bis(trifluoromethanesulfonate)zirconium (complex 19) To a stirred suspension of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenolato)]zirconium dichloride (complex 1) (0.572 g, 0.598 mmol) in toluene (5 mL) heated to 110 °C was added a solution of silver(I) trifluoromethanesulfonate (0.394 g, 1.53 mmol, 2.56 equiv) in toluene (10 mL). The reaction was stirred and heated to 110 °C for 2 hours. The reaction was filtered over celite and the filtered solid was further extracted with diethyl ether. The combined filtrates were concentrated under a stream of nitrogen and then concentrated under high vacuum to give the product as an off-white solid containing toluene (2 equiv) (0.743 g, 90% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ7.56-7.49(m,4H),7.43(d,2H,J=7.7Hz),7.32(td,2H,J=7.6,1.3Hz),7.14-6.99(m,4H),6.41-6.36(m,1H) ,6.33-6.29(m,2H),2.30-2.22(m,12H),2.21-2.13(m,6H),2.02-1.93(m,6H),1.90-1.81(m,6H),1.21(s,18H).

[0163] Synthesis of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)]bis(4-cyclohexylthiobenzyl)zirconium (complex 20) To a stirred suspension of activated magnesium powder (0.086 g, 3.5 mmol, 2.1 equiv) in diethyl ether (15 mL) was added dropwise a solution of 4-cyclohexylthiobenzyl bromide (AA) (0.491 g, 1.72 mmol) in diethyl ether (5 mL). The reaction was stirred at room temperature for 4 hours. The reaction was filtered over celite on a glass fiber plug and the filtrate was titrated against iodine to give a concentration of 79.6 mM. Then, to a stirred solution of [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)]bis(trifluoromethanesulfonate)zirconium (complex 19) (0.200 g, 0.169 mmol) in toluene (10 mL) was added the prepared 4-cyclohexylthiobenzylmagnesium bromide solution (4.3 mL, 79.6 mM, 0.342 mmol, 2 eq). The reaction was stirred and heated to 70 °C for 20 h. Then, additional 4-cyclohexylthiobenzylmagnesium bromide (2.0 mL, 79 .6mM, 0.16mmol, 0.94 equivalent). The reaction was stirred and heated at 70°C for 2 hours. The reaction was then further heated to reflux for 4 hours. The reaction was filtered on diatomaceous earth and further extracted from the reaction with additional toluene (2mL). The combined toluene filtrate was concentrated under a nitrogen stream and then concentrated under high vacuum. The residue was mixed with hexane (15mL) and heated to gentle reflux. The mixture was removed from the heating, and while still hot, the supernatant was removed. The remaining solid was concentrated under high vacuum to obtain the product as an off-white solid (0.135g, 61% yield). 1 H NMR (400 MHz, C 6 D 6 ): δ7.61(d,2H,J=2.6Hz),7.42(dd,2H,J=7.5,1.5Hz),7.33(d,4H,J=8.2Hz),7.11(d,2H,J=2.5Hz),7. 04-6.92(m,6H),6.78(d,4H,J=8.1Hz),6.51-6.44(m,1H),6.37-6.31(m,2H),2.90(tt,2H,J=10.7,3.7H z),2.54-2.44(m,6H),2.41(d,2H,J=11.1Hz),2.39-2.31(m,6H),2.24-2.14(m,6H),2.06-1.92(m,10H ),1.88-1.78(m,6H),1.67-1.56(m,4H),1.45-1.18(m,24H),1.18-0.99(m,6H),0.12(d,2H,J=10.9Hz). Complex solubility

[0164] General procedure: A measured amount of the complex is added to a tared vial, followed by a stir bar. Dry isohexane is added in small portions and the resulting mixture is stirred after each addition of isohexane. If a clear solution has formed, the solubility is reported as a range, with the lower limit of the solubility calculated using the total solvent volume added to obtain a homogeneous solution and the upper limit of the solubility calculated using the total solvent volume measured before a homogeneous solution was obtained. If the mixture remains heterogeneous (visible solids or turbidity), the upper limit of the solubility is calculated using the total solvent volume added. If a deviation from this procedure is used, the method is reported as follows. The toluene content is the equivalent of toluene associated with the complex molecules.

[0165] The formula used to calculate the solubility is shown below. The co-crystallization solvent present in the complex is included in the mass and molecular weight of the complex (formula weight). The density of isohexane used in the calculation is 0.672 g / ml. The solubility data for complex 14 was obtained from co-pending U.S. patent application 63 / 338169. Complex 14 was co-crystallized with 1.4 equivalents of methylcyclohexane.

[0166] Solubility (mM) = [10 6 ]×[(grams of complex) / (molecular weight of complex, g / mol)] / [total volume of solvent, mL)].

[0167] Solubility (wt%) =

[100] x [(grams of complex) / [(grams of complex) + (total volume of solvent, mL) x (density of solvent, g / mL)]]. Table 1. Solubility of complexes in isohexane *Complex 8 recrystallized; RT = ambient room temperature; **Solubility reached at 30 °C

[0168] Complex 2 To a tared vial was added [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)](2-butene-1,4-diyl)zirconium (Complex 2) (0.0304 g, containing 0.64 equivalents of hexane, 30.6 μmol). A stirring bar and dry isohexane (10.0 mL) were added. The vial was sealed and the mixture was stirred at room temperature for 30 minutes, then the contents of the vial were heated to 40°C and the contents were stirred at this temperature for 30 minutes. The contents of the vial were then heated to 50°C. The contents of the vial were completely dissolved. The contents of the vial were then cooled to room temperature and stirred overnight, and by the next morning, the contents of the vial remained in solution.

[0169] Complex 3 To a tared vial was added [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol)](2-methyl-2-butene-1,4-diyl)zirconium (Complex 3) (0.0152 g, 15.9 μmol). A stir bar and dry isohexane (5.0 mL) were added. The vial was sealed and the mixture was stirred at room temperature overnight. The contents of the vial were then heated to 30 °C for 20 minutes. The contents of the vial were then heated in 5 °C increments for 20 minutes until all solids dissolved. All solids dissolved at 50 °C. The solution was allowed to cool to room temperature and stirred overnight. By the next morning, the contents of the vial remained in solution.

[0170] Complex 5 To a tared vial was added [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-phenol)]dimethylzirconium (Complex 5) (0.0167 g, 17.4 mol, containing 0.2 eq of toluene). A stirring bar and dry isohexane (5.0 mL) were added. The vial was sealed and the mixture was stirred at room temperature. Isohexane was added portionwise to the mixture. The complex did not completely dissolve when 8.0 mL of isohexane was added, but after a total of 10.0 mL of isohexane was added, the complex dissolved upon stirring.

[0171] Complex 5a Separately, a portion of complex 5 was extracted with n-hexane (15.0 mL) and filtered on diatomaceous earth. The filtrate was concentrated in vacuo to give a small amount of complex 5 without toluene but containing n-hexane (0.61 equiv). This sample (0.0148 g, 14.9 mol) was added to a tared vial and isohexane was added in 0.5 mL increments with stirring until a total of 2.0 mL of isohexane was added. This suspension was stirred for 2 hours. Isohexane was then added in 0.5 mL increments until 5.0 mL. Isohexane was then added in 0.5 mL increments until 8.0 mL. The resulting suspension was then heated to 30°C, at which point the complex was completely dissolved. The mixture was then allowed to cool to room temperature, at which point a solid precipitated.

[0172] Complex 7 To a tared vial was added [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-pentyl)-[1,1'-biphenyl]-2-phenol)](2-methylbut-2-ene-1,4-diyl)zirconium (0.0160 g, 15.7 μmol). Isohexane was added in 0.5 mL portions to a total of 1.0 mL. The resulting suspension was stirred for 3.5 hours. Then, isohexane was added in portions to a total of 5.0 mL, and the resulting suspension was stirred overnight. Isohexane was added in 0.5 mL portions to 6.0 mL, and the suspension was stirred for 50 minutes. Isohexane was added to a total of 6.5 mL, and the suspension was stirred for 25 minutes. Isohexane was added to a total of 7.0 mL, and the suspension was stirred for 15 minutes. Isohexane was added to a total of 7.5 mL, at which time all solids were dissolved.

[0173] Complex 8 [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-phenol)]dimethylzirconium (complex 8) was mixed with hexanes. The mixture was filtered through celite and glass wool. The filtrate was allowed to stand at room temperature overnight to promote precipitation. The resulting mixture was then filtered through celite and glass wool again. The filtrate was cooled to -35°C for 3 days, resulting in the precipitation of a white cluster. The cluster was isolated and concentrated under high vacuum for 5 hours to remove any residual toluene. The resulting solid was weighed and added tared vial (0.0129 g, 0.52 eq hexane, 12.0 μmol). A stir bar was added to the vial. While stirring, isohexane was added in 0.5 mL increments (stirring for 15 minutes between additions) until 2.5 mL was reached, at which point most of the material had dissolved. The reaction mixture was stirred overnight. By the next morning, the mixture had become white and cloudy. Therefore, additional isohexane was added in 0.5 mL increments until a total of 4.0 mL was reached, at which point the mixture remained cloudy white. The sealed vial was heated to 70° C., at which point the mixture remained cloudy white.

[0174] Complex 10 To a tared vial was added [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyldimethylsilyl)-[1,1'-biphenyl]-2-ol)](2-methylbut-2-ene-1,4-diyl)zirconium (Complex 10) (0.0160 g, containing 0.4 eq toluene, 15.0 mmol) and a stir bar. While stirring, isohexane was added in 0.5 ml increments (stirring at least 15 minutes between additions) until 5.0 mL was reached. The mixture (a cloudy tan suspension) was then heated to 30 °C and then the mixture was heated an additional 5 °C (the mixture was stirred for at least 15 minutes for each temperature change) until the mixture reached 50 °C, at which point the mixture remained a cloudy tan suspension.

[0175] Complex 11 To a tared vial was added [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(octyl)-[1,1'-biphenyl]-2-phenol)]dimethylzirconium (0.0156 g, 15.2 μmol, containing 0.1 eq toluene). Then, with stirring, isohexane was added to 5.0 mL and added in portions until 14.0 mL, at which point the mixture remained a suspension.

[0176] Complex 13 To a tared vial was added [2',2"'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(octyl)-[1,1'-biphenyl]-2-phenol)](2-methyl-2-butene-1,4-diyl)zirconium (complex 13) (0.0147 g, 13.8 μmol). Then, dry isohexane (0.1 mL) was added. Then, additional dry isohexane (0.1 mL) was added. The complex dissolved completely. Polymerization Example

[0177] Toluene (ExxonMobil Chemical-anhydrous, N 2 A solution of the procatalyst was prepared in isohexane (ExxonMobil Chemical-polymer grade and purified as described below) (98%) or isohexane (ExxonMobil Chemical-polymer grade). The procatalyst solution was typically 0.25 mmol / L.

[0178] Solvents, polymer-grade toluene and / or isohexane, were supplied by ExxonMobil Chemical Co. and purified by passing through a series of columns: two 500 cc OxyClear cartridges in series from Labclear (Oakland, California), followed by a 100 mL column filled with dry Molecular sieves (8-12 mesh; Aldrich Chemical Company) and two 500 cc columns in series, and Two 500 cc columns of molecular sieves (8-12 mesh; Aldrich Chemical Company) were connected in series.

[0179] Polymer grade propylene (C3) was used and further purified by passing it through a series of columns: a 2250cc Oxyclear cartridge from Labclear, followed by A 2250 cc column was filled with molecular sieves (8-12 mesh; Aldrich Chemical Company) and then Molecular sieves (8-12 mesh; Aldrich Chemical Company) were used in two 500 cc columns connected in series, followed by a 500 cc column filled with Selexsorb CD (BASF), and finally a 500 cc column filled with Selexsorb COS (BASF).

[0180] Activation of the procatalyst was by dimethylanilinium tetrakisperfluorophenylborate (Boulder Scientific or Albemarle Corp; Act ID = A) or (hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate (Boulder Scientific; Act ID = B) supplied as a 10 wt % solution in methylcyclohexane. The activator was typically used as a 0.25 mmol / L solution in toluene or isohexane.

[0181] Tri-n-octylaluminum (TnOAl or TNOA, neat, AkzoNobel) was also used as a scavenger before the activator and procatalyst were introduced into the reactor. TNOA was typically used as a 5 mmol / L solution in toluene or isohexane. Reactor Description and Preparation:

[0182] In an inert atmosphere (N 2 The polymerization was carried out in a dry box using an autoclave equipped with an external heater for temperature control, a glass insert (internal volume of the reactor 22.5 mL), a septum inlet, a regulated supply of nitrogen and propylene and equipped with a disposable PEEK mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110° C. or 115° C. for 5 hours and then at 25° C. for 5 hours. Propylene Polymerization (PP):

[0183] The reactor is prepared as described above, then heated to 40°C and then purged with propylene gas at atmospheric pressure. Toluene or isohexane, liquid propylene (1.0 mL) and scavenger (TNOA, 0.5 μmol) are added via a syringe. The reactor is then brought to process temperature (70°C or 100°C) while stirring at 800RPM. The activator solution, followed by the precatalyst solution, is injected into the reactor under process conditions via a syringe. The reactor temperature is monitored and typically maintained within + / -1°C. The polymerization is stopped by adding a mixture of about 50 psi compressed dry air gas to the autoclave for about 30 seconds. The polymerization is quenched based on a predetermined pressure loss (maximum quenching value) or up to 30 minutes. The reactor is cooled and vented. The polymer is isolated after the solvent is removed in a vacuum. The actual quenching time (s) is reported as the quenching time (s). The reported yield includes the total weight of the polymer and the residual catalyst. The catalyst activity is reported as grams of polymer / mmol transition metal compound / hour reaction time (g / mmol·hr). Propylene homopolymerization examples are reported in Table 2, and additional characterization is reported in Table 3. Polymer characterization

[0184] For analytical testing, polymer sample solutions were prepared by dissolving the polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity, obtained from Sigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%, obtained from Aldrich) at 165°C in a shaker oven for approximately 3 hours. The typical concentration of polymer in solution was 0.1-0.9 mg / mL and the BHT concentration was 1.25 mg BHT / mL TCB. The samples were cooled to 135°C for testing.

[0185] High temperature size exclusion chromatography was performed using an automated "Rapid GPC" system as described in U.S. Patent Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407 and 6,294,388, each of which is incorporated herein by reference. Molecular weight (weight average molecular weight (Mw), number average molecular weight (Mn)) and z-average molecular weight (Mz)) and molecular weight distribution (MWD = Mw / Mn), which is sometimes also referred to as the polydispersity (PDI) of the polymer, are measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector (ELSD) and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) between 5000 and 3,390,000). Alternatively, the samples are measured using a Symyx Technology GPC equipped with a dual wavelength infrared detector and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) between 580 and 3,039,000). Samples were run using three Polymer Laboratories: PLgel 10 μm Mixed-B 300×7.5 mm columns in series with an eluent flow rate of 2.0 mL / min (135°C sample temperature, 165°C oven / column) (250 μl of polymer in TCB solution was injected into the system). Column normal time difference correction was not used. A 10 μm HPLC-MS / MS column available from Symyx Technologies was used. Numerical analysis was performed using the Automation Studio software available from Freeslate or the Automation Studio software available from Freeslate. The molecular weights obtained are relative to linear polystyrene standards. The molecular weight data are reported in Table 2 under the headings Mn, Mw, Mz and PDI as defined above.

[0186] Differential Scanning Calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting points of the polymers. The samples were pre-annealed at 220°C for 15 minutes and then allowed to cool to room temperature overnight. The samples were then heated to 220°C at a rate of 100°C / min and then cooled at a rate of 50°C / min. Melting points were collected during the heating stage. The results are reported in Table 2 under the heading Tm (°C).

[0187] 13 C NMR spectroscopy was used to characterize some of the polypropylene polymer samples prepared in the experiments collected in Table 2. This data is collected in Table 3. Unless otherwise stated, the data used for13 C NMR spectra of polymer samples dissolved in d 2 -1,1,2,2-tetrachloroethane and used at 125°C 13 The samples were recorded on an NMR spectrometer with a C NMR frequency of 150 MHz. The polymer resonance peak reference mmmm = 21.8 ppm. The calculations involved in the characterization of polymers by NMR followed the works of FA Bovey, "Polymer Conformation and Configuration", Academic Press, New York 1969 and J. Randall, "Polymer Sequence Determination, Carbon-13 NMR Method", Academic Press, New York, 1977.

[0188] The stereo defects measured as "stereo defects / 10,000 monomer units" are calculated by multiplying the sum of the intensities of the mmrr, mmrm+rrmr and rmrm resonance peaks by 5000. The intensity used in the calculation is normalized to the total number of monomers in the sample. The method for measuring 2,1-regio defects / 10,000 monomers and 1,3-regio defects / 10,000 monomers follows standard methods. Additional references include Grassi, A. et al. Macromolecules, 1988, v.21, pp.617-622 and Busico et al. Macromolecules, 1994, v.27, pp.7538-7543. Average meso run length = 10000 / [(stereo defect / 10000C)+(2,1-region defect / 10000C)+(1,3-region defect / 10000C)].

[0189] The polymerization results are collected in Tables 2 and 3 below. "Ex#" represents the example number. Example numbers starting with "C" are comparative examples. "Cat ID" identifies the procatalyst used in the experiment. The corresponding number identifying the procatalyst (also called procatalyst, catalyst, complex or compound) is located in the synthetic experimental section. T (℃) is the polymerization temperature typically maintained within + / -1℃. "Yield" is the polymer yield and is not corrected for catalyst residues. "Quenching Time (s)" is the actual duration of the polymerization run in seconds. For propylene homopolymerization runs, the quenching value represents the maximum set pressure loss (conversion) of propylene (for PP runs) during polymerization. Activity is reported in grams of polymer / mmol catalyst / hour.

[0190] Standard polymerization conditions included 0.015 μmol catalyst complex, 1.1 equivalents activator, 0.5 μmol TNOA scavenger, 1.0 ml propylene, 4.1 ml total solvent, quench value at 8 psi pressure loss, or a maximum reaction time of 30 minutes. Activator A was N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator and activator B was (hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate. When activator A was used, both the procatalyst and activator solutions were in toluene. When activator B was used, both the procatalyst and activator solutions were in isohexane. A small amount of methylcyclohexane (MCH) was generated by activator B, which was provided by the manufacturer as a 10 wt % solution in methylcyclohexane.

[0191] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It is understood that ranges including combinations of any two values, such as any lower limit value combined with any upper limit value, any combination of any two lower limits, and / or any combination of any two upper limits are contemplated unless otherwise stated. Certain lower limits, upper limits, and ranges appear in one or more claims below. All numerical values ​​are "about" or "approximately" indicative values, and take into account experimental errors and deviations that would be expected by a person of ordinary skill in the art. Any value in the table may provide an endpoint defining a range of its corresponding measurement or property, with an additional + / - 10%.

[0192] All documents described herein, including any priority documents and / or test procedures are incorporated by reference in all jurisdictions not inconsistent with the present invention. It is apparent from the above overview and specific embodiments that, although the form of the present disclosure has been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Therefore, it is not desired that the present disclosure be limited in this manner.

[0193] While the present disclosure has been described in terms of a number of embodiments and examples, those skilled in the art, after reading this disclosure, will appreciate that other embodiments can be devised without departing from the scope and spirit of the present disclosure.

Claims

1. A catalyst compound represented by formula (I): in: M is a Group 3, 4 or 5 metal; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or any two or more adjacent R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 may be linked to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 17 , R 18 and R 19 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 17 and R 18 , R 18 and R 19 or R 17 and R 19 One or more pairs of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; L is a Lewis base; each X is independently a hydrocarbyl ligand or a substituted hydrocarbyl ligand, wherein at least one X is a non-aromatic hydrocarbyl ligand containing nine or more carbon atoms, or a substituted hydrocarbyl ligand containing at least five or more carbon atoms, or when n is 2, two X together can be a hydrocarbyl or substituted hydrocarbyl containing four or more carbon atoms and forming a 5-membered cyclic ring structure with M; n is 1, 2, or 3; m is 0, 1, or 2; n+m is not greater than 4; Any two L groups may be linked together to form a bidentate Lewis base; and The X group may be linked to the L group to form a monoanionic bidentate group.

2. The catalyst compound of claim 1, wherein n is 2, m is 0 or 1 (preferably 0), two Xs are represented by one of formulas Ia, Ib, Ic or Id, and R 20 , R 20 '、R 21 , R 21 '、R 22 , R 22 '、R 23 , R 23 ' are independently hydrogen or C1-C 20 A hydrocarbon radical, in which the dashed line represents the bond to the metal atom M, 3. The catalyst compound of claim 1, wherein n is 2, at least one X is C9-C 40 Non-aromatic hydrocarbon ligand, preferably C9-C 20 Non-aromatic hydrocarbon ligands, or more preferably C 10 -C 20 Non-aromatic hydrocarbon ligands, or more preferably C 12 -C 20 A non-aromatic hydrocarbon ligand, and the other X is C1-C 40 Hydrocarbyl ligand or substituted hydrocarbyl ligand, preferably C1-C 20 A hydrocarbyl ligand or a substituted hydrocarbyl ligand.

4. The catalyst compound of claim 1, wherein at least one X is C5-C 40 Substituted hydrocarbon ligand, preferably C5-C 30 Substituted hydrocarbon ligand, preferably C7-C 30 Substituted hydrocarbyl ligands, more preferably C 10 -C 30 Substituted hydrocarbyl ligands, or more preferably C 12 -C 30 Substituted hydrocarbyl ligands.

5. The catalyst compound of claim 4, wherein the substituted hydrocarbyl ligand comprises a ligand selected from the group consisting of SiR 30 3.GeR 30 3. OR 30 , SR 30 NR 30 2 heteroatom-containing group, wherein each R 30 Independently C1-C 10 Hydrocarbyl, preferably selected from C1-C 10 Alkyl, C7-C 10 Alkyl or C7-C 10 Aralkyl.

6. The catalyst compound of claim 1, wherein m is 0, n is 2, and the two Xs together are C4-C 40 A hydrocarbon group or a substituted hydrocarbon group.

7. The catalyst compound of claim 2, wherein m is 0, n is 2, and both X are represented by Formula Ic, R 20 , R 20 '、R 21 , R 22 , R 23 , R 23 ' are each independently hydrogen or C1-C 20 Hydrocarbon.

8. The catalyst compound of claim 2, wherein m is 0, n is 2, both X are represented by Formula Ic, R 20 , R 20 '、R 23 , R 23 'are independently hydrogen, each R 21 and R 22 are independently hydrogen or a hydrocarbon group, or R 21 and R 22 One of them may be hydrogen and the other may be hydrogen or a hydrocarbon group, preferably hydrogen or a C1-C 20 Hydrocarbyl, more preferably hydrogen or C1-C 10 The hydrocarbon group is more preferably hydrogen, methyl or 4-methylpent-3-enyl.

9. The catalyst compound of claim 2, wherein R 4 and R 5 is adamantyl, R 2 and R 7 It is C4-C 40 A hydrocarbon group, preferably a C4-C8 hydrocarbon group, more preferably a tert-butyl hydrocarbon group, m is 0, n is 2, both X are represented by formula Ic, preferably R 20 , R 20 '、R 23 , R 23 ' is hydrogen, and each R 21 and R 22 is hydrogen or a hydrocarbon group, preferably R 21 and R 22 One is hydrogen and the other is a hydrocarbon group.

10. The catalyst compound of any preceding claim, wherein R 21 and R 22 One of them may be hydrogen, and the other one may be C1-C 20 Hydrocarbyl, preferably C1-C 10 Hydrocarbon.

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

12. A catalyst system comprising an activator, preferably a non-aromatic hydrocarbon, and optionally a support material, and a catalyst compound according to any preceding claim.

13. A homogeneous solution comprising: an aliphatic hydrocarbon solvent; and At least one catalyst compound of any one of claims 1-11, wherein the concentration of the at least one catalyst compound is 0.20 wt% or greater (or 0.25 wt% or greater, or 0.30 wt% or greater, or 0.35 wt% or greater, or 0.40 wt% or greater, or 0.50 wt% or greater, or 1.0 wt% or greater, or 2.0 wt% or greater).

14. The homogeneous solution of claim 13, wherein the aliphatic hydrocarbon solvent is isohexane, cyclohexane, methylcyclohexane, pentane, isopentane, heptane, an isoparaffin solvent, a non-aromatic cyclic solvent, or a combination thereof.

15. A process for producing a propylene-based or ethylene-based polymer or copolymer, comprising: Propylene and / or ethylene and optional comonomers are polymerized by contacting propylene and / or ethylene and optional comonomers with the catalyst system of claim 12 in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to form a propylene-based or ethylene-based polymer or copolymer.

16. The process of claim 15, wherein the catalyst system and the activator are fed separately into the one or more reactors.

17. The process of claim 15, wherein the catalyst system and the activator are premixed prior to feeding into the one or more reactors.

Images