BR112017022405B1 - BRIDGED BI-AROMATIC PHENOL LIGAND, METHOD FOR PREPARING A BRIDGED BI-AROMATIC PHENOL LIGAND, TRANSITION METAL COMPOUND, CATALYST COMPOSITION, SUPPORTED CATALYST COMPOSITION, AND PROCESS FOR POLYMERIZING OLEFINS - Google Patents

Abstract

BRIDGED BI-AROMATIC LIGANDS AND OLEFIN POLYMERIZATION CATALYSTS PREPARED THEREOF. Novel bridged bi-aromatic phenol ligands and transition metal catalyst compounds derived therefrom are disclosed. Also disclosed are methods for making the transition metal ligands and compounds, and polymerization processes using the transition metal compounds for the production of olefin polymers.

Description

Field

[0001] The present disclosure is directed to bridged biaromatic ligands and transition metal compounds prepared therefrom. The disclosure is also directed to methods of preparing the ligands and transition metal compounds, and to methods of using the transition metal compounds as catalyst components in the polymerization of olefins.

Fundamentals

[0002] A major focus of the polyolefin industry in recent years has been the development of new catalysts that provide new and improved products. Bulky binder transition metal compounds, for example, are now widely used in catalyst compositions to produce polyolefin polymers, such as polyethylene polymers.

[0003] It is recognized in the art that small differences in the molecular structure of a catalyst compound can greatly impact catalyst performance and that this is generally governed by the structure of the ligand. Therefore, considerable effort has been expended on designing novel ligand structures that can lead to catalysts with improved performance. WO 03/09162 discloses bridged biaromatic ligands, methods for their preparation, and transition metal compounds derived therefrom.

[0004] It would be desirable to provide new bridged biaromatic ligands and methods for their synthesis. It would also be desirable to provide new transition metal compounds that can polymerize olefins with useful activity.

Summary

[0005] In one aspect, there is provided a bridged biaromatic phenol ligand of formula (I): wherein each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 is independently selected from the group consisting of hydride, halide, optionally substituted hydrocarbyl, optionally substituted hydrocarbyl containing heteroatom, alkoxy, aryloxy, silyl, boryl, dialkylamino, alkylthio, arylthio, and selene; optionally, two or more R groups may combine into ring structures, with such ring structures having from 3 to 100 non-hydrogen atoms in the ring; A is a bridging group having from one to 50 non-hydrogen atoms; Y and Y' are independently selected from O, S, NRa, and PRa, wherein Ra is optionally substituted hydrocarbyl; Ar is independently optionally substituted aryl or optionally substituted heteroaryl.

[0006] Each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 may be independently selected from the group consisting of hydride, halide, and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, boryl, dialkylamino, alkylthio, arylthio, and seleno.

[0007] Each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 may be independently selected from the group consisting of hydride, halide, and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxy, and aryloxy.

[0008] Each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 may be independently selected from the group consisting of hydride, fluoro, chloro, and optionally substituted alkyl, heteroalkyl, aryl, and heteroaryl.

[0009] In any of the preceding embodiments, the bridging group A may be selected from the group consisting of optionally substituted divalent hydrocarbyl and divalent hydrocarbyl-containing heteroatom.

[0010] In any of the previously disclosed embodiments, the bridging group A may be selected from the group consisting of optionally substituted divalent alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl, and silyl.

[0011] In any of the previously disclosed embodiments, the bridging group A can be represented by the general formula—(QR132-z")z—wherein each Q is carbon or silicon and each R can be the same or different from the others, such that each R13 is selected from the group consisting of hydride and optionally substituted hydrocarbyl and hydrocarbyl-containing heteroatom, and optionally two or more R13 groups can be joined in a ring structure with 3 to 50 atoms in the ring structure not counting hydrogen atoms; z' is an integer from 1 to 10; and z" is 0, 1, or 2.

[0012] In any of the previously disclosed embodiments, Ar may be, independently, optionally substituted phenyl, naphthyl, biphenyl, anthracenyl, or phenanthrenyl.

[0013] In any of the previously disclosed embodiments, Ar can be, independently, optionally substituted thiophene, pyridine, isoxazole, pyrazole, pyrrole, furan, or benzo-fused analogs of these rings.

[0014] In any of the previously disclosed embodiments, each occurrence of Ar is the same.

[0015] The bridging biaromatic phenol ligand of formula (I) may be of formula (II): in any of the previously disclosed modalities.

[0016] In another aspect, a method is provided for preparing a bridged biaromatic phenol ligand of formula (I) or formula (II), the method comprising at least one step of halogenating an aromatic ring and at least one step of aryl coupling.

[0017] The method may comprise at least one Negishi coupling step. The method may comprise at least one Suzuki coupling step. The method may comprise both at least one Negishi coupling step and at least one Suzuki coupling step.

[0018] The method may comprise the steps of: a) treating a bridged biaromatic phenol of formula (III) with a halogen source to produce a tetrahalo-bridged biaromatic phenol of formula (IV); and b) treating the tetrahalo-bridged biaromatic phenol of formula (IV) with an arylboron compound (ArBRb2 or ArBF3-M+) in the presence of a catalyst, to produce the bridged biaromatic phenol ligand of formula (I); wherein each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 is independently selected from the group consisting of hydride, halide, optionally substituted hydrocarbyl, optionally substituted hydrocarbyl containing heteroatom, alkoxy, aryloxy, silyl, boryl, dialkylamino, alkylthio, arylthio and selene; optionally two or more groups R1 to R12 may combine in ring structures with such ring structures having from 3 to 100 non-hydrogen atoms in the ring; A is a bridging group having from one to 50 non-hydrogen atoms; Y and Y' are independently selected from O, S, NRa, and PRa, wherein Ra is optionally substituted hydrocarbyl; Ar is independently optionally substituted aryl or optionally substituted heteroaryl; X is halo; Rb is independently selected from hydride, alkyl, hydroxy, and alkoxy, wherein when both Rb are alkoxy, they may optionally combine to form a ring structure of formula BO2Rb2, and wherein M+ is an alkali metal cation.

[0019] The method may comprise the steps of: a) treating a halophenol of formula (V) with a bridged diboron compound of formula (VI) in the presence of a catalyst to produce the bridged biaromatic phenol of formula (III); b) treating the bridged biaromatic phenol of formula (III) with a halogen source to produce a tetrahalo-bridged biaromatic phenol of formula (IV); and c) treating the tetrahalo-bridged biaromatic phenol of formula (IV) with an aryl-boron compound (ArBRb2 or ArBF3-M+) in the presence of a catalyst, to produce the bridged biaromatic phenol ligand of formula (I); in each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 is independently selected from the group consisting of hydride, halide, optionally substituted hydrocarbyl, optionally substituted hydrocarbyl containing heteroatom, alkoxy, aryloxy, silyl, boryl, dialkyl amino, alkylthio, arylthio, and selene; optionally, two or more R groups may combine into ring structures, with such ring structures having from 3 to 100 non-hydrogen atoms in the ring; A is a bridging group having from one to 50 non-hydrogen atoms; Y and Y' are independently selected from O, S, NRa, and PRa, wherein Ra is optionally substituted hydrocarbyl; Z and Z' are independently selected from BRb2 and BF3-M+, wherein Rb is independently selected from hydride, alkyl, hydroxy, and alkoxy, wherein when both Rb are alkoxy, they may optionally combine to form a ring structure of formula BO2Rb2, and wherein M+ is an alkali metal cation; Ar is independently optionally substituted aryl or optionally substituted heteroaryl; X is halo.

[0020] In any of the embodiments disclosed herein, each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 may be independently selected from the group consisting of hydride, halide, and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, boryl, dialkylamino, alkylthio, arylthio, and seleno.

[0021] In any of the embodiments disclosed herein, each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 may be independently selected from the group consisting of hydride, halide, and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, dialkylamino, alkylthio, and arylthio.

[0022] In any of the previously disclosed embodiments, the bridging group A may be selected from the group consisting of optionally substituted divalent hydrocarbyl and divalent hydrocarbyl-containing heteroatom.

[0023] In any of the previously disclosed embodiments, the bridging group A can be selected from the group consisting of optionally substituted divalent alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocycle, heterocarbocycle, aryl, heteroaryl, and silyl.

[0024] In any of the previously disclosed embodiments, the bridging group A can be represented by the general formula—(QR132-z")z—wherein each Q is carbon or silicon and each R13 can be the same or different from the others, such that each R13 is selected from the group consisting of hydride and optionally substituted hydrocarbyl and hydrocarbyl-containing heteroatom, and optionally two or more R13 groups can be joined in a ring structure with 3 to 50 atoms in the ring structure not counting hydrogen atoms; z' is an integer from 1 to 10; and z" is 0, 1, or 2.

[0025] A major advantage of the methods described herein is that the number of reaction steps to access the ligands is low. For example, the disclosed ligands can be prepared from a bromophenol in three or four reaction steps.

[0026] In any of the previously disclosed embodiments, the catalyst may comprise a nickel or palladium catalyst.

[0027] In any of the previously disclosed embodiments, the palladium catalyst may comprise a palladium phosphine catalyst.

[0028] In any of the previously disclosed embodiments, the catalyst may further comprise a base.

[0029] In any of the previously disclosed embodiments, the base may comprise an alkali metal carbonate, alkali metal phosphate, alkali metal hydroxide, alkali metal alkoxide, or an amine.

[0030] In any of the previously described embodiments, X may be bromine or chlorine. The halogen source may be bromine or chlorine.

[0031] In any of the previously disclosed embodiments, the arylboron compound can be an optionally substituted arylborane or an optionally substituted heteroarylborane.

[0032] In any of the previously disclosed embodiments, the arylboron compound may be an optionally substituted arylboronic acid or an optionally substituted heteroarylboronic acid.

[0033] In any of the embodiments previously disclosed herein, the aryl-boron compound can be an optionally substituted aryl boronic ester or cyclic aryl boronic ester or an optionally substituted heteroaryl boronic ester or cyclic heteroaryl boronic ester.

[0034] In any of the previously disclosed embodiments, the aryl-boron compound can be an optionally substituted aryl trifluoroborate or an optionally substituted heteroaryl trifluoroborate.

[0035] In another aspect there is provided a binder of formula (I) or formula (II) prepared by any of the methods previously disclosed.

[0036] In another aspect, there is provided a transition metal compound formed from any of the above-described ligands. The transition metal compound may comprise a titanium atom, a zirconium atom, or a hafnium atom.

[0037] In another aspect, there is provided a catalyst composition comprising one or more transition metal compounds as previously disclosed herein and one or more activators. The activator may comprise one or more alumoxanes. The activator may comprise methylalumoxane.

[0038] In another aspect, there is provided a supported catalyst composition comprising one or more transition metal compounds as previously disclosed herein, one or more activators, and one or more support materials. The activator may comprise one or more alumoxanes. The activator may comprise methylalumoxane. The support may be silica.

[0039] The catalyst composition or supported catalyst composition may comprise two or more transition metal compounds. The transition metal compounds may be selected from any of those previously disclosed, or at least one of the transition metal compounds may be different from those previously disclosed. For example, at least one of the transition metal compounds may be a metallocene.

[0040] In another aspect, a process is provided for polymerizing olefins, the process comprising: contacting the olefins with one or more catalyst compositions or supported catalyst compositions comprising at least one transition metal compound as disclosed hereinbefore in a reactor under polymerization conditions to produce an olefin polymer or copolymer.

Brief description of the drawings

[0041] Figures 1 and 2 depict the chemical structures of exemplary compounds according to the present disclosure.

[0042] Figures 3 to 5 depict exemplary reaction schemes in accordance with the present disclosure.

Detailed description

[0043] Before the present compounds, components, compositions and/or methods are disclosed and described, it should be understood that, unless otherwise indicated, this invention is not limited to compounds, components, compositions, reagents, reaction conditions, ligands, transition metal compounds or the like, as such may vary, unless otherwise specified. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0044] It should also be noted that, as used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless otherwise specified. Thus, for example, reference to "a halogen atom," such as in a moiety "substituted with a halogen atom," includes more than one halogen atom, such that the moiety may be substituted with two or more halogen atoms, reference to "a substituent" includes one or more substituents, reference to "a ligand" includes one or more ligands, and the like.

[0045] As used herein, all references to the Periodic Table of the Elements and their groups are to the NEW NOTATION published in HAWLEY'S CONDENSED CHEMICAL DICTIONARY, Thirteenth Edition, John Wiley & Sons, Inc. (1997) (reprinted with permission of IUPAC), unless reference is made to the earlier IUPAC form indicated with Roman numerals (also appearing therein), or unless otherwise indicated.

[0046] Disclosed herein are binders, catalyst compounds, catalyst compositions, and supported catalyst compositions for use in the polymerization of olefins that are advantageous to prepare and use. Also disclosed herein are methods for preparing the binders, catalyst compounds, catalyst compositions, and supported catalyst compositions, and polymerization processes using the catalyst compositions and supported catalyst compositions for producing olefin polymers.

General Definitions

[0047] As used herein, a "catalyst composition" includes one or more catalyst compounds used to polymerize olefins and at least one activator or, alternatively, at least one cocatalyst. The catalyst composition may include any suitable number of catalyst compounds in any combination as described herein, as well as any activator or cocatalyst in any combination as described herein.

[0048] As used herein, a "supported catalyst composition" includes one or more catalyst compounds used to polymerize olefins and at least one activator or, alternatively, at least one cocatalyst and at least one support. The supported catalyst composition may include any suitable number of catalyst compounds in any combination as described herein, as well as any activator or cocatalyst in any combination as described herein. A "catalyst composition" may also contain one or more additional components known in the art to reduce or eliminate reactor fouling, such as continuity additives.

[0049] As used herein, a "catalyst compound" may include any compound that, when activated, is capable of catalyzing the polymerization or oligomerization of olefins, wherein the catalyst compound comprises at least one atom from Group 3 to 12, and optionally at least one leaving group attached thereto.

[0050] The term "independently selected" is used herein to indicate that the R groups, e.g., R1, R2, R3, R4, and R5, may be identical or different (e.g., R1, R2, R3, R4, and R5 may all be substituted alkyls, or R1 and R2 may be a substituted alkyl and R3 may be an aryl, etc.). The use of the singular includes the use of the plural, and vice versa (e.g., a hexane solvent includes hexanes). A named R group will generally have the structure that is recognized in the art as corresponding to the R groups bearing that name. The terms "compound" and "complex" are generally used interchangeably in this specification, but those skilled in the art may recognize certain compounds as complexes and vice versa. For purposes of illustration, certain representative groups are defined herein. These definitions are intended to supplement and illustrate, not preclude, definitions known to those skilled in the art.

[0051] "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur and that the description includes instances in which the event or circumstance occurs and instances where it does not. For example, the phrase "optionally substituted hydrocarbyl" means that a hydrocarbyl moiety may or may not be substituted and that the description includes both unsubstituted hydrocarbyl and hydrocarbyl where there is substitution.

[0052] The term "alkyl" as used herein refers to a branched or unbranched saturated hydrocarbon group typically, though not necessarily, containing 1 to about 50 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl, and the like. Generally, though again not necessarily, the alkyl groups herein may contain from 1 to about 12 carbon atoms. The term "lower alkyl" intends an alkyl group of one to six carbon atoms, specifically one to four carbon atoms. "Substituted alkyl" refers to alkyl substituted with one or more substituent groups (e.g., benzyl or chloromethyl) and the terms "heteroatom-containing alkyl" and "heteroalkyl" refer to alkyl in which at least one carbon atom is replaced by a heteroatom (e.g., -CH2OCH3 is an example of a heteroalkyl).

[0053] The term "alkenyl" as used herein refers to a branched or unbranched hydrocarbon group typically, though not necessarily, containing 2 to about 50 carbon atoms and at least one double bond, such as ethenyl, n-propenyl, iso-propenyl, n-butenyl, iso-butenyl, octenyl, decenyl, and the like. Generally, though again not necessarily, the alkenyl groups herein contain from 2 to about 12 carbon atoms. The term "lower alkenyl" refers to an alkenyl group of two to six carbon atoms, specifically from two to four carbon atoms. "Substituted alkenyl" refers to alkenyl substituted with one or more substituent groups, and the terms "heteroatom-containing alkenyl" and "heteroalkenyl" refer to alkenyl in which at least one carbon atom is replaced by a heteroatom.

[0054] The term "alkynyl" as used herein refers to a branched or unbranched hydrocarbon group typically, though not necessarily, containing 2 to about 50 carbon atoms and at least one triple bond, such as ethynyl, n-propynyl, isopropynyl, n-butynyl, isobutynyl, octynyl, decynyl, and the like. Generally, though again not necessarily, alkynyl groups herein may contain from 2 to about 12 carbon atoms. The term "lower alkynyl" refers to an alkynyl group of two to six carbon atoms, specifically three or four carbon atoms. "Substituted alkynyl" refers to alkynyl substituted with one or more substituent groups, and the terms "heteroatom-containing alkynyl" and "heteroalkynyl" refer to alkynyl in which at least one carbon atom is replaced by a heteroatom.

[0055] The term "alkoxy" as used herein intends an alkyl group attached through a single terminal ether bond; that is, an "alkoxy" group may be represented as -O-alkyl where alkyl is as defined above. A "lower alkoxy" group refers to an alkoxy group having one to six, more specifically one to four, carbon atoms. The term "aryloxy" is used similarly with aryl as defined below. The term "hydroxy" refers to -OH.

[0056] Likewise, the term "alkylthio" as used herein intends an alkyl group attached through a single terminal thioether bond; that is, an "alkylthio" group may be represented as -S-alkyl where alkyl is as defined above. A "lower alkylthio" group refers to an alkylthio group having one to six, more specifically one to four, carbon atoms. The term "arylthio" is used similarly, with aryl as defined below. The term "thioxy" refers to -SH.

[0057] The term "allenyl" is used herein in the conventional sense to refer to a molecular segment having the structure -CH=C=CH2. An "allenyl" group may be unsubstituted or substituted with one or more non-hydrogen substituents.

[0058] The term "aryl," as used herein, and unless otherwise specified, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, covalently bonded, or attached to a common group such as a methylene or ethylene moiety. More specific aryl groups contain one aromatic ring or two or three fused or bonded aromatic rings, for example, phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, and the like. Aryl substituents can have 1 to about 200 carbon atoms, typically 1 to about 50 carbon atoms, and specifically 1 to about 20 carbon atoms. "Substituted aryl" refers to an aryl moiety substituted with one or more substituent groups (e.g., tolyl, mesityl, and perfluorophenyl), and the terms "heteroatom-containing aryl" and "heteroaryl" refer to aryl in which at least one carbon atom is replaced by a heteroatom (e.g., rings such as thiophene, pyridine, isoxazole, pyrazole, pyrrole, furan, etc., or benzo-fused analogs of these rings are included in the term "heteroaryl"). In some embodiments herein, the multi-ring moieties are substituents, and in such an embodiment, the multi-ring moiety may be attached to an appropriate atom. For example, "naphthyl" may be 1-naphthyl or 2-naphthyl; "anthracenyl" may be 1-anthracenyl, 2-anthracenyl, or 9-anthracenyl; and "phenanthrenyl" can be 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, or 9-phenanthrenyl.

[0059] The term "aralkyl" refers to an alkyl group having an aryl substituent, and the term "aralkylene" refers to an alkylene group having an aryl substituent; the term "alkaryl" refers to an aryl group having an alkyl substituent, and the term "alkarylene" refers to an arylene group having an alkyl substituent.

[0060] The terms "halo" and "halogen" are used in the conventional sense to refer to a chloro, bromo, fluoro, or iodo substituent. The terms "haloalkyl", "haloalkenyl," or "haloalkynyl" (or "halogenated alkyl", "halogenated alkenyl," or "halogenated alkynyl") refer to an alkyl, alkenyl, or alkynyl group, respectively, in which at least one of the hydrogen atoms in the group has been replaced by a halogen atom.

[0061] The term "heteroatom-containing" as in a "heteroatom-containing hydrocarbyl group" refers to a molecule or molecular fragment in which one or more carbon atoms are replaced by an atom other than carbon, for example, nitrogen, oxygen, sulfur, phosphorus, boron, or silicon. Similarly, the term "heteroalkyl" refers to a heteroatom-containing alkyl substituent, the term "heterocyclic" refers to a heteroatom-containing cyclic substituent, the term "heteroaryl" refers to a heteroatom-containing aryl substituent, and the like. When the term "heteroatom-containing" appears before a list of possible heteroatom-containing groups, the term is intended to apply to each member of that group. That is, the expression "alkyl, alkenyl and alkynyl containing a heteroatom" should be interpreted as "alkyl containing a heteroatom, alkenyl containing a heteroatom and alkynyl containing a heteroatom".

[0062] "Hydrocarbyl" refers to hydrocarbyl radicals containing 1 to about 50 carbon atoms, specifically 1 to about 24 carbon atoms, more specifically 1 to about 16 carbon atoms, including branched or unbranched saturated or unsaturated species such as alkyl groups, alkenyl groups, aryl groups, and the like. The term "lower hydrocarbyl" refers to a hydrocarbyl group of one to six carbon atoms, specifically one to four carbon atoms. "Substituted hydrocarbyl" refers to a hydrocarbyl substituted by one or more substituent groups, and the terms "heteroatom-containing hydrocarbyl" and "heterohydrocarbyl" refer to a hydrocarbyl in which at least one carbon atom is replaced by a heteroatom.

[0063] By "substituted" as in "substituted hydrocarbyl", "substituted aryl", "substituted alkyl", "substituted alkenyl" and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, hydrocarbylene, alkyl, alkenyl, aryl or other moiety, at least one hydrogen atom bonded to a carbon atom is replaced by one or more substituents that are functional groups such as hydroxyl, alkoxy, alkylthio, phosphino, amino, halo, silyl and the like. When the term "substituted" appears before a list of possible substituted groups, the term is intended to apply to each member of that group. That is, the expression "substituted alkyl, alkenyl and alkynyl" should be interpreted as "substituted alkyl, substituted alkenyl and substituted alkynyl". Similarly, "alkyl, alkenyl and optionally substituted alkynyl" should be interpreted as "optionally substituted alkyl, optionally substituted alkenyl and optionally substituted alkynyl".

[0064] By "divalent" as in "divalent hydrocarbyl", "divalent alkyl", "divalent aryl" and the like, it is meant that the hydrocarbyl, alkyl, aryl or other moiety is attached at two points to atoms, molecules or moieties with the two points of attachment being covalent bonds. The term "aromatic" is used in its usual sense, including unsaturation that is essentially delocalized across multiple bonds, such as around a ring."

[0065] As used herein, the term "silyl" refers to the radical -SiZ1Z2Z3, where each of Z1, Z2, and Z3 is independently selected from the group consisting of hydride and alkyl, alkenyl, alkynyl, heteroatom-containing alkyl, heteroatom-containing alkenyl, heteroatom-containing alkynyl, aryl, heteroaryl, alkoxy, aryloxy, amino, silyl, and combinations thereof.

[0066] As used herein, the term "boryl" refers to the group -BZ1Z2, where each of Z1 and Z2 is as defined above.

[0067] As used herein, the term "phosphino" refers to the group -PZ1Z2, where each of Z1 and Z2 is as defined above. As used herein, the term "phosphine" refers to the group PZ1Z2Z3, where each of Z1, Z2, and Z3 is as defined above. The term "amino" is used herein to refer to the group -NZ1Z2, where each of Z1 and Z2 is as defined above. The term "amine" is used herein to refer to the group NZ1Z2Z3, where each of Z1, Z2, and Z3 is as defined above.

[0068] The term "saturated" refers to the lack of double and triple bonds between atoms of a radical group such as ethyl, cyclohexyl, pyrrolidinyl, and the like. The term "unsaturated" refers to the presence of one or more double and triple bonds between atoms of a radical group such as vinyl, acetylide, oxazolinyl, cyclohexenyl, acetyl, and the like.

[0069] Other abbreviations used herein include: "iPr" to refer to isopropyl; "tBu" to refer to tertbutyl; "Me" to refer to methyl; "Et" to refer to ethyl; and "Ph" to refer to phenyl.

[0070] The bridged biaromatic ligands disclosed herein have the following general formula (I): wherein each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 is independently selected from the group consisting of hydride, halide, optionally substituted hydrocarbyl, optionally substituted hydrocarbyl containing heteroatom, alkoxy, aryloxy, silyl, boryl, dialkylamino, alkylthio, arylthio, and selene; optionally, two or more R groups may combine into ring structures, with such ring structures having from 3 to 100 non-hydrogen atoms in the ring; A is a bridging group having from one to 50 non-hydrogen atoms; Y and Y' are independently selected from O, S, NRa, and PRa, wherein Ra is optionally substituted hydrocarbyl; Ar is independently optionally substituted aryl or optionally substituted heteroaryl.

[0071] Binders may also have the following formula (II): wherein each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 is independently selected from the group consisting of hydride, halide, optionally substituted hydrocarbyl, optionally substituted hydrocarbyl containing heteroatom, alkoxy, aryloxy, silyl, boryl, dialkyl amino, alkylthio, arylthio, and selene; optionally, two or more R groups may combine into ring structures, with such ring structures having from 3 to 100 non-hydrogen atoms in the ring; A is a bridging group having from one to 50 non-hydrogen atoms; A is a bridging group having from one to 50 non-hydrogen atoms; Ar is independently optionally substituted aryl or optionally substituted heteroaryl.

[0072] Each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 may be hydride or optionally substituted alkylor aryl. R2 and R8 may be optionally substituted alkyl, and each of R1, R3, R4, R5, R6, R7, R9, R10, R11, and R12 may be hydride.

[0073] The bridging group A may be optionally substituted alkyl.

[0074] Ar may be optionally substituted phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, or thiophene, pyridine, isoxazole, pyrazole, pyrrole, furan, etc., or benzo-fused analogs. Optional substituents may be alkyl groups.

[0075] The ligands may have the following structure: wherein Ar may be optionally substituted phenylphenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, or thiophene, pyridine, isoxazole, pyrazole, pyrrole, furan, or benzo-fused analogs, and the bridging group A is a divalent alkyl.

[0076] R2 and R8 may be optionally substituted alkyl.

[0077] The ligands may have the following structure: where Rx, R2 and R8 are alkyl, and n = 0 to 6.

[0078] Specific ligands disclosed herein include:

Ligand synthesis

[0079] The ligands disclosed herein can be prepared by a variety of methods. In general, the ligands can be prepared by employing tetrabromination of a bridged phenyl phenol and aryl coupling. The aryl coupling can be Suzuki coupling and/or Negishi coupling.

[0080] A major advantage of the methods described herein is that the number of reaction steps to access the ligands is low. For example, the disclosed ligands can be prepared from a bromophenol in three or four reaction steps.

[0081] The bridged biaromatic ligand syntheses disclosed in WO 03/09162 suffer from an abundance of synthetic steps that add time and cost to a synthesis. The Suzuki couplings disclosed in WO 03/091162 were performed on protected phenols (THP, Bn, MOM, etc.), which add steps due to the necessary protections and deprotections. However, given the protic solvents used in these reactions, it was hypothesized that a free phenol would not interfere with the coupling. Indeed, a Suzuki coupling with bromocresol and phenylboronic acid was successful and in high yield. Other boronic acids were also coupled to bromocresol without difficulty as shown below:

[0082] The following diagrams illustrate general methods for preparing binders.

[0083] Schemes 1 and 2 illustrate the Suzuki coupling of a common brominated phenol to a bridged diboronic acid.

[0084] Schemes 3 and 4 illustrate the tetrahalogenation of a bridged biaromatic phenol.

[0085] Schemes 5 and 6 illustrate the Suzuki coupling of tetrahalogenated phenols with aryl boronic acid.

[0086] In any of the above methods, each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 may be independently selected from the group consisting of hydride and optionally substituted alkyl or aryl.

[0087] In any of the above methods, Y and Y' may be O.

[0088] In any of the above methods, A may be selected from the group consisting of optionally substituted divalent alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocycle, heterocarbocycle, aryl, heteroaryl, and silyl.

[0089] In any of the above methods, A may be optionally substituted alkyl.

[0090] In any of the foregoing methods, the palladium catalyst may comprise a palladium phosphine compound, for example, bis(tri-tert-butylphosphine)palladium (Pd(PPh3)4), tetrakis(triphenylphosphine)palladium(0) (Pd(dppe2), bis[1,2-bis(diphenylphosphino)ethane]palladium(0) (Pd(dppf)), 1,1'-bis(diphenylphosphino)ferrocene palladium, (2,2'-bis(diphenylphosphino)-1,1'-binaphthylpalladium (Pd(BINAP).

[0091] In any of the above methods, the palladium catalyst may comprise a palladium compound and one or more phosphines. For example, tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3) and Pd(OAc)2 and one or more phosphine compounds.

[0092] In any of the above methods, X may be bromine or chlorine. The halogen source may be bromine or chlorine.

[0093] In any of the above methods, the Ar-boron compound may be an optionally substituted aryl boronic acid or an optionally substituted heteroaryl boronic acid.

[0094] In any of the above methods, the Ar-boron compound may be an optionally substituted aryl boronic ester or an optionally substituted heteroaryl boronic ester.

[0095] In any of the above methods, the Ar-boron compound may be an optionally substituted aryl trifluoroborate or an optionally substituted heteroaryl trifluoroborate.

[0096] In any of the above methods, the Ar-boron compound may be an optionally substituted arylborane or an optionally substituted heteroarylborane.

[0097] In any of the above methods, a base may be used in conjunction with the palladium catalyst.

[0098] In any of the above methods, the base may comprise an alkali metal carbonate, alkali metal phosphate, alkali metal hydroxide, alkali metal alkoxide, or an amine.

[0099] The base may comprise sodium or potassium carbonate or sodium or potassium phosphate.

[00100] In an illustrative embodiment and referring to the structures in Figure 1 and the reaction scheme in Figure 3: treatment of 1,3-bis(2-bromophenoxy)propane with n-butyllithium followed by trimethyl borate and then HCl afforded (propane-1,3-diylbisoxy)bis(2,1-phenylene)diboronic acid (9). The diboronic acid, 2-bromocresol, SPhos, and potassium phosphate were dissolved in degassed THF and water, then stirred at room temperature overnight to afford 2',2''-(Propane-1,3-diylbis(oxy))bis(5-methyl-[1,1'-biphenyl]-2-ol) (10). The diphenolic compound (10) was dissolved in dichloromethane and treated with bromine. The reaction was quenched with saturated sodium bicarbonate to yield 6',6''-(Propane-1,3-diylbisoxy)bis(3,3'-dibromo-5-methyl-[1,1'-biphenyl]-2-ol) (11). The brominated compound was combined with phenylboronic acid, SPhos, and potassium phosphate in THF/H2O, and the mixture was stirred at room temperature overnight to yield 6'',6''''''-(Propane-1,3-diylbisoxy)bis(5'-methyl-[1,1':3',1'':3',1'''-quaterphenyl]-2'-ol) (12).

[00101] Figures 4 and 5 illustrate other exemplary reaction schemes. Catalyst compounds

[00102] The catalyst compounds may be prepared by any suitable synthetic method, and the synthetic method is not critical to the present disclosure. A useful method of preparing the catalyst compounds of the present disclosure is by reacting a suitable metal compound, e.g., one with a displaceable anionic ligand, with the bridged biaromatic ligands of this disclosure. Non-limiting examples of suitable metal compounds include organometallics, metal halides, sulfonates, carboxylates, phosphates, organoborates (including fluoro-containing and other subclasses), acetonates, sulfides, sulfates, tetrafluoroborates, nitrates, perchlorates, phenoxides, alkoxides, silicates, arsenates, borohydrides, naphthenates, cyclooctadienes, conjugated complexes with dienes, thiocyanates, cyanates, and metal cyanides. The metal compound can be an organometallic or metal halide. The metal compound can be an organometallic.

[00103] The metal of the organometallic compound may be selected from Groups 1 through 16, or a transition metal selected from elements of Groups 3 through 13 and elements of the Lanthanide series. The metal may be selected from elements of Groups 3 through 7. The metal may be a Group 4 metal, titanium, zirconium, or hafnium.

[00104] The metal compound may, for example, be a metal hydrocarbyl such as: a metal alkyl, a metal aryl, a metal arylalkyl; a metal silylalkyl; a metal diene, a metal amide; or a metal phosphide. The metal compound may be a zirconium or hafnium hydrocarbyl. The transition metal compound may be a zirconium arylalkyl.

[00105] An exemplary reaction is shown below:

[00106] Examples of useful and preferred metal compounds include: (i) tetramethylzirconium, tetraethylzirconium, zirconium dichloride (η4-1,4-diphenyl-1,3-butadiene), bis(triethylphosphine), and zirconium dichloride (η4-1,4-diphenyl-1,3-butadiene) bis(tri-npropylphosphine), tetrakis[trimethylsilylmethyl]zirconium, tetrakis[dimethylamino]zirconium, dichlorodibenzylzirconium, chlorotribenzylzirconium, trichlorobenzylzirconium, bis[dimethylamino]bis[benzyl]zirconium, and tetrabenzylzirconium; (ii) tetramethyltitanium, tetraethyltitanium, titanium dichloride (η4-1,4-diphenyl-1,3-butadiene), bis(triethylphosphine), and titanium dichloride (η4-1,4-diphenyl-1,3-butadiene)bis(tri-npropylphosphine), tetrakis[trimethylsilylmethyl]titanium, tetrakis[dimethylamino]titanium, dichlorodibenzyltitanium, chlorotribenzyltitanium, trichlorobenzyltitanium, bis[dimethylamino]bis[benzyl]titanium, and tetrabenzyltitanium; and(iii) tetramethylhafnium, tetraethylhafnium, hafnium dichloride (η4-1,4-diphenyl-1,3-butadiene), bis(triethylphosphine) and hafnium dichloride (η4-1,4-diphenyl-1,3-butadiene) bis (tri-npropylphosphine), tetrakis[trimethylsilylmethyl]hafnium, tetrakis[dimethylamino]hafnium, dichlorodibenzylhafnium, chlorotribenzylhafnium, trichlorobenzylhafnium, bis[dimethylamino]bis[benzyl]hafnium, and tetrabenzylhafnium.

Catalyst and supported catalyst compositions

[00107] The catalyst compositions disclosed herein may comprise one or more catalyst compounds as disclosed herein and one or more activators as disclosed herein.

[00108] Supported catalyst compositions as disclosed herein may comprise one or more supports as disclosed herein, one or more catalyst compounds as disclosed herein, and one or more activators as disclosed herein.

[00109] The catalyst compositions and the supported catalyst compositions may comprise one or more of the catalyst compounds as previously disclosed herein, together with another catalyst compound, such as a metallocene catalyst compound or a Group V atom catalyst compound. Other suitable catalyst compounds include, but are not limited to: (pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2, (tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2, (tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2, Me2Si(indenyl)2MX2, Me2Si(tetrahydroindenyl)2MX2, (n-propylcyclopentadienyl)2MX2, (n-butylcyclopentadienyl)2MX2, (1-methyl, 3-butylcyclopentadienyl) ... cyclopentadienyl)2MX2,HN(CH2CH2N(2,4,6-Me3phenyl))2MX2,HN(CH2CH2N(2,3,4,5,6-Me5phenyl))2MX2,(propyl cyclopentadienyl)(tetramethylcyclopentadienyl)MX2,(butyl cyclopentadienyl)2MX2,(propyl cyclopentadienyl)2MX2, and mixtures thereof, wherein M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1 to C5 alkyls or alkenyls.

[00110] The supported catalyst composition may be in the form of a substantially dry powder or be in the form of a paste in at least one liquid carrier. Non-limiting examples of liquid carriers include mineral oils, aromatic hydrocarbons, or aliphatic hydrocarbons.

Activator Compounds

[00111] An activator is broadly defined as any combination of reagents that increases the rate at which a transition metal compound oligomerizes or polymerizes unsaturated monomers, such as olefins. Catalyst compounds may be activated for oligomerization and/or polymerization catalysis in any manner sufficient to permit cationic coordination or oligomerization and/or polymerization.

[00112] Additionally, the activator may be a Lewis base, such as, for example, diethyl ether, dimethyl ether, ethanol, or methanol. Other activators that may be used include those described in WO 98/07515, such as tris(2,2',2"-naphafluorobiphenyl) fluoroaluminate.

[00113] Activator combinations may be used. For example, alumoxanes and ionizing activators may be used in combinations, see for example, EP-B1 0 573 120, WO 94/07928 and WO 95/14044 and US Patents 5,153,157 and 5,453,410. WO 98/09996 describes the activation of metallocene catalyst compounds with perchlorates, periodates and iodates including their hydrates. WO 98/30602 and WO 98/30603 describe the use of lithium (2,2'-bisphenyl-ditrimethylsilicate).4THF as an activator for a metallocene catalyst compound. WO 99/18135 describes the use of organo-boron-aluminum activators. EP-B1-0 781 299 describes the use of a silium salt in combination with a compatible non-coordinating anion. WO 2007/024773 suggests the use of activator supports which may comprise a chemically treated solid oxide, a clay mineral, a silicate mineral, or any combination thereof. Activation methods such as the use of radiation (see EP-B1-0 615 981), electrochemical oxidation, and the like are also contemplated as activation methods for the purpose of rendering the neutral metallocene catalyst compound or precursor to a metallocene cation capable of polymerizing olefins. Other activators or methods for activating a metallocene catalyst compound are described, for example, in US Patents 5,849,852, 5,859,653, and 5,869,723 and PCT WO 98/32775.

[00114] Alumoxanes can also be used as an activator in the catalyst composition. Alumoxanes are oligomeric compounds generally containing subunits --Al(R)--O-- where R is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, and isobutulalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the extractable ligand is a halide. Mixtures of different alumoxanes and modified alumoxanes can also be used. For further descriptions, see U.S. Patents 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP 0 561 476 A1, EP 0 279 586 B1, EP 0 516 476 A, EP 0 594 218 A1 and WO 94/10180.

[00115] Alumoxanes can be produced by hydrolysis of the corresponding trialkylaluminum compound. MMAO can be produced by hydrolysis of trimethylaluminum and a higher trialkylaluminum such as triisobutylaluminum. MMAOs are generally more soluble in aliphatic solvents and more stable during storage. There are a variety of methods for preparing alumoxane and modified alumoxanes, non-limiting examples of which are described in, for example, U.S. Patents 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, Nos. 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256, and 5,939,346 and European Publications EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218, and EP-B1-0 586 665, WO 94/10180, and WO 99/15534. Visually clear methylaluminoxane may be used. A cloudy or gelled alumoxane may be filtered to produce a clear solution, or the clear alumoxane may be decanted from the cloudy solution. Another alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name modified methyl alumoxane type 3A, disclosed in U.S. Patent 5,041,584).

[00116] A neutral or ionic ionizing or stoichiometric activator, such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaptyl boron metalloid precursor, polyhalogenated heteroborane anions (see, for example, WO 98/43983), boric acid (see, for example, U.S. Patent 5,942,459), or combinations thereof, may also be used. Neutral or ionic activators may be used alone or in combination with alumoxane or modified alumoxane activators.

[00117] Examples of neutral stoichiometric activators may include substituted borontris, tellurium, aluminum, gallium, indium, or mixtures thereof. The three substituent groups may each be independently selected from the group of alkyls, alkenyls, halogen, substituted alkyls, aryls, arylides, alkoxy, and halides. The three substituent groups may be independently selected from the group of mono- or multicyclic halogenated aryls, alkyls, and alkenyl compounds (including halosubstituted ones) and mixtures thereof; or alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and aryl groups having 3 to 20 carbon atoms (including substituted aryls). Alternatively, the three groups are alkyls with 1 to 4 carbon groups, phenyl, naphthyl, or mixtures thereof. The three groups can be halogenated, for example, fluorinated aryl groups. In still other illustrative examples, the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfluoronapthyl boron.

[00118] Ionic stoichiometric activator compounds may contain an active proton, or some other cation associated with, but not coordinated or only loosely coordinated with, the remaining ionization compound ion. Such and similar compounds are described, for example, in European Publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Patents 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124.

Supports

[00119] The catalyst compounds described above may be combined with one or more supports using one of the support methods well known in the art or as described below. For example, the catalyst compound may be used in a supported form, such as deposited on, contacted with, or incorporated into, adsorbed or absorbed on, or onto the support.

[00120] As used herein, the term "support" refers to compounds comprising Group 2, 3, 4, 5, 13, and 14 oxides and chlorides. Suitable supports include, for example, silica, magnesia, titania, zirconia, montmorillonite, phyllosilicate, alumina, silica-alumina, silica chromium, silica-titania, magnesium chloride, graphite, magnesia, titania, zirconia, montmorillonite, phyllosilicate, and the like.

[00121] The support may have an average particle size in the range of from about 0.1 to about 500 μm, or from about 1 to about 200 μm, or from about 1 to about 50 μm, or from about 5 to about 50 μm.

[00122] The support may have an average pore size in the range of about 10 to about 1000 Å, or about 50 to about 500 Å, or 75 to about 350 Å.

[00123] The support may have a surface area in the range of from about 10 to about 700 m2/g, or from about 50 to about 500 m2/g, or from about 100 to about 400 m2/g.

[00124] The support may have a pore volume in the range of from about 0.1 to about 4.0 cc/g, or from about 0.5 to about 3.5 cc/g, or from about 0.8 to about 3.0 cc/g.

[00125] The support, such as an inorganic oxide, may have a surface area in the range of about 10 to about 700 m/g, a pore volume in the range of about 0.1 to about 4.0 cc/g, and an average particle size in the range of about 1 to about 500 μm. Alternatively, the support may have a surface area in the range of about 50 to about 500 m/g, a pore volume of about 0.5 to about 3.5 cc/g, and an average particle size of about 10 to about 200 μm. The surface area of the support may be in the range of about 100 to about 400 m2/g, a pore volume of about 0.8 to about 3.0 cc/g, and an average particle size of about 5 to about 100 μm.

[00126] The catalyst compounds may be supported on the same supports or on separate supports together with an activator, or the activator may be used in an unsupported form, or may be deposited on a different support than the supported catalyst compounds.

[00127] There are various other methods in the art for supporting a polymerization catalyst compound. For example, the catalyst compound may contain a polymer binding ligand as described, for example, in U.S. Patent Nos. 5,473,202 and 5,770,755; the catalyst may be spray-dried as described, for example, in U.S. Patent No. 5,648,310; the support used with the catalyst may be functionalized as described in European Publication EP-A-0 802 203, or at least one substituent or leaving group is selected as described in U.S. Patent No. 5,688,880.

Polymerization processes

[00128] Polymerization processes may include solution, gas phase, slurry phase, and a high pressure process, or a combination thereof. In illustrative embodiments, a slurry phase or gas phase polymerization of one or more olefins, at least one of which is ethylene or propylene, is provided. Optionally, the reactor is a gas phase fluidized bed polymerization reactor.

[00129] The catalyst compositions or supported catalyst compositions as described herein are suitable for use in any prepolymerization and/or polymerization process over a wide range of temperatures and pressures. Temperatures may be in the range of -60°C to about 280°C; from 50°C to about 200°C; from 60°C to 120°C; from 70°C to 100°C; or from 80°C to 95°C.

[00130] The present process may be directed to a solution, high pressure, slurry or gas phase polymerization process of one or more olefin monomers having 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms and more preferably 2 to 8 carbon atoms. The process is particularly well suited for the polymerization of two or more olefins or comonomers such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene or the like.

[00131] Other olefins useful in the present process include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or unconjugated dienes, polyenes, vinyl monomers, and cyclic olefins. Useful monomers may include, but are not limited to, norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, alkyl-substituted styrene, ethylidene norbornene, dicyclopentadiene, and cyclopentene. In an illustrative embodiment of the present process, an ethylene copolymer is produced, wherein with ethylene, a comonomer having at least one alpha-olefin having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and more preferably from 4 to 8 carbon atoms, is polymerized in a gas phase process. In one embodiment of the present process, ethylene or propylene is polymerized with at least two different comonomers, optionally one of which may be a diene, to form a terpolymer.

[00132] The present process may be directed to a polymerization process, particularly a gas phase or gas phase process, for polymerizing propylene alone or with one or more other monomers including ethylene and/or other olefins having 4 to 12 carbon atoms. The polymerization process may comprise contacting ethylene and optionally an alpha-olefin with one or more of the catalyst compositions or supported catalyst compositions as previously described in a reactor under polymerization conditions to produce the ethylene polymer or copolymer.

[00133] Suitable gas-phase polymerization processes are described, for example, in U.S. Patents 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661, 5,668,228, 5,627,242, 5,665,818, and 5,677,375, and in European Publications EP-A-0 794 200, EP-A-0 802 202, EP-A2 0 891 990, and EP-B-634 421.

[00134] A slurry polymerization process generally utilizes pressures in the range of about 1 to about 50 atmospheres and even higher and temperatures in the range of 0°C to about 120°C. In a slurry polymerization, a solid particulate polymer slurry is formed in a liquid polymerization diluent medium to which ethylene and comonomers and often hydrogen are added along with the catalyst. The slurry including diluent may be intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor. The liquid diluent used in the polymerization medium is typically an alkane having 3 to 7 carbon atoms, preferably a branched alkane. The medium employed must be liquid under the polymerization conditions and relatively inert. When a propane medium is used, the process must be operated above the critical temperature and pressure of the reaction diluent. Preferably, a hexane or isobutane medium is used.

[00135] A preferred polymerization process is referred to as a particle-form polymerization, or a slurry process in which the temperature is maintained below the temperature at which the polymer enters solution. Such a technique is well known in the art and described in, for example, U.S. Patent 3,248,179. Other slurry processes include those employing a spiral reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof. Non-limiting examples of slurry processes include continuous cycle processes or stirred tank processes. In addition, other examples of slurry processes are described in U.S. Patent 4,613,484. Examples of slurry processes are described in U.S. Patents 4,271,060, 5,001,205, 5,236,998, and 5,589,555.

Examples

[00136] It is to be understood that, although the present invention has been described in conjunction with its specific embodiments, the foregoing description is intended to illustrate and not to limit the scope of the disclosure. Other aspects, advantages, and modifications will be apparent to those skilled in the art to which the disclosure belongs. Accordingly, the following examples are presented to provide those skilled in the art with a complete disclosure and description of how to prepare and use the disclosed compositions, and are not intended to limit the scope of the disclosure.

[00137] General: All reagents were purchased from commercial vendors and used as received unless otherwise indicated. Analytical thin layer chromatography (TLC) was performed on selective plates (200 μm) pre-coated with a fluorescent indicator. Visualization was performed using ultraviolet light (254 nm). Flash column chromatography was performed with Sigma Aldrich 60 Å silica gel (70 - 230 Mesh). NMR spectra were recorded on a Bruker 400 NMR with chemical shifts referred to residual solvent peaks (CDCl3: 7.27 ppm for 1H, 77.29 ppm for 13C; C6D6: 7.15 ppm for 1H, 77.39 ppm for 13C). Melting points are reported uncorrected. Abbreviations: SPhos - Chloro(2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II); PTSA - para-toluenesulfonic acid.

[00138] General procedure for Suzuki coupling: In an appropriately sized vial, 2-Bromo-p-cresol (1 equiv), aryl boronic acid (1.5 equiv), and palladium tetrachlorophenylphosphine (0.02 equiv) were dissolved in degassed toluene to form a 0.2 M solution relative to cresol. A 2 M solution of sodium carbonate (4 equiv) in degassed H2O:MeOH (4:1) was added, and the mixture was refluxed to completion (typically overnight). The reaction was cooled and the layers separated. The aqueous layer was extracted twice with ethyl acetate, and the combined organic layers were washed with brine, dried over MgSO4 or Na2SO4, filtered, and concentrated under reduced pressure.

[00139] 5-Methyl-[1,1'-biphenyl]-2-ol (1): Using the general procedure above, a white solid was isolated by column chromatography in 81% yield: 1H NMR (400 MHz, C6D6, δ): 2.10 (s, 3 H), 6.69 (m, 3 H), 7.12 (m, 2 H), 7.15 (m, 1 H), 7.35 (m, 2 H).

[00140] 2',5-Dimethyl-[1,1'-biphenyl]-2-ol (2): Using the general procedure above, a white solid was isolated by column chromatography (30:70 actone:isohexane) in 75% yield: Rf = 0.25 (30:70 acetone:isohexane); 1H NMR (400 MHz, CDCl3, δ): 2.20 (s, 3 H), 2.33 (s, 3 H), 4.65 (br s, 1 H), 6.70 (d, J = 6.8 Hz, 1 H), 6.94 (s, 1 H), 7.10 (m, 1 H), 7.33 (m, 4 H).

[00141] 3',5,5'-Trimethyl-[1,1'-biphenyl]-2-ol (3): Using the above general procedure, a white solid was isolated by column chromatography (30:70 actone:isohexane) in 75% yield: Rf = 0.32 (20:80 acetone:isohexane); 1H NMR (400 MHz, CDCl3, δ): 2.34 (s, 3 H), 2.41 (s, 6 H), 5.19 (br s, 1 H), 6.91 (d, J = 8.4 Hz, 1 H), 7.08 (m, 5 H).

[00142] 2',5,5'-Trimethyl-[1,1'-biphenyl]-2-ol (4): Using the above general procedure, a white solid was isolated by column chromatography (10% actone/isohexane) in 80% yield: Rf = 0.26 (10:90 acetone:isohexane); 1H NMR (400 MHz, CDCl 3 , δ): 2.15 (s, 3 H), 2.32 (s, 3 H), 2.36 (s, 3 H), 4.66 (br s, 1 H), 6.89 (d, J = 8.4 Hz, 1 H), 6.93 (m, 1 H), 7.07 (m, 2 H), 7.21 (m, 1 H), 7.26 (m, 1 H).

[00143] 4-Methyl-2-(naphthalen-1-yl)phenol (5): Using the general procedure above, the product was isolated by column chromatography (30% acetone:isohexane) in 77% yield as a pale yellow oil: 1H NMR (500 MHz, CDCl3, δ): 2.37 (s, 3 H), 4.67 (s, 1 H), 6.98 (d, J = 9 Hz, 1 H), 7.09 (s, 1 H), 7.09 (m, 1 H), 7.56 (m, 4 H), 7.70 (d, J = 8 Hz, 1 H), 7.93 (m, 2 H); 13C NMR (100 MHz, CDCl3, δ): 20.8, 115.6, 126.0 - 134.5 (14 C), 151.2; IR (cm-1): 3519, 3045, 2920, 1590, 1496, 1333, 1276, 1183, 781.

[00144] 4-Methyl-2-(2-methylnaphthalen-1-yl)phenol (6): Following the general procedure above, substituting aryl boronic acid for 2-methylnaptyl-pinacol borane, the product was purified by silica gel chromatography (10% acetone/isohexane) in 49% yield as a pale yellow oil which solidified upon standing. Rf = 0.32 (30:70 acetone:isohexane); 1H NMR (400 MHz, CDCl3, δ): 2.29 (s, 3 H), 2.36 (s, 3 H), 4.42 (s, 1 H), 6.95 (s, 1 H), 7.00 (d, J = 4.0 Hz, 1 H), 7.19 (d, J = 8 Hz, 1 H), 7.44 (m, 4 H), 7.86 (t, J = 8.0 Hz, 2 H); 13C NMR (100 MHz, CDCl3, δ): 20.7, 20.8, 115.4, 125.0, 125.5, 125.8, 126.8, 128.2, 128.7, 129.0, 130.1, 130.2, 131.5, 131.6, 132.5, 133.2, 135.8, 151.1; IR (cm-1): 3498, 3426, 3050, 2922, 2860, 1617, 1594, 1497, 1335, 1275, 1228, 1188, 814.

[00145] 3-Bromo-3',5,5'-trimethyl-[1,1'-biphenyl]-2-ol (7): Phenol (3) (1 g, 4.7 mmol) was dissolved in methylene chloride and cooled to -35 °C. Bromide (0.3 mL, 5.6 mmol) was added slowly and the solution was stirred at room temperature overnight. The reaction was quenched with saturated sodium bicarbonate solution and extracted 3 times with methylene chloride. The combined organic portions were washed with sodium metabisulfite and brine, then dried over MgSO4, filtered, and concentrated. Rf = 0.30 (10:90 ethyl acetate:isohexane); 1H NMR (400 MHz, CDCl3, δ): 2.33 (s, 3 H), 2.49 (s, 6 H), 5.07 (br s, 1 H), 6.87 (d, J = 8.4 Hz, 1 H), 7.03 (m, 2 H), 7.19 (s, 2 H); 13C NMR (100 MHz, CDCl3, δ): 24.7 (2 C), 25.2, 115.1, 127.4, 128.4, 129.1, 129.9, 130.3, 130.8, 131.6, 136.0, 139.4, 139.5, 150.3; IR (cm-1): 3533, 2921, 1499, 1464, 1381, 1237, 1029, 814.

[00146] (Butane-1,4-diylbis(oxy))bis(2,1-phenylene)diboronic acid (8): To 1,4-bis(2-bromophenoxy)butane (5 g, 12.5 mmol) dissolved in 40 mL of THF, n-butyllithium (11 mL of 2.5 M) was added. The reddish-brown solution was stirred cold for 2 h. Trimethyl borate (5.6 mL, 50 mmol) was added as the solution slowly turned colorless and stirred overnight at room temperature. The reaction was quenched with conc. HCl and condensed to a white solid. The solid was washed with ether to give the diboronic acid in 68% yield: 1H NMR (400 MHz, DMSO-d6, δ): 1.92 (app br s, 4 H), 4.10 (app br s, 4 H), 6.93 (t, J = 8.0 Hz, 2 H), 7.00 (d, J = 8.0 Hz, 2 H), 7.36 (m, 2 H), 7.55 (m, 2 H), 7.72 (s, 4 H).

[00147] (Propane-1,3-diylbisoxy)bis(2,1-phenylene)diboronic acid (9): 1,3-Bis(2-bromophenoxy)propane (3.1 g, 8 mmol) was prepared according to established procedures and dissolved in 10 mL of THF, then cooled to -70 °C. n-Butyllithium (6.4 mL of 2.5 M) was added and the deep red reaction mixture was stirred for 1 h. Trimethyl borate (3.5 mL, 24 mmol) was added as the solution slowly turned colorless and warmed to room temperature over 1 h. The reaction was quenched with 10% HCl and extracted with three portions of ether. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated. The product was recrystallized from dichloromethane to give a white powder: 1H NMR (400 MHz, DMSO, δ): 2.25 (m, 2 H), 4.19 (m, 4 H), 6.93 (m, 2 H), 6.99 (d, J = 8.0 Hz, 2 H), 7.36 (m, 2 H), 7.53 (m, 2 H), 7.74 (m, 2 H); 13C NMR (100 MHz, DMSO-d6, δ): 28.7, 64.1, 65.0, 111.2 (2 C), 114.5 (2 C), 120.5, 120.6, 131.5 (2 C), 138.4 (2 C).

[00148] 2',2'''-(Propane-1,3-diylbis(oxy))bis(5-methyl-[1,1'-biphenyl]-2-ol) (10): The above diboronic acid (600 mg, 1.89 mmol), 2-bromocresol (800 mg, 4.2 mmol), SPhos (50 mg, 0.07 mmol), and potassium phosphate (1.6 g, 7.56 mmol) were dissolved in degassed THF and water, then stirred at room temperature overnight. The reaction mixture was extracted with 4 portions of ether, and the combined organic layers washed with brine, dried (Na2SO4), filtered, and concentrated. Column chromatography (30% acetone/isohexane eluent) gave the cross-coupled product in 74% yield as a pale yellow oil: Rf = 0.37 (acetone/isohexane 30:70); 1H NMR (400 MHz, CDCl3, δ): 2.11 (qn, J = 6.0 Hz, 2 H), 2.33 (s, 6 H), 4.10 (t, J = 6.0 Hz, 4 H), 6.02 (s, 2 H), 6.91 (m, 4 H), 7.05 (m, 2 H), 7.14 (m, 4 H), 7.35 (m, 4 H); 13C NMR (100 MHz, CDCl3, δ): 20.7 (2 C), 28.9, 65.8 (2 C), 113.5 (2 C), 117.0 (2 C), 122.6 (2 C), 126.0 (2 C), 127.7 (2 C), 129.4 (2 C), 129.9 (2 C), 130.1 (2 C), 131.8 (2 C), 132.4 (2 C), 151.5 (2 C), 154.9 (2 C); IR (cm-1): 4307, 3028, 2923, 1597, 1499, 1445, 1270, 1229, 1113, 1054, 909, 818.

[00149] 6',6''-(Propane-1,3-diylbisoxy)bis(3,3'-dibromo-5-methyl-[1,1'-biphenyl]-2-ol) (11): The above diphenolic compound (620 mg, 1.38 mmol) was dissolved in 40 mL of dichloromethane. Bromine (0.158 mL, 3.47 mmol) was added slowly, and the reaction was stirred at room temperature for 1 h. The reaction was quenched with saturated sodium bicarbonate, and the organic layer was washed with sodium metabisulfite and brine, then dried (Na2SO4), filtered, and concentrated. The tetrabrominated compound was recrystallized from ether: 1H NMR (400 MHz, CDCl3, δ): 2.05 (qn, J = 6.0 Hz, 2 H), 2.23 (s, 6 H), 4.00 (t, J = 6.0 Hz, 4 H), 5.72 (s, 2 H), 6.81 (d, J = 8.0 Hz, 2 H), 6.87 (d, J = 4 Hz, 2 H), 7.30 (d, J = 4.0 Hz, 2 H), 7.37 (d, J = 4.0 Hz, 2 H), 7.45 (m, 2 H); 13C NMR (100 MHz, CDCl3, δ): 20.5 (2 C), 28.6, 65.2 (2 C), 111.0 (2 C), 114.0 (2 C), 114.7 (2 C), 126.8 (2 C), 129.1 (2 C), 131.4 (4 C), 132.4 (2 C), 132.9 (2 C), 134.4 (2 C), 147.9 (2 C), 154.6 (2 C); IR (cm-1): 3500, 2924, 1588, 1472, 1387, 1280, 1234, 1127, 1085, 808.

[00150] 6'',6''''''-(Propane-1,3-diylbisoxy)bis(5'-methyl-[1,1':3',1'':3',1'''-quaterphenyl]-2'-ol) (12): The above brominated compound (420 mg, 0.55 mmol) was combined with phenylboronic acid (304 mg, 2.49 mmol), SPhos (40 mg, 0.055 mmol), and potassium phosphate (583 mg, 2.75 mmol) in 40 mL of degassed THF/H2O. The mixture was stirred at room temperature overnight, and then extracted with 2 portions of ether. The combined organic layers were washed with brine, dried (Na2SO4), filtered, and concentrated. The residue was purified by column chromatography giving the phenylated product as a pale yellow solid: mp = 82 - 89 °C; Rf = 0.44 (acetone/isohexane 30:70); 1H NMR (400 MHz, CD2Cl2, δ): 2.17 (m, 2 H), 2.34 (s, 6 H), 4.18 (t, J = 8.0 Hz, 4 H), 5.8 (s, 2 H), 13C NMR (100 MHz, CD2Cl2, δ): 20.8 (2 C), 29.4, 65.9 (2 C), 113.7 (2 C), 127.0 - 131.7 (36 C), 135.3 (2 C), 139.3 (2 C), 140.8 (2 C), 148.7 (2 C), 155.3 (2 C).

[00151] Zr complex (13): The above diphenol (200 mg, 0.268 mmol) was dissolved in 15 mL of toluene and cooled to -35 °C. Dibenzylzirconium hydrochloride dichloride (105 mg, 0.268 mmol) was added and the reaction was heated to 60 °C until a precipitate formed (approximately 3 h). The toluene was removed and the solid washed with hexane giving the zirconium complex as a pale cream-colored powder: 1H NMR (400 MHz, CD2Cl2, δ): 1.53 (m, 2 H), 2.34 (s, 3H), 2.38 (s, 3H), 3.76 (m, 2 H), 4.15 (m, 2 H), 7.14 - 7.89 (m, 30 H).

[00152] 2',2''-(butane-1,4-diylbisoxy)bis(5-methyl-[1,1'-biphenyl]-2-ol) (14): Diboronic acid (3 g, 9.1 mmol), 2-bromocresol (3.4 g, 18.1 mmol), SPhos (130 mg, 0.18 mmol), and potassium phosphate (7.7 g, 36 mmol) in 200 mL THF/H2O were added and stirred at room temperature overnight. The layers were separated and the aqueous layer extracted twice with ether. The combined organic layers were washed with brine and 10% HCl, dried (Na2SO4), filtered, and concentrated. The brown residue was purified by silica gel column chromatography (30% ethyl acetate/isohexane), giving the product as a pale yellow oil: 1H NMR (400 MHz, CDCl3, δ): 1.81 (m, 4 H), 2.31 (s, 6 H), 3.98 (m, 4 H), 6.22 (s, 2 H), 6.88 (m, 4 H), 7.03 (m, 6 H), 7.32 (m, 4 H); 13C NMR (100 MHz, CDCl3, δ): 20.8 (2 C), 25.9 (2 C), 69.3 (2 C), 113.5 (2 C), 117.4 (2 C), 122.6 (2 C), 126.4 (2 C), 128.1 (2 C), 129.3 (2 C), 130.0 (2 C), 130.2 (2 C), 131.9 (2 C), 132.7 (2 C), 151.7 (2 C), 155.0 (2 C); IR (cm-1): 3397, 3027, 2945, 1597, 1499, 1444, 1268, 1229, 1112, 818

[00153] 6',6''-(butane-1,4-diylbis(oxy))bis(3,3'-dibromo-5-methyl-[1,1'-biphenyl]-2-ol)(15): The above diphenolic compound (700 mg, 1.5 mmol) and triethylamine (0.30 mL, 2.2 mmol) were dissolved in 10 mL of dichloromethane. Bromine (0.095 mL, 1.84 mmol) was added slowly, and the reaction was stirred at room temperature overnight. The reaction was quenched with saturated sodium bicarbonate, and the organic layer was washed with sodium metabisulfite and brine, then dried (Na2SO4), filtered, and concentrated. The resulting white powder was obtained in 95% yield by recrystallization from ether: 1 H NMR (400 MHz, CDCl 3 , δ): 1.75 (m, 4 H), 2.27 (s, 6 H), 3.93 (m, 4 H), 5.99 (s, 2 H), 6.79 (d, J = 12.0 Hz, 2 H), 6.94 (m, 2 H), 7.40 (m, 2 H), 7.45 (m, 4 H); 13C NMR (125 MHz, CDCl3, δ): 20.5 (2 C), 25.8 (2 C), 69.1 (2 C), 111.3 (2 C), 114.1 (2 C), 114.8 (2 C), 125.8 (2 C), 129.4 (2 C), 131.3 (2 C), 131.5 (2 C), 132.2 (2 C), 132.9 (2 C), 134.6 (2 C), 148.0 (2 C), 155.0 (2 C).

[00154] 6'',6'''''-(butane-1,4-diylbisoxy)bis(2,2''',5,5',5'''-pentamethyl-[1,1':3',1'':3'',1'''-quaterphenyl]-2'-ol) (16): The above brominated compound (700 mg, 0.908 mmol) was combined with 2,5-dimethylphenylboronic acid (613 mg, 4.1 mmol), SPhos (64 mg, 0.09 mmol), and potassium phosphate (1.5 g, 7.2 mmol) in 80 mL of degassed THF/H2O. The mixture was stirred at room temperature overnight, and then extracted with 2 portions of ether. The combined organic layers were washed with brine, dried (Na2SO4), filtered, and concentrated. The residue was purified by column chromatography giving the phenylated product as a pale yellow solid: 1H NMR (400 MHz, CDCl3, δ): 1.83 (m, 4 H), 2.16 - 2.36 (m, 30 H), 4.03 (4 H), 5.96 (s, 2 H), 6.95 (m, 4 H), 7.07 (m, 10 H), 7.28 (m, 2 H), 7.36 (m, 2 H); 13C NMR (100 MHz, CDCl3, δ): 20.4 - 23.5 (10 C), 26.7 (2 C), 69.8 (2 C), 113.5 (2 C), 118.2 (2 C), 126.9 - 141.8 (42 C), 149.2 (2 C), 154.9 (2 C); IR (cm-1): 3539, 3384, 3015, 2920, 1609, 1493, 1461, 1382, 1228, 908, 811.

[00155] Zr complex (17): To compound (16) (200 mg, 0.23 mmol) dissolved in 15 mL of toluene, dibenzylzirconium dichloride (90 mg, 0.23 mmol) was added at -35 °C. The mixture was heated at 70 °C for 3 h, then concentrated to an oil. Upon dissolving the oil in hexane, a little solid precipitated and was washed with pentane: 1H NMR (400 MHz, CD2Cl2, δ): 1.41 (m, 4 H), 2.26 - 2.47 (m, 30 H), 4.13 (m, 2 H), 4.54 (m, 2 H), 5.95 (d, J = 8.0 Hz, 2 H), 7.30 (m, 22 H).

[00156] 6',6''-(butane-1,4-diylbisoxy)bis(5-methyl-3,3'-di(naphthalen-1-yl)-[1,1'-biphenyl]-2-ol) (18): Brominated compound (15) (400 mg, 0.519 mmol) was combined with 2-naphthylboronic acid (402 mg, 2.3 mmol), palladium tetrachlorophenylphosphine (30 mg, 0.025 mmol), and sodium carbonate (770 mg, 7.26 mmol) in 20 mL of degassed tol/H2O. The mixture was heated at 90 °C overnight, and then extracted with 2 portions of ether. The combined organic layers were washed with brine, dried (Na2SO4), filtered, and concentrated. The residue was purified by column chromatography (20% acetone/isohexane) giving the tetranaphthylated product as a white powder in 52% yield: 1H NMR (400 MHz, CDCl3, δ): 1.9 (m, 4 H), 2.31 (s, 6 H), 4.04 (m, 4 H), 7.00 (m, 2 H), 7.10 (m, 2 H), 7.21 (m, 2 H), 7.50 (m, 16 H), 7.62 (m, 2 H), 7.91 (m, 10 H), 8.03 (d, J = 12.4 Hz, 2 H); 13C NMR (100 MHz, CDCl3, δ): 20.7 (2 C), 23.1, 26.2, 69.3 (2 C), 112.9 (2 C), 125.6 - 134.4 (52 C), 134.8 (2 C), 137.1 (2 C), 139.8 (2 C), 149.3 (2 C), 154.7 (2 C); IR (cm-1): 3393, 3043, 2950, 1710, 1600, 1497, 1465, 1226, 779.

[00157] Zr complex (19): Ligand (18) (200 mg, 0.208 mmol) was dissolved in 15 mL of toluene and cooled to -35 °C. Dibenzylzirconium dihydrochloride dichloride (82 mg, 0.208 mmol) was added and the reaction was heated to 90 °C until a precipitate formed (approximately 3 h). The toluene was removed and the solid was washed with hexane giving the zirconium complex as a white powder: 1H NMR (500 MHz, tol-d8, 90 °C, δ): 1.64 (m, 4 H), 2.12 (s, 3 H), 2.17 (s, 3 H), 3.72 (m, 4 H), 5.51 (s, 1 H), 6.78 (d, J = 8.5 Hz, 2 H), 7.06 (m, 2 H), 7.30 (m, 19 H), 7.64 (m, 10 H), 7.87 (d, J = 8.5 Hz, 2 H), 8.06 (d, J = 8.5 Hz, 2 H).

[00158] General procedure for catalyst support: Zirconium complex, typically 15 to 30 mg, was dissolved in toluene and a solution of methylalumoxane (MAO, Albemarle, 30 wt % in toluene) was added. Silica gel (Grace-Davison 757 pretreated at 600°C) was added and the slurry was stirred until thoroughly mixed (approximately 5 minutes). The toluene was then removed under vacuum to give a dry, free-flowing powder.

Laboratory polymerization tests

[00159] A 2 L autoclave was charged with fine granular sodium chloride under an inert N2 atmosphere. 5 g of methylalumoxane-treated silica was added to the reactor by pressurizing it with a N2 pulse. The reactor temperature was adjusted to 85°C. The reactor was compounded with hydrogen, 1-hexene, and ethylene such that the reactor setpoint pressure was 1516 kPa (220 psig) and the 1-hexene/ethylene molar ratio was established. A pre-weighed catalyst charge, between 10-15 mg, was pressurized into the reactor. The reactor setpoint pressure was adjusted to 1516 kPa (220 psig). Ethylene was fed to the reactor to maintain this setpoint. H2 and 1-hexene were also fed to the reactor so that their setpoint concentration and C6/C2 ratio, respectively, were maintained. After one hour of run time, the polymer product was recovered and weighed.

[00160] The table below collects the results of the polymerization and characterization tests of the polymer:

[00161] All catalysts showed good productivity and produced high molecular weight ethylene-1-hexene copolymers. "% Recovery" refers to the % of polymer recovered from the reactor. "Me" refers to the number of short chain end groups as measured by NMR spectroscopy.

[00162] For the sake of brevity, only certain intervals are explicitly disclosed here. However, intervals from any lower bound may be combined with any upper bound to recite an interval not explicitly recited, just as intervals from any lower bound may be combined with any other lower bound to recite an interval not explicitly recited, just as any upper bound may be combined with any other upper bound to recite an interval not explicitly recited.

[00163] All cited documents are hereby incorporated in their entirety by reference for all countries in which such incorporation is authorized and to the extent such disclosure is consistent with the description of this disclosure.

Claims (10)

1. Bridged biaromatic phenol ligand of formula (I); characterized in that each of R2 and R8 is a hydrocarbyl containing from 1 to 4 carbon atoms; A is a divalent alkyl having from 3 to 9 carbon atoms; Ar is, independently, aryl, alkaryl, or naphthyl; wherein "aryl" refers to an aromatic substituent containing a single aromatic ring; and wherein "aralkyl" refers to an aryl group having an alkyl substituent. 2. The bridged biaromatic phenol ligand according to claim 1, of formula (II): characterized by the fact that each of R2 and R8 is a hydrocarbyl having 1 carbon atom and A is a divalent alkyl having 3 to 4 carbon atoms. 3. A method for preparing a bridged biaromatic phenol ligand according to either of claims 1 and 2, comprising the steps of: a) treating a bridged biaromatic phenol of formula (III) with a halogen source to produce a tetrahalo-bridged biaromatic phenol of formula (IV); and b) treating the tetrahalo-bridged biaromatic phenol of formula (IV) with an arylboron compound (ArBRb2 or ArBF3-M+) in the presence of a catalyst, to produce the bridged biaromatic phenol ligand of formula (I); wherein R2 and R8 are each a hydrocarbyl containing 1 to 4 carbon atoms; A is a divalent alkyl having 3 to 9 carbon atoms; Ar is, independently, aryl, alkaryl, or naphthyl; wherein "aryl" refers to an aromatic substituent containing a single aromatic ring; and wherein "aralkyl" refers to an aryl group having an alkyl substituent; X is halo; Rb is independently selected from hydride, alkyl, hydroxy, and alkoxy, wherein when both of Rb are alkoxy, they can optionally combine to form a ring structure of the formula BO2Rb2, and wherein M+ is an alkali metal cation. 4. The method of claim 3, wherein the catalyst comprises palladium or nickel; or wherein the catalyst is a palladium phosphine catalyst; or wherein the catalyst further comprises a base; or wherein the catalyst further comprises a base that is an alkali metal carbonate or alkali metal phosphate. 5. The method of either claim 3 or claim 4, wherein X is bromine or chlorine; or wherein the aryl-boron compound is an optionally substituted aryl boronic acid, an optionally substituted heteroaryl boronic acid, an optionally substituted aryl boronic ester, an optionally substituted heteroaryl boronic ester, an optionally substituted aryl trifluoroborate, an optionally substituted heteroaryl trifluoroborate, an optionally substituted aryl borane, or an optionally substituted heteroaryl borane. 6. A transition metal compound comprising a bridged biaromatic phenol ligand as defined in either of claims 1 and 2, wherein the ligand comprises a titanium atom, a zirconium atom, or a hafnium atom. 7. Catalyst composition, characterized by the fact that it comprises one or more transition metal compounds, as defined in claim 6, and one or more activators, wherein one or more activators comprises methylalumoxane. 8. Supported catalyst composition, characterized by the fact that it comprises one or more transition metal compounds, as defined in claim 6, one or more activators and one or more support materials, wherein the one or more activators comprises methylalumoxane and the one or more support materials comprises silica. 9. The catalyst composition or supported catalyst composition of any one of claims 7 or 8, further comprising metallocene as another transition metal compound. 10. A process for polymerizing olefins, the process comprising:- contacting the olefins with one or more catalyst compositions or supported catalyst compositions as defined in any one of claims 7 to 9 in a reactor under polymerization conditions to produce an olefin polymer or copolymer.