CN113423742B - Bis (arylphenoxide) lewis base catalysts and methods thereof - Google Patents

Abstract

The present disclosure relates to bis (arylphenoxide) lewis base catalysts. The catalysts, catalyst systems, and methods of the present disclosure can provide high Wen Yixi polymerization, propylene polymerization, or copolymerization because the bis (arylphenoxide) lewis base catalysts are stable at high polymerization temperatures and have good activity at high polymerization temperatures. A stable catalyst with good activity can provide for the formation of polymers with high molecular weights and the ability to produce increased amounts of polymer in a given reactor compared to conventional catalysts. Thus, the present disclosure illustrates a high activity catalyst capable of operating at high reactor temperatures while producing polymers with controlled molecular weights and/or robust isotacticity.

Description

Bis (arylphenoxide) lewis base catalysts and methods thereof

The inventors:Georgy P.Goryunov，Vladislav A.Popov，Dmitry V.Uborsky，Alexander Z.Voskoboynikov，John R.Hagadorn，Irene C.Cai，Hua Zhou，Jo Ann M.Canich

priority

The present invention claims priority and equity from USSN 62/804,372 filed on 12 th 2 nd 2019 and european patent application number 19179811.5 filed on 12 th 6 th 2019, the disclosures of which are incorporated herein in their entireties.

FIELD

The present disclosure relates to bis (arylphenoxide) lewis base transition metal complexes, catalyst systems including bis (arylphenoxide) lewis base transition metal complexes, and polymerization processes for producing polyolefin polymers, such as polyethylene-based polymers and polypropylene-based polymers.

Background

Olefin polymerization catalysts have great utility in industry and polyolefins are widely used commercially due to their robust physical properties. There is therefore an interest in finding new catalyst systems which increase the market value of the catalyst and allow the production of polymers with improved properties.

Polyolefins such as polyethylene typically have a comonomer such as hexene incorporated in the polyethylene backbone. These copolymers provide altered physical properties compared to polyethylene alone and are typically produced in low pressure reactors using, for example, solution, slurry or gas phase polymerization processes. The polymerization may be carried out in the presence of a catalyst system such as those employing Ziegler-Natta catalysts, chromium-based catalysts, or metallocene catalysts.

In addition, the procatalysts (neutral unactivated complexes) should be thermally stable at or above ambient temperature, as they are often stored for several weeks before use. The performance of a given catalyst is strongly affected by the reaction conditions, such as monomer concentration and temperature. For example, solution processes that benefit from operating at temperatures above 120 ℃ are particularly challenging for catalyst development. At such high reactor temperatures, it is often difficult to maintain high catalyst activity and high molecular weight capability because both properties fall off fairly consistently with increasing reactor temperature. For a desired range of polyolefin products, from High Density Polyethylene (HDPE) to elastomers (e.g., thermoplastic elastomer (TPE), ethylene-propylene-diene (EPDM)), many different catalyst systems may be required, as it is unlikely that a single catalyst will be able to address all of the needs for producing these various polyolefin products. The stringent requirements required to develop and produce new polyolefin products make the determination of suitable catalysts for a given product and production process a highly challenging endeavor.

New and improved catalysts, catalyst systems and methods for the polymerization of olefins are needed in order to achieve, for example, narrow polydispersity index and high molecular weight polymer properties. Furthermore, there remains a need to develop high activity catalysts that are capable of operating at high reactor temperatures while producing polymers with high molecular weights (e.g., catalysts with high stability and good activity at high polymerization temperatures). In the case of polypropylene, there is also a need to provide catalysts and methods for isotactic polypropylene having one or more of the foregoing properties.

References cited in the information disclosure statement (37 cfr 1.97 (h)): US 7,030,256; baier, m.et al (2014) "Post-Metallocenes in the Industrial Production of Poly-plekins," angel. Chem. Int. Ed., volume 53, pages 9722-9744; KR 2018/022137; WO 2016/172110.

SUMMARY

The present invention relates to transition metal compounds comprising a tridentate dianionic ligand chelated to a group 4 transition metal, wherein the tridentate ligand cooperates with the metal using two anionic oxygen donors and one neutral heterocyclic nitrogen donor to form a pair of eight-membered metal ring systems.

The present disclosure also relates to catalyst compounds represented by formula (I):

Wherein:

m is a group 3, 4 or 5 metal;

A ¹ and A ² Independently an aromatic group;

j is a heterocyclic Lewis base, preferably having six ring atoms;

l is a Lewis base;

x is an anionic ligand;

n is 1, 2 or 3;

m is 0, 1 or 2;

n+m is not more than 4;

R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ and R is ⁸ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹ And R is ² 、R ² And R is ³ 、R ³ And R is ⁴ 、R ⁵ And R is ⁶ 、R ⁶ And R is ⁷ Or R is ⁷ And R is ⁸ One or more of the substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings can join to form additional rings;

any two L groups can be joined together to form a bidentate lewis base;

the X group may be joined to the L group to form a monoanionic bidentate group; and

any two X groups may be joined together to form a dianionic ligand group.

In yet another embodiment, the present disclosure provides a catalyst system comprising an activator and a catalyst of the present disclosure.

In yet another embodiment, the present disclosure provides a polymerization process comprising a) contacting one or more olefin monomers with a catalyst system comprising: i) An activator and ii) a catalyst of the present disclosure.

In yet another embodiment, the present disclosure provides a polyolefin formed from the catalyst system and/or method of the present disclosure.

In another class of embodiments, the present disclosure provides a process for producing an ethylene alpha-olefin copolymer comprising reacting ethylene and at least one C in at least one continuous stirred tank reactor or loop reaction ₃ -C ₂₀ Contacting an alpha-olefin with a catalyst system to polymerize ethylene and at least one C ₃ -C ₂₀ Alpha-olefins.

In another class of embodiments, the present disclosure provides a process for producing propylene alpha-olefin copolymers comprising reacting propylene and at least one ethylene and/or at least one C in at least one continuous stirred tank reactor or loop reactor ₄ -C ₂₀ Contacting an alpha-olefin with a catalyst system to polymerize propylene and at least one ethylene and/or C ₄ -C ₂₀ Alpha-olefins.

In at least one embodiment, the catalyst compound represented by formula (I) is characterized by two eight-membered metallocene rings. The first of these eight-membered metallocene rings contains atoms from the group consisting of: metal M, phenolate oxygen, two carbons of the phenolate aryl group, aryl group A ¹ And two atoms from the bridging lewis base group J. The second of these eight-membered metallocene rings contains atoms from the group consisting of: metal M, phenolate oxygen, two carbons of the phenolate aryl group, aryl group A ² And two atoms from the bridging lewis base group J.

Detailed description of the preferred embodiments

The present disclosure provides catalyst compounds, catalyst systems comprising catalyst compounds comprising a bis (arylphenoxide) lewis base tridentate ligand coordinated to a transition metal center to form two eight-membered rings, and uses thereof. The catalyst compounds of the present disclosure may be zirconium or hafnium-containing compounds having one or more aryl and/or heteroaryl ligands substituted and linked with a bis (arylphenoxide) lewis base. In another class of embodiments, the present disclosure relates to a polymerization process for producing polyolefin polymers from a catalyst system comprising one or more olefin polymerization catalysts, at least one activator, and optionally a support. The polyolefin polymer may be a polyethylene polymer or a polypropylene polymer.

Bis (arylphenoxide) lewis base tridentate ligands are a class of tridentate ligands that may use heterocyclic rings, such as pyridine groups. Such ligands may include bis (arylphenoxide) heterocyclic or bis (arylphenoxide) heterocyclic ligands. These ligands coordinate to the transition metal in a "tridentate" manner, meaning that the ligand forms three distinct bonds with the metal center. Bis (arylphenoxide) heterocyclic complexes are for example characterized in that the ligands combine in a tridentate manner to form two octa-metallocene rings. With the ligand coordinated to the metal in this way, the complex is considered chiral (i.e., lacks a symmetrical mirror surface). Without being bound by theory, it was found that these complexes can be used for the production of polypropylene and C ₃ And other polymers of higher alpha-olefins, because chirality favors the production of poly (alpha-olefins) of high isotacticity.

The catalysts, catalyst systems, and methods of the present disclosure can provide high Wen Yixi polymerization, propylene polymerization, ethylene alpha-olefin (e.g., ethylene-1-butene) copolymerization, or propylene alpha-olefin copolymerization because the bis (arylphenoxide) lewis base catalysts are stable at high polymerization temperatures and have good activity at high polymerization temperatures. A stable catalyst with good activity can provide the formation of polymers with high molecular weights and the ability to produce increased amounts of polymer in a given reactor compared to conventional catalysts, as polymerization generally occurs at higher rates at higher temperatures.

For the purposes of this disclosure, numbering schemes of the periodic table groups are used as described in Chemical And Engineering News, volume 63 (5), page 27 (1985). Thus, a "group 4 metal" is an element from group 4 of the periodic table, such as Hf, ti or Zr.

The following abbreviations may be used herein: me is methyl, et is ethyl, ph is phenyl, tBu is t-butyl, MAO is methylaluminoxane, NMR is nuclear magnetic resonance, t is time, s is seconds, h is hours, psi is pounds per square inch gauge, psig is side per square inch gauge, equiv is equivalent, RPM is revolutions per minute.

The specification describes transition metal complexes. The term complex is used to describe a molecule in which a secondary ligand coordinates to a central transition metal atom. The ligand is bulky and stably bound to the transition metal, thereby maintaining its influence during the use of the catalyst, e.g. the polymerization process. The ligand may be coordinated to the transition metal by covalent and/or electron donating coordinates or an intermediate bond. The transition metal complexes are typically activated to perform their polymeric or oligomeric function using activators, not bound by theory, that are believed to generate cations as a result of the removal of anionic groups (commonly referred to as leaving groups) from the transition metal.

As used herein, "olefin polymerization catalyst(s)" refers to any catalyst, such as an organometallic complex or compound, that is capable of coordination polymerization addition, wherein successive monomers are added into the monomer chain at the organometallic active center.

The terms "substituent", "group" and "moiety" may be used interchangeably.

"conversion" is the amount of monomer converted to polymer product and is reported as mole percent and is calculated based on the polymer yield and the amount of monomer fed to the reactor.

"catalyst Activity" is a measure of how active a catalyst is and is reported as grams of product polymer (P) produced per millimole of catalyst (cat) used per hour (gP. Mmolecat ^-1 .h ^-1 )。

The term "heteroatom" refers to any group 13-17 element, excluding carbon. Heteroatoms may include B, si, ge, sn, N, P, as, O, S, se, te, F, cl, br and I. The term "heteroatom" may include the aforementioned elements with attached hydrogen, e.g., BH ₂ 、SiH ₂ 、OH、NH、NH ₂ Etc. The term "substituted heteroatom" describes that one or more of these hydrogen atoms is substituted with a hydrocarbyl group or a substituentIs substituted by the hydrocarbyl group(s).

An "olefin" or "olefin" is a linear, branched or cyclic compound of carbon and hydrogen having at least one double bond. For the purposes of this specification and the appended claims, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of from 35 to 55 weight percent, it is understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and that the derived units are present at from 35 to 55 weight percent based on the weight of the copolymer. "Polymer" has two or more monomer units that are the same or different. "homopolymer" is a polymer having the same monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. "terpolymer" is a polymer having three monomer units that are different from one another. "different" as used in reference to monomer units means that the monomer units differ from each other by at least one atom or are isomerically different. Thus, as used herein, the definition of copolymer includes terpolymers. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50mol% ethylene derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50mol% propylene derived units, and so on. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50mol% ethylene derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50mol% propylene derived units, and so on.

The term "alpha-olefin" refers to an olefin ((R) having a terminal carbon-to-carbon double bond in its structure ¹ R ² )-C＝CH ₂ Wherein R is ¹ And R is ² Can independently be hydrogen or any hydrocarbyl group; for example R ¹ Is hydrogen and R ² Is an alkyl group). "Linear alpha-olefins" are alpha-olefins as defined in this paragraph, wherein R ¹ Is hydrogen, and R ² Is hydrogen or a linear alkyl group。

For the purposes of this disclosure, ethylene should be considered an alpha-olefin.

As used herein, and unless otherwise specified, the term "C _n "means hydrocarbon(s) having n carbon atoms per molecule, where n is a positive integer. The term "hydrocarbon" means a class of compounds containing carbon-bonded hydrogen and encompasses mixtures of (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different n values. Similarly, "C _m -C _y "group or compound" refers to a group or compound that contains a total number of carbon atoms in the range of m-y. Thus C ₁ -C ₅₀ Alkyl group means an alkyl group containing a total number of carbon atoms ranging from 1 to 50.

Unless otherwise indicated (e.g., "substituted hydrocarbyl", "substituted aryl", etc.), the term "substituted" means that at least one hydrogen atom has been replaced by at least one non-hydrogen group, e.g., a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, e.g., 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 Instead, where q is 1 to 10 and each R is independently a hydrocarbyl or halocarbyl group, and two or more R may join together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or where at least one heteroatom has been inserted into the hydrocarbyl ring.

The term "substituted hydrocarbyl" means a group (e.g., a functional group, such as-NR:, in which at least one hydrogen atom of the hydrocarbyl group has been replaced with at least one heteroatom (e.g., halogen, such as Br, cl, F, or I) or heteroatom-containing group (e.g., a functional group ₂ 、-OR*、-SeR*、-TeR*、-PR* ₂ 、-AsR* ₂ 、-SbR* ₂ 、-SR*、-BR* ₂ 、-SiR* ₃ 、-GeR* ₃ 、-SnR* ₃ 、-PbR* ₃ Which is provided withWherein q is 1 to 10 and each R is independently a hydrocarbyl or halocarbon group, and two or more R may join together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure) or a hydrocarbyl group in which at least one heteroatom is inserted within the hydrocarbyl ring. The term "hydrocarbyl-substituted phenyl" means a phenyl group having 1, 2, 3, 4, or 5 hydrogen groups replaced with hydrocarbyl or substituted hydrocarbyl groups. For example, a "hydrocarbyl-substituted phenyl" group may be represented by the formula:

wherein R is ^a 、R ^b 、R ^c 、R ^d And R is ^e Each of which may be independently selected from hydrogen, C ₁ -C ₄₀ Hydrocarbon or C ₁ -C ₄₀ Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals (provided that R ^a 、R ^b 、R ^c 、R ^d And R is ^e At least one of which is other than H), or R ^a 、R ^b 、R ^c 、R ^d And R is ^e Two or more of which may be joined together to form C ₄ -C ₆₂ A cyclic or polycyclic hydrocarbon ring structure, or a combination thereof.

The term "substituted aromatic" means an aromatic group having 1 or more hydrogen groups that have been replaced by a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

The term "substituted phenyl" means a phenyl group having 1 or more hydrogen groups that have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

The term "substituted carbazole" means a carbazole group having 1 or more hydrogen groups that have been replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a heteroatom-containing group.

The term "substituted naphthyl" means a naphthyl group having 1 or more hydrogen groups that have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

The term "substituted anthracyl" means an anthracyl group having 1 or more hydrogen groups that have been replaced by a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

The term "substituted fluorenyl" means a fluorenyl group having 1 or more hydrogen groups that have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

The term "substituted benzyl" means a benzyl group having 1 or more hydrogen groups that have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group, e.g., a substituted benzyl group represented by the formula:

wherein R is ^a’ 、R ^b’ 、R ^c’ 、R ^d’ And R is ^e’ And Z is each independently selected from hydrogen, C ₁ -C ₄₀ Hydrocarbon or C ₁ -C ₄₀ Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals (provided that R ^a’ 、R ^b’ 、R ^c’ 、R ^d’ And R is ^e’ And at least one of Z is not H), or R ^a’ 、R ^b’ 、R ^c’ 、R ^d’ And R is ^e’ And two or more of Z are joined together to form C ₄ -C ₆₂ A cyclic or polycyclic ring structure, or a combination thereof.

The terms "alkoxy" and "alkoxy" refer to an alkyl or aryl group bonded to an oxygen atom, e.g., an alkyl ether or aryl ether group/residue bonded to an oxygen atom and may include where the alkyl/aryl group is C ₁ -C ₁₀ Those of hydrocarbon groups. The alkyl groups may be linear, branched or cyclic. The alkyl groups may be saturated or unsaturated. Examples of suitable alkoxy groups may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and phenoxy.

The term "alkenyl" means a straight, branched or cyclic hydrocarbon group having one or more double bonds. These alkenyl groups may be optionally substituted. Examples of suitable alkenyl groups may include ethenyl, propenyl, allyl, 1, 4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, including substituted analogs thereof.

In the present disclosure, the terms "alkyl group" and "alkyl" may be used interchangeably. For the purposes of this disclosure, an "alkyl group" is defined as C ₁ -C ₁₀₀ Alkyl groups, which may be linear, branched or cyclic. Examples of such groups may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, including substituted analogs thereof. A substituted alkyl group is a group in which at least one hydrogen atom of the alkyl group has been replaced by at least one non-hydrogen group, such as a hydrocarbon 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 or-PbR ₃ Substituted, and each R is independently a hydrocarbyl or a halocarbyl group, and two or more R may join together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted into the hydrocarbyl ring.

The term "aryl" or "aryl group" means aromatic rings and substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl means an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom such as N, O or S. As used herein, the term "aromatic" also refers to pseudo-aromatic heterocycles, which are heterocyclic substituents having similar properties and structure (nearly planar) as aromatic heterocyclic ligands, but are by definition not aromatic; the term aromatic also refers to substituted aromatic compounds.

The term "aralkyl" means an aryl group in which hydrogen has been replaced by an alkyl or substituted alkyl group. For example, 3,5' -di-tert-butylphenyl indenyl is an indene substituted with an aralkyl group. When an aralkyl group is a substituent on another group, it is bonded to the group through an aryl group. For example, in formula (AI), the aryl moiety is bonded to E.

The term "alkylaryl" means an alkyl group in which hydrogen has been replaced by an aryl or substituted aryl group. For example, phenethylindenyl is an indene substituted with an ethyl group bonded to a phenyl group. When an alkylaryl group is a substituent on another group, it is bonded to the group through an alkyl group. For example, in formula (AI), the alkyl moiety is bonded to E.

When an isomer of a specified alkyl, alkenyl, alkoxy, or aryl group (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl) is present, references to one member of the group (e.g., n-butyl) should explicitly disclose the remaining isomers in the group (e.g., isobutyl, sec-butyl, and tert-butyl). Likewise, references to alkyl, alkenyl, alkoxy, or aryl groups without specifying a particular isomer (e.g., butyl) explicitly disclose all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has six ring atoms and tetrahydrofuran has 5 ring atoms.

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

The terms "hydrocarbyl group (hydrocarbyl radical)", "hydrocarbyl group (hydrocarbyl group)" or "hydrocarbyl" may be used interchangeably and are defined to mean a group consisting of only hydrogen and carbon atoms. For example, the hydrocarbon group may be C ₁ -C ₁₀₀ A group which may be linear, branched or cyclic, and when cyclicMay 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.

As used herein, unless otherwise indicated, a "low comonomer content" is defined as a polyolefin having less than 8 weight percent comonomer, based on the total weight of the polyolefin. As used herein, "high comonomer content" is defined as a polyolefin having greater than or equal to 8 weight percent comonomer, based on the total weight of the polyolefin.

As used herein, mn is the number average molecular weight, mw is the weight average molecular weight, and Mz is the z average molecular weight, wt% is the weight percent and mol% is the mole percent. Molecular Weight Distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., mw, mn, mz) are g/mol.

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

Unless otherwise indicated, all melting points (Tm) are Differential Scanning Calorimetry (DSC) secondary melts.

A "catalyst system" is a combination of at least one catalyst compound, at least one or activator, optionally a co-activator, and optionally a support material. The terms "catalyst compound", "catalyst complex", "transition metal compound", "procatalyst compound" and "procatalyst complex" may be used interchangeably. When "catalyst system" is used to describe the pair prior to activation, it means the unactivated catalyst complex (procatalyst) along with the activator and optionally the co-activator. When it is used to describe this pair after activation, it means that the complex is activated and the activator or other charge balancing moiety. The transition metal compound may be neutral (as in a procatalyst) or charged species with a counterion (as in an activated catalyst system). For the purposes of this disclosure and the claims thereto, when a catalyst system is described as comprising a neutral stable form of a component, one of ordinary skill in the art will fully understand that the ionic form of the component is the form that reacts with the monomer to produce a polymer. The polymerization catalyst system is a catalyst system that can polymerize monomers into polymers. Furthermore, the catalyst compounds and activators represented by the formulas herein are intended to include both neutral and ionic forms of the catalyst compounds and activators.

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

An "anionic ligand" is a negatively charged ligand that provides one or more pairs of electrons to a metal ion. A "lewis base" is a charge neutral ligand that provides one or more pairs of electrons to a metal ion. Examples of lewis bases include ethyl 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 (arylphenoxide) lewis base ligands are tridentate ligands that bind to a metal through two anion donors (phenoxide) and one heterocyclic lewis base donor (e.g., a pyridine group). Bis (arylphenoxide) heterocyclic ligands are tridentate ligands bound to the metal via two anion donors (phenoxide) and one heterocyclic lewis base donor.

Scavengers are compounds that can be added to promote polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. Co-activators (which are not scavengers) may also be used in combination with the activator to form an active catalyst. In at least one embodiment, the co-activator may be premixed with the transition metal compound to form an alkylated transition metal compound.

Non-coordinating anions (NCA) are defined as meaning anions which are not coordinated to the catalyst metal cations or which are coordinated to the metal cations but are only weakly coordinated. The term NCA is also defined to include multicomponent NCA-containing activators such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, which contain acidic cationic groups and non-coordinating anions. The term NCA is also defined to include neutral lewis acids such as tris (pentafluorophenyl) boron, which can react with catalysts to form activated species by abstraction of anionic groups. A lewis acid is defined as a compound or element that can react with an electron donor to form a bond. The NCA coordination is sufficiently weak that lewis base, such as olefin monomer, can displace it from the catalyst center. Any metal or metalloid that can form a compatible weakly coordinating complex can be used or contained in the non-coordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon.

The term "continuous" means a system that operates without interruption or stopping. For example, a continuous process for preparing a polymer would be one in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

Solution polymerization means a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or blends thereof. Solution polymerization may be homogeneous. Homogeneous polymerization is a polymerization in which the polymer product is dissolved in the polymerization medium. Suitable systems may not be cloudy, as described in Oliveira, J.V. et al, ind. Eng. Chem. Res.,2000, volume 29, page 4627.

Bulk polymerization means a polymerization process in which the monomer and/or comonomer being polymerized is used as a solvent or diluent with little or no use of an inert solvent as a solvent or diluent. A small portion of the inert solvent may be used as a support for the catalyst and scavenger. The bulk polymerization system contains less than 25 wt% of an inert solvent or diluent, such as less than 10 wt%, such as less than 1 wt%, such as 0 wt%.

Transition metal complex

In at least one embodiment, the present disclosure relates to novel catalyst compounds having a bis (aromatic phenoxide) lewis base tridentate ligand coordinated to a group 3, 4, or 5 transition metal center, forming two octamembered rings.

The catalyst compound may be represented by formula (I):

Wherein:

m is a group 3, 4 or 5 metal;

A ¹ and A ² Independently an aromatic group, such as an aromatic hydrocarbyl group;

j is a heterocyclic Lewis base, preferably having six ring atoms;

l is a Lewis base;

x is an anionic ligand;

n is 1, 2 or 3;

m is 0, 1 or 2;

n+m is not more than 4;

R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ and R is ⁸ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbyl, or heteroatom-containing group, or R ¹ And R is ² 、R ² And R is ³ 、R ³ And R is ⁴ 、R ⁵ And R is ⁶ 、R ⁶ And R is ⁷ Or R is ⁷ And R is ⁸ One or more of which may be joined to form one or more substituted hydrocarbyl rings, unsubstitutedA substituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings can join to form additional rings;

any two L groups can be joined together to form a bidentate lewis base;

the X group may be joined to the L group to form a monoanionic bidentate group; and

any two X groups may be joined together to form a dianionic group.

In at least one embodiment, A ¹ Represented by the formula:

wherein the method comprises the steps of

Represents a linkage to a catalyst compound, and R ⁹ 、R ¹⁰ 、R ¹¹ And R is ¹² Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ⁹ And R is ¹⁰ 、R ¹⁰ And R is ¹¹ Or R ¹¹ And R is ¹² One or more of which 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. In an alternative embodiment, R ⁹ 、R ¹⁰ 、R ¹¹ And R is ¹² Each independently is hydrogen or C ₁ -C ₄₀ A hydrocarbon group.

In at least one embodiment, A ² Represented by the formula:

wherein the method comprises the steps of

Represents a linkage to a catalyst compound, and R ¹³ 、R ¹⁴ 、R ¹⁵ And R is ¹⁶ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹³ And R is ¹⁴ 、R ¹⁴ And R is ¹⁵ Or R ¹⁵ And R is ¹⁶ One or more of which 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. In an alternative embodiment, R ¹³ 、R ¹⁴ 、R ¹⁵ And R is ¹⁶ Each independently is hydrogen or C ₁ -C ₄₀ A hydrocarbon group. In an alternative embodiment, R ⁹ 、R ¹⁰ 、R ¹¹ 、R ¹² 、R ¹³ 、R ¹⁴ 、R ¹⁵ And R is ¹⁶ Independently hydrogen or C ₁ -C ₄₀ Hydrocarbyl radicals, e.g. C ₂ -C ₂₀ A hydrocarbon group.

In an embodiment of the invention, J is cyclic with 6 ring atoms, one of which is a heteroatom.

In at least one embodiment, J is represented by the formula:

wherein the method comprises the steps of

Represents a linkage to a catalyst compound, and R ¹⁷ 、R ¹⁸ And R is ¹⁹ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹⁷ And R is ¹⁸ 、R ¹⁸ And R is ¹⁹ Or R ¹⁷ And R is ¹⁹ One or more of which 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. For example, R ¹⁷ 、R ¹⁸ And R is ¹⁹ May be hydrogen.

In at least one embodiment, the catalyst compound represented by formula (I) is represented by formula (I I):

wherein:

m is a group 3, 4 or 5 metal;

l is a Lewis base;

x is an anionic ligand;

n is 1, 2 or 3;

m is 0, 1 or 2;

n+m is not more than 4;

R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ and R is ⁸ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹ And R is ² 、R ² And R is ³ 、R ³ And R is ⁴ 、R ⁵ And R is ⁶ 、R ⁶ And R is ⁷ Or R is ⁷ And R is ⁸ 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 And R is ¹² Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ⁹ And R is ¹⁰ 、R ¹⁰ And R is ¹¹ Or R ¹¹ And R is ¹² One or more ofOne or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms;

R ¹³ 、R ¹⁴ 、R ¹⁵ and R is ¹⁶ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹³ And R is ¹⁴ 、R ¹⁴ And R is ¹⁵ Or R ¹⁵ And R is ¹⁶ 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 ¹⁷ 、R ¹⁸ and R is ¹⁹ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹⁷ And R is ¹⁸ 、R ¹⁸ And R is ¹⁹ Or R is ¹⁷ And R is ¹⁹ May be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms;

any two L groups can be joined together to form a bidentate lewis base;

The X group may be joined to the L group to form a monoanionic bidentate group; and

any two X groups may be joined together to form a dianionic ligand group.

For example, M of formula (I) or formula (II) may be a group 3,4 or 5 metal, e.g., M may be a group 4 metal. The group 4 metal may include zirconium, titanium and hafnium. In at least one embodiment, M is zirconium or hafnium.

Each L of formula (I) or formula (II) may be independently selected from ethers, amines, phosphines, thioethers, esters, et ₂ O、MeOtBu、Et ₃ N、PhNMe ₂ 、MePh ₂ N, tetrahydrofuran and twoMethyl sulfide, and each X may be independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrogen, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino. In at least one embodiment, n of formula (I) or formula (II) is 2 and each X is independently chloro or methyl.

The lewis base (J) of formula (I) may be selected from cyclic lewis bases. Lewis base J is a bridging A ¹ And A ² The divalent group of the group coordinates to the metal center M as a neutral 2 electron donor. The lewis base J may be aromatic or non-aromatic heterocyclic. The lewis base J may be a heterocyclic lewis base having 5 or 6 ring atoms. In at least one embodiment, J is a group 15-containing heterocycle, or a group 16-containing heterocycle, e.g., J is a nitrogen-containing heterocycle, an oxygen-containing heterocycle, a phosphorus-containing heterocycle, or a sulfur-containing heterocycle, e.g., the 5-membered heterocyclic Lewis base may include thiazole, isothiazole, 1,2, 4-thiadiazole, 1,2, 5-thiadiazole, 1,3, 4-thiadiazole, thiophene,

Azole, i->

Azole,/->

Oxazolines (e.g. 2->

Oxazoline, 3->

Oxazoline, 4->

Oxazoline) and (I) of the plant>

Oxazolidine, imidazole, furan, thiophene, pyrrole,Pyrazole, 1,2, 3-triazole, 1,2, 4-triazole, boroles, phosphole, azaphosphole, or isomers thereof, substituted or unsubstituted.

R of formula (I) or formula (II) ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ Each of which may be independently selected from hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, or phosphino, or R ¹ And R is ² 、R ² And R is ³ 、R ³ And R is ⁴ 、R ⁵ And R is ⁶ 、R ⁶ And R is ⁷ Or R is ⁷ And R is ⁸ One or more of which 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.

In at least one embodiment, R of formula (I) or formula (II) ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ Independently selected from 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 hydrocarbyl groups and all isomers of substituted hydrocarbyl groups, including trimethylsilylpropyl, trimethylsilylmethyl, trimethylsilylethyl, phenyl, or all isomers of hydrocarbyl-substituted phenyl, including methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, diethylphenyl, triethylphenyl, propylphenyl, dipropylphenyl, tripropylphenyl, dimethylethylphenyl, dimethylpropylphenyl, dimethylbutylphenyl, or dipropylmethylphenyl.

For example, R of formula (I) or formula (II) ⁴ And R is ⁵ Can be independently C ₁ -C ₁₀ Alkyl radicals, e.g. R ⁴ And R is ⁵ May be a tert-butyl group. In at least one embodiment, R ⁴ And R is ⁵ Independently selected from unsubstituted phenyl, substituted phenyl, unsubstituted carbazole, substituted carbazole, unsubstituted naphthyl, substituted naphthyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted fluorenyl, or substituted fluorenyl, heteroatom, or heteroatom-containing group, e.g., R ⁴ And R is ⁵ Can independently be unsubstituted phenyl or 3, 5-di-tert-butylbenzyl. In addition, (1) R ⁴ Can be C ₁ -C ₁₀ Alkyl (e.g. R ⁴ May be tert-butyl) and R ⁵ Can be aryl, or (2) R ⁵ Can be C ₁ -C ₁₀ Alkyl (e.g. R ⁵ May be tert-butyl) and R ⁴ May be aryl. Alternatively, R ⁴ And/or R ⁵ Can be independently heteroatoms such as R ⁴ And R is ⁵ May be a halogen atom (e.g., br, cl, F or I). Alternatively, R ⁴ And/or R ⁵ Can independently be silyl groups, e.g. R ⁴ And R is ⁵ Can be a trialkylsilyl or triarylsilyl group, wherein alkyl is C ₁ -C ₃₀ Alkyl (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl, cyclopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., isopentyl, cyclopentyl), hexyl (e.g., cyclohexyl), octyl (e.g., cyclohexyl), 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 is C ₆ -C ₃₀ Aryl (e.g., phenyl, benzyl, and naphthyl). Usefully, R ⁴ And R is ⁵ May be triethylsilyl. R is R ⁴ And R is ⁵ The identity of the polymer product can be used to control the molecular weight of the polymer product. For example, when R ⁴ And R is ⁵ When one or both of them is t-butyl, the catalyst compound may provide a polymerAmount of polymer. In contrast, when R ⁴ 、R ⁵ Or R is ⁴ And R is ⁵ Where phenyl, the catalyst compound may provide a low molecular weight polymer.

In at least one embodiment, each R of formula (I) or formula (II) ² And R is ⁷ Independently C ₁ -C ₁₀ Alkyl radicals, e.g. R ² And R is ⁷ Independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dimethylphenyl, t-butyl, isopropyl, or an isomer thereof.

R of formula (II) (or formula (I) when applicable) 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 is ¹⁹ Each of which may independently be hydrogen or C ₁ -C ₁₀ Alkyl radicals, e.g. 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 is 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 is ¹⁹ Is hydrogen. Alternatively, R of formula (II) (or formula (I), when applicable) 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 is ¹⁹ Independently of each other, hydrogen, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, or trimethylsilyl.

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

/>

/>

in at least one embodiment, the catalyst compound represented by formula (I) is selected from:

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 in which the process(s) described herein are carried out. The same activator may be used for the transition metal compound, however, two different activators such as a non-coordinating anion activator and an alumoxane may be used in combination.

The two transition metal compounds (procatalysts) may be used in any ratio. (A) The molar ratio of transition metal compound to (B) transition metal compound may be in the range of 1:1000 to 1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1, alternatively 1:1 to 100:1, alternatively 1:1 to 75:1, and alternatively 5:1 to 50:1 (A: B). The specific ratio selected will depend on the exact procatalyst, activation process and end product desired. In at least one embodiment, when two procatalysts are used (wherein both are activated with the same activator), the mole percent may be 10% to 99.9% a to 0.1% to 90% b, alternatively 25% to 99% a to 0.5% to 75% b, alternatively 50% to 99% a to 1% to 50% b, and alternatively 75% to 99% a to 1% to 10% b, based on the molecular weight of the procatalyst.

Activating agent

The terms "cocatalyst" and "activator" are used interchangeably herein.

The catalyst systems described herein may comprise a catalyst complex and an activator such as an alumoxane or a non-coordinating anion as described above, and may be formed by combining the catalyst components described herein with the activator (including combining them with a support such as silica) in any manner known from the literature. The catalyst system may also be added to or produced in solution or bulk polymerization (in monomers). The catalyst systems of the present disclosure may have one or more activators and one, two, or more catalyst components. An activator is defined as any compound that can activate any of the catalyst compounds described above by converting a neutral metal compound to a catalytically active metal compound cation. Non-limiting activators may include, for example, aluminoxanes, aluminum alkyls, ionizing activators (which may be neutral or ionic), and cocatalysts of conventional type. Suitable activators may include aluminoxane compounds, modified aluminoxane compounds, and ionizing, anionic precursor compounds that abstract reactive sigma-bonded metal ligands, thereby rendering the metal compounds cationic and providing charge-balancing non-coordinating or weakly coordinating anions, such as non-coordinating anions.

In at least one embodiment, the catalyst system comprises an activator and a catalyst compound of formula (I) or formula (II).

Aluminoxane activator

Aluminoxane activators are used as activators in the catalyst systems described herein. Aluminoxanes generally contain-Al (R) ^a”’ ) Oligomer compounds of the O-subunit, wherein R ^a”’ Is an alkyl group. Examples of alumoxanes include Methylalumoxane (MAO), modified Methylalumoxane (MMAO), ethylalumoxane, and isobutylalumoxane. Alkylaluminoxanes and modified alkylaluminoxane are suitable as catalyst activatorsEspecially when the abstractable ligand is an alkyl, halo, alkoxy or amino group. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. It may be appropriate to use visually clear methylaluminoxane. The cloudy or gelled aluminoxane can be filtered to produce a clear solution or the clear aluminoxane can be decanted from the cloudy solution. Useful alumoxane is Modified Methylalumoxane (MMAO) co-catalyst type 3A (commercially available from Akzo Chemicals, inc. Under the trade name Modified Methylalumoxane type 3A, incorporated herein by reference in patent No. US5,041,584). Another useful alumoxane is a solid polymethylalumoxane as described in US9,340,630, US 8,404,880 and US 8,975,209, which are incorporated herein by reference.

When the activator is an alumoxane (modified or unmodified), at least one embodiment selects a maximum activator amount of at most 5000-fold molar excess of Al/M relative to the catalyst compound (per metal catalytic site). The minimum activator to catalyst compound ratio may be 1:1 molar ratio. Alternative ranges may include 1:1-500:1, alternatively 1:1-200:1, alternatively 1:1-100:1, or alternatively 1:1-50:1.

In alternative embodiments, little or no aluminoxane is used in the polymerization process described herein. For example, the aluminoxane may be present in zero mole percent, alternatively the aluminoxane may be present in a molar ratio of aluminum to transition metal of the catalyst compound of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

Ionizing/non-coordinating anion activators

The term "non-coordinating anion" (NCA) means an anion that is not coordinated to a cation or is only weakly coordinated to a cation, thereby maintaining sufficient instability to be displaced by a lewis base. "compatible" non-coordinating anions are those that are not degraded to neutrality when the initially formed complex decomposes. In addition, the anion will not transfer an anionic substituent or fragment to the cation so that it forms a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions useful in accordance with the present disclosure are those that are compatible, stabilize transition metal cations in the sense that their ionic charge is balanced by +1, and yet remain sufficiently labile to allow displacement during polymerization. The ionizing activators useful herein generally comprise NCA, particularly compatible NCA.

It is within the scope of the present disclosure to use a neutral or ionic ionizing activator. It is also within the scope of the present disclosure to use neutral or ionic activators, alone or in combination with aluminoxane or modified aluminoxane activators. For a description of suitable activators, see US 8,658,556 and US 6,211,105.

The catalyst systems of the present disclosure may include at least one non-coordinating anion (NCA) activator. In at least one embodiment, a boron-containing NCA activator represented by the formula:

Zd+(Ad-)

wherein: z is (L-H) or a reducible Lewis acid; l is a Lewis base; h is hydrogen; (L-H) is a Bronsted acid; ad-is a boron-containing non-coordinating anion having a charge d-; d is 1, 2 or 3.

Cationic component Z _d ⁺ Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids, which are capable of protonating or abstracting moieties such as alkyl or aryl groups from the bulky ligand transition metal catalyst precursor to produce cationic transition metal species, may be included.

Activating cations Z _d ⁺ It is also possible to have structural parts such as silver,

(tropillium), carbon->

Ferrocene->

And mixtures, e.g. carbon- >

And ferrocene->

Z _d ⁺ Can be triphenylcarbon->

The reducible Lewis acid may be triarylcarbon +.>

(wherein aryl may be substituted or unsubstituted, e.g., of the formula (Ar) ₃ C ⁺ ) Those represented wherein Ar is aryl or is heteroatom-bound, C ₁ -C ₄₀ Hydrocarbyl or substituted C ₁ -C ₄₀ Hydrocarbyl-substituted aryl groups, such as reducible lewis acids "Z" may comprise a group of formula: (Ph) ₃ C) Those represented, wherein Ph is a substituted or unsubstituted phenyl group, e.g., substituted with C ₁ -C ₄₀ Hydrocarbyl or substituted C ₁ -C ₄₀ Hydrocarbyl radicals, e.g. C ₁ -C ₂₀ Alkyl or aromatic compounds or substituted C ₁ -C ₂₀ Alkyl or aromatic compounds, e.g. Z is triphenylcarbon +>

When Z is _d ⁺ Is an activating cation (L-H) _d ⁺ When it is a Bronsted acid, it is capable of donating a proton to the transition metal catalyst precursor, thereby generating a transition metal cation comprising ammonium, oxygen

Phosphonium, monosilane->

And mixtures thereof, such as methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylanilineAmmonium of amines, dioctadecyl methylamine, phosphonium of triethylphosphine, triphenylphosphine and diphenylphosphine, oxygen of ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane

Sulfonium from sulfides such as diethyl sulfide, tetrahydrothiophene, and mixtures thereof.

Anionic component A ^d- Comprising a compound having the formula [ M ] ^k+ Q _n ] ^d- Wherein k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6 (e.g., 1, 2, 3 or 4); n-k=d; m is an element selected from group 13 of the periodic Table of elements, such as boron or aluminum, and Q is independently hydrogen, a bridged or unbridged dialkylamino, halo, alkoxy, aryloxy, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halogen substituted hydrocarbyl group, with the proviso that Q is halo in no more than 1 occurrence, and wherein Q is a halogen. Each Q may be a fluorinated hydrocarbyl group having from 1 to 20 carbon atoms, e.g., each Q is a fluorinated aryl group, and e.g., each Q is a pentafluorophenyl group. Suitable A ^d- Examples of (c) also include diboron compounds as disclosed in US 5,447,895, which is incorporated herein by reference in its entirety.

Illustrative but non-limiting examples of boron compounds that can be used as activating cocatalysts are those described (and particularly those specifically enumerated) as activators in US 8,658,556, which is incorporated herein by reference.

Ionic activator Z _d ⁺ (A ^d- ) May be one or more of the following: n, N-dimethylanilinium tetrakis (perfluorophenyl) borate, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, dioctadecyl-methylammonium tetrakis (perfluorobiphenyl) borate, N-dimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, triphenylcarbon tetrakis (perfluoronaphthyl) borate

Triphenylcarbon tetrakis (perfluorobiphenyl) borate>

Triphenylcarbon +.4-bis (trifluoromethyl) phenyl) borate>

Or triphenylcarbon +.>

Alternatively, the activator compound is represented by formula (AI):

[R ¹ R ² R ³ EH] _d ⁺ [M ^k+ Q _n ] ^d- (AI)

wherein:

e is nitrogen or phosphorus, preferably nitrogen;

d is 1, 2 or 3 (preferably 3); k is 1, 2 or 3 (preferably 3); n is 1, 2, 3, 4, 5 or 6 (preferably 4, 5 or 6); n-k=d (preferably d is 1, 2 or 3, k is 3, n is 4, 5 or 6, preferably when M is B, n is 4);

R ¹ 、R ² and R is ³ Each independently is hydrogen, optionally substituted C ₁ -C ₄₀ Alkyl (e.g. branched or linear alkyl), or optionally substituted C ₅ -C ₅₀ Aryl (alternatively R) ¹ 、R ² And R is ³ Independently unsubstituted or substituted with at least one of: halo, C ₅ -C ₅₀ Aryl, C ₆ -C ₃₅ Aralkyl, C ₆ -C ₃₅ Alkylaryl, and at C ₅ -C ₅₀ In the case of aryl radicals C ₁ -C ₅₀ An alkyl group); wherein R is ¹ 、R ² And R is ³ Containing a total of 15 or more carbon atoms (e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 37 or more carbon atoms, e.g., 40 or more carbon atoms, e.g., 45 or more carbon atoms), preferably R ¹ 、R ² And R is ³ At least one of which is C ₃ -C ₄₀ Hydrocarbyl radicals (e.g. C ₃ -C ₄₀ Alkyl, or e.g. C ₇ -C ₄₀ An alkyl group);

m is an element selected from group 13 of the periodic Table of elements, preferably B or Al, preferably B; and

each Q is independently a hydrogen group, a bridged or unbridged dialkylamino group, a halo group, an alkoxy group, an aryloxy group, a hydrocarbyl group, a substituted hydrocarbyl group, a halocarbyl group, a substituted halocarbyl group, or a halogen substituted hydrocarbyl group, preferably a fluorinated aryl group, such as fluoro-phenyl or fluoro-naphthyl, more preferably a perfluorophenyl or perfluoronaphthyl group.

In any embodiment of formula (AI), R ¹ 、R ² And R is ³ May be independently selected from:

1) Optionally substituted linear alkyl (e.g., methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl (n-icosyl), n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, or n-triacontyl);

2) Optionally substituted branched alkyl (e.g., alkyl-butyl, alkyl-pentyl, alkyl-hexyl, alkyl-heptyl, alkyl-octyl, alkyl-nonyl, alkyl-decyl, alkyl-undecyl, alkyl-dodecyl, alkyl-tridecyl, alkyl-tetradecyl, alkyl-pentadecyl, alkyl-hexadecyl, alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl, alkyl-eicosyl (including polyalkyl analogs, i.e., dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl, dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl, dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl, dialkyl-tetradecyl, dialkyl-pentadecyl)A group, dialkyl-hexadecyl, dialkyl-heptadecyl, dialkyl-octadecyl, dialkyl-nonadecyl, dialkyl-eicosyl, trialkyl-butyl, trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl, trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl, trialkyl-tetradecyl, trialkyl-pentadecyl, trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl, and trialkyl-eicosyl, and the like), and isomers thereof, wherein each alkyl group is independently C ₁ -C ₄₀ (or C) ₂ -C ₃₀ Or C ₃ -C ₂₀ ) Linear, branched or cyclic alkyl groups), preferably the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or triacontyl);

3) Optionally substituted aralkyl groups such as (methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, tridecylphenyl, tetradecylphenyl, pentadecylphenyl, hexadecylphenyl, heptadecylphenyl, octadecylphenyl, nonadecylphenyl, eicosylphenyl, heneicosyl phenyl, docosylphenyl, tricosylphenyl, tetracosylphenyl, pentacosylphenyl, hexacosylphenyl, heptacosylphenyl, octacosylphenyl, nonacosylphenyl, triacontylphenyl, 3, 5-trimethylhexylphenyl, dioctylphenyl, 3, 5-trimethylhexylphenyl, 2,2,3,3,4-pentamethylpentylphenyl and the like);

4) Optionally substituted silyl groups, e.g. trialkylsilyl groups, each of whichThe alkyl groups are independently optionally substituted C ₁ -C ₂₀ Alkyl groups (e.g., trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, etc.) Triheptylsilyl, trioctylsilyl, trinonylsilyl, tridecylsilyl, tri-undecylsilyl, and Tri-dodecyl silyl, tri-tridecyl silyl, tri-tetradecyl silyl, tri-pentadecyl silyl, tri-hexadecyl silyl, tri-heptadecyl silyl, tri-octadecylsilyl, tri-nonadecyl silyl, tri-eicosyl silyl);

5) Optionally substituted alkoxy (e.g. -OR wherein R is optionally substituted C) ₁ -C ₂₀ Alkyl or aryl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, phenyl, alkylphenyl (e.g., methylphenyl, propylphenyl, etc.), naphthyl, or anthracyl);

6) Halogen (e.g., br or Cl); and

7) Halogen-containing groups (e.g., bromomethyl, bromophenyl, etc.).

For more information on activators represented by formula (IA) useful herein, see US2019-0330139 and US2019-0330139, which are incorporated herein by reference. Useful activators include N-methyl-4-nonadecyl-N-octadecyl-anilinium tetrakis (perfluoronaphthalen-2-yl) borate and N-methyl-4-nonadecyl-N-octadecyl-anilinium tetrakis (perfluorophenyl) borate.

Bulky activators may also be used herein as NCA. "bulky activator" as used herein refers to an anionic activator represented by the formula:

/>

or (b)

Wherein:

each R ^A Independently halo, such as fluoro;

ar is a substituted or unsubstituted aryl group (e.g., substituted or unsubstituted phenyl), e.g., substituted with C ₁ -C ₄₀ Hydrocarbyl radicals such as C ₁ -C ₂₀ Alkyl or aromatic compounds.

Each R ^B Independently halo, C ₆ -C ₂₀ Substituted aromatic hydrocarbon groups or of the formula-O-Si-R ^D Monosilaneoxy group of (C), wherein R ^D Is C ₁ -C ₂₀ Hydrocarbyl or hydrocarbylsilyl groups (e.g. R ^B Is a fluoro or perfluorinated phenyl group);

each R ^C Is halo, C ₆ -C ₂₀ Substituted aromatic hydrocarbon groups or of the formula-O-Si-R ^D Monosilaneoxy group of (C), wherein R ^D Is C ₁ -C ₂₀ Hydrocarbyl or hydrocarbylsilyl groups (e.g. R ^D Is fluoro or C ₆ Perfluorinated aromatic hydrocarbon groups); wherein R is ^B And R is ^C May form one or more saturated or unsaturated, substituted or unsubstituted rings (e.g. R ^B And R is ^C Forming a perfluorinated phenyl ring);

l is a Lewis base; (L-H) ⁺ Is a Bronsted acid; d is 1, 2 or 3;

wherein the anion has a molecular weight greater than 1,020g/mol; and

wherein at least three of the substituents on the B atom each have a number greater than

Alternatively greater than

Or alternatively greater than->

Molecular volume of (2).

For example, (Ar) ₃ C) _d ⁺ Can be (Ph) ₃ C) _d ⁺ Wherein Ph is a substituted or unsubstituted phenyl group, e.g. substituted with C ₁ -C ₄₀ Hydrocarbyl or substituted C ₁ -C ₄₀ Hydrocarbyl radicals, e.g. C ₁ -C ₂₀ Alkyl or aromatic compounds or substituted C ₁ -C ₂₀ Alkyl or aromatic compounds.

"molecular volume" is used herein as an approximation of the spatial steric bulk of the activator molecule in solution. Comparing substituents having different molecular volumes allows substituents having smaller molecular volumes to be considered "smaller" than substituents having larger molecular volumes. In contrast, substituents having a larger molecular volume may be considered to be "more bulky" than substituents having a smaller molecular volume.

The molecular volumes may be calculated as reported in "a Simple" Back of the Envelope "Method for Estimating the Densities and Molecular Volumes of Liquids and Solids", journal of Chemical Education, volume 71 (11), month 11, 1994, pages 962-964, which is incorporated herein by reference. Using the following calculation

Molecular Volume (MV) in units: mv=8.3v _s Wherein V is _s Is a scaled volume (scaled volume). V (V) _s Is the sum of the relative volumes of the constituent atoms and is calculated from the formula of the substituents using the table below. For the fused rings, each fused ring V _S The reduction is 7.5 percent.

Element(s)	Relative volume
		H	1
Short cycle 1, li to F	2
		The 2 nd shortest period, na to Cl	4
1 st long period, K to Br	5
		Period 2, rb to I	7.5
3 rd long period, cs to Bi	9

A list of suitable bulky activators is found in US 8,658,556, which is incorporated herein by reference.

In another embodiment, one or more of the NCA activators is selected from the activators described in US 6,211,105.

In a preferred embodiment, the activator is selected from one or more of the following: triaryl carbon

(e.g. triphenylcarbon tetraphenylborate->

Triphenylcarbon tetrakis (pentafluorophenyl) borate >

Triphenylcarbon tetrakis- (2, 3,4, 6-tetrafluorophenyl) borate

Triphenylcarbon tetrakis (perfluoronaphthyl) borate>

Triphenylcarbon tetrakis (perfluorobiphenyl) borate>

Triphenylcarbon +.4-bis (trifluoromethyl) phenyl) borate>

)。

In another embodiment, the activator is selected from one or more of the following: trialkylammonium tetrakis (pentafluorophenyl) borate, N-dialkylanilinium tetrakis (pentafluorophenyl) borate, dioctadecyl-methylammonium tetrakis (perfluoronaphthyl) borate, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (pentafluorophenyl) borate, trialkylammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate, N-dialkylanilinium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate, trialkylammonium tetrakis (perfluoronaphthyl) borate, N-perfluoronaphthyl) borate, N-dialkylanilinium borate, trialkylammonium tetrakis (perfluorobiphenyl) borate, N-dialkylanilinium tetrakis (perfluorobiphenyl) borate, trialkylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, N-dialkylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, N-dialkyl- (2, 4, 6-trimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate (wherein alkyl is methyl, ethyl, propyl, N-butyl, sec-butyl or tert-butyl).

Suitable activator to catalyst ratios, for example, all NCA activator to catalyst ratios, may be about 1:1 molar ratio. Alternative ranges include 0.1:1-100:1, alternatively 0.5:1-200:1, alternatively 1:1-500:1, alternatively 1:1-1000:1. Particularly useful ranges are 0.5:1-10:1, e.g., 1:1 to 5:1.

It is also within the scope of the present disclosure that the catalyst compound may be combined with a combination of aluminoxane and NCA (see, for example, US 5,153,157,US 5,453,410,EP 0 573 120 B1,WO 1994/007928 and WO 1995/014044, which discuss the use of a combination of aluminoxane and an ionizing activator).

The chain transfer agents which may be used are hydrogen, alkylaluminoxane, of the formula AlR ₃ 、ZnR ₂ A compound of formula (wherein each R is independently C ₁ -C ₈ Aliphatic groups such as methyl, ethyl, propyl, butyl, pentyl, hexyloctyl, or isomers thereof) or combinations thereof such as diethyl zinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof.

In addition, the catalyst system of the present disclosure may include a metal hydro carbyl chain transfer agent represented by the formula:

Al(R') _3-v (R”) _v

wherein each R' may independently be C ₁ -C ₃₀ The hydrocarbyl group and/or each R' may independently be C with a terminal vinyl group ₄ -C ₂₀ A hydrocarbenyl group; and v may be 0.1 to 3.

In embodiments of the invention, the activators described herein have a solubility in methylcyclohexane of greater than 10mM (or greater than 20mM or greater than 50 mM) at 25℃ (stirring for 2 hours) and/or a solubility in isohexane of greater than 1mM (or greater than 10mM or greater than 20 mM) at 25℃ (stirring for 2 hours).

The present disclosure relates to catalyst systems comprising an activator compound represented by formula (IA) and a metallocene transition metal compound, to the use of such activator compound for activating transition metal compounds in catalyst systems for polymerizing olefins, and to methods of polymerizing olefins comprising contacting one or more olefins under polymerization conditions with a catalyst system comprising a metallocene transition metal compound and such activator compound, wherein no aromatic solvent, such as toluene, is present (e.g. at zero mol%, or at less than 1mol%, preferably the catalyst system, polymerization reaction, and/or polymer produced is free of detectable aromatic hydrocarbon solvents, such as toluene.

The polyalphaolefins produced herein preferably contain 0ppm (or less than 1ppm, or less than 5ppm, or less than 10 ppm) aromatic hydrocarbons. Preferably, the polyalphaolefins produced herein contain 0ppm (or less than 1ppm, or less than 5ppm, or less than 10 ppm) toluene.

The catalyst system used herein preferably contains 0ppm (or less than 1ppm, or less than 5ppm, or less than 10 ppm) aromatic hydrocarbons. Preferably, the catalyst system used herein contains 0ppm (or less than 1ppm, or less than 5ppm, or less than 10 ppm) toluene.

Optional scavenger or co-activator

In addition to these activator compounds, scavengers or co-activators may be used. The alkylaluminum or aluminoxane compounds that can be used as scavengers or co-activators can include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, methylaluminoxane (MAO), modified Methylaluminoxane (MMAO), MMAO-3A, and diethyl zinc.

Optional support material

In embodiments herein, the catalyst system may include an inert support material. The support material may be a porous support material such as talc and inorganic oxides. Other support materials include zeolites, clays, organoclays or other organic or inorganic support materials, or mixtures thereof.

The support material may be an inorganic oxide in finely divided form. Suitable inorganic oxide materials for use in the catalyst systems herein may include group 2, 4, 13, and 14 metal oxides such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be employed, alone or in combination with the silica or alumina, may be magnesia, titania, zirconia. However, other suitable support materials may be employed, such as finely divided functionalized polyolefins, e.g., finely divided polyethylene. Examples of suitable carriers may include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolite, talc, clay. In addition, combinations of these support materials may be used, for example silica-chromium, silica-alumina, silica-titania. In at least one embodiment The carrier material is selected from Al ₂ O ₃ 、ZrO ₂ 、SiO ₂ 、SiO ₂ /Al ₂ O ₃ 、SiO ₂ /TiO ₂ Silica clay, silica/clay, or mixtures thereof.

Support materials such as inorganic oxides may have a surface area of about 10m ² /g to about 700m ² In the range of/g, the pore volume is about 0.1cm ³ /g to about 4.0cm ³ In the range of/g, the average particle size is in the range of about 5 μm to about 500. Mu.m. The surface area of the support material may be about 50m ² /g to about 500m ² In the range of/g, the pore volume is about 0.5cm ³ /g to about 3.5cm ³ And/g, and an average particle size of from about 10 μm to about 200. Mu.m. For example, the surface area of the support material is about 100m ² /g to about 400m ² In the range of/g, the pore volume is about 0.8cm ³ /g to about 3.0cm ³ In the range of/g, the average particle size is from about 5 μm to about 100. Mu.m. The average pore size of the support materials useful in the present disclosure is in

For example->

To about->

And e.g. +.>

To about

Within a range of (2). In at least one embodiment, the support material is a high surface area amorphous silica (surface area = 300m ² Gm, pore volume of 1.65cm ³ /gm). For example, a suitable silica may be that available as DAVISON from Davison Chemical Division of W.R.Grace and Company ^TM 952 or DAVISON ^TM 955, a silica sold under the trade name of 955. In other embodiments, DAVISON is used ^TM 948. Alternatively, the silica may be, for example, ES-70 that has been calcined (e.g., at 875 ℃) ^TM Silica (Malvern, pa., PQ Corporation).

The carrier material should be dry, i.e. free of absorbed water. Drying of the support material may be achieved by heating or calcining at about 100 ℃ to about 1,000 ℃, for example at least about 600 ℃. When the support material is silica, it is heated to at least 200 ℃, such as from about 200 ℃ to about 850 ℃, and such as at about 600 ℃; and for a period of time of about 1 minute to about 100 hours, about 12 hours to about 72 hours, or about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups to produce the supported catalyst system of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

The support material having reactive surface groups (e.g., hydroxyl groups) is slurried in a nonpolar solvent and the resulting slurry is contacted with a solution of the catalyst compound and the activator. In at least one embodiment, the slurry of support material is first contacted with the activator for a period of time in the range of from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours. The solution of catalyst compound is then contacted with the separated support/activator. In at least one embodiment, the supported catalyst system is generated in situ. In alternative embodiments, the slurry of support material is first contacted with the catalyst compound for a period of time in the range of from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours. The slurry of supported catalyst compound is then contacted with an activator solution.

The mixture of catalyst, activator, and support is heated from about 0 ℃ to about 70 ℃, e.g., from about 23 ℃ to about 60 ℃, e.g., at room temperature. The contact time may be from about 0.5 hours to about 24 hours, such as from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.

Suitable non-polar solvents are materials in which all of the reactants used herein (e.g., activators and catalyst compounds) are at least partially soluble and liquid at the reaction temperature. The nonpolar solvent may be an alkane such as isopentane, hexane, n-heptane, octane, nonane, and decane, but various other materials may be used including cycloalkanes such as cyclohexane, aromatics such as benzene, toluene, and ethylbenzene.

Polymerization process

The present disclosure relates to polymerization processes wherein monomers (e.g., ethylene, propylene) and optional comonomers are contacted with a catalyst system comprising an activator and at least one catalyst compound as described above. The catalyst compound and activator may be combined in any order. The catalyst compound and activator may be combined prior to contact with the monomer. Alternatively, the catalyst compound and activator may be introduced separately into the polymerization reactor, where they are subsequently reacted to form the active catalyst.

Monomers include substituted or unsubstituted C ₂ -C ₄₀ Alpha-olefins, e.g. C ₂ -C ₂₀ Alpha-olefins, e.g. C ₂ -C ₁₂ Alpha-olefins such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In at least one embodiment, the monomers include ethylene and optionally a comonomer comprising one or more C ₃ -C ₄₀ Olefins, e.g. C ₄ -C ₂₀ Olefins, e.g. C ₆ -C ₁₂ An olefin. C (C) ₃ -C ₄₀ The olefin monomers may be linear, branched or cyclic. C (C) ₃ -C ₄₀ The cyclic olefin may be strained (strained) or unstrained (unstrained), monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups. In another embodiment, the monomers include propylene and optionally a comonomer comprising one or more ethylene or C ₄ -C ₄₀ Olefins, e.g. C ₄ -C ₂₀ Olefins, e.g. C ₆ -C ₁₂ An olefin. C (C) ₄ -C ₄₀ The olefin monomers may be linear, branched or cyclic. C (C) ₄ -C ₂₀ The cyclic olefins may be strained or unstrained, monoCyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.

Exemplary C ₂ -C ₄₀ The olefin monomers and optional comonomers may include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, ethylidene norbornene, vinyl norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1, 5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives, such as norbornene, norbornadiene, and dicyclopentadiene.

The polymerization process of the present disclosure may be performed in any suitable manner. Any suitable suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process may be used. Such a process may be operated in batch, semi-batch or continuous mode. Both homogeneous polymerization processes and slurry processes may be used. A bulk homogeneous process may be used. Alternatively, no solvent or diluent (other than in small amounts used as a support for the catalyst system or other additives, or in amounts found with monomers, such as propane in propylene) is present or added to the reaction medium. In another embodiment, the process is a slurry process. As used herein, the term "slurry polymerization process" means a polymerization process conducted in a hydrocarbon solvent wherein a supported catalyst is employed and monomers are polymerized on the supported catalyst particles at a temperature below the melting point of the polymer produced. At least 95 wt% of the polymer product derived from the supported catalyst is in pellet form as solid particles (insoluble in the diluent).

Suitable diluents/solvents for the polymerization may include non-coordinating inert liquids. Examples of diluents/solvents for the polymerization may include straight chain and Branched hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof, such as commercially available (Isopar ^TM ) The method comprises the steps of carrying out a first treatment on the surface of the Perhalogenated hydrocarbons, e.g. perfluorinated C ₄ -C ₁₀ Alkanes, chlorobenzene, and aromatics and alkyl-substituted aromatics such as benzene, toluene, mesitylene, and xylenes. Suitable solvents may also include liquid olefins, which may act as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In at least one embodiment, an aliphatic hydrocarbon solvent is used as the solvent, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, e.g., the aromatic compound is present in the solvent at less than 1 wt%, e.g., less than 0.5 wt%, e.g., less than 0 wt%, based on the weight of the solvent.

In at least one embodiment, the monomers and comonomers used in the polymerization are fed at a concentration of 60% by volume of solvent or less, such as 40% by volume or less, such as 20% by volume or less, based on the total volume of the feed stream. In at least one embodiment, the polymerization is carried out in a bulk process.

The polymerization may be carried out at any temperature and/or pressure suitable to obtain the desired polymer. Typical temperatures and/or pressures include temperatures in the range of about 0 ℃ to about 300 ℃, such as about 20 ℃ to about 200 ℃, such as about 35 ℃ to about 160 ℃, such as about 80 ℃ to about 160 ℃, such as about 90 ℃ to about 140 ℃, and pressures in the range of about 0.1MPa to about 25MPa, such as about 0.45MPa to about 6MPa, or about 0.5MPa to about 4 MPa.

In a suitable polymerization, the reaction is run for a period of up to 300 minutes, such as from about 5 minutes to about 250 minutes, such as from about 10 minutes to about 120 minutes, such as from about 20 minutes to about 90 minutes, such as from about 30 minutes to about 60 minutes. In a continuous process, the run time may be the average residence time of the reactor.

In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of from 0.001psig to 50psig (0.007 kPa to 345 kPa), such as from 0.01psig to 25psig (0.07 kPa to 172 kPa), such as from 0.1psig to 10psig (0.7 kPa to 70 kPa).

In at least one embodiment, little or no aluminoxane is used in the process for producing the polymer. For example, the aluminoxane may be present in zero mole percent, alternatively the aluminoxane may be present in a molar ratio of aluminum to transition metal of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

In at least one embodiment, polymerization: 1) At a temperature of from 0 ℃ to 300 ℃ (e.g., from 25 ℃ to 250 ℃, e.g., from 80 ℃ to 160 ℃, e.g., from 100 ℃ to 140 ℃); 2) At a pressure of from atmospheric pressure to 10MPa (e.g. 0.35MPa to 10MPa, e.g. 0.45MPa to 6MPa, e.g. 0.5MPa to 4 MPa); 3) In an aliphatic hydrocarbon solvent (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, decane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; for example wherein the aromatic compound is present in the solvent at less than 1 wt%, for example less than 0.5 wt%, for example at 0 wt%, based on the weight of the solvent); 4) Wherein the catalyst system used in the polymerization comprises less than 0.5 mole%, such as 0 mole% aluminoxane, optionally the aluminoxane is present in a molar ratio of aluminum to transition metal of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1; 5) Polymerization occurs in one reaction zone; 6) Optionally in the absence of a scavenger (e.g., a trialkylaluminum compound) (e.g., present at zero mole percent, or the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, e.g., less than 50:1, e.g., less than 15:1, e.g., less than 10:1); and 7) optionally hydrogen is present at a partial pressure of 0.001psig to 50psig (0.007 kPa to 345 kPa) (e.g., 0.01psig-25psig (0.07 kPa to 172 kPa), such as 0.1psig to 10psig (0.7 kPa to 70 kPa)). In at least one embodiment, the catalyst system used in the polymerization comprises no more than one catalyst compound. A "reaction zone" (also referred to as a "polymerization zone") is a vessel in which polymerization occurs, such as a stirred tank reactor or a loop reactor. When multiple reactors are used in a continuous polymerization process, each reactor is considered to be a separate polymerization zone. For multistage polymerization in a batch polymerization process, each polymerization stage is considered a separate polymerization zone. In at least one embodiment, polymerization occurs in one reaction zone. Room temperature was 23 ℃, unless otherwise indicated.

In at least one embodiment, the present disclosure provides a process for producing an ethylene-based polymer comprising: ethylene is polymerized to form an ethylene-based polymer by contacting ethylene with the catalyst system of the present disclosure described above in one or more continuous stirred tank reactors or loop reactors in series or in parallel at a reactor pressure of 0.05MPa to 1,500MPa and a reactor temperature of 30 ℃ to 230 ℃. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of from about 5psig to about 300psig, such as from about 10psig to about 250psig, such as from about 30psig to about 200psig, such as from about 20psig to about 150psig, such as from about 50psig to about 100psig (e.g., 75 psig). In at least one embodiment, the catalyst has an activity of at least 5,000g P.mmolecat ^-1 .h ^-1 For example about 5,000 gP.mmolecat ^-1 .h ^-1 -1,000,000gP.mmolcat ^-1 .h ^-1 For example about 7,500 gP.mmolecat ^-1 .h ^-1 -900,000gP.mmolcat ^-1 .h ^-1 For example about 10,000 gP.mmolecat ^-1 .h ^-1 -750,000gP.mmolcat ^-1 .h ^-1 Or about 12,500g P.mmolecat ^-1 .h ^-1 -600,000gP.mmolcat ^-1 .h ^-1 。

In another embodiment, the present disclosure provides a process for producing a propylene-based polymer comprising: polymerizing propylene in the form by contacting propylene with the catalyst system of the present disclosure described above in one or more continuous stirred tank reactors or loop reactors in series or in parallel at a reactor pressure of from 0.5MPa to 1,500MPa and a reactor temperature of from 30 ℃ to 230 °c To form a propylene-based polymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of from about 10psig to about 300psig, such as from about 20psig to about 250psig, such as from about 30psig to about 200psig, such as from about 40psig to about 150psig, such as from about 50psig to about 100psig (e.g., 75 psig). In at least one embodiment, the catalyst has an activity of at least 100 gP.mmolecat ^-1 .h ^-1 For example 100 gP.mmolecat ^-1 .h ^-1 -6,000,000gP.mmolcat ^-1 .h ^-1 For example 200 gP.mmolecat ^-1 .h ^-1 -5,000,000gP.mmolcat ^-1 .h ^-1 Or 300 gP.mmolecat ^-1 .h ^-1 -1,500,000gP.mmolcat ^-1 .h ^-1 。

In another embodiment, the present disclosure provides a method of producing an ethylene alpha-olefin copolymer comprising: by reacting ethylene and at least one C in one or more continuous stirred tank reactors or loop reactors in series or in parallel at a reactor pressure of from 0.05MPa to 1,500MPa and a reactor temperature of from 30℃to 230 DEG C ₃ -C ₂₀ Contacting an alpha-olefin with the catalyst system described above to polymerize ethylene and at least one C ₃ -C ₂₀ Alpha-olefins to form ethylene alpha-olefin copolymers. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of from about 10psig to about 300psig, such as from about 20psig to about 250psig, such as from about 30psig to about 200psig, such as from about 40psig to about 150psig, such as from about 50psig to about 100psig (e.g., 75 psig), or from about 150psig to about 300psig (e.g., 200 psig). In at least one embodiment, the catalyst has an activity of at least 1,000 gP.mmolecat ^-1 .h ^-1 For example about 1,000 gP.mmolecat ^-1 .h ^-1 -about 10,000,000gp ^-1 .h ^-1 For example about 1,500 gP.mmolecat ^-1 .h ^-1 -about 8,000,000gp ^-1 .h ^-1 For example about 1,800 gP.mmolecat ^-1 .h ^-1 -about 1,000,000gp ^-1 .h ^-1 Or about 10,000g P.mmolecat ^-1 .h ^-1 -about 8,000,000gp ^-1 .h ^-1 。

In another embodiment, the present disclosureThere is provided a process for producing a propylene alpha-olefin copolymer comprising: by reacting propylene and at least one ethylene and/or at least one C in one or more continuous stirred tank reactors or loop reactors in series or in parallel at a reactor pressure of from 0.05MPa to 1,500MPa and a reactor temperature of from 30 ℃ to 230 DEG C ₃ -C ₂₀ Contacting an alpha-olefin with the catalyst system described above to polymerize propylene and at least one ethylene and/or at least one C ₄ -C ₂₀ Alpha-olefins to form ethylene alpha-olefin copolymers. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of from about 10psig to about 300psig, such as from about 20psig to about 250psig, such as from about 30psig to about 200psig, such as from about 40psig to about 150psig, such as from about 50psig to about 100psig (e.g., 75 psig), or from about 150psig to about 300psig (e.g., 200 psig). In at least one embodiment, the catalyst has an activity of at least 1,000 gP.mmolecat ^-1 .h ^-1 For example about 1,000 gP.mmolecat ^-1 .h ^-1 -about 10,000,000gp ^-1 .h ^-1 For example about 1,500 gP.mmolecat ^-1 .h ^-1 -about 8,000,000gp ^-1 .h ^-1 For example about 1,800 gP.mmolecat ^-1 .h ^-1 -about 1,000,000gp ^-1 .h ^-1 Or about 10,000g P.mmolecat ^-1 .h ^-1 -about 500,000 gP.mmolecat ^-1 .h ^-1 。

In at least one embodiment, the conversion of olefin monomer is at least 10%, such as 20% or more, such as 30% or more, such as 50% or more, such as 80% or more, based on the polymer yield and weight of monomer entering the reaction zone.

In at least one embodiment, little or no aluminoxane is used in the process for producing the polymer. For example, the aluminoxane is present in zero mole percent, alternatively the aluminoxane is present in a molar ratio of aluminum to transition metal of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

In at least one embodiment, little or no scavenger is used in the process for producing the ethylene polymer. For example, the scavenger (e.g., trialkylaluminum) is present at zero mole percent, alternatively the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, such as less than 50:1, such as less than 15:1, such as less than 10:1.

Other additives may also be used in the polymerization as desired, such as one or more scavengers, hydrogen, aluminum alkyls, or chain transfer agents (e.g., alkylaluminoxane, of the formula AlR ₃ Or ZnR ₂ A compound of formula (wherein each R is independently C ₁ -C ₈ Aliphatic groups such as methyl, ethyl, propyl, butyl, pentyl, hexyloctyl, or isomers thereof) or combinations thereof, such as diethyl zinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof).

Solution polymerization

In at least one embodiment, the polymerization process using the catalyst compounds of the present disclosure is a solution polymerization process.

Solution polymerization is a polymerization process in which a polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or blends thereof. Solution polymerization is generally homogeneous. Homogeneous polymerization is a polymerization in which the polymer product is dissolved in the polymerization medium. Such systems are not cloudy as described in Ol ivira, j.v. (2000), ind.Eng, chem.Res., volume 29, page 4627. Solution polymerization may include polymerization in a continuous reactor, wherein the polymer formed, the starting monomer supplied, and the catalyst material are agitated to reduce or avoid concentration gradients, and wherein the monomer acts as a diluent or solvent or wherein a hydrocarbon is used as a diluent or solvent. Suitable processes may be operated at temperatures of from about 0 ℃ to about 250 ℃, such as from about 50 ℃ to about 170 ℃, such as from about 80 ℃ to about 150 ℃, such as from about 100 ℃ to about 140 ℃, and/or at pressures of about 0.1MPa or greater, such as 2MPa or greater. The upper pressure limit is not critical but may be about 200MPa or less, for example 120MPa or less, for example 30MPa or less. Temperature control in the reactor can be obtained by balancing the heat of polymerization, typically with reactor cooling, by reactor jacket or cooling coils to cool the contents of the reactor, autorefrigeration, pre-cooling of the feed, evaporation of liquid medium (diluent, monomer or solvent), or a combination of all three. An adiabatic reactor with pre-cooled feed may also be used. The purity, type and amount of solvent can be optimized to obtain the maximum catalyst productivity for a particular type of polymerization. The solvent may also be introduced as a catalyst support. Depending on the pressure and temperature, the solvent may be introduced as a gas phase or as a liquid phase. Advantageously, the solvent may be maintained in the liquid phase and introduced as a liquid. The solvent may be introduced into the polymerization reactor in the feed.

The processes described herein may be solution polymerization processes, which may be conducted in a batch manner (e.g., batch, semi-batch) or in a continuous process. Suitable reactors may include tank, loop and tube designs. In at least one embodiment, the process is carried out in a continuous manner and uses a dual loop reactor in a series configuration. In at least one embodiment, the process is conducted in a continuous mode and uses a dual Continuous Stirred Tank Reactor (CSTR) in a series configuration. Furthermore, the process may be carried out in a continuous manner and a tube reactor may be used. In another embodiment, the process is conducted in a continuous manner and uses one loop reactor and one CSTR in a series configuration. The process may also be carried out in a batch mode and may use a single stirred tank reactor.

Polyolefin products

The present disclosure relates to compositions of matter produced by the methods described herein.

In at least one embodiment, the methods described herein produce C ₂ -C ₂₀ Olefin homopolymers (e.g. polyethylene, polypropylene), or C ₂ -C ₂₀ Olefin copolymers (e.g. ethylene-octene, ethylene-propylene) and/or propylene-alpha-olefin copolymers, e.g. C ₃ -C ₂₀ Copolymers (e.g., propylene-hexene copolymers or propylene-octene copolymers). In at least one embodiment, the methods described herein produce C ₃ -C ₂₀ Isotactic olefin homopolymers such as isotactic polypropylene, for example highly isotactic polypropylene.

The term "isotactic" is defined as based on passage ¹³ Analysis by C NMR has at leastA pentad isotactic of 20% or more. The term "highly isotactic" is defined in terms of passage ¹³ Analysis by C NMR has 50% or more isotactic pentads.

In at least one embodiment, the ethylene or propylene based polymer (homopolymer) has one or more of the following: mw values of 1,000g/mol or greater, for example, from about 1,000g/mol to about 3,000,000g/mol, for example, from about 25,000g/mol to about 2,000,000g/mol, or from about 3,000,000g/mol to about 10,000,000g/mol, for example, from about 5,000,000g/mol to about 7,500,000g/mol; mn values of 1,000g/mol or greater, for example, from about 1,000g/mol to about 2,000,000g/mol, for example, from about 100,000g/mol to about 1,200,000g/mol, or from about 2,000,000g/mol to about 10,000,000g/mol, for example, from about 5,000,000g/mol to about 7,500,000g/mol; the Mz value is 5,000g/mol or greater, for example, from about 1,000g/mol to about 10,000,000g/mol, for example, from about 100,000 to about 6,000,000g/mol, or from about 10,000,000g/mol to about 25,000,000g/mol.

In at least one embodiment, the ethylene or propylene based polymer has a Mw/Mn (PDI) value of from 1 to 20, such as from 5 to 20, such as from 10 to 20, or from 1 to 5, such as from 1.5 to about 3.

In at least one embodiment, the ethylene or propylene based polymer has a melting point (Tm) of at least 100 ℃, such as from about 100 ℃ to about 150 ℃, such as from about 100 ℃ to about 140 ℃.

In at least one embodiment, the ethylene or propylene based polymer has a melting point (Tm) of less than 100 ℃, such as from about 30 ℃ to about 80 ℃, such as from about 40 ℃ to about 70 ℃.

In at least one embodiment, the propylene-based polymer has one or more of the following: mw values of about 500g/mol or greater, such as from about 500g/mol to about 200,000g/mol, such as from about 2,000g/mol to about 100,000g/mol, or such as from about 1,000g/mol to about 400,000g/mol; mn values of 500g/mol or greater, for example, from about 500g/mol to about 250,000g/mol, for example, from about 10,000g/mol to about 100,000, or from 1,000g/mol to about 500,000; the Mz value is 2,000g/mol or greater, for example, from about 2,000g/mol to about 400,000g/mol, for example, from about 10,000g/mol to about 200,000g/mol, or from about 1,000g/mol to about 750,000g/mol.

In at least one embodiment, the propylene-based polymer has a Mw/Mn (PDI) value of from 1 to 3, such as from 1 to 2.5.

In at least one embodiment, the propylene-based polymer has a melting point (Tm) of at least 50 ℃, such as 100 ℃ to 170 ℃, such as 120 ℃ to 150 ℃.

In at least one embodiment, the ethylene or propylene based polymer is an ethylene alpha-olefin copolymer or propylene alpha-olefin copolymer having one or more of the following: mw values of 1,000g/mol or greater, for example, from about 1,000g/mol to about 1,500,000g/mol, for example, from about 15,000g/mol to about 750,000g/mol, or from about 500,000g/mol to about 10,000,000g/mol, for example, from about 3,500,000g/mol to about 7,500,000g/mol; mn values of 2,000g/mol or greater, for example, from about 2,000g/mol to about 1,000,000g/mol, for example, from about 50,000g/mol to about 750,000g/mol, or from about 100,000g/mol to about 500,000g/mol, or from about 250,000g/mol to about 5,000,000g/mol; the Mz value is 5,000g/mol or greater, for example, from about 5,000g/mol to about 10,000,000g/mol, for example, from about 20,000g/mol to about 4,000,000g/mol, or from about 4,000,000g/mol to about 7,500,000g/mol.

In at least one embodiment, the ethylene alpha-olefin copolymer or propylene alpha-olefin copolymer has a comonomer content of 0.1 wt% to 99 wt%, such as 1 wt% to 40 wt%, such as 40 wt% to 95 wt%, such as 20 wt% to 50 wt%, such as 15 wt% to 30 wt%.

In at least one embodiment, the ethylene alpha olefin copolymer or propylene alpha olefin copolymer has a Mw/Mn (PDI) value of from about 1 to about 40, such as from about 1 to about 30, such as from about 1 to about 20, such as from about 1 to about 10, such as from about 1 to about 5, or from 20 to 40.

In at least one embodiment, the ethylene alpha-olefin copolymer or propylene alpha-olefin copolymer has a melting point (Tm) of at least 40 ℃, such as from about 40 ℃ to about 140 ℃, such as from about 90 ℃ to about 120 ℃.

GPC 4-D

For the purposes of the claims, and unless otherwise indicated, by using high temperature gel permeation chromatography (PolymeDetermination of moment and distribution of molecular weight (Mw, mn, mz, mw/Mn et al), comonomer content and branching index (g') by r Char GPC-IR), wherein multichannel bandpass filter based infrared detector integrated IR5 has a coverage of about 2,700cm ^-1 -about 3,000cm ^-1 And (represents saturated C-H stretching vibration). Three Agilent PLgel 10- μm hybrid-B LS columns were used to provide polymer separation. Reagent grade 1,2, 4-Trichlorobenzene (TCB) (from Sigma-Aldrich) containing 300ppm antioxidant BHT was used as the mobile phase at a nominal flow rate of 1.0mL/min and a nominal injection volume of 200. Mu.L. The entire system including transfer lines, columns and detectors can be contained in an oven maintained at 145 ℃. A given amount of sample can be weighed and sealed in a standard vial with-10 μl of flow marker (heptane) added. After loading the vials in the autosampler, the oligomers or polymers may be automatically dissolved in an instrument with-8 ml of added TCB solvent at-160 ℃ with continuous shaking. The sample solution concentration may be from-0.2 mg/ml to-2.0 mg/ml, with lower concentrations being used for higher molecular weight samples. The concentration (c) at each point in the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal (I) using the following equation: c=αi, where α is the mass constant measured using polyethylene or polypropylene standards. Mass recovery can be calculated from the ratio of the integrated area of the concentration chromatogram within the elution volume to the injection mass (which is equal to the predetermined concentration times the injection loop volume). Conventional molecular weights (IR MW) were determined by combining a generic calibration relationship with column calibration, which was performed with a series of monodisperse Polystyrene (PS) standards ranging from 700 to 10M gm/mol. MW at each elution volume was calculated using the following equation:

Wherein variables with the subscript "PS" represent polystyrene, and those without the subscript represent test samples. In this method, α _PS =0.67 and K _PS 0.000175, as disclosed and calculated in literature (Sun, t. Et al, macromolecules 2001, volume 34, page 6812)For the purposes of the present invention and claims thereof, α and K of other materials except for the ethylene-propylene copolymer α=0.695+ (0.01 x (propylene weight fraction)) and k= 0.000579- (0.0003502 x (propylene weight fraction)), for linear propylene polymers α=0.705 and k= 0.0002288, for linear butene polymers α=0.695 and k= 0.000181, for ethylene-butene copolymers α 0.695 and K0.000579 x (1-0.0087 x w2b+0.000018 x (w 2 b)/(2) (where w2b is the bulk weight percent of butene comonomer), for ethylene-hexene copolymers α 0.695 and K is 0.000579 x (1-0.0075 x w2 b) (where w2b is the bulk weight percent of hexene comonomer), for ethylene-octene copolymers α 0.695 and K is 0.000579 x (1-0.697) and for all other monomers α=0. 0.000579. Unless otherwise indicated, concentrations are in g/cm ³ Expressed in units, the molecular weight is expressed in g/mole, and the intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g.

By corresponding to CH ₂ And CH (CH) ₃ The ratio of IR5 detector intensities of the channels (which are calibrated with a series of PE and PP homo/copolymer standards of predetermined nominal values by NMR or FTIR) determines the comonomer composition. In particular, this provides methyl groups per 1,000 total carbons (CH ₃ /1000 TC). Then by applying chain end correction to CH ₃ The Short Chain Branching (SCB) content per 1000TC (SCB/1000 TC) as a function of molecular weight was calculated assuming each chain was linear and terminated at each end by a methyl group. The weight% comonomer is then obtained from the following expression, wherein for C ₃ 、C ₄ 、C ₆ 、C ₈ The isocomonomers f are 0.3, 0.4, 0.6, 0.8, etc., respectively:

w2＝f*SCB/1000TC。

by taking into account CH between integration limits of concentration chromatograms ₃ And CH (CH) ₂ The entire signal of the channel obtained the bulk composition of the polymer from both GPC-IR and GPC-4D analyses. First, the following ratios are obtained:

then apply CH ₃ And CH (CH) ₂ Calibration of the same signal ratio (e.g. CH previously obtained as a function of molecular weight ₃ /1000 TC) to obtain the bulk CH ₃ /1000TC. Bulk methyl chain ends/1,000TC (bulk CH) are obtained by weighted average chain end correction over the molecular weight range ₃ End/1000 TC). Then

w2b=f bulk CH3/1000TC

Body SCB/1000TC = body CH3/1000 TC-body CH3 end/1000 TC and body SCB/1000TC is converted to body w2 in the same manner as described above.

The LS detector is 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram was determined by analyzing the LS output using a Zimm model for static light scattering (Light Scattering from Polymer Solutions, huglin, M.B. editor, academic Press, 1972):

where ΔR (θ) is the excess Rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined from IR5 analysis, A ₂ Is the second dimension coefficient, P (θ) is the form factor of the monodisperse random coil, and K _o Is the optical constant of the system:

wherein N is _A Is the avogalileo constant, and (dn/dc) is the refractive index increment of the system. TCB has a refractive index n=1.500 at 145 ℃ and λ=665 nm. For analysis of polyethylene homopolymers, ethylene-hexene copolymers and ethylene-octene copolymers dn/dc= 0.1048ml/mg and a ₂ =0.0015; for analysis of ethylene-butene copolymers, dn/dc= 0.1048 (1-0.00126 w 2)ml/mg and A ₂ =0.0015, where w2 is the weight percent of butene comonomer.

The specific viscosity was measured using a high temperature Agilent (or Viscotek Corporation) viscometer with four capillaries arranged in a wheatstone bridge configuration, and two pressure sensors. One sensor measures the total pressure drop across the detector and the other sensor, placed between the two sides of the bridge, measures the pressure difference. Calculating the specific viscosity eta of the solution flowing through the viscometer from their outputs _s . From equation [ eta ]]＝η _s Calculation of the intrinsic viscosity [ eta ] at each point in the chromatogram]Where c is the concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point was calculated as

Wherein alpha is _ps Is 0.67 and K _ps 0.000175.

The branching index (g 'is calculated as follows using the output of the GPC-IR5-LS-VIS method' _vis ). Average intrinsic viscosity [ eta ] of sample] _avg The calculation is performed by:

where the sum is taken from all chromatographic slices i between the integration limits. Branching index g' _vis Is defined as

Wherein M is _V Is the viscosity average molecular weight based on the molecular weight determined by LS analysis and K and α are for a reference linear polymer, which for the purposes of the present invention and claims thereof, for ethylene, propylene, diene monomer copolymers α=0.700 and k= 0.0003931, for linear propylene polymers α=0.705 and k= 0.0002288, for linear butene polymers α=0.695 and k= 0.000181, for ethylene-butene copolymers α is 0.695 and K is 0.000579 (1-0.0087 w2b+0.000018 (w 2 b)/(2) (where w2b is the bulk weight percent of butene comonomer), for ethylene-hexene copolymers α is 0.695 and K is 0.000579) * (1-0.0075 x w2 b) (where w2b is the bulk weight percent of hexene comonomer), α is 0.695 and K is 0.000579 x (1-0.0077 x w2 b) (where w2b is the bulk weight percent of octene comonomer) for ethylene-octene copolymers, and α=0.695 and k= 0.000579 for all other linear ethylene polymers. Unless otherwise indicated, concentrations are in g/cm ³ Expressed in units, the molecular weight is expressed in g/mole, and the intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g. The calculation of the w2b value is as discussed above.

Blends of

In another embodiment, the polymer produced herein (e.g., polyethylene or polypropylene) is combined with one or more additional polymers prior to formation into a film, molded part, or other article. Other useful polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymers of propylene and ethylene and/or butene and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethyl methacrylate or any other polymer polymerizable by high pressure free radical processes, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymers, styrenic block copolymers, polyamides, polycarbonates, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 ester, polyacetal, polyvinylidene fluoride, polyethylene glycol and/or polyisobutylene.

In at least one embodiment, the polymer (e.g., polyethylene or polypropylene) is present in the above blend in an amount of 10 wt% to 99 wt%, such as 20 wt% to 95 wt%, such as at least 30 wt% to 90 wt%, such as at least 40 wt% to 90 wt%, such as at least 50 wt% to 90 wt%, such as at least 60 wt% to 90 wt%, such as at least 70 to 90 wt%, based on the weight of the polymer in the blend.

The above-described blends may be produced by mixing a polymer of the present disclosure with one or more polymers (as described above), by connecting the reactors together in series to make a reactor blend, or by using more than one catalyst in the same reactor to produce multiple polymer species. The polymers may be mixed together prior to being placed into the extruder or may be mixed in the extruder.

Conventional equipment and methods may be used, for example, by dry blending the individual components and then melt mixing them in a mixer, or by mixing the components together directly in a mixer, such as a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin screw extruder, which may include a compounding extruder and a side arm extruder used directly downstream of the polymerization process, which may include blending powders or pellets of the resin at the film extruder hopper. In addition, additives may be included in the blend, in one or more components of the blend, and/or in products formed from the blend, such as films, as desired. Such additives are well known in the art and may include, for example: a filler; antioxidants (e.g. hindered phenols such as IRGANOX available from Ciba-Geigy ^TM 1010 or IRGANOX ^TM 1076 A) is provided; phosphites (e.g. IRGAFOS available from Ciba-Geigy) ^TM 168 A) is provided; an anti-sticking (anti-sticking) additive; tackifiers such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; a UV stabilizer; a heat stabilizer; an anti-blocking agent; a release agent; an antistatic agent; a pigment; a colorant; a dye; a wax; silicon oxide; a filler; talc.

Film and method for producing the same

Any of the foregoing polymers, such as the foregoing polypropylene or blends thereof, may be used in a variety of end use applications. Such applications include, for example, single or multi-layer blown, extruded and/or shrink films. These films may be formed by any number of well known extrusion or coextrusion techniques, such as blown film (blown bubble film) processing techniques, wherein the composition may be extruded through an annular die in the molten state and then expanded to form a uniaxially or biaxially oriented melt, then cooled to form a tubular blown film, which may then be cut axially and stretched to form a flat film. The film may then be unoriented, uniaxially oriented, or biaxially oriented to the same or different extents. One or more layers of the film may be oriented in the transverse and/or longitudinal directions to the same or different extents. The uniaxial orientation may be accomplished using a common cold drawing (cold drawing) method or hot drawing (hot drawing) method. Biaxial orientation may be accomplished using a tenter frame apparatus or a double bubble process, and may occur before or after bringing the individual layers together. For example, a polyethylene layer may be extrusion coated or laminated to an oriented polypropylene layer or polyethylene and polypropylene may be co-extruded together into a film and then oriented. Likewise, the oriented polypropylene may be laminated to the oriented polyethylene, or the oriented polyethylene may be coated onto the polypropylene and then optionally the combination may be even further oriented. For example, the film is oriented in the Machine Direction (MD) at a ratio of up to 15, such as from about 5 to about 7, and in the Transverse Direction (TD) at a ratio of up to 15, such as from about 7 to about 9. However, in another embodiment, the film is oriented to the same extent in both the MD and TD directions.

Film thickness may vary depending on the intended application; however, films having a thickness of 1 μm to 50 μm may be suitable. Films intended for packaging may be 10 μm to 50 μm thick. The thickness of the sealing layer may be 0.2 μm to 50 μm. The sealing layer may be present on both the inner and outer surfaces of the film or may be present only on the inner or outer surfaces.

In another embodiment, one or more of the layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwaves. In at least one embodiment, one or both surface layers are modified by corona treatment.

List of aspects

The present disclosure provides, inter alia, the following aspects, each of which may be considered to optionally include any alternative aspect.

Clause 1. Catalyst compound, represented by formula (I):

wherein:

m is a group 3, 4 or 5 metal;

A ¹ and A ² Independently an aromatic group, such as an aromatic hydrocarbyl group;

j is a heterocyclic Lewis base, such as a 6 membered heterocyclic ring;

l is a Lewis base;

x is an anionic ligand;

n is 1, 2 or 3;

m is 0, 1 or 2;

n+m is not more than 4;

R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ and R is ⁸ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹ And R is ² 、R ² And R is ³ 、R ³ And R is ⁴ 、R ⁵ And R is ⁶ 、R ⁶ And R is ⁷ Or R is ⁷ And R is ⁸ One or more of the substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings can join to form additional rings;

any two L groups can be joined together to form a bidentate lewis base;

the X group may be joined to the L group to form a monoanionic bidentate group; and

any two X groups may be joined together to form a dianionic ligand group.

Clause 2. The catalyst compound of clause 1, wherein A ¹ Represented by the formula:

wherein the method comprises the steps of

Represents the linkage to the catalyst compound, and

R ⁹ 、R ¹⁰ 、R ¹¹ and R is ¹² Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ⁹ And R is ¹⁰ 、R ¹⁰ And R is ¹¹ Or R ¹¹ And R is ¹² One or more of which 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.

Clause 3. The catalyst compound of clause 1 or 2, wherein A ² Represented by the formula:

wherein the method comprises the steps of

Represents the linkage to the catalyst compound, and

R ¹³ 、R ¹⁴ 、R ¹⁵ and R is ¹⁶ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹³ And R is ¹⁴ 、R ¹⁴ And R is ¹⁵ Or R ¹⁵ And R is ¹⁶ One or more of which 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.

Clause 4. The catalyst compound of any of clauses 1 to 3, wherein J is selected from the group consisting of pyridine, thiazole,

Azole,/->

Oxazolines, imidazoles, furans or thiophenes.

Clause 5 the catalyst compound of any of clauses 1 to 4, wherein J is represented by the formula:

wherein the method comprises the steps of

Represents the linkage to the catalyst compound, and

R ¹⁷ 、R ¹⁸ and R is ¹⁹ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹⁷ And R is ¹⁸ 、R ¹⁸ And R is ¹⁹ Or R is ¹⁷ And R is ¹⁹ One or more of which 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.

Clause 6 the catalyst compound of any of clauses 1 to 5, wherein J is represented by the formula:

Wherein the method comprises the steps of

Represents the linkage to the catalyst compound, and

R ¹⁷ 、R ¹⁸ and R is ¹⁹ Is hydrogen.

Clause 7 the catalyst compound of any of clauses 1 to 6, wherein the complex is represented by the formula (I I):

wherein M, L, X, m, n is as defined in clause 1;

R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ and R is ⁸ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹ And R is ² 、R ² And R is ³ 、R ³ And R is ⁴ 、R ⁵ And R is ⁶ 、R ⁶ And R is ⁷ Or R is ⁷ And R is ⁸ 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 and R is ¹² Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ⁹ And R is ¹⁰ 、R ¹⁰ And R is ¹¹ Or R ¹¹ And R is ¹² 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 ¹³ 、R ¹⁴ 、R ¹⁵ and R is ¹⁶ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹³ And R is ¹⁴ 、R ¹⁴ And R is ¹⁵ Or R ¹⁵ And R is ¹⁶ One or more of which may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles A ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms; and

R ¹⁷ 、R ¹⁸ and R is ¹⁹ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹⁷ And R is ¹⁸ 、R ¹⁸ And R is ¹⁹ Or R is ¹⁷ And R is ¹⁹ One or more of which 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.

The catalyst compound of any of clauses 1-7, wherein M is zirconium or hafnium.

The catalyst compound of any of clauses 1-8, wherein m = 0, n = 2, and X is selected from the group consisting of halogen and hydrocarbyl groups containing 1 to 8 carbons.

Clause 10 the catalyst compound of any of clauses 1-9, wherein R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ Each independently selected from hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, phosphino, or R ¹ And R is ² 、R ² And R is ³ 、R ³ And R is ⁴ 、R ⁵ And R is ⁶ 、R ⁶ And R is ⁷ Or R is ⁷ And R is ⁸ One or more of which 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.

Clause 11 the catalyst compound of any of clauses 1-10, wherein R ⁴ And R is ⁵ Independently C ₁ -C ₁₀ An alkyl group.

Clause 12. The catalyst compound of clause 11, wherein R ⁴ And R is ⁵ Is tert-butyl.

Clause 13.The catalyst compound of any one of clauses 1-10, wherein R ⁴ And R is ⁵ Is aryl.

Clause 14. The catalyst compound of clause 13, wherein R ⁴ And R is ⁵ Is phenyl or carbazole.

Clause 15. The catalyst compound of clause 13, wherein R ⁴ And R is ⁵ Is Et ₃ Si。

Clause 16. The catalyst compound of clause 13, wherein R ⁴ And R is ⁵ Is 3, 5-di-tert-butyl benzyl.

Clause 17 the catalyst compound of any of clauses 1-10, wherein R ² And R is ⁷ Independently C ₁ -C ₁₀ An alkyl group.

Clause 18 the catalyst compound of any of clauses 1-10, wherein R ² And R is ⁷ Is methyl.

Clause 19 the catalyst compound of any of clauses 1-18, wherein 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 is ¹⁹ Each independently is hydrogen or C ₁ -C ₁₀ An alkyl group.

Clause 20 the catalyst compound of any of clauses 1-19, wherein 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 is ¹⁹ Independently is hydrogen, methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, or trimethylsilyl.

Clause 21 the catalyst compound of any of clauses 1-20, wherein 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 is ¹⁹ Is hydrogen.

The catalyst compound of any one of clauses 1-21, wherein n is 2 and each X is independently chloro, benzyl or methyl.

Clause 23 the catalyst compound of any of clauses 1-22, wherein the catalyst compound is selected from the group consisting of:

clause 24 the catalyst compound of clause 1, wherein the catalyst compound is selected from the group consisting of:

/>

/>

clause 25 the catalyst compound of clause 1, wherein the catalyst compound is selected from the group consisting of:

clause 26. Catalyst system comprising an activator and the catalyst compound of any of clauses 1 to 25.

Clause 27. The catalyst system of clause 26, further comprising a support material.

Clause 28. The catalyst system of clause 26 or 27, wherein the support material is selected from the group consisting of Al ₂ O ₃ 、ZrO ₂ 、SiO ₂ 、SiO ₂ /Al ₂ O ₃ 、SiO ₂ /TiO ₂ Silica clay, silica/clay, or mixtures thereof.

The catalyst system of any one of clauses 26 to 28, wherein the activator comprises a non-coordinating anion activator.

The catalyst system of any one of clauses 26 to 29, wherein the activator is represented by the formula:

(Z) _d ⁺ (A ^d- )

wherein Z is (L-H) or a reducible Lewis acid, L is a Lewis base, H is hydrogen, (L-H) ⁺ Is a Bronsted acid; a is that ^d- Is a non-coordinating anion having a charge d-; and d is an integer from 1 to 3.

The catalyst system of any one of clauses 26 to 29, wherein the activator compound is represented by the formula (AI):

[R ¹ R ² R ³ EH] _d ⁺ [M ^k+ Q _n ] ^d- (AI)

wherein:

e is nitrogen or phosphorus, preferably nitrogen;

d is 1, 2 or 3 (preferably 3); k is 1, 2 or 3 (preferably 3); n is 1, 2, 3, 4, 5 or 6 (preferably 4, 5 or 6); n-k=d (preferably d is 1, 2 or 3, k is 3, n is 4, 5 or 6, preferably when M is B, n is 4);

R ¹ 、R ² and R is ³ Each independently is hydrogen, optionally substituted C ₁ -C ₄₀ Alkyl (e.g. branched or linear alkyl), or optionally substituted C ₅ -C ₅₀ Aryl (alternatively R) ¹ 、R ² And R is ³ Independently unsubstituted or substituted with at least one of: halo, C ₅ -C ₅₀ Aryl, C ₆ -C ₃₅ Aralkyl, C ₆ -C ₃₅ Alkylaryl, and at C ₅ -C ₅₀ In the case of aryl radicals C ₁ -C ₅₀ An alkyl group); wherein R is ¹ 、R ² And R is ³ Containing a total of 15 or more carbon atoms (e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms)For example 37 or more carbon atoms, for example 40 or more carbon atoms, for example 45 or more carbon atoms), preferably R ¹ 、R ² And R is ³ At least one of which is C ₃ -C ₄₀ Hydrocarbyl radicals (e.g. C ₃ -C ₄₀ Alkyl, or e.g. C ₇ -C ₄₀ An alkyl group);

m is an element selected from group 13 of the periodic Table of elements, preferably B or Al, preferably B; and

each Q is independently a hydrogen group, a bridged or unbridged dialkylamino group, a halo group, an alkoxy group, an aryloxy group, a hydrocarbyl group, a substituted hydrocarbyl group, a halocarbyl group, a substituted halocarbyl group, or a halogen substituted hydrocarbyl group, preferably a fluorinated aryl group, such as fluoro-phenyl or fluoro-naphthyl, more preferably a perfluorophenyl or perfluoronaphthyl group.

The catalyst system of any one of clauses 26 to 31, wherein the activator is one or more of the following:

N-methyl-4-nonadecyl-N-octadecyl-anilinium tetrakis (perfluoronaphthalen-2-yl) borate,

N-methyl-4-nonadecyl-N-octadecyl-anilinium tetrakis (perfluorophenyl) borate,

n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,

dioctadecyl methyl ammonium tetrakis (pentafluorophenyl) borate,

octacosanyl methyl ammonium tetrakis (perfluoronaphthyl) borate,

triphenylcarbon tetrakis (pentafluorophenyl) borate

Trimethyl ammonium tetrakis (perfluoronaphthyl) borate,

triethylammonium tetrakis (perfluoronaphthyl) borate,

tripropylammonium tetrakis (perfluoronaphthyl) borate,

tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) borate,

tri (tert-butyl) ammonium tetrakis (perfluoronaphthyl) borate,

N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate,

n, N-diethylanilinium tetrakis (perfluoronaphthyl) borate,

n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (perfluoronaphthyl) borate),

tetra (perfluoronaphthyl) boronic acid

Triphenylcarbon tetrakis (perfluoronaphthyl) borate

Triphenylborate tetrakis (perfluoronaphthyl)

Triethylsilane tetra (perfluoronaphthyl) borate

Benzene tetra (perfluoronaphthyl) borate (diazonium)

)，

Trimethyl ammonium tetrakis (perfluorobiphenyl) borate,

triethylammonium tetrakis (perfluorobiphenyl) borate,

tripropylammonium tetrakis (perfluorobiphenyl) borate,

tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate,

tri (tert-butyl) ammonium tetrakis (perfluorobiphenyl) borate,

n, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate,

n, N-diethylanilinium tetrakis (perfluorobiphenyl) borate,

n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (perfluorobiphenyl) borate),

tetra (perfluorobiphenyl) boronic acid

Triphenylcarbon tetrakis (perfluorobiphenyl) borate

Triphenylborate tetrakis (perfluorobiphenyl)

Triethylsilane tetra (perfluorobiphenyl) borate

Benzene tetra (perfluorobiphenyl) borate (diazonium

)，

[ 4-tert-butyl-PhNMe ₂ H][(C ₆ F ₃ (C ₆ F ₅ ) ₂ ) ₄ B]，

The preparation method comprises the steps of carrying out trimethyl ammonium tetraphenyl borate,

triethylammonium tetraphenylborate, which is prepared from a mixture of water and a solvent,

tripropylammonium tetraphenylborate is used as a catalyst,

tri (n-butyl) ammonium tetraphenylborate,

Tri (tert-butyl) ammonium tetraphenyl borate,

tetraphenylboronic acid N, N-dimethylanilinium,

tetraphenylboronic acid N, N-diethylanilinium,

tetraphenylboronic acid N, N-dimethyl- (2, 4, 6-trimethylanilinium),

tetraphenylboronic acid

Triphenylcarbon tetraphenyl borate

Triphenylboronic acid tetraphenyl salt

Triethylsilane tetraphenylborate

Tetraphenylboronic acid benzene (diazonium)

),

Trimethyl ammonium tetrakis (pentafluorophenyl) borate,

triethylammonium tetrakis (pentafluorophenyl) borate,

tripropylammonium tetrakis (pentafluorophenyl) borate,

tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate,

tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate,

n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,

n, N-diethylanilinium tetrakis (pentafluorophenyl) borate,

n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (pentafluorophenyl) borate,

tetrakis (pentafluorophenyl) borate

Triphenylcarbon tetrakis (pentafluorophenyl) borate

Triphenylborate tetrakis (pentafluorophenyl)

Triethylsilane tetra (pentafluorophenyl) borate

Benzene tetra (pentafluorophenyl) borate (diazonium

)，

Trimethyl ammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,

triethylammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,

tripropylammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,

tri (n-butyl) ammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,

dimethyl (tert-butyl) ammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,

N, N-dimethylanilinium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,

n, N-diethylanilinium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,

n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate),

tetrakis (2, 3,4, 6-tetrafluorophenyl) borate

Triphenylcarbon tetrakis (2, 3,4, 6-tetrafluorophenyl) borate

Triphenyltetrakis (2, 3,4, 6-tetrafluorophenyl) borate

Triethylsilane tetrakis (2, 3,4, 6-tetrafluorophenyl) borate

Benzene tetrakis (2, 3,4, 6-tetrafluorophenyl) borate (diazonium

)，

Trimethylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

triethylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

tripropylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

tri (n-butyl) ammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

tri (tert-butyl) ammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

n, N-dimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

n, N-diethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate),

tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

Triphenylcarbon tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

/>

Triphenyltetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

Triethylsilane tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

Benzene tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate (diazonium

)，

Di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate,

dicyclohexylammonium tetrakis (pentafluorophenyl) borate,

tris (o-tolyl) borate

Tris (2, 6-dimethyl) tetrakis (pentafluorophenyl) boratePhenyl group

Triphenylcarbon tetrakis (pentafluorophenyl) borate

1- (4- (tris (pentafluorophenyl) borate) -2,3,5, 6-tetrafluorophenyl) pyrrolidine

A tetrakis (pentafluorophenyl) borate salt, and a method of preparing the same,

4- (tris (pentafluorophenyl) boronic acid) -2,3,5, 6-tetrafluoropyridine, and

triphenylcarbon tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

The catalyst system of any one of clauses 26 to 32, further comprising a metal hydro carbyl chain transfer agent represented by the formula:

Al(R') _3-v (R”) _v

wherein each R' is independently C ₁ -C ₃₀ A hydrocarbyl group; each R' is independently C having a terminal vinyl group ₄ -C ₂₀ A hydrocarbenyl group; and v is 0.1 to 3.

The catalyst system of any one of clauses 26 to 33, wherein the activator comprises an alkylaluminoxane.

The catalyst system of any one of clauses 26 to 34, wherein the aluminoxane is present in a molar ratio of aluminum to the transition metal of the catalyst compound of 100:1 or greater.

Clause 36. A method of producing an ethylene-based polymer comprising: ethylene is polymerized by contacting ethylene with the catalyst system of any one of clauses 26 to 35 in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05MPa to 1,500MPa and a reactor temperature of 30 ℃ to 230 ℃.

Clause 37 the method of clause 36, wherein the catalyst has 5,000g P.mmolecat ^-1 .h ^-1 -1,000,000gP.mmolcat ^-1 .h ^-1 Is a compound of formula (I).

The method of clause 38, wherein the ethylene-based polymer has a Mw of 1,000 to 3,000,000, a mn of 1,000 to 2,000,000, a mz of 1,000-10,000,000, and a PDI of 1 to 20.

The method of any of clauses 39, 36 to 38, wherein the ethylene-based polymer has a PDI of 1-5.

The method of any of clauses 40, 36 to 39, wherein the ethylene-based polymer has a PDI of 10 "20.

The method of any of clauses 41, 36 to 40, wherein the ethylene-based polymer has a melting point of 100 ℃ to 150 ℃.

Clause 42. A method of producing a propylene-based polymer comprising: propylene is polymerized by contacting propylene with the catalyst system of any one of clauses 26 to 35 in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of 0.05MPa to 1,500MPa and a reactor temperature of 30 ℃ to 230 ℃ to form a propylene-based polymer.

Clause 43 the method of clause 42, wherein the catalyst has 100 gP.mmolecat ^-1 .h ^-1 -6,000,000gP.mmolcat ^-1 .h ^-1 Is a compound of formula (I).

Clause 44 the method of claim 42 or 43, wherein the propylene-based polymer has a Mw of 500 to 150,000, a Mn of 500 to 100,000, a Mz of 2,000 to 400,000, and a PDI of 1 to 3.

The method of any of clauses 45, 42 to 44, wherein the propylene-based polymer has a melting point of 50 ℃ to 170 ℃.

Clause 46. A method of producing an ethylene alpha-olefin copolymer comprising: by reacting ethylene and at least one C in one or more continuous stirred tank reactors or loop reactors in series or in parallel at a reactor pressure of from 0.05MPa to 1,500MPa and a reactor temperature of from 30℃to 230 DEG C ₃ -C ₂₀ Contacting an alpha-olefin with the catalyst system of any one of clauses 25 to 34, thereby polymerizing ethylene and at least one C ₃ -C ₂₀ Alpha-olefins to form ethylene alpha-olefin copolymers.

Clause 47 the method of clause 46, wherein the catalyst has 1,000g P.mmolecat ^-1 .h ^-1 -10,000,000gP.mmolcat ^-1 .h ^-1 Is a compound of formula (I).

The method of claim 46 or 47, wherein the ethylene alpha-olefin copolymer has a Mw of from 5,000 to 150,000, a Mz of from 5,000 to 10,000,000, a Mn of from 2,000 to 400,000, and a PDI of from 1 to 40.

Clause 49 the method of any of clauses 46 to 48, wherein the ethylene alpha-olefin copolymer has a PDI of 1-5.

The method of any of clauses 46 to 48, wherein the ethylene alpha-olefin copolymer has a PDI of 20-40.

The method of any of clauses 46 to 50, wherein the ethylene alpha-olefin copolymer has a melting point of 40 ℃ to 140 ℃.

Clause 52. Transition metal compounds formed by chelation of a tridentate dianionic bis (arylphenoxide) heterocyclic ligand with a group 3, 4, or 5 transition metal, wherein the tridentate ligand coordinates to the metal to form a pair of octa-metallocene rings.

Clause 53. The transition metal compound of clause 52, wherein the bis (arylphenoxide) heterocyclic ligand coordinates to the metal center to form a pair of octa-metallocene rings.

Clause 54. The catalyst compound of clause 1, is formed by chelation of a tridentate dianionic ligand with a group 4 transition metal, wherein the tridentate ligand coordinates to the metal to form a pair of eight membered metallocene rings.

Clause 55. Catalyst system comprising an activator and the transition metal compound of clause 54.

Examples

General considerations for synthesis

Unless otherwise indicated, all reagents were purchased from commercial suppliers (Sigma Aldrich) and used in the received state. By N ₂ Purging the solvent and passing

And (5) drying the molecular sieve. Unless otherwise indicated, all chemical operations were performed in a nitrogen atmosphere. Sigma Aldrich silica gel was used +.>

(70 mesh-230 mesh) flash column chromatography using a defined solvent system. All anhydrous solvents were purchased from Fisher Chemical and degassed and dried over molecular sieves prior to use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and degassed and dried over molecular sieves before use. Use at 250MHz, 400MHz or 500MHz by dissolving about 10mg of sample in C ₆ D ₆ 、CD ₂ Cl ₂ 、CDCl ₃ 、D ₈ Solutions prepared in toluene or other deuterated solvents ¹ H NMR spectroscopic data. The chemical shift (delta) present is relative to the protium remaining in the deuterated solvent for C ₆ D ₆ 、CD ₂ Cl ₂ 、CDCl ₃ 、D ₈ Toluene was at 7.15ppm, 5.32ppm, 7.24ppm and 2.09ppm, respectively.

Synthesis of ligand and catalyst (or Complex)

2- (3 '-tert-butyl-2' - (methoxymethoxy) -5 '-methyl- [1,1' -biphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxapentaborane

To 4.23g (174 mmol) of vacuum dried magnesium powder were added 150mL of dry THF and 10.0g (34.8 mmol) of 1-bromo-3-tert-butyl-2- (methoxymethoxy) -5-methylbenzene. The reaction mixture was stirred overnight at 55℃and then a solution of 6.99g (36.5 mmol) of 1-bromo-2-chlorobenzene in 100mL of THF was added dropwise over 3 hours. The resulting suspension was stirred overnight at 55℃and then after cooling the solution to 0℃9.70g (52.2 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan were added. The resulting mixture is in a chamberStirred at temperature overnight and then the mixture was poured into 500mL of water. The crude product was extracted with 3x100mL of dichloromethane. By Na (Na) ₂ SO ₄ The combined organic extracts were dried and evaporated to near dryness. The residue was purified by flash chromatography on silica gel 60 (40 μm-63 μm; eluent: hexane-ethyl acetate=15:1 volumes). Yield 7.20g (50%) yellow oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.75(dd,J＝0.9,7.4Hz,1H),7.49-7.20(m,4H),7.11(d,J＝1.9Hz,1H),6.85(d,J＝1.7Hz,1H),4.44(d,J＝15.0Hz,2H),3.21(s,3H),2.30(s,3H),1.47(s,9H),1.15(s,6H),1.20(s,6H)。

2-methyl-4-phenyl-6H-dibenzo [ c, e ] [1,2] oxaporin-6-ol

To 2.70g (111 mmol) of vacuum dried magnesium powder were added 150mL of dry THF and 6.84g (22.3 mmol) of 1-bromo-3-phenyl-2- (methoxymethoxy) -5-methylbenzene. The reaction mixture was stirred overnight at 55℃and then a solution of 4.35g (22.7 mmol) of 1-bromo-2-chlorobenzene in 50mL of THF was added dropwise over 3 hours. The resulting suspension was stirred at 55℃overnight, then after cooling the suspension to 0℃6.22g (33.4 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan were added. The resulting mixture was stirred at room temperature overnight, and then the mixture was poured into 100mL of water. The crude product was extracted with 3x100mL of dichloromethane. By Na (Na) ₂ SO ₄ The combined organic extracts were dried and evaporated to near dryness. The residue was purified by flash chromatography on silica gel 60 (40 μm-63 μm; eluent: hexane-ethyl acetate=10:1 volumes). Yield 3.10g (46%) of beige powder. ¹ H NMR(CDCl ₃ ,400MHz):δ8.13-8.32(m,1H),7.98-8.13(m,1H),7.95(dd,J＝1.83,6.04Hz,1H),7.56-7.79(m,2H),7.33-7.50(m,4H),7.21-7.29(m,1H),7.02-7.14(m,1H),4.53(s,1H),2.44-2.54(m,3H)。

4- (9H-carbazol-9-yl) -2-methyl-6H-dibenzo [ c, e ] [1,2] oxabanin-6-ol

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To 900mg (37.1 mmol) of vacuum dried magnesium powder were added 50mL of dry THF and 2.94g (7.42 mmol) of 1-bromo-3- (9H-carbazol-9-yl) -2- (methoxymethoxy) -5-methylbenzene. The reaction mixture was stirred at 55deg.C overnight, then a solution of 1.49g (7.79 mmol) of 1-bromo-2-chlorobenzene in 20mL of THF was added dropwise for 3 hours. The resulting suspension was stirred at 5℃overnight, then after cooling the suspension to 0℃2.07g (11.1 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan were added. The resulting mixture was stirred at room temperature overnight, and then the mixture was poured into 100mL of water. The crude product was extracted with 3x100mL of dichloromethane. By Na (Na) ₂ SO ₄ The combined organic extracts were dried and evaporated to near dryness. The residue was purified by flash chromatography on silica gel 60 (40 μm-63 μm; eluent: hexane-ethyl acetate=10:1 volumes). Yield 1.05g (36%) dark red oil. ¹ H NMR(CDCl ₃ ,400MHz):δ8.26(d,J＝8.32Hz,1H),8.12-8.17(m,2H),8.11(d,J＝2.11Hz,1H),8.06(dd,J＝0.94,7.49Hz,1H),7.73-7.80(m,1H),7.49(dt,J＝0.89,7.37Hz,1H),7.35-7.40(m,3H),7.24-7.30(m,2H),7.17(td,J＝0.79,8.18Hz,2H),4.29(s,1H),2.53(s,3H)。

3',5' -di-tert-butyl-2- (methoxymethoxy) -5-methyl-1, 1' -biphenyl

A solution of 69.8g (259 mmol) of 3, 5-di-tert-butyl-bromobenzene in 400mL of dry THF was added dropwise to 6.30g (259 mmol) of vacuum dried magnesium turnings in 100mL of dry THF at 60℃over 30 min. The resulting solution was heated under reflux for 1 hour and then cooled to room temperature. Then 50.0g (216 mmol) of 2-bromo-1- (methoxymethoxy) -4-methylbenzene and 0.7g (1.3 mmol) of Pd (P) were added subsequently ^t Bu ₃ ) ₂ . The resulting mixture was stirred at 60 ℃ overnight, then the mixture was poured into 500mL of water. With 3X400mL of dichloromethaneExtracting the crude product. By Na (Na) ₂ SO ₄ The combined organic extracts were dried and evaporated to near dryness. The residue was distilled using a Kugelrohr apparatus (90 ℃,0.3 mbar) to give 73.0g (99%) of the title product as a colourless oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.40-7.47(m,3H),7.22(d,J＝1.65Hz,1H),7.11-7.19(m,2H),5.11(s,2H),3.43(s,3H),2.40(s,3H),1.42(s,18H)。

2- (3 ',5' -di-tert-butyl-2- (methoxymethoxy) -5-methyl- [1,1' -biphenyl ] -3-yl) -4, 5-tetramethyl-1, 3, 2-dioxapentaborane

To a solution of 30.0g (88.1 mmol) of 3',5' -di-tert-butyl-2- (methoxymethoxy) -5-methyl-1, 1' -biphenyl in 1000mL of diethyl ether was added dropwise 70.5mL (176 mmol, 2.5M) of hexane at 0deg.C ⁿ BuLi. The resulting suspension was stirred at room temperature for 3 hours, then 53.9mL (264 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added in one portion at-50 ℃. The resulting mixture was stirred at room temperature overnight, then the mixture was poured into 1,000ml of water. The crude product was extracted with 3x500mL of dichloromethane. By Na (Na) ₂ SO ₄ The combined organic extracts were dried and evaporated to near dryness. The residue was triturated with 30mL of methanol and the precipitate obtained was filtered and then washed with 30mL of methanol. The precipitate was dried under reduced pressure to give 26.1g (64%) of the title product (2- (3 ',5' -di-tert-butyl-2- (methoxymethoxy) -5-methyl- [1,1' -biphenyl) as a white powder]-3-yl) -4, 5-tetramethyl-1, 3, 2-dioxapentaborane). ¹ HNMR(CDCl ₃ ,400MHz):δ7.61(s,1H),7.34-7.44(m,3H),7.26-7.31(m,1H),4.82(s,2H),2.81(s,3H),2.38(s,3H),1.39(m,30H)。

2-bromo-3 ",5" -di-tert-butyl-2 '- (methoxymethoxy) -5' -methyl-1, 1':3',1 "-terphenyl

To 13.0g (27.9 mmol) of 2- (3 ',5' -di-tert-butyl) -2- (methoxymethoxy) -5-methyl- [1,1' -biphenyl]A solution of-3-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 100mL of 1, 4-dioxan was added 8.69g (30.7 mmol) of 1-bromo-2-iodobenzene, 9.63g (69.7 mmol) of potassium carbonate, and 50mL of water. After purging the obtained mixture with argon for 10 minutes, 1.61g (1.39 mmol) of Pd (PPh) was added ₃ ) ₄ . The mixture was stirred at 90 ℃ for 12 hours, then the mixture was cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3X 100 mL). By Na (Na) ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40 μm-63 μm; eluent: hexane). Yield 12.0g (87%) of a colorless glassy oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.72(d,J＝7.98Hz,1H),7.47-7.54(m,3H),7.33-7.47(m,2H),7.19-7.31(m,2H),7.09(d,J＝1.65Hz,1H),4.29-4.42(m,2H),2.63(s,3H),2.44(s,3H),1.41(s,18H)。

2', 2' - (pyridine-2, 6-diyl) bis (3-tert-butyl-5-methyl- [1,1' -biphenyl ] -2-ol)

To 3.00g (7.31 mmol) of 2- (3 '-tert-butyl) -2' - (methoxymethoxy) -5 '-methyl- [1,1' -biphenyl]A solution of 2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 70mL of toluene was added 866mg (3.65 mmol) of 2, 6-dibromopyridine, 1.94g (18.3 mmol) of sodium carbonate, 50mL of water and 10mL of methanol. The resulting mixture was purged with argon for 10 minutes followed by the addition of 0.42g (0.365 mmol) of Pd (PPh) ₃ ) ₄ . The mixture was stirred at 90 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3×50 mL) and taken up in Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. To the resulting oil was added 50mL of THF, 50mL of methanol and 1mL of 12N hydrochloric acid. The reaction mixture was stirred at 60℃overnight and then The mixture was then poured into 200mL of water. The resulting mixture was extracted with dichloromethane (3×50 mL) and taken up in Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40 μm-63 μm; eluent: hexane-ethyl acetate=10:1 volumes). Yield 1.50g (74%) of a mixture of the two isomers as white foam. ¹ H NMR(CDCl ₃ ,400MHz):δ7.29-7.55(m,9H),6.24-7.19(m,8H),2.24+1.99(s,6H),1.17+0.94(s,18H)。

2, 2'- (pyridine-2, 6-diyl) bis (5' -methyl- [1,1':3',1 '-terphenyl ] -2' -phenol)

To 1.50g (5.24 mmol) of 2-methyl-4-phenyl-6H-dibenzo [ c, e][1,2]A solution of oxaporin-6-ol in 30mL of toluene was added 620mg (2.62 mmol) of 2, 6-dibromopyridine, 1.39g (13.1 mmol) of sodium carbonate, 28mL of water and 10mL of methanol. After purging the obtained mixture with argon for 10 minutes, 0.30g (0.262 mmol) of Pd (PPh) was added ₃ ) ₄ . The mixture was stirred at 90 ℃ for 12 hours, then the mixture was cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3×50 mL) and taken up in Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. To the resulting oil was added 50mL of THF, 50mL of methanol and 1mL of 12N hydrochloric acid. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The resulting mixture was extracted with dichloromethane (3×50 mL) and taken up in Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40 μm-63 μm; eluent: hexane-ethyl acetate=10:1 volumes). Yield 910mg (58%) of white foam. ¹ H NMR(CDCl ₃ ,400MHz):δ7.46-7.58(m,6H),7.38(br.s,4H),7.12-7.28(br.s,8H),7.09(d,2H,J＝7.87Hz),6.88(br.s,6H),6.40(br.s,1H),2.05(br.s,6H)。

2', 2' "- (pyridine-2, 6-diyl) bis (3- (9H-carbazol-9-yl) -5-methyl- [1,1' -biphenyl ] -2-ol)

To 730mg (1.95 mmol) of 4- (9H-carbazol-9-yl) -2-phenyl-6H-dibenzo [ c, e][1,2]A solution of oxaporin-6-ol in 10mL of toluene was added 184mg (0.80 mmol) of 2, 6-dibromopyridine, 424mg (4.00 mmol) of sodium carbonate, 10mL of water and 5mL of methanol. After purging the obtained mixture with argon for 10 minutes, 100mg (0.08 mmol) of Pd (PPh) was added ₃ ) ₄ . The mixture was stirred at 90 ℃ for 12 hours, then the mixture was cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3X 50 mL). By Na (Na) ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. To the resulting oil was added 50mL of THF, 50mL of methanol and 1mL of 12N hydrochloric acid. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The resulting mixture was extracted with dichloromethane (3X 50 mL). By Na (Na) ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40 μm-63 μm; eluent: hexane-ethyl acetate=10:1 volumes). Yield 400mg (53%) of white foam. ¹ H NMR(CDCl ₃ ,400MHz):δ8.08(d,J＝8.65Hz,4H),7.64-7.71(m,1H),7.09-7.38(m,21H),7.04(br.s.,3H),6.92(br.s.,4H),2.17(br.s.,6H)。

2', 2' - (pyridine-2, 6-diyl) bis (3, 5-di-tert-butyl-5 ' -methyl- [1,1':3', 1' -terphenyl ] -2' -phenol)

To a solution of 3.34g (6.74 mmol) of 2-bromo-3 ",5" -di-tert-butyl-2 '- (methoxymethoxy) -5' -methyl-1, 1':3',1 "-terphenyl in 120mL of dry THF at 0-78℃was added dropwise 2.96mL (7.41 mmol, 2.5M) in hexane ⁿ BuLi. The reaction mixture was stirred at this temperature for 1 hour, then 1.38g (10.1 mmol) was addedZinc chloride. The resulting solution was warmed to room temperature and evaporated to near dryness. Then, 100mL of THF was added to the residue, followed by 800mg (3.37 mmol) of 2, 6-dibromopyridine, 120mg (1.35 mmol) of Pd ₂ (dba) ₃ And 0.9mL of 0.3M in toluene ^t Bu ₃ P (2.7 mmol). The mixture was stirred at 60 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3X 50 mL). By Na (Na) ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40 μm-63 μm; eluent: hexane-ethyl acetate=10:1 volumes) to give 0.8g of intermediate a (2, 6-bis (3 ",5" -di-tert-butyl-2 '- (methoxymethoxy) -5' -methyl- [1,1':3',1 "-terphenyl) ]-2-yl) pyridine) and 1.21g (34%) of monoarylate B (2-bromo-6- (3 ', 5' -di-tert-butyl-2 ' - (methoxymethoxy) -5' -methyl- [1,1':3', 1' -terphenyl)]-2-yl) pyridine) as a by-product. To intermediate A was added 20mL of THF, 20mL of methanol, and 1mL of 12N hydrochloric acid. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The resulting mixture was extracted with dichloromethane (3X 50 mL). By Na (Na) ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40 μm-63 μm; eluent: hexane-ethyl acetate=10:1 volumes). Yield 620mg (10%) of product a as white foam. ¹ H NMR(CDCl ₃ 400MHz, product a) delta 7.36-7.46 (m, 7H), 7.33 (br.s., 2H), 7.26 (br.s., 4H), 7.14 (t, j=7.38 hz, 2H), 7.05-7.12 (m, 4H), 6.76-6.95 (m, 2H), 6.52 (br.s., 1H), 6.12 (br.s., 1H), 2.28 (br.s., 6H), 1.35 (s, 36H). ¹ H NMR(CDCl ₃ 400MHz, product B) delta 7.76-7.85 (m, 1H), 7.43-7.55 (m, 3H), 7.33-7.38 (m, 1H), 7.27-7.33 (m, 2H), 7.11-7.18 (m, 2H), 7.05 (d, J=1.19 Hz, 2H), 7.00 (d, J=7.61 Hz, 1H), 4.15 (s, 2H), 2.47 (s, 3H), 2.39 (s, 3H), 1.32 (s, 18H).

3', 5' -di-tert-butyl-2- (6- (3 ' - (tert-butyl) -2' -hydroxy-5 ' -methyl- [1,1' -biphenyl ] -2-yl) pyridin-2-yl) -5' -methyl- [1,1':3', 1' -terphenyl ] -2' -phenol

To 1.14g (1.99 mmol) of 2-bromo-6- (3 ', 5' -di-tert-butyl-2 ' - (methoxymethoxy) -5' -methyl- [1,1':3', 1' -terphenyl)]A solution of-2-yl) pyridine in 10mL of toluene was added 817mg (1.99 mmol) of 2- (3 '-tert-butyl) -2' - (methoxymethoxy) -5 '-methyl- [1,1' -biphenyl]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan, 530mg (5.00 mmol) sodium carbonate, 10mL water and 5mL methanol. After purging the obtained mixture with argon for 10 minutes, 115mg (0.10 mmol) of Pd (PPh) were added ₃ ) ₄ . The mixture was stirred at 90 ℃ for 12 hours, then the mixture was cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3X 50 mL). By Na (Na) ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. To the resulting oil was added 50mL of THF, 50mL of methanol and 1mL of 12N hydrochloric acid. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The resulting mixture was extracted with dichloromethane (3X 50 mL). By Na (Na) ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40 μm-63 μm; eluent: hexane-ethyl acetate=10:1 volumes). Yield 750mg (55%) of the mixture of two isomers as white foam. ¹ H NMR(CDCl ₃ ,400MHz):δ7.39-7.57(m,6H),7.33(br.s.,3H),7.16-7.23(m,2H),7.00-7.16(m,4H),6.97(br.s.,1H),6.91(br.s.,1H),6.86(m,1H),6.70(s,1H),6.32(br.s.,1H),2.02-2.32(m,6H),1.35(br.s.,9H),1.30(br.s 9H),1.10(br.s.,9H)。

[2', 2' - (pyridine-2, 6-diyl) bis (3- (tert-butyl) -5-methyl- [1,1' -biphenyl ] -2-ol) ] hafnium dimethyl (catalyst 1)

To a suspension of 115mg (0.360 mmol) of hafnium tetrachloride in 30mL of dry toluene at room temperature was added 0.600mL (1.62 mmol, 2.7M) of diethyl ether in one portionMeMgBr. The resulting suspension was stirred for 20 minutes. 200mg (0.360 mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3-tert-butyl-5-methyl- [1,1' -biphenyl) are then added dropwise over 5 minutes]-2-phenol) in 10mL of dry toluene. The reaction mixture was stirred at room temperature overnight and then the mixture was evaporated to near dryness. The resulting solid was extracted with 2x20mL of hot methylcyclohexane and the combined organic extracts were filtered through a thin pad of Celite 503. The filtrate was evaporated to dryness. The resulting solid was washed with 5mL of n-pentane and then dried under reduced pressure. Yield 170mg (62%) of white solid. C (C) ₄₁ H ₄₅ HfNO ₂ Is calculated by analysis: c,64.60, H,5.95, N,1.84. The discovery is as follows: and C64.95,H 6.22,N 1.62. ¹ H NMR(CDCl ₃ ,400MHz):δ7.70(t,J＝7.82Hz,1H),7.54(dt,J＝1.33,7.60Hz,2H),7.28-7.35(m,4H),7.14(d,J＝7.76Hz,2H),7.03-7.10(m,4H),6.78(d,J＝1.77Hz,2H),2.26(s,6H),1.44(s,18H),-0.78(s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz):δ158.28,157.65,142.01,139.54,137.72,132.70,132.28,132.14,131.22,130.76,129.02,128.50,128.21,127.37,127.26,126.32,125.22,48.46,34.90,30.12,20.79。

[2, 2'- (pyridine-2, 6-diyl) bis (5' -methyl- [1,1':3',1 '-terphenyl ] -2' -phenol) ] hafnium dimethyl (catalyst 2)

To a suspension of 269mg (0.839 mmol) of hafnium tetrachloride in 30mL of dry toluene was added at room temperature 1.40mL (3.78 mmol, 2.7M) of MeMgBr in diethyl ether in one portion. The resulting suspension was stirred for 20 minutes. 500mg (0.839 mmol) of 2, 2' - (pyridine-2, 6-diyl) bis (5 ' -methyl- [1,1':3', 1' -terphenyl) are then added dropwise to the suspension over 5 minutes ]-2' -phenol) in 10mL of dry toluene. The reaction mixture was stirred at room temperature overnight and then the mixture was evaporated to near dryness. The resulting solid was extracted with 2x20mL of hot methylcyclohexane and the combined organic extracts were filtered through a thin pad of Celite 503. The filtrate was evaporated to dryness. The resulting solid was washed with 5mL of n-pentaneAnd then dried under reduced pressure. Yield 310mg (46%) of white solid. C (C) ₄₅ H ₃₇ HfNO ₂ Is calculated by analysis: c,67.37, H,4.65, N,1.75. The discovery is as follows: and C67.65,H 4.90,N 1.63. ¹ H NMR(CDCl ₃ ,400MHz):δ7.83-7.91(m,4H),7.30-7.38(m,5H),7.01-7.26(m,7H),6.87(dd,J＝0.61,2.38Hz,2H),6.83(dt,J＝1.39,7.57Hz,2H),6.55(dd,J＝1.11,7.76Hz,2H),6.21-6.32(m,3H),2.13(s,6H),-0.40(s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz):δ141.23,139.20,138.95,131.93,131.84,131.11,130.77,130.58,129.79,129.58,129.03,128.95,127.82,127.37,126.22,124.69,47.50,20.55。

[2', 2' - (pyridine-2, 6-diyl) bis (3- (9H-carbazol-9-yl) -5-methyl- [1,1' -biphenyl ] -2-ol) ] hafnium dimethyl (catalyst 3)

To a suspension of 165mg (0.517 mmol) of hafnium tetrachloride in 30mL of dry toluene was added at room temperature 0.860mL (2.33 mmol, 2.7M) of MeMgBr in diethyl ether. The resulting suspension was stirred for 20 minutes. 400mg (0.517 mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3- (9H-carbazol-9-yl) -5-methyl- [1,1' -biphenyl) are then added dropwise over 5 minutes]-2-phenol) in 10mL of dry toluene. The reaction mixture was stirred at room temperature overnight and then the mixture was evaporated to near dryness. The resulting solid was extracted with 2x20mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The resulting solid was washed with 5mL of n-pentane and then dried under reduced pressure. Yield 276mg (54%) of white solid. C (C) ₅₇ H ₄₃ HfN ₃ O ₂ Is calculated by analysis: c,69.83, h,4.42, n,4.29. The discovery is as follows: and C70.07,H 4.57,N 4.10. ¹ H NMR(C ₆ D ₆ ,400MHz):δ8.19-8.34(m,2H),8.05(d,J＝7.65Hz,2H),7.42-7.48(m,J＝8.21Hz,2H),7.33-7.42(m,4H),7.24(ddd,J＝1.16,7.12,8.23Hz,2H),6.87-7.15(m,12H),6.33-6.40(m,1H),6.26(dt,J＝1.22,7.60Hz,2H),6.17-6.24(m,2H),5.91(dd,J＝0.94,7.60Hz,2H),2.02(s,6H),-1.48(s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz):δ156.54,154.89,140.95,140.73,139.38,138.83,132.98,132.04,130.76,130.65,129.98,128.99,128.63,128.19,127.95,127.43,125.59,125.48,125.26,125.16,124.93,123.88,122.33,120.29,119.61,119.07,119.01,112.31,109.11,45.72,20.53。

[2', 2' - (pyridine-2, 6-diyl) bis (3-tert-butyl-5-methyl- [1,1' -biphenyl ] -2-ol) ] zirconium dimethyl (catalyst 4)

To a suspension of 80mg (0.342 mmol) zirconium tetrachloride in 30mL dry toluene at-35℃was added MeMgBr in 0.570mL (1.54 mmol, 2.7M) diethyl ether in one portion. The resulting suspension was stirred for 30 minutes. Then 190mg (0.342 mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3- (tert-butyl) -5-methyl- [1,1' -biphenyl) are added dropwise over 5 minutes]-2-phenol) in 10mL of dry toluene. The reaction mixture was stirred at room temperature overnight and then evaporated to near dryness. The resulting solid was extracted with 2x20mL of hot methylcyclohexane and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The resulting solid was washed with 5mL of n-pentane and then dried under reduced pressure. Yield 110mg (47%) of white solid. C (C) ₄₁ H ₄₅ ZrNO ₂ Is calculated by analysis: c,72.95, h,6.72, n,2.07. The discovery is as follows: and C73.23,H 6.94,N 1.82. ¹ H NMR(CDCl ₃ ,400MHz):δ7.69(t,J＝7.76Hz,1H),7.45-7.56(m,2H),7.21-7.34(m,4H),7.11(d,J＝7.76Hz,2H),6.96-7.07(m,4H),6.70-6.79(m,2H),2.24(s,6H),1.43(s,18H),-0.57(s,6H)。

[2, 2'- (pyridine-2, 6-diyl) bis (5' -methyl- [1,1':3',1 '-terphenyl ] -2' -phenol) ] zirconium dimethyl (catalyst 5)

200mg (0.335 mmol) of tetrad at-35℃to 200mgA suspension of zirconium chloride in 30mL of dry toluene was added at a time to MeMgBr in 0.560mL (1.51 mmol, 2.7M) of diethyl ether. The resulting suspension was stirred for 30 minutes. 200mg (0.335 mmol) of 2, 2' - (pyridine-2, 6-diyl) bis (5 ' -methyl- [1,1':3', 1' -terphenyl) are then added dropwise over 5 minutes]-2' -phenol) in 10mL of dry toluene. The reaction mixture was stirred at room temperature overnight and then evaporated to near dryness. The resulting solid was extracted with 2x20mL of hot methylcyclohexane and the combined organic extracts were filtered through a thin pad of Celite 503. The filtrate was evaporated to dryness. The resulting solid was washed with 5mL of n-pentane and then dried under reduced pressure. Yield 46mg (19%) of white solid. C (C) ₄₅ H ₃₇ ZrNO ₂ Is calculated by analysis: c,75.59, H,5.22, N,1.96. The discovery is as follows: and C75.71,H 5.43,N 1.73. ¹ H NMR(CDCl ₃ ,400MHz):δ7.69(d,J＝7.21Hz,4H),7.52-7.57(m,1H),7.34-7.42(m,8H),7.28-7.34(m,2H),7.09(d,J＝2.11Hz,2H),6.88(d,J＝7.76Hz,2H),6.83(d,J＝2.22Hz,2H),6.72-6.78(m,2H),6.33(d,J＝7.54Hz,2H),2.24(s,6H),-0.83(s,6H)。

[ 3', 5' -Di-tert-butyl-2- (6- (3 ' - (tert-butyl) -5' -methyl-2 ' -oxy- [1,1' -biphenyl ] -2-yl) pyridin-2-yl) -5' -methyl- [1,1':3', 1' -terphenyl ] -2' -phenol ] hafnium dimethyl (catalyst 6)

To a suspension of 139mg (0.436 mmol) of hafnium tetrachloride in 30mL of dry toluene was added at room temperature MeMgBr in 0.676mL (1.96 mmol, 2.9M) of diethyl ether in one portion. The resulting suspension was stirred for 20 minutes. 300mg (0.436 mmol) of 3', 5' -di-tert-butyl-2- (6- (3 '- (tert-butyl) -2' -hydroxy-5 '-methyl- [1,1' -biphenyl) are then added dropwise over 5 minutes ]-2-yl) pyridin-2-yl) -5' -methyl- [1,1':3',1 "-terphenyl]-a solution of 2' -phenol in 10mL of dry toluene. The reaction mixture was stirred at room temperature overnight and then evaporated to near dryness. The resulting solid was extracted with 2x20mL toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. By usingThe resulting solid was washed with 5mL of n-pentane and then dried under reduced pressure. Yield 293mg (75%) of a white solid. C (C) ₅₁ H ₅₇ HfNO ₂ Is calculated by analysis: c,68.48, h,6.42, n,1.57. The discovery is as follows: and C68.75,H 6.64,N 1.39. ¹ H NMR(C ₆ D ₆ ,400MHz):δ8.01(br.s.,2H),7.66(br.s.,1H),7.41(br.s.,1H),7.37(br.s.,1H),7.25(br.s.,1H),7.13(br.s.,4H),7.05(br.s.,1H),6.90-7.03(m,2H),6.76(br.s.,1H),6.56-6.67(m,1H),6.53(br.s.,1H),6.39(br.s.,1H),6.25(br.s.,1H),2.23(br.s.,3H),1.46(br.s.,27H),-0.10(br.s.,3H),-0.48(br.s.,3H)。 ¹³ C NMR(CDCl ₃ ,100MHz):δ159.30,158.22,157.94,157.59,150.85,143.35,142.37,140.73,139.40,138.84,135.15,133.55,133.35,132.83,132.39,131.83,131.36,130.98,130.80,130.71,130.62,129.66,127.92,127.27,126.04,125.38,124.77,124.08,122.14,49.69,49.48,35.53,32.28,30.56,23.07,21.43,20.95,14.64。

[ 2', 2' - (pyridine-2, 6-diyl) bis (3, 5-di-tert-butyl-5 ' -methyl- [1,1':3', 1' -terphenyl ] -2' -phenol) ] hafnium dimethyl (catalyst 7)

To a suspension of 152mg (0.475 mmol) of hafnium tetrachloride in 30mL of dry toluene was added at room temperature MeMgBr in 0.740mL (2.14 mmol, 2.9M) of diethyl ether in one portion. The resulting suspension was stirred for 20 minutes. 390mg (0.475 mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3, 5-di-tert-butyl-5 '-methyl- [1,1':3', 1' -terphenyl) are then added dropwise over 5 minutes]-2' -phenol) in 10mL of dry toluene. The reaction mixture was stirred at room temperature overnight and then the mixture was evaporated to near dryness. The resulting solid was extracted with 2x20mL of boiling toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The resulting solid was washed with 5mL of n-pentane and then dried under reduced pressure. Yield 358mg (74%) of white solid. C (C) ₆₁ H ₆₉ HfNO ₂ Is calculated by analysis: c,71.36, H,6.77, N,1.36. The discovery is as follows: c71.55 the number of the components,H 6.94，N 1.32。 ¹ H NMR(C ₆ D ₆ ,400MHz,70℃):δ7.68(d,J＝1.65Hz,4H),7.62(t,J＝1.51Hz,2H),7.28(d,J＝7.61Hz,2H),7.08-7.15(m,5H),6.98-7.07(m,2H),6.81-6.87(m,4H),6.67(d,J＝7.52Hz,2H),6.47(t,J＝7.66Hz,1H),6.34(d,J＝7.70Hz,2H),2.16(s,6H),1.44(s,36H),-0.52(s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz,70℃):δ158.12,156.99,150.79,143.00,140.77,138.94,133.12,132.91,132.18,131.53,130.44,129.66,129.40,128.88,128.68,127.69,124.75,124.69,121.92,49.09,35.54,32.32,20.90。

((4- (methoxymethoxy) -1, 3-phenylene) bis (propane-2, 2-diyl)) diphenyl

To a solution of 30.0g (90.8 mmol) of 2, 4-bis (2-phenylpropan-2-yl) phenol in 500mL of THF was added 3.81g (95.3 mmol, 60 wt% in mineral oil) of sodium hydride in portions at room temperature. 7.60mL (99.9 mmol) of methoxymethyl chloride was added dropwise to the resulting suspension at room temperature for 10 minutes. The resulting mixture was stirred overnight and then poured into 500mL of water. The product was extracted with dichloromethane (3X 300 mL) and extracted with 5% NaHCO ₃ Washing the combined organic extracts with Na ₂ SO ₄ Dried and then evaporated to dryness. Yield 34.0g (quantity) of pale yellow oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.49(d,J＝2.3Hz,1H),7.37–7.42(m,4H),7.25–7.32(m,5H),7.15–7.19(m,2H),7.00(d,J＝8.5Hz,1H),4.68(s,2H),3.06(s,3H),1.84(s,6H),1.74(s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz):δ153.09,151.59,150.96,143.14,137.65,127.90,127.58,126.72,125.63,125.49,125.41,124.75,114.23,93.75,55.28,42.59,42.04,30.99,29.55。

2- (2- (methoxymethoxy) -3, 5-bis (2-phenylpropan-2-yl) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxapentaborane

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To a solution of 15.0g (40.1 mmol) of ((4- (methoxymethoxy) -1, 3-phenylene) bis (propane-2, 2-diyl)) diphenyl in 400mL of dry diethyl ether was added dropwise over 20 minutes 32.0mL (80.2 mmol) of 2.5M in hexane at 0 ℃ ⁿ BuLi. The reaction mixture was stirred at room temperature for 3 hours, then cooled to-80℃before 24.5mL (120 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxapentaborane was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 400mL of water. The resulting mixture was extracted with dichloromethane (3×300 mL) and taken up in Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. Yield 20.0g (amount) of colorless viscous oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.49(d,J＝2.4Hz,1H),7.34(d,J＝2.5Hz,1H),7.29(d,J＝4.7Hz,4H),7.06–7.22(m,6H),4.13(s,2H),3.10(s,3H),1.74(s,6H),1.61(s,6H),1.32(s,12H)。

¹³ C NMR(CDCl ₃ ,100MHz)：δ156.94,151.72,150.92,143.88,140.51,131.17,129.39,127.81,127.70,126.74,125.82,125.41,124.95,98.10,83.57,82.74,56.52,42.66,42.22,30.88,30.11,26.15,25.36,24.76,13.85。

2 '-bromo-2- (methoxymethoxy) -3, 5-bis (2-phenylpropan-2-yl) -1,1' -biphenyl

To a solution of 20.0g (40.0 mmol) of 2- (2- (methoxymethoxy) -3, 5-bis (2-phenylpropan-2-yl) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 200mL of 1, 4-dioxan was then added 12.5g (44.0 mmol) of 2-bromoiodobenzene, 13.8g (100 mmol) of potassium carbonate, and 100mL of water. After purging the obtained mixture with argon for 10 minutes, 2.30g (2.00 mmol) of Pd (PPh) were added ₃ ) ₄ . The mixture was stirred at 100 ℃ for 12 hours, cooled to room temperature and then diluted with 100mL of water. The resulting mixture was extracted with dichloromethane (3 x200 mL) and taken up in Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. By passing throughFlash chromatography the residue was purified on silica gel 60 (40-63 um, eluent: hexane-dichloromethane=10:1 volumes). Yield 15.6g (74%) of yellow viscous oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.62(dd,J＝7.9,1.1Hz,1H),7.49(d,J＝2.4Hz,1H),7.35–7.39(m,7H),7.30(d,J＝4.4Hz,4H),7.22–7.26(m,1H),7.13–7.18(m,1H),7.08(d,J＝2.4Hz,1H),3.51(d,J＝4.7Hz,1H),3.44(d,J＝4.7Hz,1H),2.73(s,3H),1.82(s,3H),1.80(s,3H),1.76(s,3H),1.75(s,3H)。 ¹³ C NMR(CDCl ₃ ,100MHz)：δ151.47,150.67,150.48,144.76,142.49,140.96,134.66,132.53,132.15,128.72,128.45,127.93,127.89,126.75,125.94,125.58,125.53,125.23,124.33,97.59,56.12,42.82,42.41,31.08,30.85,30.22,30.06。

2- (2 '- (methoxymethoxy) -3',5 '-bis (2-phenylpropan-2-yl) - [1,1' -biphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxapentaborane

To a solution of 15.6g (29.5 mmol) of 2 '-bromo-2- (methoxymethoxy) -3, 5-bis (2-phenylpropan-2-yl) -1,1' -biphenyl in 250mL of dry THF at-80℃over 20 min was added dropwise 15.4mL (38.4 mmol) of 2.5M in hexane ⁿ BuLi. The reaction mixture was stirred at this temperature for 1 hour, after which 10.8mL (53.1 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300mL of water. The mixture thus obtained was extracted with dichloromethane (3×300 mL) by Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-diethyl ether=10:1 volumes). Yield 9.90g (58%) of a colorless glassy oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.82(d,J＝7.2Hz,1H),7.30–7.43(m,8H),7.20–7.27(m,5H),7.12–7.17(m,1H),7.08(d,J＝2.4Hz,1H),3.57(d,J＝4.1Hz,1H),3.27(d,J＝4.1Hz,1H),2.70(s,3H),1.81(s,3H),1.79(s,3H),1.78(s,3H),1.69(s,3H),1.22(s,12H)。 ¹³ C NMR(CDCl ₃ ,100MHz)：δ152.03,151.10,149.74,146.07,143.65,141.71,137.16,134.63,130.40,129.69,128.49,127.79,127.69,126.73,126.05,125.99,125.41,125.31,125.12,96.52,83.13,56.13,42.70,42.38,31.27,31.02,29.42,24.80,24.58。

2', 2' "- (pyridine-2, 6-diyl) bis (3, 5-bis (2-phenylpropane-2-yl) - [1,1' -biphenyl ] -2-ol)

To 3.63g (6.30 mmol) of 2- (2 '- (methoxymethoxy) -3',5 '-bis (2-phenylpropan-2-yl) - [1,1' -biphenyl]A solution of 2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 14mL of 1, 4-dioxan is then added 745mg (3.15 mmol) of 2, 6-dibromopyridine, 5.13g (15.8 mmol) of cesium carbonate, and 7mL of water. After purging the obtained mixture with argon for 10 minutes, 315mg (0.315 mmol) of Pd (PPh) were added ₃ ) ₄ . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3×50 mL) and taken up in Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. To the resulting oil was then added 30mL of THF, 30mL of methanol, and 2mL of 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 500mL of water. The crude product was extracted with dichloromethane (3×35 mL) and extracted with 5% nahco ₃ Washing the combined organic extracts with Na ₂ SO ₄ Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate=10:1 volumes). Yield 2.22g (79%) of a mixture of the two isomers as white foam. ¹ H NMR(CDCl ₃ ,400MHz):δ7.05–7.40(m,29H),6.82–6.90(m,2H),6.73(d,J＝7.8Hz,2H),4.85+5.52(s,2H),1.31–1.65(m,24H)。 ¹³ C NMR(CDCl ₃ 100 MHz) delta 158.02,151.02 (wide), 149.77 (wide), 148.46 (wide), 141.56,140.17 (wide), 136.75 (wide), 134.89 (wide), 131.31 (wide), 130.62 (wide), 128.32,128.23,127.78,127.72,126.57,125.71,125.61,125.33,124.68 (wide), 122.22 (wide), 42.39 (wide)) 41.99,30.97 (width), 30.77 (width), 29.53 (width), 29.34 (width).

[2', 2' - (pyridine-2, 6-diyl) bis (3, 5-bis (2-phenylpropane-2-yl) - [1,1' -biphenyl ] -2-ol) hafnium dimethyl (catalyst 9)

To a suspension of 144mg (0.450 mmol) of hafnium tetrachloride in 50mL of dry toluene was added 698ul (2.03 mmol) of 2.9M MeMgBr in diethyl ether at 0deg.C by syringe. To the resulting suspension 400mg (0.450 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (3, 5-bis (2-phenylpropane-2-yl) - [1,1' -biphenyl) are immediately added in one portion ]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2x20mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane, the precipitate obtained was filtered off, washed with 2x5mL of n-hexane and then dried in vacuo. Yield 335mg (68%) of white-beige solid. C (C) ₆₇ H ₆₅ HfNO ₂ Is calculated by analysis: c,73.51, H,5.98, N,1.28. The discovery is as follows: and C73.85,H 6.12,N 1.13. ¹ H NMR(C ₆ D ₆ ,400MHz):δ7.33–7.35(m,6H),7.23-7.24(m,4H),7.03–7.20(m,15H),6.98(t,J＝7.2Hz,2H),6.86(d,J＝7.4Hz,2H),6.58(t,J＝7.6Hz,1H),6.33(d,J＝7.8Hz,2H),1.96(s,6H),1.76(s,6H),1.61(s,6H),1.60(s,6H),-0.74(s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz)δ158.12,157.62,151.61,150.77,142.27,138.95,138.69,136.28,132.75,132.18,131.68,130.74,127.67,127.40,126.91,126.83,126.65,126.20,125.21,124.88,48.42,42.89,42.32,32.58,30.96,30.84,28.46。

9- (2- (methoxymethoxy) -5-methylphenyl) -9-methyl-9H-fluorene

In the roomTo a solution of 19.1g (67.0 mmol) 4-methyl-2- (9-methyl-9H-fluoren-9-yl) phenol in 100mL THF was added 13.9mL (80.0 mmol) diisopropylethylamine at a time. To the resulting solution was added dropwise 6.10mL (80.0 mmol) of methoxymethyl chloride at room temperature for 10 minutes. The resulting mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3×150 mL) and extracted with 5% nahco ₃ Washing the combined organic extracts with Na ₂ SO ₄ Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate=20:1 volumes). Yield 13.3g (60%) of white powder. ¹ H NMR(CDCl ₃ ,400MHz):δ7.76(d,J＝7.43Hz,2H),7.58(d,J＝2.0Hz,1H),7.28(td,J＝7.4,1.2Hz,2H),7.17(td,J＝7.4,1.2Hz,2H),7.11(m,2H),6.99(ddd,J＝8.2,2.1,0.7Hz,1H),6.70(d,J＝8.2Hz,1H),4.20(s,2H),2.65(s,3H),2.41(s,2H),1.75(s,3H)。

2- (2- (methoxymethoxy) -5-methyl-3- (9-methyl-9H-fluoren-9-yl) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan

To a solution of 13.3g (40.0 mmol) 9- (2- (methoxymethoxy) -5-methylphenyl) -9-methyl-9H-fluorene in 400mL dry diethyl ether was added dropwise 32.0mL (80.2 mmol) of 2.5M n-butyllithium in hexane at 0deg.C for 20 min. The reaction mixture was stirred at room temperature for 3 hours, then cooled to-80℃and 18.0mL (88.0 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxapentaborane was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 400mL of water. The crude product was extracted with dichloromethane (3×300 mL) and purified by Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was triturated with 100mL of methanol, the resulting precipitate was filtered off on a frit (G4), washed with 10mL of methanol, and then dried in vacuo. Yield 13.2g (72%) of white solid. ¹ H NMR(CDCl ₃ ,400MHz):δ7.75(d,J＝7.5Hz,2H),7.61(d,J＝2.0Hz,1H),7.28(m,3H),7.16(td,J＝7.4,1.0Hz,2H),7.07(d,J＝7.5Hz,2H),3.93(s,2H),2.78(s,3H),2.39(s,3H),1.71(s,3H),1.24(s,12H)。

9- (2 '-bromo-2- (methoxymethoxy) -5-methyl- [1,1' -biphenyl ] -3-yl) -9-methyl-9H-fluorene

To a solution of 5.06g (11.1 mmol) 2- (2- (methoxymethoxy) -5-methyl-3- (9-methyl-9H-fluoren-9-yl) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 40mL 1, 4-dioxane was then added 3.45g (12.2 mmol) 2-bromoiodobenzene, 3.84g (27.8 mmol) potassium carbonate, and 20mL water. After purging the obtained mixture with argon for 10 minutes, 0.64g (0.60 mmol) of Pd (PPh) was added ₃ ) ₄ . The mixture was stirred at 100 ℃ for 12 hours, cooled to room temperature and then diluted with 100mL of water. The crude product was extracted with dichloromethane (3×200 mL) and taken up over Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane=10:1 volumes). Yield 5.14g (95%) yellow viscous oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.81(d,J＝7.5Hz,2H),7.70(br.s,1H),7.53(d,J＝8.0Hz,1H),7.17–7.38(m,8H),7.08(m,1H),7.00(br.s,1H),3.31(m,2H),2.51(s,3H),2.39(s,3H),1.85(s,3H)。 ¹³ C NMR(CDCl ₃ ,100MHz):δ150.91,140.56,140.03,139.75,137.58,135.15,132.21,131.91,130.96,129.03,128.31,127.11,126.59,124.07,97.94,55.39,52.92,28.26,21.15。

2- (2 '- (methoxymethoxy) -5' -methyl-3 '- (9-methyl-9H-fluoren-9-yl) - [1,1' -biphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxapentaborane

To 5.14g (10.6 mmol) of 9- (2 '-bromo-2- (methoxymethoxy) -5-methyl- [1,1' -co-at-80 ℃Benzene]A solution of-3-yl) -9-methyl-9H-fluorene in 150mL of dry THF was added dropwise with 5.52mL (13.8 mmol) of 2.5M n-butyllithium in hexane for 20 min. The reaction mixture was stirred at this temperature for 1 hour, after which 3.90mL (19.1 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300mL of water. The crude product was extracted with dichloromethane (3×300 mL) and purified by Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-diethyl ether=10:1 volumes). Yield 3.60g (64%) of a colorless glassy oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.80(d,J＝7.3Hz,2H),7.66(d,J＝6.8Hz,1H),7.58(s,1H),7.20–7.39(m,8H),7.13(d,J＝7.2Hz,1H),6.89(s,1H),3.71(br.s,1H),3.02(br.s,1H),2.48(s,3H),2.43(s,3H),1.84(s,3H),1.19(br.s,6H),1.12(br.s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz)：δ150.12,145.14,136.97,136.66,133.85,132.21,130.95,130.02,129.16,127.91,125.95,97.01,83.20,55.65,53.13,28.63,24.96,24.13,20.97。

2', 2' "- (pyridine-2, 6-diyl) bis (5-methyl-3- (9-methyl-9H-fluoren-9-yl) - [1,1' -biphenyl ] -2-ol)

To 3.60g (6.76 mmol) of 2- (2 '- (methoxymethoxy) -5' -methyl-3 '- (9-methyl-9H-fluoren-9-yl) - [1,1' -biphenyl)]A solution of 2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 20mL of 1, 4-dioxan is then added 800mg (3.38 mmol) of 2, 6-dibromopyridine, 5.51g (17.0 mmol) of cesium carbonate, and 10mL of water. After purging the obtained mixture with argon for 10 minutes 390mg (0.338 mmol) of Pd (PPh) were added ₃ ) ₄ . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3×50 mL) and taken up in Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. To the resulting oil was then added 30mL of THF,30mL of methanol and 2mL of 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 500mL of water. The crude product was extracted with dichloromethane (3×35 mL) and extracted with 5% nahco ₃ Washing the combined organic extracts with Na ₂ SO ₄ Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate=10:1 volumes). Yield 2.30g (85%) of a mixture of the two isomers as white foam. ¹ H NMR(CDCl ₃ ,400MHz):δ7.60–7.79(m,4H),6.85–7.46(m,25H),6.67(d,J＝7.8Hz,2H),4.77+4.40(2br.s,2H),2.33–2.46(m,6H),1.70(br.s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz)δ157.25,152.29,149.04,148.66,139.96,138.99,136.35,135.23,131.16,131.02,130.40,130.25,130.08,129.66,128.71,128.19,128.06,127.95,127.63,127.21,126.99,126.79,123.72,123.29,121.57,120.14,119.96,53.37,53.11,27.48,20.83。

[2', 2' - (pyridine-2, 6-diyl) bis (5-methyl-3- (9-methyl-9H-fluoren-9-yl) - [1,1' -biphenyl ] -2-ol) ] hafnium dimethyl (catalyst 10)

To a suspension of 160mg (0.500 mmol) hafnium tetrachloride in 50mL of dry toluene was added 775ul (2.25 mmol) of 2.9M MeMgBr in diethyl ether at 0deg.C in one portion by syringe. To the resulting suspension 400mg (0.500 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (5-methyl-3- (9-methyl-9H-fluoren-9-yl) - [1,1' -biphenyl) were immediately added in one portion]-2-phenol]. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2x20mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane, the precipitate obtained was filtered off, washed with 2x5mL of n-hexane and then dried in vacuo. Yield 212 mg (42%) as white-beige solid. C (C) ₆₁ H ₄₉ HfNO ₂ Is calculated by analysis: c,72.79, H,4.91, N,1.39. The discovery is as follows: c73.05 the number of the components,H 5.14，N 1.22。 ¹ H NMR(C ₆ D ₆ ,400 MHz):δ8.87(d,J＝7.3 Hz,2H),7.81(m,2H),7.70(d,J＝7.7 Hz,2H),7.68(m,2H),7.30–7.45(m,8H),7.14–7.25(m,8H),6.97(br.s,2H),6.78(d,J＝2.3 Hz,2H),6.56–6.66(m,3H),2.52(s,6H),1.86(s,6H),0.08(s,6H)。 ¹³ C NMR(C ₆ D ₆ ,100 MHz)δ159.60,157.61,154.95,154.49,142.23,140.12,139.92,138.24,133.25,132.00,131.70,131.14,130.83,129.97,129.79,127.90,127.83,127.09,126.89,126.84,126.65,125.16,124.98,120.18,119.52,56.53,50.23,20.44。

3,4,4,7,7-pentamethyl-4, 5,6, 7-tetrahydrobenzo [ b ] thiophene

To a solution of 55.3g (563 mmol) of 3-methylthiophene was added 103g (563 mmol) of 2, 5-dichloro-2, 5-dimethylhexane. To the resulting solution was added 75.0g (563 mmol) of aluminum trichloride in portions at 0℃for 1 hour. The resulting suspension was stirred at room temperature overnight, and then the mixture was poured into 500mL of crushed ice. The crude product was extracted with dichloromethane (3×300 mL) and purified by Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was recrystallized twice from methanol. Yield 23.5g (20%) of white solid. ¹ H NMR(CDCl ₃ ,400MHz):δ6.71(d,J＝0.9Hz,1H),2.34(d,J＝0.9Hz,3H),1.71(s,4H),1.34(s,6H),1.31(s,6H)。

2- (2- (methoxymethoxy) -5-methylphenyl) -3,4,4,7,7-pentamethyl-4, 5,6, 7-tetrahydrobenzo [ b ] thiophene

To 10.0g (48.0 mmol) of 3,4,4,7,7-pentamethyl-4, 5,6, 7-tetrahydrobenzo [ b ] at-80 ℃]A solution of thiophene in 200mL of THF was added dropwise with 19.2mL (48.0 mmol) of 2.5M n-butyllithium in hexane for 20 minutes. The resulting solution was stirred at 0deg.C for 1 hour, followed by the addition of 9.80g (72.0 mmol) of ZnCl ₂ . Further, 880mg (0.96 mmol) of Pd was then added ₂ (dba) ₃ 390mg (1.92 mmol) ^t Bu ₃ P and 11.1g (48.0 mmol) of 2-bromo-1- (methoxymethoxy) -4-methylbenzene. The resulting solution was stirred at 60 ℃ overnight, and then this mixture was poured into 500mL of water. The crude product was extracted with dichloromethane (3×300 mL) and purified by Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane). Yield 12.9g (75%) of a colorless oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.15(s,1H),7.11(s,2H),5.07(s,2H),3.39(s,3H),2.34(s,3H),2.18(s,3H),1.75(s,4H),1.38(s,6H),1.37(s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz)：δ152.94,146.00,140.74,133.37,133.17,131.24,130.72,129.32,125.77,116.40,95.69,55.91,38.48,35.69,34.39,34.29,32.65,28.43,20.43,16.04。

2- (2 '-bromo-2- (methoxymethoxy) -5-methyl- [1,1' -biphenyl ] -3-yl) -3,4,4,7,7-pentamethyl-4, 5,6, 7-tetrahydrobenzo [ b ] thiophene

To 10.0g (27.9 mmol) of 2- (2- (methoxymethoxy) -5-methylphenyl) -3,4,4,7,7-pentamethyl-4, 5,6, 7-tetrahydrobenzo [ b ] at-80 ℃]A solution of thiophene in 200mL of THF was added dropwise with 11.1mL (27.9 mmol) of 2.5M n-butyllithium in hexane for 20 minutes. The resulting solution was stirred at 0℃1 Shore, followed by the addition of 4.56g (33.5 mmol) of ZnCl ₂ . Further, 511mg (0.56 mmol) of Pd was then added ₂ (dba) ₃ 225mg (1.12 mmol) ^t Bu ₃ P and 8.70g (30.7 mmol) of 2-bromoiodobenzene. The resulting solution was stirred at 60 ℃ overnight, and then this mixture was poured into 500mL of water. The crude product was extracted with dichloromethane (3×300 mL) and purified by Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane). Yield 2.90g (20%) of a colorless viscous oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.65(d,J＝7.3Hz,1H),7.39(dd,J＝7.5,1.8Hz,1H),7.35(td,J＝7.3,0.9Hz,1H),7.18–7.21(m,2H),7.04(d,J＝1.6Hz,1H),4.38(m,2H),2.71(s,3H),2.37(s,3H),2.23(s,3H),1.70(m,4H),1.33–1.35(m,12H)。 ¹³ C NMR(CDCl ₃ ,100MHz)：δ150.32,146.54,141.00,140.07,135.40,134.05,133.00,132.96,132.48,131.98,131.15,130.75,129.37,128.67,126.90,124.20,98.44,55.88,38.43,35.66,34.41,34.31,32.64,28.52,28.29,20.65,16.02。

2- (2 '- (methoxymethoxy) -5' -methyl-3 '- (3,4,4,7,7-pentamethyl-4, 5,6, 7-tetrahydrobenzo [ b ] thiophen-2-yl) - [1,1' -biphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxapentaborane

To 2.90g (5.61 mmol) of 2- (2 '-bromo-2- (methoxymethoxy) -5-methyl- [1,1' -biphenyl at-80 ℃]-3-yl) -3,4,4,7,7-pentamethyl-4, 5,6, 7-tetrahydrobenzo [ b ] ]A solution of thiophene in 50mL of THF was added dropwise with 2.70mL (6.73 mmol) of 2.5M n-butyllithium in hexane for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, after which 1.95mL (9.53 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 100mL of water. The crude product was extracted with dichloromethane (3×300 mL) and purified by Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-diethyl ether=10:1 volumes). Yield 2.15g (68%) of a colorless glassy oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.75(d,J＝7.5Hz,1H),7.42(m,2H),7.30–7.32(m,1H),7.11(s,1H),7.03(s,1H),4.35(s,2H),2.73(s,3H),2.33(s,3H),2.21(s,3H),1.71(s,4H),1.34(s,6H),1.32(s,6H),1.21(s,12H)。 ¹³ C NMR(CDCl ₃ 100 MHz): delta 150.40,146.10,144.07,140.58,137.23,134.07,133.48,132.24,131.99,131.44,130.09,129.66,128.79,126.19,98.49,83.40,56.04,38.43,35.66,34.33,34.25,32.66,28.41,24.58 (width), 20.58,15.94。

2', 2' "- (pyridine-2, 6-diyl) bis (5-methyl-3- (3,4,4,7,7-pentamethyl-4, 5,6, 7-tetrahydrobenzo [ b ] thiophen-2-yl) - [1,1' -biphenyl ] -2-ol)

To 1.24g (2.21 mmol) of 2- (2 ' - (methoxymethyloxy) -5' -methyl-3 ' - (3,4,4,7,7-pentamethyl-4, 5,6, 7-tetrahydrobenzo [ b)]Thiophen-2-yl) - [1,1' -biphenyl]A solution of 2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 10mL of 1, 4-dioxan is then added 262mg (1.11 mmol) of 2, 6-dibromopyridine, 1.80g (5.53 mmol) of cesium carbonate, and 5mL of water. After purging the obtained mixture with argon for 10 minutes 130mg (0.110 mmol) of Pd (PPh) were added ₃ ) ₄ . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3×50 mL) by Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. To the resulting oil was then added 30mL of THF, 30mL of methanol, and 1mL of 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 500mL of water. The crude product was extracted with dichloromethane (3×35 mL) and extracted with 5% nahco ₃ Washing the combined organic extracts with Na ₂ SO ₄ Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate=10:1 volumes). Yield 0.80g (84%) of white foam. ¹ H NMR(CDCl ₃ ,400MHz):δ7.28–7.43(m,9H),7.02(d,J＝7.8Hz,2H),6.99(d,J＝2.2Hz,2H),6.89(br.s,2H),2.20(s,6H),1.85(br.s,6H),1.68(s,8H),1.31(s,12H),1.26(s,12H)。 ¹³ C NMR(CDCl ₃ ,100MHz)δ158.51,148.72,147.10,141.29,139.87,137.11,135.81,134.18,131.85,131.53,131.27,130.20,129.56,129.36,128.79,128.30,127.67,122.46,122.04,38.62,35.85,34.53,34.33,32.62,28.47,20.25,15.59。

[2', 2' - (pyridine-2, 6-diyl) bis (5-methyl-3- (3,4,4,7,7-pentamethyl-4, 5,6, 7-tetrahydrobenzo [ b ] thiophen-2-yl) - [1,1' -biphenyl ] -2-ol) ] hafnium dimethyl (catalyst 11)

To a suspension of 112mg (0.350 mmol) hafnium tetrachloride in 50mL of dry toluene was added 540ul (2.25 mmol) of 2.9M MeMgBr in diethyl ether at 0 ℃ in one portion by syringe. To the resulting suspension was immediately added 300mg (0.350 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (5-methyl-3- (3,4,4,7,7-pentamethyl-4, 5,6, 7-tetrahydrobenzo [ b) in one portion ]Thiophen-2-yl) - [1,1' -biphenyl]-2-phenol]. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2x20mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane, the precipitate obtained was filtered off, washed twice with 5mL of n-hexane and then dried in vacuo. Yield 274mg (71%) of white-beige solid. C (C) ₅₉ H ₆₅ HfNO ₂ S ₂ Is calculated by analysis: c,66.68, h,6.16, n,1.32. The discovery is as follows: and C66.92,H 6.29,N 1.28. ¹ H NMR(C ₆ D ₆ ,400MHz):δ7.42–7.44(m,2H),7.31–7.39(m,4H),7.27(dd,J＝2.3,0.6Hz,2H),7.20-7.24(m,2H),6.96(dd,J＝2.4,0.7Hz,2H),6.37–6.43(m,3H),2.56(s,6H),2.15(s,6H),1.69–1.89(m,8H),1.65(s,6H),1.58(s,6H),1.49(s,6H),1.37(s,6H),-0.34(s,6H)。 ¹³ C NMR(C ₆ D ₆ ,100MHz)δ157.68,156.28,144.77,141.87,141.56,138.56,133.86,133.45,132.70,132.61,132.20,131.69,130.79,130.19,129.37,129.08,126.68,125.02,124.29,47.74,38.91,36.09,34.56,34.42,33.37,32.69,29.20,28.11,20.23,16.69。

2 '-isopropyl-2- (methoxymethoxy) -5-methyl-1, 1' -biphenyl

500 g (167 mmol) of vacuum dried magnesium turnings was added to 4.06gmL of dry THF. Next, 30.0g (151 mmol) of 2-isopropyl bromobenzene was added dropwise to the reaction mixture for 1 hour, maintaining a slight reflux. Further, 2.21g (4.32 mmol) of ^t Bu ₃ P) ₂ Pd and 25.0g (108 mmol) of 2-bromo-1- (methoxymethoxy) -4-methylbenzene. The resulting solution was stirred at 60 ℃ overnight, and then this mixture was poured into 500mL of water. The crude product was extracted with dichloromethane (3×300 mL) and purified by Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane). Yield 19.9g (68%) of a colourless oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.41–7.49(m,2H),7.28(td,J＝7.5,1.8Hz,1H),7.20–7.23(m,3H),7.07(s,1H),5.09(m,2H),3.39(s,3H),2.96(sept,J＝6.9Hz,1H),2.42(s,3H),1.31(d,J＝6.9Hz,3H),1.17(d,J＝6.9Hz,3H)。 ¹³ C NMR(CDCl ₃ ,100MHz)：δ152.30,147.24,137.49,131.88,131.68,130.92,130.09,128.80,127.58,125.05,124.89,115.04,94.93,55.72,30.01,24.66,23.28,20.50。

2- (2 '-isopropyl-2- (methoxymethoxy) -5-methyl- [1,1' -biphenyl ] -3-yl) -4, 5-tetramethyl-1, 3, 2-dioxapentaborane

To a solution of 19.8g (73.2 mmol) of 2 '-isopropyl-2- (methoxymethoxy) -5-methylphenyl) -1,1' -biphenyl in 400mL of dry diethyl ether was added dropwise 44.0mL (109 mmol) of 2.5M n-butyllithium in hexane at 0℃for 20 min. The reaction mixture was stirred at room temperature for 3 hours, then cooled to-80℃and 29.6mL (146 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 400mL of water. The crude product was extracted with dichloromethane (3×300 mL) and purified by Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified using a Kugelrohr apparatus (0.1 mbar,150 ℃). Yield 16.5g (57%) of a colorless viscous oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.61(d,J＝2.1Hz,1H),7.37(d,J＝7.8Hz,1H),7.31(td,J＝7.1,1.5Hz,1H),7.23(m,1H),7.17(td,J＝7.2,1.2Hz,1H),7.13(d,J＝2.4Hz,1H),4.82(s,2H),2.95(sept.,J＝6.9Hz,1H),2.76(s,3H),2.35(s,3H),1.38(s,12H),1.25(d,J＝6.9Hz,3H),1.12(d,J＝6.9Hz,3H)。 ¹³ C NMR(CDCl ₃ ,100MHz)：δ157.73,147.18,137.83,136.57,135.35,135.20,132.37,131.05,127.37,125.00,124.71,100.47,83.55,55.94,29.82,25.15,24.78,24.75,23.00,20.52。

2-bromo-2 "-isopropyl-2 '- (methoxymethoxy) -5' -methyl-1, 1':3',1" -terphenyl

To 16.4g (41.5 mmol) of 2- (2 '-isopropyl-2- (methoxymethoxy) -5-methyl- [1,1' -biphenyl)]A solution of-3-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 100mL of 1, 4-dioxan is then added 11.7g (41.5 mmol) of 2-bromoiodobenzene, 14.4g (104 mmol) of potassium carbonate, and 50mL of water. After purging the obtained mixture with argon for 10 minutes, 2.40g (2.10 mmol) of Pd (PPh) was added ₃ ) ₄ . The mixture was stirred at 100 ℃ for 12 hours, cooled to room temperature and then diluted with 100mL of water. The crude product was extracted with dichloromethane (3×200 mL) and taken up over Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane=10:1 volumes). Yield 11.9g (68%) of a mixture of the two isomers as yellow viscous oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.66–7.69(m,1H),7.30–7.43(m,5H),7.19–7.26(m,2H),7.04–7.14(m,2H),4.25–4.33(m,2H),3.16+3.04(2sept,J＝6.9Hz,1H),2.57+2.54(2s,3H),2.40(s,3H),1.33+1.30(2d,J＝6.9Hz,3H),1.18+1.07(2d,J＝6.9Hz,3H)。 ¹³ C NMR(CDCl ₃ 100MHz, resonance assigned to the minor isomer marked with an asterisk): δ 152.61,152.53, 150.84,150.11, 143.52,142.90, 140.42,140.34, 138.78,138.65, 138.27,137.99, 136.33,135.73, 135.62,135.35,135.09,134.90,134.76,134.00,133.63,131.64,130.78,130.71*,129.90,129.84*,127.58,126.93*,101.49*,101.37,58.89*,58.82,33.13*,32.94,28.13,26.21*,26.12,23.78。

2- (2 '-isopropyl-2' - (methoxymethoxy) -5 '-methyl- [1,1':3', 1' -terphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxapentaborane

To a solution of 7.0g (16.5 mmol) of 2-bromo-2 "-isopropyl-2 '- (methoxymethoxy) -5' -methyl-1, 1':3',1" -terphenyl in 150mL of dry THF at-80℃was added dropwise 7.90mL (19.7 mmol) of 2.5M n-butyllithium in hexane for 20 min. The reaction mixture was stirred at this temperature for 1 hour, after which 5.72mL (28.1 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300mL of water. The crude product was extracted with dichloromethane (3×200 mL) and taken up over Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-diethyl ether=10:1 volumes). Yield 5.20g (67%) of a colorless glassy oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.75(d,J＝7.3Hz,1H),7.44(m,2H),7.39(d,J＝7.9Hz,1H),7.32(m,3H),7.19(t,J＝7.4Hz,1H),7.02(br.s,1H),6.99(s,1H),4.29(br.s,2H),3.05(sept,J＝6.8Hz,1H),2.54(s,3H),2.34(s,3H),1.20(s,12H),1.18–1.24(br.s,6H)。 ¹³ C NMR(CDCl ₃ 100 MHz): delta 149.34,135.10,134.09,131.61,130.77,130.15,129.61,127.48,126.19,125.28,124.76,98.27,83.35,55.88,29.91,25.30,24.48 (width), 23.14,20.70.

2', 2' - (pyridine-2, 6-diyl) bis (2-isopropyl-5 ' -methyl- [1,1':3', 1' -terphenyl ] -2' -phenol)

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To 1.50g (3.18 mmol) of 2- (2') "-isopropyl-2 '- (methoxymethoxy) -5' -methyl- [1,1':3',1 "-terphenyl]A solution of 2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 8mL of 1, 4-dioxan is then added 376mg (1.59 mmol) of 2, 6-dibromopyridine, 2.61g (8.00 mmol) of cesium carbonate, and 4mL of water. After purging the obtained mixture with argon for 10 minutes, 180mg (0.159 mmol) of Pd (PPh) was added ₃ ) ₄ . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3×100 mL) and taken up in Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. To the resulting oil was then added 20mL of THF, 20mL of methanol, and 1mL of 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 50mL of water. The crude product was extracted with dichloromethane (3×30 mL) and extracted with 5% nahco ₃ Washing the combined organic extracts with Na ₂ SO ₄ Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate=1:1 volume). Yield 0.75g (70%) of a mixture of the two isomers as white foam. ¹ H NMR(CDCl ₃ ,400MHz):δ7.30–7.50(m,14H),6.85–7.18(m,9H),2.69(br.s,2H),2.25(br.s,6H),1.06(br.s,12H)。 ¹³ C NMR(CDCl ₃ 100 MHz) δ 158.32,148.05 (wide), 147.71,139.75,137.07 (wide), 136.07,135.68,131.47,130.92,130.59,130.53,130.39,130.22,128.88 (wide), 128.58,128.00,127.84,125.58,125.39,121.97,29.76,24.38,23.47,20.35.

[ 2', 2' - (pyridine-2, 6-diyl) bis (2-isopropyl-5 ' -methyl- [1,1':3', 1' -terphenyl ] -2' -phenol) ] hafnium dimethyl (catalyst 8)

To a suspension of 141mg (0.441 mmol) of hafnium tetrachloride in 50mL of dry toluene was added 684ul (1.99 mmol) of 2.9M MeMgBr in diethyl ether at 0deg.C by syringe. To the resulting suspension was immediately added 300mg (0.441 mmol) of 2",2" "' - (pyridine-2, 6-)Di-base) bis (2-isopropyl-5 '-methyl- [1,1':3', 1' -terphenyl)]-2' -phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2x20mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane, the precipitate obtained was filtered off, washed with 2x5mL of n-hexane and then dried in vacuo. Yield 271mg (69%) of white-beige solid. C (C) ₅₁ H ₄₉ HfNO ₂ Is calculated by analysis: c,69.10, H,5.57, N,1.58. The discovery is as follows: and C69.42,H 6.79,N 1.40. ¹ H NMR(C ₆ D ₆ ,400MHz):δ7.33–7.44(m,9H),7.05–7.23(m,11H),6.48–6.56(m,3H),3.55(sept.,J＝6.8Hz,2H),2.23(s,6H),1.50(d,J＝6.9Hz,6H),1.10(d,J＝6.9Hz,6H),-0.75(s,6H)。 ¹³ C NMR(C ₆ D ₆ ,100MHz)δ157.61,157.53,149.22,141.74,139.87,139.14,133.34,133.00,132.35,131.99,131.44,131.04,130.53,129.66,129.31,128.90,127.64,126.04,125.78,125.39,125.29,47.37,31.06,26.24,22.68,21.78,21.07。

2 '-bromo-2- (methoxymethoxy) -5-methyl-1, 1' -biphenyl

To a solution of 19.5g (70.0 mmol) 2- (2- (methoxymethoxy) -5-methylphenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 200mL 1, 4-dioxane was then added 21.8g (77.0 mmol) 2-bromoiodobenzene, 24.2g (175 mmol) potassium carbonate, and 100mL water. After purging the obtained mixture with argon for 10 minutes, 2.03g (1.80 mmol) of Pd (PPh) was added ₃ ) ₄ . The mixture was stirred at 100 ℃ for 12 hours, cooled to room temperature and then diluted with 100mL of water. The crude product was extracted with dichloromethane (3×200 mL) and taken up over Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane=10:1 volumes). Yield 11.1g (52%) yellow viscous oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.65(dd,J＝8.0,1.2Hz,1H),7.28–7.37(m,2H),7.12–7.23(m,3H),5.07(m,2H),3.37(s,3H),2.35(s,3H)。 ¹³ C NMR(CDCl ₃ ,100MHz)：δ152.19,140.01,132.31,131.49,131.33,131.15,130.95,129.72,128.59,126.90,124.16,115.14,95.13,55.94,20.51。

2- (2 ' - (methoxymethoxy) -5' -methyl- [1,1' -biphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxapentaborane

To a solution of 11.1g (36.1 mmol) of 2 '-bromo-2- (methoxymethoxy) -5-methyl-1, 1' -biphenyl in 250mL of dry THF at-80℃was added dropwise 12.5mL (36.1 mmol) of 2.5M n-butyllithium in hexane for 20 min. The reaction mixture was stirred at this temperature for 1 hour, after which 12.5mL (61.4 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300mL of water. The crude product was extracted with dichloromethane (3×200 mL) and taken up over Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-diethyl ether=10:1 volumes). Yield 10.9g (86%) of a colorless glassy oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.73(d,J＝7.5Hz,1H),7.43(m,1H),7.25–7.34(m,2H),6.98–7.08(m,3H)。 ¹³ C NMR(CDCl ₃ ,100MHz)：δ152.03,143.76,133.88,131.79,131.30,129.76,129.65,128.56,126.11,116.81,95.79,83.34,55.96,24.57,20.62。

2', 2' - (pyridine-2, 6-diyl) bis (5-methyl- [1,1' -biphenyl ] -2-ol)

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To 10.9g (30.9 mmol) of 2- (2 ' - (methoxymethoxy) -5' -methyl- [1,1' -biphenyl)]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxolanA solution of borane in 200mL of 1, 4-dioxane was then added 3.66g (15.5 mmol) of 2, 6-dibromopyridine, 25.2g (77.3 mmol) of cesium carbonate, and 100mL of water. After purging the obtained mixture with argon for 10 minutes, 1.79g (1.55 mmol) of Pd (PPh) were added ₃ ) ₄ . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3×100 mL) and taken up in Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. To the resulting oil was then added 200mL of THF, 200mL of methanol and 10mL of 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 500mL of water. The crude product was extracted with dichloromethane (3×130 mL) and extracted with 5% nahco ₃ Washing the combined organic extracts with Na ₂ SO ₄ Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate=1:1 volume). Yield 2.02g (29%) of a mixture of the two isomers as white foam. ¹ H NMR(CDCl ₃ ,400MHz):δ7.34–7.53(m,9H),6.66–6.97(m,8H),2.13(br.s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz)δ157.94,151.19,139.18,136.68,136.49,132.07,132.01,131.97,131.51,131.44,130.09,129.41,129.39,129.31,128.85,128.54,128.42,127.88,122.59,117.16,20.29。

2', 2' "- (pyridine-2, 6-diyl) bis (3-bromo-5-methyl- [1,1' -biphenyl ] -2-ol)

400mg (0.902 mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (5-methyl- [1,1' -biphenyl) are introduced at room temperature]-2-phenol) in 50mL of dichloromethane, 320mg (1.804 mmol) of NBS in 50mL of dichloromethane was added dropwise for 1 hour. The reaction mixture was stirred at room temperature overnight, then cooled to room temperature and diluted with 50mL of water. The crude product was extracted with dichloromethane (3×20 mL) and extracted with 5% nahco ₃ Washing the combined organic extracts with Na ₂ SO ₄ Dried and then evaporated to dryness. Collecting and recoveringThe rate was 502mg (99%) of red foam. ¹ H NMR(CDCl ₃ ,400MHz):δ7.45–7.56(m,7H),7.35(m,2H),7.19(m,2H),7.04(m,2H),6.58(br.s,2H),2.09(br.s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz)δ157.95,148.41,138.75,136.89,136.60,132.01,131.32,131.26,131.13,130.65,129.91,128.74,128.29,122.62,112.28,20.05。

[2', 2' - (pyridine-2, 6-diyl) bis (3-bromo-5-methyl- [1,1' -biphenyl ] -2-ol) ] hafnium dimethyl (catalyst 13)

To a suspension of 266mg (0.831 mmol) of hafnium tetrachloride in 60mL of dry toluene was added 1.30mL (3.73 mmol) of 2.9M MeMgBr in diethyl ether at 0deg.C in one portion by syringe. To the resulting suspension 500mg (0.831 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (3-bromo-5-methyl- [1,1' -biphenyl) were immediately added in one portion ]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2x20mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane, the precipitate obtained was filtered off, washed with 2x5mL of n-hexane and then dried in vacuo. Yield 429mg (64%) of white-beige solid. C (C) ₃₃ H ₂₇ Br ₂ HfNO ₂ Is calculated by analysis: c,49.06, h,3.37, n,1.73. The discovery is as follows: and C49.36,H 3.58,N 1.55. ¹ H NMR(CD ₂ Cl ₂ ,400MHz)：δ7.67(t,J＝7.8Hz,1H),7.64(td,J＝7.6,1.4Hz,2H),7.52(td,J＝7.6,1.3Hz,2H),7.39(dd,J＝7.6,0.8Hz,2H),7.29(dd,J＝7.6,0.9Hz,2H),7.27(dd,J＝2.1,0.6Hz,2H),7.06(d,J＝7.8Hz,2H),6.91(dd,J＝2.1,0.6Hz,2H),2.23(s,6H),-0.76(s,6H)。 ¹³ C NMR(CD ₂ Cl ₂ ,100MHz)δ157.09,156.58,140.93,140.04,133.35,132.97,132.56,131.81,131.57,131.33,129.60,129.54,129.45,129.13,128.73,126.05,113.69,48.48,20.52。

[2', 2' - (pyridine-2, 6-diyl) bis (5-methyl- [1,1' -biphenyl ] -2-ol) ] hafnium dimethyl (catalyst 14)

To a suspension of 144mg (0.451 mmol) of hafnium tetrachloride in 40mL of dry toluene was added 700ul (2.01 mmol) of 2.9M MeMgBr in diethyl ether at 0deg.C by syringe. 200mg (0.451 mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (5-methyl- [1,1' -biphenyl) are immediately added in one portion to the resulting suspension]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2x20mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane, the precipitate obtained was filtered off, washed with 2x5mL of n-hexane and then dried in vacuo. Yield 110mg (37%) of white-beige solid. C (C) ₃₃ H ₂₉ HfNO ₂ Is calculated by analysis: c,60.97, H,4.50, N,2.15. The discovery is as follows: and C61.28,H 4.77,N 2.02. ¹ H NMR(CD ₂ Cl ₂ ,400MHz)：δ7.60(td,J＝7.6,1.3Hz,2H),7.57(t,J＝7.8Hz,1H),7.47(td,J＝7.5,1.2Hz,2H),7.42(d,J＝7.6Hz,2H),7.18(dd,J＝7.6,1.1Hz,2H),6.98(d,J＝7.8Hz,2H),6.96(dd,J＝8.5,2.2Hz,2H),6.89(d,J＝2.1Hz,2H),6.67(d,J＝8.1Hz,2H),2.23(s,6H),-0.86(s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz)δ159.53,156.61,141.39,139.02,133.13,131.51,131.13,130.97,129.88,129.37,129.30,127.89,127.42,124.96,118.42,45.88,20.51。

N- (2-methylallyl) -N- (p-tolyl) acetamide

To a suspension of 7.05g (176 mmol, 60 wt% in mineral oil) of sodium hydride in 500mL of THF was added in portions 25.0g (168 mmol) of N-p-tolylacetamide at 0deg.C. The resulting suspension was stirred at room temperature for 2 hours. Next to this, the process is carried out,the reaction mixture was cooled to 0deg.C and 18.3g (201 mmol) of 3-chloro-2-methylpropan-1-ene was added in one portion followed by 8mL of HMPA. The resulting suspension was stirred at 55℃overnight and then poured into 200mL of water. The crude product was extracted with toluene (3X 100 mL) and purified by Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified using a Kugelrohr apparatus (0.35 mbar,130 ℃). Yield 32.9g (97%) of a colourless oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.06(m,2H),6.92(m,2H),4.67(m,1H),4.57(m,1H),4.14(s,2H),2.23(s,3H),1.76(s,3H),1.63(s,3H)。 ¹³ C NMR(CDCl ₃ ,100MHz)δ169.91,140.42,140.14,137.14,129.68,127.09,112.69,54.52,22.26,20.62,19.88。

1- (3, 5-trimethylindolin-1-yl) ethan-1-one

To a suspension of 36.1g (271 mmol) of aluminum trichloride in 35mL of chlorobenzene was added dropwise 25.0g (123 mmol) of N- (2-methylallyl) -N- (p-tolyl) acetamide at 115 ℃. The resulting mixture was stirred at 115℃for 1 hour, then diluted with 100mL of toluene and poured into 200mL of crushed ice. The organic layer was separated and then washed with 100mL of 2M HCl and 100mL of water, passed through Na ₂ SO ₄ Dried and then evaporated to dryness. The residue was triturated with 100mL of n-pentane, the precipitate obtained (G4) was filtered off, washed with 50mL of n-pentane and then dried in vacuo. Yield 18.4g (74%) of a pale pink solid. ¹ H NMR(CDCl ₃ ,400MHz):δ8.04(d,J＝8.2Hz,1H),6.99(d,J＝7.5Hz,1H),6.91(s,1H),3.74(s,2H),2.30(s,3H),2.19(s,3H),1.33(s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz)δ168.31,140.42,139.17,133.39,128.09,122.34,116.60,63.72,40.09,28.55,23.96,21.03。

1- (7-bromo-3, 5-trimethylindolin-1-yl) ethan-1-one

To a solution of 18.4g (90.7 mmol) of 1- (3, 5-trimethylindolin-1-yl) ethan-1-one in 370mL of DMF was added dropwise a solution of 16.9g (95.3 mmol) of NBS in 100mL of DMF at 0℃for 1 hour. The resulting solution was stirred at room temperature overnight and then poured into 2 liters of water. The crude product was extracted with diethyl ether (3×150 mL), the combined organic extracts were washed with 3×100mL of water, and extracted with Na ₂ SO ₄ Dried and then evaporated to dryness. Yield 23.6g (92%) of a colourless solid. ¹ H NMR(CDCl ₃ ,400MHz):δ7.18(s,1H),6.86(s,1H),3.82(br.s,2H),2.28(s,3H),2.27(s,3H),1.23(s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz)δ146.48,138.99,136.94,132.12,121.64,112.27,65.22,42.15,28.54,25.84,23.47,20.73。

7-bromo-3, 5-trimethylindoline

To a solution of 23.6g of 1- (7-bromo-3, 5-trimethylindolin-1-yl) ethan-1-one in 500mL of 4M HCl was added 10mL of methanol, and the resulting mixture was refluxed for 6 hours. Further, 250mL of 25% aqueous ammonia was carefully added to the reaction mixture at 0deg.C. The crude product was extracted with diethyl ether (3×150 mL), the combined organic extracts were washed with 3×100mL of water, and extracted with Na ₂ SO ₄ Dried and then evaporated to dryness. The residue was purified by vacuum distillation, boiling point 94℃at 1mbar. Yield 18.0g (82%) yellow oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.02(s,1H),6.79(s,1H),3.49(br.s,1H),3.35(d,J＝0.9Hz,2H),2.27(s,3H),1.32(d,J＝0.9Hz,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz)δ146.27,139.68,129.76,129.48,121.66,102.99,61.15,43.13,27.50,20.52。

7-bromo-1- (4-methoxybenzyl) -3, 5-trimethylindoline

To a solution of 7.0g (29.2 mmol) of 7-bromo-3, 5-trimethylindoline in 100mL of DMF was added 1.40g (34.5 mmol, 60 wt% in mineral oil) of sodium hydride at a time followed by 8.03g (51.5 mmol) of 4-methoxybenzyl chloride. The reaction mixture was stirred at room temperature overnight and then poured into 300mL of water. The crude product was extracted with diethyl ether (3×150 mL), the combined organic extracts were washed with 3×100mL of water, and extracted with Na ₂ SO ₄ Dried and then evaporated to dryness. Excess 4-methoxybenzyl chloride was distilled off using a Kugelrohr apparatus. Yield 10.7g (quantitative) pale yellow oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.30(d,J＝8.5Hz,2H),7.08(s,1H),6.88(d,J＝8.5Hz,2H),6.76(s,1H),4.72(s,2H),3.81(s,3H),3.10(s,2H),2.25(s,3H),1.21(s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz)δ158.61,145.14,143.24,132.76,131.17,129.73,129.69,129.17,122.09,113.69,103.06,67.91,55.21,53.89,40.28,28.52,20.24。

1- (4-methoxybenzyl) -3, 5-trimethyl-7- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) indoline

To a solution of 10.7g (29.2 mmol) of 7-bromo-1- (4-methoxybenzyl) -3, 5-trimethylindoline in 200mL of dry THF at-80℃was added dropwise 12.5mL (31.3 mmol) of 2.5M n-butyllithium in hexane for 20 min. The reaction mixture was stirred at this temperature for 1 hour, then 9.02mL (44.7 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 200mL of water. The crude product was extracted with dichloromethane (3×100 mL) and taken up over Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. Yield 7.67g (63%) of a colorless viscous oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.31(d,J＝8.5Hz,2H),7.28(d,J＝1.4Hz,1H),6.88(d,J＝1.4Hz,1H),6.85(d,J＝8.5Hz,2H),4.48(s,2H),3.80(s,3H),2.99(s,2H),2.25(s,3H),1.24(s,12H),1.21(s,6H)。 ¹³ C NMR(CDCl ₃ ,100MHz):δ158.44,139.83,134.95,131.57,129.38,126.39,125.62,113.79,113.41,83.46,67.95,56.46,55.19,39.51,28.55,24.62,20.57。

7- (2-bromophenyl) -1- (4-methoxybenzyl) -3, 5-trimethylindoline

To a solution of 7.67g (18.8 mmol) of 1- (4-methoxybenzyl) -3, 5-trimethyl-7- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) indoline in 40mL of 1, 4-dioxane was then added 6.93g (24.5 mmol) of 2-bromoiodobenzene, 15.4g (47.1 mmol) of cesium carbonate, and 20mL of water. After purging the obtained mixture with argon for 10 minutes, 1.10g (0.94 mmol) of Pd (PPh) was added ₃ ) ₄ . The mixture was stirred at 100 ℃ for 12 hours, cooled to room temperature and then diluted with 100mL of water. The crude product was extracted with dichloromethane (3×200 mL) and taken up over Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane=10:1 volumes). Yield 5.66g (70%) of yellow viscous oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.61(dd,J＝8.0,1.0Hz,1H),7.40(dd,J＝7.6,1.6Hz,1H),7.28(td,J＝7.5,1.1Hz,1H),7.12(td,J＝7.8,1.7Hz,1H),7.10(d,J＝8.4Hz,2H),6.91(d,J＝1.5Hz,1H),6.80(d,J＝8.4Hz,2H),6.73(d,J＝0.9Hz,1H),3.79(m,2H),3.79(s,3H),3.56(m,2H),2.93(m,2H),2.32(s,3H),1.31(s,3H),1.28(s,3H)。 ¹³ C NMR(CDCl ₃ ,100MHz):δ158.41,145.65,141.74,140.57,132.37,131.58,131.09,130.27,129.24,128.56,127.06,126.98,124.54,122.93,122.34,113.47,68.23,55.18,54.26,39.61,28.22,27.38,20.63。

1- (4-methoxybenzyl) -3, 5-trimethyl-7- (2- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) indoline

To a solution of 5.66g (13.0 mmol) of 7- (2-bromophenyl) -1- (4-methoxybenzyl) -3, 5-trimethylindoline in 100mL of dry THF at-80℃was added dropwise 5.45mL (13.6 mmol) of 2.5M n-butyllithium in hexane for 20 min. The reaction mixture was stirred at this temperature for 1 hour, after which 4.05mL (19.5 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300mL of water. The crude product was extracted with dichloromethane (3×100 mL) and taken up over Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-diethyl ether=10:1 volumes). Yield 6.10g (97%) of a colorless glassy oil. ¹ H NMR(CDCl ₃ ,400MHz):δ7.68(d,J＝7.3Hz,1H),7.41(d,J＝7.6Hz,1H),7.32(t,J＝7.6Hz,1H),7.21(t,J＝7.3Hz,1H),7.01(d,J＝8.5Hz,2H),6.76(s,1H),6.72(s,1H),6.72(d,J＝8.5Hz,2H),3.74(s,3H),3.69(br.s,2H),2.95(s,2H),2.25(s,3H),1.19(br.s,24H)。 ¹³ C NMR(CDCl ₃ ,100MHz):δ158.39,145.60,145.49,140.50,134.04,131.39,130.73,129.66,129.47,129.12,127.39,126.09,125.83,121.33,113.27,83.12,67.43,55.14,55.03,39.86,28.55,24.84,20.65。

2, 6-bis (2- (3, 5-trimethylindolin-7-yl) phenyl) pyridine

To a solution of 6.00g (12.4 mmol) of 1- (4-methoxybenzyl) -3, 5-trimethyl-7- (2- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) indoline in 30mL of 1, 4-dioxane was then added 1.34g (5.64 mmol) of 2, 6-dibromopyridine, 11.0g (33.9 mmol) of cesium carbonate, and 15mL of water. After purging the obtained mixture with argon for 10 minutes 651mg (0.564 mmol) of Pd (PPh) were added ₃ ) ₄ . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3×50 mL) and taken up in Na ₂ SO ₄ The combined organic extracts were dried and then evaporated to dryness. To the resulting oil were then added 64mL of trifluoroacetic acid and 9.60g of p-toluenesulfonic acid. The reaction mixture was stirred at 70℃overnight and then poured into 500mL of saturated K ₂ CO ₃ Is a kind of medium. The crude product was extracted with dichloromethane (3X 100 mL) and extracted with 5% NaHCO ₃ Washing the combined organic extracts with Na ₂ SO ₄ Dried and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate=10:1 volumes). Yield 2.13g (70%) of a mixture of the two isomers as white foam. ¹ H NMR(CDCl ₃ ,400MHz):δ7.25–7.42(m,9H),6.96(m,2H),6.76(m,4H),3.43(br.s,2H),2.80(br.s,4H),2.25(br.s,6H),1.09(br.s,12H)。 ¹³ C NMR(CDCl ₃ ,100MHz)δ158.65,145.74,139.59,138.44,138.09,130.80,130.32,128.82,128.59,127.63,127.37,123.04,121.56,61.33,46.17,41.56,31.57,27.31,22.64,20.87,14.11,11.51。

[2, 6-bis (2- (3, 5-trimethylindol inide) phenyl) pyridine ] hafnium dimethyl (catalyst 12)

To a suspension of 233mg (0.727 mmol) of hafnium tetrachloride in 60mL of dry toluene was added 1.12mL (3.27 mmol) of 2.9M MeMgBr in diethyl ether at 0deg.C in one portion by syringe. To the resulting suspension was immediately added 400mg (0.727 mmol) of 2, 6-bis (2- (3, 5-trimethylindolin-7-yl) phenyl) pyridine in one portion. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2x20mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane, the precipitate obtained was filtered off, washed with 2x5mL of n-hexane and then dried in vacuo. Yield 252mg (46%) of orange solid. C (C) ₄₁ H ₄₃ HfN ₃ Is calculated by analysis: c,65.11, H,5.73, N,5.56. The discovery is as follows: c65.35, H5.94, N5 .32。 ¹ H NMR(C ₆ D ₆ ,400MHz):δ7.19–7.29(m,8H),6.79(s,2H),6.65(s,2H),6.44(m,3H),4.11(d,J＝10.8Hz,2H),3.87(d,J＝10.8Hz,2H),2.24(s,6H),1.29(s,6H),1.25(s,6H),-0.04(s,6H)。 ¹³ C NMR(C ₆ D ₆ ,100MHz)δ157.24,157.02,145.91,142.26,139.06,134.35,133.01,131.84,131.26,129.98,127.97,125.09,124.55,124.07,122.92,68.87,58.30,42.81,30.91,29.59,21.19。

2-bromo-4, 6-di-tert-amylphenol

Dichloromethane (120 mL) and 2, 4-di-tert-amylphenol (14.1 g,60.1 mmol) were combined in a round bottom flask. A solution of dichloromethane (3 mL) and bromine (9.60 g,60.1 mmol) was added dropwise over 5 minutes under nitrogen. At the end of the addition a pale yellow solution formed. The mixture was stirred for 15 min and then extracted with water (3×150 mL) and brine (50 mL). Then pass through MgSO ₄ The separated organics were dried and filtered. Volatiles were removed to provide the product as a near colorless oil. Yield: 18.1g,95.9%.

1-bromo-2- (methoxymethoxy) -3, 5-di-tert-pentylbenzene

2-bromo-4, 6-di-tert-amylphenol (18.1 g,57.7 mmol) was dissolved in THF (200 mL) and NaH (1.66 g,69.2 mmol) was added in small portions over 10 minutes. Chloromethyl methyl ether (5.57 g,69.2 mmol) was added dropwise after 30 minutes. The mixture was stirred overnight and then evaporated to a residue, which was further dried under reduced pressure. Diethyl ether (100 mL) and water (100 mL) were added to the residue. The organics were separated and then passed through Na ₂ SO ₄ And (5) drying. Evaporation of the volatiles provided the product as a nearly colorless oil. Yield: 12.8g,62.1%.

2 '-bromo-2- (methoxymethoxy) -3, 5-di-tert-amyl-1, 1' -biphenyl

To 1-bromo-2- (methoxymethoxy) -3, 5-di-tert-pentylbenzene (1.63 g,4.55 mmol) was added hexane (15 mL) to form a clear solution. BuLi in hexane (2.85 mL,4.55 mmol) was added dropwise over 1 minute. The mixture was stirred for 10 minutes and then heated to 45 ℃. A solution of 1-bromo-2-chlorobenzene (0.532 g,4.55 mmol) in hexane (3 mL) was then added dropwise over 50 minutes. After one hour the volatiles were evaporated and the residue was dried under reduced pressure. The residue was extracted with diethyl ether (15 mL) and filtered through Celite on a frit disc. Evaporation of the volatiles provided the product as a yellow oil. Yield: 1.73g,87.7%.

(2 '- (methoxymethoxy) -3',5 '-di-tert-amyl- [1,1' -biphenyl ] -2-yl) lithium

Hexane (45 mL) and 2 '-bromo-2- (methoxymethoxy) -3, 5-di-tert-pentyl-1, 1' -biphenyl (1.71 g,3.95 mmol) were combined to form a clear colorless solution. BuLi in hexane (2.47 mL,3.95 mmol) was added dropwise over a few minutes at-20 ℃. The mixture was stirred at this temperature for 3 hours then the colorless solid was collected on a frit disc, washed with cold hexane (2 x15 mL) and dried under reduced pressure. Yield: 1.15g,80.9%.

2', 2' - (pyridine-2, 6-diyl) bis (3, 5-di-tert-amyl- [1,1' -biphenyl ] -2-ol)

To ZnCl ₂ (0.481 g,3.53 mmol) tetrahydrofuran (15 mL) was added and the mixture stirred to form a clear colorless solution. To the solution was added solid (2 '- (methoxymethoxy) -3',5 '-di-tert-amyl- [1,1' -biphenyl) at-20 ℃]2-yl) lithium (1.16 g,3.21 mmol) and little tetrahydrofuran (2 mL). The solution was heated to ambient temperature and stirred for 2 hours. Then add2, 6-dibromopyridine (0.365 g,1.54 mmol) and Pd (P (t-Bu) were added ₃ ) ₂ (0.024 g,0.047 mmol) and the mixture was warmed to 60 ℃. After 17 hours the volatiles were evaporated on a rotary evaporator and the residue was extracted with ether (40 mL) and water (20 mL). The aqueous layer was removed and the organics were washed with additional water (2×20 mL) then brine. By Na (Na) ₂ SO ₄ The organics were dried and filtered. Removal of volatiles provided a yellow oil that was mixed with tetrahydrofuran (15 mL), methanol (15 mL) and concentrated HCl (0.7 mL). The mixture was heated to 60 ℃. After 5 hours the volatiles were evaporated and the residue was extracted with ether (40 mL). The organics were washed with water (2×40 mL) then brine. By Na (Na) ₂ SO ₄ The organics were dried and evaporated to a yellow oil. In SiO ₂ The crude product was purified by chromatography eluting with 2-6% etoac in hexanes. Yield: 0.757g,70.7%.

[2', 2' - (pyridine-2, 6-diyl) bis (3, 5-di-tert-amyl- [1,1' -biphenyl ] -2-ol) ] dibenzyl zirconium (catalyst 15). To tetrabenzyl zirconium (0.0614 g,0.135 mmol) and 2', 2' "- (pyridine-2, 6-diyl) bis (3, 5-di-tert-amyl- [1,1' -biphenyl ] -2-phenol) (0.0937 g,0.135 mmol) was added benzene (3 mL) to form a clear orange solution. After 30 minutes the volatiles were evaporated with a nitrogen stream to near dryness to provide an orange oil. Hexane (1.5 mL) was added. A solution is formed from which crystals immediately begin to form. After a few hours the crystalline solid was isolated and washed with cold hexane (2 x1 mL) to provide a colourless solid which was dried under reduced pressure. Yield: 59mg,45%.

Triethyl5-methyl-2- ((tetrahydro-2H-pyran-2-yl) oxy) phenyl) silane

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Chlorotriethylsilane (1.885 g,12.5 mmol) was added to 11.9mmol of (5-methyl-2- ((tetrahydro-2H-pyran-2-yl) oxy) phenyl) lithium in 50mL of THF. The reaction was stirred at 40 ℃ overnight. The reaction was concentrated to remove THF. The resulting mixture was extracted with pentane and filtered to remove all solids. Purification by chromatography on silica gel with 10-15% dichloromethane in pentaneThe crude product was rinsed. Yield: 3.20g (88%). ¹ H NMR(C ₆ D ₆ ,400MHz):δ7.11(m,2H),7.03(d,1H),5.39(t,1H),3.88(td,1H),3.62(dt,1H),2.28(s,3H),1.58–2.05(m,5H),1.56(s,1H),0.95(t,9H),0.85(m,6H)。

(5-methyl-2- ((tetrahydro-2H-pyran-2-yl) oxy) -3- (triethylsilyl) phenyl) lithium

To a solution of 2.30g (7.5 mmol) of triethyl (5-methyl-2- ((tetrahydro-2H-pyran-2-yl) oxy) phenyl) silane in 8mL diethyl ether was added 3.0mL of a 2.5M solution of n-butyllithium in hexane. The reaction was stirred at ambient temperature for 2 hours and then concentrated to a solid. The resulting solid was suspended in pentane and collected by filtration. The solid was washed with pentane and dried in vacuo to give a white powder. Yield 1.77g (76%).

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

To a slurry of 1.5g (4.8 mmol) of (5-methyl-2- ((tetrahydro-2H-pyran-2-yl) oxy) -3- (triethylsilyl) phenyl) lithium in diethyl ether (about 50 mL) was added dropwise a solution of 0.965g (5.0 mmol) of 1-bromo-2-chlorobenzene in 20mL of diethyl ether at ambient temperature. The reaction was stirred at ambient temperature for 1 hour and then at 40 ℃ overnight. The reaction was then filtered to remove all solids. Purification by chromatography on silica gel, eluting the crude product with 10-16% dichloromethane in hexane. Yield: 0.649g (29%). ¹ H NMR(C ₆ D ₆ ,400MHz):δ7.48(dd,1H),7.37(d,1H),7.26(dd,1H),6.86-7.09(m,2H),6.74(m,1H),4.44(dd,1H),3.62(dd,1H),2.96(dt,1H),2.16(d,3H),1.34–1.49(m,3H),1.18(m,16H),0.88(m,2H)。

(5 '-methyl-2' - ((tetrahydro-2H-pyran-2-yl) oxy) -3'- (triethylsilyl) - [1,1' -biphenyl ] -2-yl) lithium

To a solution of 0.649g (1.4 mmol) of (2 '-bromo-5-methyl-2- ((tetrahydro-2H-pyran-2-yl) oxy) - [1,1' -biphenyl ] -3-yl) triethylsilane in 10mL of pentane at 0deg.C was added dropwise 0.59mL of a 2.5M solution of n-butyllithium in hexane. The reaction was stirred for 20 minutes and then diluted with additional pentane. The resulting mixture was filtered through a glass frit funnel. The filtrate (fi-trie) was washed with pentane and dried in vacuo to give a white powder. Yield 0.453g (83%).

2', 2' "- (pyridine-2, 6-diyl) bis (5-methyl-3- (triethylsilyl) - [1,1' -biphenyl ] -2-ol)

To 0.453g (1.17 mmol) of (5 '-methyl-2' - ((tetrahydro-2H-pyran-2-yl) oxy) -3'- (triethylsilyl) - [1,1' -biphenyl ] -2-yl) and 0.167g (1.22 mmol) of zinc chloride was added THF (about 10 mL). The resulting mixture was stirred until all solids were dissolved (about 10 minutes). To the solution were added 0.189g (0.57 mmol) of 2, 6-diiodopyridine and 2.6mg (0.003 mmol) of chloro [2- (dicyclohexylphosphino) -3, 6-dimethoxy-2 ',4',6 '-triisopropyl-1, 1' -biphenyl ] [2- (2-aminoethyl) phenyl ] palladium (II). The resulting mixture was stirred overnight at 50 ℃ and then filtered through alumina and exposed to air. The reaction was diluted with 5mL of methanol and 0.1mL of 10% HCl was added. The reaction was stirred at ambient temperature for 4 hours. The reaction was concentrated under nitrogen and purified by chromatography on silica gel eluting the crude product with 10% dichloromethane in hexane. Yield 135mg (38%).

[2', 2' "- (pyridine-2, 6-diyl) bis (5-methyl-3- (triethylsilyl) - [1,1' -biphenyl ] -2-ol) ] hafnium dimethyl (catalyst 16). To a suspension of 24mg (0.074 mmol) of hafnium tetrachloride in 1.5mL of toluene was added dropwise a 3.0M solution of 0.1mL of MeMgBr in diethyl ether at 0 ℃, followed by a dropwise addition of a solution of 50mg (0.074 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (5-methyl-3- (triethylsilyl) - [1,1' -biphenyl ] -2-ol) in 3mL of toluene. The reaction mixture was stirred at ambient temperature for 35 minutes and then concentrated in vacuo. Pentane was added to the resulting residue and then removed under vacuum. The resulting solid was extracted with toluene. The combined extracts were filtered through a glass fiber plug. Concentrating the filtrate under vacuum; pentane was added to the resulting residue and then removed under vacuum to give an off-white solid. Yield 40mg (62%).

[2', 2' "- (pyridine-2, 6-diyl) bis (5-methyl-3- (triethylsilyl) - [1,1' -biphenyl ] -2-ol) ] zirconium dimethyl (catalyst 17). To a suspension of 17mg (0.074 mmol) zirconium tetrachloride in 1.5mL toluene was added dropwise a 3.0M solution of 0.1mL MeMgBr in diethyl ether at 0 ℃, followed by a drop wise addition of a solution of 50mg (0.074 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (5-methyl-3- (triethylsilyl) - [1,1' -biphenyl ] -2-ol) in 3mL toluene. The reaction mixture was stirred at ambient temperature for 35 minutes and then concentrated in vacuo. Pentane was added to the resulting residue and then removed under vacuum. The resulting solid was extracted with toluene. The combined extracts were filtered through a glass fiber plug. Concentrating the filtrate under vacuum; pentane was added to the resulting residue and then removed under vacuum to give a tan solid. Yield 29mg (49%).

Hexene polymerization using borate activator and catalyst 15. The tared vials were charged with isopar E (3 mL) and 1-hexene (1 mL). The vials were heated to 50 ℃. A toluene solution (0.100 mL) of bis (hydrogenated tallow) methyl ammonium tetrakis (pentafluorophenyl) borate (550 nmol) was then added. A toluene solution (0.100 mL) of catalyst 15 (500 nmol) was then added and the mixture was shaken. The mixture became viscous within a few seconds. The volatiles were evaporated at 120 ℃ under reduced pressure after 45 minutes to provide poly (hexene) as a clear viscous oil. Yield 0.7g. This example illustrates that a mixture of catalyst 15 and bis (hydrogenated tallow) methyl ammonium tetrakis (pentafluorophenyl) borate activator is effective for the polymerization of 1-hexene.

Hexene polymerization using borate activator and tetrabenzyl zirconium. The tared vials were charged with isopar E (3 mL) and 1-hexene (1 mL). The vials were heated to 50 ℃. A toluene solution (0.100 mL) of bis (hydrogenated tallow) methyl ammonium tetrakis (pentafluorophenyl) borate (550 nmol) was then added. A toluene solution of zirconium tetrabenzyl (500 nmol) (0.100 mL) was then added and the mixture was shaken. The mixture did not become sticky. The volatiles were evaporated at 120 ℃ under reduced pressure after 45 minutes to provide only trace amounts of residue without any poly (hexene) observed. Yield 0.0g. This example illustrates that a mixture of zirconium tetrabenzyl and bis (hydrogenated tallow) methyl ammonium tetrakis (pentafluorophenyl) borate activator was ineffective for the polymerization of 1-hexene.

Hexene polymerization using borate activator and in situ formed catalyst. The tared vials were charged with isopar E (3 mL) and 1-hexene (1 mL). The vials were heated to 50 ℃. A toluene solution (0.100 mL) of bis (hydrogenated tallow) methyl ammonium tetrakis (pentafluorophenyl) borate (550 nmol) was then added. A toluene solution (0.100 mL) of 2', 2' - (pyridine-2, 6-diyl) bis (3, 5-di-tert-amyl- [1,1' -biphenyl ] -2-ol) (500 nmol) was then added. Finally, a toluene solution (0.100 mL) of zirconium tetrabenzyl (500 nmol) was added and the mixture was shaken. The mixture became viscous within a few seconds. The volatiles were evaporated at 120 ℃ under reduced pressure after 45 minutes to provide poly (hexene) as a clear viscous oil. Yield 0.7g. This example illustrates that a mixture of bis (hydrogenated tallow) methyl ammonium tetrakis (pentafluorophenyl) borate activator, 2 '"- (pyridine-2, 6-diyl) bis (3, 5-di-tert-amyl- [1,1' -biphenyl ] -2-ol) and zirconium tetrabenzyl is effective for the polymerization of 1-hexene.

The three hexene polymerization experiments above demonstrate that the active olefin polymerization catalyst can be formed in situ by the reaction of a bis (phenol) ligand with a suitable transition metal reagent. In this example, zirconium tetrabenzyl is used as the transition metal reagent, but other transition metal compounds containing alkyl or hydrogen groups (preferably group 4) are also suitable. Group 4 halides (e.g. ZrCl ₄ 、HfCl ₄ ) Mixtures with main group organometals (e.g., alkyl lithium, grignard reagents, organoaluminum, organozinc) can also be used as transition metal reagents to form active catalyst mixtures by reaction with bis (phenolic) ligands. Bis (phenolic) ligands featuring neutral lewis base donors bridging a pair of phenolic groups may be suitable for use in the transfer of a transition metalThe reactants react to form an active polymerization catalyst.

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Polymerization examples

Solvent, polymer grade toluene and/or isohexane were supplied and purified by ExxonMobil Chemical co. Through a series of columns: two 500cm series from Labclear (Okland, california) ³ Oxyclear cylinder, followed by filling with dry

Two tandem 500cm molecular sieves (8 mesh-12 mesh, aldrich Chemical Company) ³ Column and filled with dry +.>

Two tandem 500cm molecular sieves (8 mesh-12 mesh, aldrich Chemical Company) ³ And (5) a column.

1-octene (98%) was dried by filtration over Basic alumina (Aldrich Chemical Company, brockman Basic 1) after stirring over Na-K alloy overnight (Aldrich Chemical Company). Tri (n-octyl) aluminum (TNOA) was purchased from Aldrich Chemical Company or Akzo Nobel and used in the received state.

The polymer grade ethylene was further purified by passing it through a series of columns: 500cm from Labclear (Orchian, california) ³ Oxyclear cylinder, followed by filling with dry

500cm of molecular sieve (8-12 mesh, aldrich Chemical Company) ³ Column and filled with dry +.>

500cm of molecular sieve (8-12 mesh, aldrich Chemical Company) ³ And (5) a column.

The polymerization grade propylene was further purified by passing it through a series of columns: 2250cm from Labclear ³ Oxyclear cylinder followed by filling with

2250cm of molecular sieve (8-12 mesh, aldrich Chemical Company) ³ Columns, then two in series filled with +.>

500cm of molecular sieve (8-12 mesh, aldrich Chemical Company) ³ Column, 500cm filled with Selexsorb CD (BASF) ³ Column and 500cm finally filled with Selexsorb COS (BASF) ³ And (5) a column.

Methylaluminoxane (MAO) was purchased from Albemarle Corporation as 10 wt% in toluene. N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was purchased from Albemarle Corporation. All of the complex and activator were added to the reactor as a diluent solution in toluene. The concentrations of the solutions of activator, scavenger and complex added to the reactor were selected such that between 40 and 200 microliters of solution was added to the reactor to ensure accurate delivery.

Reactor description and preparation. In an inert atmosphere (N) ₂ ) An external heater equipped for temperature control was used in the drying oven, glass inserts (internal volume of reactor for C ₂ And C ₂ /C ₈ Run at 23.5mL for C ₃ Operation as 22.5 mL), diaphragm inlet, regulated supply of nitrogen, ethylene and propylene and equipped with a disposable polyetheretherketone mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110 ℃ or 115 ℃ for 5 hours and then 25 ℃ for 5 hours.

Ethylene Polymerization (PE) or ethylene/1-octene copolymerization (EO).The reactor was prepared as described above and then purged with ethylene. At room temperature and atmospheric pressureToluene (solvent, unless otherwise indicated), optionally 1-octene (0.1 mL when used), and optionally MAO were added via syringe. The reactor was then brought to the process temperature (typically 80 ℃) and ethylene was added to the process pressure (typically 75psig = 618.5kPa or 200psig = 1480.3 kPa) while stirring at 800 RPM. An optional scavenger solution (e.g., TNOA in isohexane) is then added to the reactor by syringe under process conditions. An optional solution of a non-coordinating activator (e.g., N-dimethylanilinium tetrakis (pentafluorophenyl) borate) is added to the reactor via an injector at process conditions, after which a solution of a procatalyst (i.e., a complex or catalyst) is added to the reactor via an injector at process conditions (in toluene). Ethylene was fed into the autoclave during polymerization (by using a computer controlled solenoid valve) to maintain reactor gauge pressure (+/-2 psi). The reactor temperature is monitored and typically maintained within +/-1 ℃. By adding about 50psi O ₂ /Ar(5mol％O ₂ ) The polymerization was stopped by feeding the gas mixture to the autoclave for about 30 seconds. The polymerization is quenched after a predetermined cumulative amount of ethylene has been added or for a maximum polymerization time of 30 minutes. The reactor was cooled and vented. The polymer was isolated after removal of the solvent in vacuo. The reported yields include the total weight of polymer and residual catalyst. The catalyst activity is reported as grams of polymer/mmol transition metal compound/hour reaction time (g/mmol/hr).

And (3) polymerizing propylene.The reactor was prepared as described above, then heated to 40 ℃ and purged with propylene gas at atmospheric pressure. Toluene (solvent, unless otherwise indicated), optionally MAO, and liquid propylene (1.0 mL) were added via syringe. The reactor was then heated to the process temperature (70 ℃ C. Or 100 ℃ C.) while stirring at 800 RPM. An optional scavenger solution (e.g., TNOA in isohexane) is then added to the reactor by syringe under process conditions. An optional solution of a non-coordinating activator (e.g., N-dimethylanilinium tetrakis (pentafluorophenyl) borate) is then added to the reactor via an injector at process conditions, after which a solution of a procatalyst (i.e., a complex or catalyst) is added to the reactor (in toluene) via an injector at process conditions. Monitoring reactor temperature and typically maintaining Within +/-1 ℃. By adding about 50psi O ₂ /Ar(5mol％O ₂ ) The polymerization was stopped by feeding the gas mixture to the autoclave for about 30 seconds. The polymerization was quenched based on a predetermined pressure loss of about 8psi or for a maximum of 30 minutes polymerization time. The reactor was cooled and vented. The polymer was isolated after removal of the solvent in vacuo. The reported yields include the total weight of polymer and residual catalyst. The catalyst activity is generally reported as grams of polymer per mmol of transition metal compound per hour of reaction time (g/mmol/hr).

Polymer characterizationFor analytical testing, a polymer sample solution was prepared by dissolving the polymer in 1,2, 4-trichlorobenzene (TCB, 99+% purity from Sigma-Aldrich) containing 2, 6-di-tert-butyl-4-methylphenol (BHT, 99%, from Aldrich) in a shaking oven (shaker over) at 165 ℃ for about 3 hours. The typical concentration of polymer in solution is between 0.1mg/mL and 0.9mg/mL, with a BHT concentration of 1.25mg of TCB for BHT/mL. The samples were cooled to 135 ℃ for testing.

Using a method as described in U.S. Pat. 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. The molecular weight (weight average molecular weight (Mw) and number average molecular weight (Mn)) and molecular weight distribution (mwd=mw/Mn), sometimes also referred to as Polydispersity (PDI) of the polymer, of the polymer were measured by gel permeation chromatography using SymyxTechnology GPC equipped with an evaporative light scattering detector and calibrated using a polystyrene standard (Polymer Laboratories: polystyrene calibration kit S-M-10: mp (peak Mw) between 5,000 and 3,390,000). Samples were run at a flow rate of 2.0 mL/min (135 ℃ sample temperature, 165 ℃ oven/column) using three Polymer Laboratories:PLgel 10 μm mix-B300X 7.5mm columns in series (250. Mu.L of polymer solution in TCB was injected into the system). No column diffusion correction was used. Using a solution available from SymyxTechnics

Data analysis was performed by software or Automation Studio software available from freeboard. The molecular weights obtained are relative to linear polystyrene standards.

Differential Scanning Calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point of the polymer. The samples were pre-annealed at 220 ℃ for 15 minutes and then allowed to cool to room temperature overnight. The sample was then heated to 220 ℃ at a rate of 100 ℃/min and then cooled at a rate of 50 ℃/min. The melting point was collected during heating.

Samples for infrared analysis were prepared by depositing a stable polymer solution onto a silanized wafer (part number S10860, symyx). By this method, between about 0.12mg and 0.24mg of polymer is deposited on the wafer unit. The samples were then analyzed on a Bruker equi nox 55FTIR spectrometer equipped with a specular reflection sample fitting for Pikes' mapir. At 2cm ^-1 Resolution 5,000cm coverage with 32 scan collections ^-1 To 500cm ^-1 Spectrum of the spectral range.

For ethylene-1-octene copolymer, the ethylene-1-octene copolymer is obtained by a method of-1,375cm ^-1 Measurement of the methyl deformation zone was used to determine the weight percent copolymer. The peak height of the band passes at-4,321 cm ^-1 The frequency doubled absorption band (ovirtone band) combination at (i) is normalized, which corrects for path length differences. Normalized peak height and from ¹ A single calibration curve of H NMR data is related to predict the% copolymer weight content in the concentration range of-2 wt% to 35 wt% for octene. Typically, R of 0.98 or greater is achieved ² Correlation. Values reported below 4.1 wt% are outside of the calibration range.

Tables 1 to 6 illustrate the results obtained for catalysts 1, 2, 3, 4, 5, 6 and 7. All catalysts were found to be active catalysts for olefin polymerization when activated with N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate or MAO, respectively.

Table 1 illustrates the ethylene polymerization results obtained using catalysts 1, 2, 3, 4 and 5. General conditions: catalyst complex = 25nmol, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator = 1.1 eq, 75psig ethylene, al (N-octyl) ₃ =500 nmol, temperature =Total volume = 5mL at 80 ℃. In all cases, a narrow PDI (1.6-3.4) was obtained. Catalysts 1 and 4 were found to be the most active catalysts for olefin polymerization when activated using N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, with catalysts 1 and 4 differing only in their metal groups Hf and Zr, respectively. The polymerization process was carried out in the presence of 500nmol of TNOA as scavenger using 25nmol of catalyst with 1.1 equivalent of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. Although catalyst 5 showed the highest catalyst activity (run 16, 573,257g P.mmolecat ^-1 .h ^-1 ) However, catalysts 1 and 4 both provided polyethylenes with the highest Mw (up to 1,630,381 g/mol), mn (up to 482,351 g/mol) and Mz (up to 5,817,836). The highest melting point of polyethylene (e.g., tm 135 ℃ to 136 ℃) is obtained when catalyst 1 or catalyst 4 is used, whereas the lowest melting point of polyethylene (e.g., tm 107 ℃) is obtained when catalyst 3 is used. Catalyst 3 was least active (run 8, 13,083 gP.mmolecat ^-1 .h ^-1 )。

TABLE 1

Table 1 (subsequent)

Table 2 illustrates the ethylene polymerization results obtained using catalysts 1, 2,3, 4 and 5. General conditions catalyst complex=25 nmol, mao activator=500 equivalent, 75psig ethylene, temperature=80 ℃, total volume=5 mL. When MAO is used as the activator, higher molecular weight polymers are obtained using catalysts 1, 2 and 3. Although catalyst 3 generally exhibits the lowest catalyst activity (run 7 to 9, 15,671 gP.mmolecat ^-1 .h ^-1 -20,566gP.mmolcat ^-1 .h ^-1 ) Catalyst 3 also provided the highest molecular weight polymer (e.g., run 8), as well as the highest melting point (Tm 136 ℃) and narrow PDI (1.8 to 1.9). Catalyst 1 exhibited similar results to catalyst 3. However, the Mn value of the polyethylene formed by catalyst 1 was lower than that of the polyethylene formed by catalyst 3 (223,959 g/mol-366,906 g/mol). Catalyst 2 also showed similar results to catalyst 3. However, the highest PDI values (11.3-15.2) were observed for the polyethylenes formed over catalyst 2. When catalyst 5 was used (runs 13 to 15), polyethylene was obtained with the lowest Mn, mw, mz, PDI and Tm, even though catalyst 5 was observed to exhibit the highest catalyst activity.

TABLE 2

Table 2 (subsequent)

Table 3 illustrates the ethylene-octene copolymerization results obtained using catalysts 1, 2, 3, 4 and 5. General conditions: catalyst complex = 25nmol, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator = 27.5nmol,0.1ml octene, al (N-octyl) ₃ =500 nmol, temperature=80 ℃, total volume=5 mL. In all cases, the melting point of the ethylene-octene copolymer (45℃to 120 ℃) is lower than that of the polyethylene homopolymer. In general, the lowest melting point is obtained for the copolymer produced using the catalyst comprising aryl substituents at positions adjacent to the phenolate oxygen (e.g., catalysts 2, 3, and 5), and the highest melting point is obtained using catalysts 1 and 4, with catalyst 4 exhibiting the highest Mn, mw, and Mz (runs 18 to 23).

TABLE 3 Table 3

Table 3 (subsequent)

Table 4 illustrates the ethylene-octene copolymerization results obtained for catalysts 1, 2, 3, 4 and 5. General conditions catalyst complex=25 nmol, mao activator=500 equivalent, 0.1mL octene, temperature=80 ℃, total volume=5 mL. Catalyst 3 provided an ethylene-octene copolymer with the highest Mw, mz and PDI and melting point of 122 ℃ while exhibiting the lowest observed catalyst activity values (runs 12 to 17) using MAO as the activator. Catalysts 1 and 4 exhibited similar results even though the catalyst activity of catalyst 4 was about 8 to 10 times higher than that of catalyst 1. The copolymers produced using catalysts 1, 4 and 5 gave narrow PDI, whereas the copolymers produced using catalysts 2 and 3 gave PDI values of 16.6-34.7.

TABLE 4 Table 4

Table 4 (subsequent)

Table 5 illustrates the propylene polymerization results obtained for catalysts 1, 2, 3, 4, 5, 6 and 7. General conditions: catalyst complex=25 nmol, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator=27.5 nmol, propylene=1 ml, al (N-octyl) ₃ =500 nmol, total volume=5 mL. In all cases, a narrow PDI (1.6-2.2) was obtained. Catalysts 1 and 4 were found to be the most active catalysts observed for olefin polymerization when activated using N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. The highest melting point of polypropylene is obtained when catalyst 1 or catalyst 4 is used (e.g., tm from 149 ℃ to 151 ℃) and the lowest melting point of polypropylene is obtained when catalyst 3 or catalyst 5 is used (e.g., tm from 52 ℃ to 55 ℃). Catalyst 3 is the least active catalyst tested (run 15, 288 gP.mmolecat ^-1 .h ^-1 ). Catalyst 4 showed the highest catalyst activity observed (run 19,4,350,000 gP.mmolecat ^-1 .h ^-1 )。

TABLE 5

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Table 5 (subsequent)

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Table 6 illustrates the propylene polymerization results obtained for catalysts 1, 2, 3, 4 and 5. General conditions catalyst complex=40 nmol, mao activator=500 equivalent, propylene=1 mL, total volume=5 mL.

When MAO is used as activator, all catalysts provide polypropylene polymers with narrow PDI (1.2-2.2). Catalysts 1 and 4 were found to be the most active catalysts tested for olefin polymerization when activated with MAO. The highest melting point of the polypropylene polymer was observed when either catalyst 1 or catalyst 4 was used (e.g., tm 133 ℃ -149 ℃), with catalyst 4 exhibiting the highest catalyst activity observed (run 20,1,088,156gp mmolecat) ^-1 .h ^-1 )。

TABLE 6

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Watch 6 (subsequent)

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Table 7 illustrates the ethylene polymerization results obtained using catalysts 8 to 14. General conditions: catalyst complex = 25nmol, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator = 1.1 eq, 75psig ethylene, al (N-octyl) ₃ =500 nmol, temperature=80 ℃, total volume=5 mL, solvent=toluene.

TABLE 7

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Table 7 (subsequent)

Table 8 illustrates the ethylene polymerization results obtained using catalyst 11. General conditions catalyst complex=25 nmol, mao activator=500 equivalent, 75psig ethylene, temperature=80 ℃, total volume=5 mL, solvent=toluene.

TABLE 8

Table 8 (subsequent)

Table 9 illustrates the ethylene-octene copolymerization results obtained using catalysts 8 to 14. General conditions: catalyst complex = 25nmol, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator = 27.5nmol,0.1ml octene, al (N-octyl) ₃ =500 nmol, temperature=80 ℃, total volume=5 mL, solvent=toluene.

TABLE 9

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Watch 9 (subsequent)

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Table 10 shows the ethylene-octene copolymerization results obtained for catalyst 11. General conditions catalyst complex=25 nmol, mao activator=500 equivalent, 0.1mL octene, temperature=80 ℃, total volume=5 mL, solvent=toluene.

Table 10

Watch 10 (Xue)

Table 11 illustrates the propylene polymerization results obtained for catalysts 8 to 14. General conditions: catalyst complex=25 nmol, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator=27.5 nmol, propylene=1 ml, al (N-octyl) ₃ =500 nmol, total volume=5 mL, solvent=isohexane.

TABLE 11

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Watch 11 (subsequent)

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Table 12 illustrates the ethylene polymerization results obtained using catalysts 16 and 17. General conditions: catalyst complex = 25nmol, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator = 1.1 eq, 75psig ethylene, al (N-octyl) ₃ =500 nmol, temperature=80 ℃, total volume=5 mL, solvent=toluene.

Table 12

Table 13 illustrates the ethylene-octene copolymerization results obtained using catalysts 16 and 17. General conditions: catalyst complex = 25nmol, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator = 27.5nmol,0.1ml octene, al (N-octyl) ₃ =500 nmol, temperature=80 ℃, total volume=5 mL, solvent=toluene.

TABLE 13

In general, the catalysts, catalyst systems, and methods of the present disclosure can provide high Wen Yixi polymerization, propylene polymerization, or copolymerization because the bis (arylphenoxide) lewis base catalysts are stable at high polymerization temperatures and have good activity at high polymerization temperatures. A stable catalyst with good activity can provide for the formation of polymers with high molecular weights and the ability to produce increased amounts of polymer in a given reactor compared to conventional catalysts.

Thus, the present disclosure illustrates a high activity catalyst capable of operating at high reactor temperatures while producing polymers with controlled molecular weights and/or robust isotacticity.

Unless otherwise specified, the terms "consisting essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements or materials, whether or not such steps, elements or materials are specifically mentioned in the present specification, as long as such steps, elements or materials do not affect the basic and novel characteristics of the present disclosure, and furthermore, they do not exclude impurities and variations commonly associated with the elements and materials used.

For the sake of brevity, only certain ranges are explicitly disclosed herein. However, a range from any lower limit may be combined with any upper limit to thereby describe a range not explicitly described, and a range from any lower limit may be combined with any other lower limit to thereby describe a range not explicitly described, and a range from any upper limit may be combined with any other upper limit in the same manner to thereby describe a range not explicitly described. In addition, each point or individual value between its two endpoints is included within the range even though not explicitly recited. Thus, each point or individual value may serve as its own lower or upper limit, combined with any other point or individual value or any other lower or upper limit, thereby recitation of ranges not explicitly recited.

All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures, so long as they are not inconsistent with the present disclosure. As will be apparent from the foregoing general description and specific embodiments, while forms of the disclosure have been illustrated and described, various changes can be made without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the disclosure be limited thereby. Likewise, for purposes of united states law, the term "comprising" is considered synonymous with the term "including". Likewise, whenever a constituent, element or group of elements is preceded by the term "comprising", it should be understood that we also contemplate the same constituent or group of elements preceded by the term "consisting essentially of", "consisting of", "selected from the group consisting of" or "being" and vice versa.

While the present disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the present disclosure.

Claims (50)

1. A catalyst compound represented by formula (I):

wherein:

m is a group 3, 4 or 5 metal;

A ¹ and A ² Independently an aromatic group;

j is a heterocyclic Lewis base;

l is a Lewis base;

x is an anionic ligand;

n is 1, 2 or 3;

m is 0, 1 or 2;

n+m is not more than 4;

R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ and R is ⁸ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹ And R is ² 、R ² And R is ³ 、R ³ And R is ⁴ 、R ⁵ And R is ⁶ 、R ⁶ And R is ⁷ Or R is ⁷ And R is ⁸ One or more of the substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings can join to form additional rings;

any two L groups can be joined together to form a bidentate lewis base;

the X group may be joined to the L group to form a monoanionic bidentate group; and

any two X groups may be joined together to form a dianionic ligand group.

2. The catalyst compound of claim 1, wherein a ¹ Represented by the formula:

wherein the method comprises the steps of

Represents the linkage to the catalyst compound, and

R ⁹ 、R ¹⁰ 、R ¹¹ and R is ¹² Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ⁹ And R is ¹⁰ 、R ¹⁰ And R is ¹¹ Or R ¹¹ And R is ¹² One or more of which 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.

3. The catalyst compound of claim 1, wherein a ² Represented by the formula:

wherein the method comprises the steps of

Represents the linkage to the catalyst compound, and

R ¹³ 、R ¹⁴ 、R ¹⁵ and R is ¹⁶ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbyl, heterogensA child, or a heteroatom-containing group, or R ¹³ And R is ¹⁴ 、R ¹⁴ And R is ¹⁵ Or R ¹⁵ And R is ¹⁶ One or more of which 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.

4. The catalyst compound of claim 1 wherein J is selected from the group consisting of pyridine, thiazole,

Azole,/->

Oxazolines, imidazoles, furans or thiophenes.

5. The catalyst compound of claim 4, wherein J is represented by the formula:

wherein the method comprises the steps of

Represents the linkage to the catalyst compound, and

R ¹⁷ 、R ¹⁸ and R is ¹⁹ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹⁷ And R is ¹⁸ 、R ¹⁸ And R is ¹⁹ Or R is ¹⁷ And R is ¹⁹ One or more of which 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.

6. The catalyst compound of claim 5, wherein R ¹⁷ 、R ¹⁸ And R is ¹⁹ Is hydrogen.

7. The catalyst compound according to claim 1, wherein the complex is represented by formula (II):

wherein:

R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ and R is ⁸ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹ And R is ² 、R ² And R is ³ 、R ³ And R is ⁴ 、R ⁵ And R is ⁶ 、R ⁶ And R is ⁷ Or R is ⁷ And R is ⁸ 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 and R is ¹² Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ⁹ And R is ¹⁰ 、R ¹⁰ And R is ¹¹ Or R ¹¹ And R is ¹² 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 ¹³ 、R ¹⁴ 、R ¹⁵ And R is ¹⁶ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon radicals, hetero atoms, or hetero atom-containing radicalsOr R is a group of ¹³ And R is ¹⁴ 、R ¹⁴ And R is ¹⁵ Or R ¹⁵ And R is ¹⁶ 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 ¹⁷ 、R ¹⁸ and R is ¹⁹ Each independently is hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, hetero, or hetero-containing groups, or R ¹⁷ And R is ¹⁸ 、R ¹⁸ And R is ¹⁹ Or R is ¹⁷ And R is ¹⁹ 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;

m is a group 3, 4 or 5 metal;

l is a Lewis base;

x is an anionic ligand;

n is 1, 2 or 3;

m is 0, 1 or 2;

n+m is not more than 4;

any two L groups can be joined together to form a bidentate lewis base;

the X group may be joined to the L group to form a monoanionic bidentate group; and

any two X groups may be joined together to form a dianionic ligand group.

8. The catalyst compound of claim 7, wherein M is zirconium or hafnium.

9. The catalyst compound of claim 8, wherein m = 0, n = 2, and X is selected from halogen or a hydrocarbyl group containing 1 to 8 carbons.

10. The catalyst compound of claim 9, wherein R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ And R is ⁸ Each independently selected from hydrogen, C ₁ -C ₄₀ Hydrocarbon radicals, C ₁ -C ₄₀ Substituted hydrocarbon, alkoxy, silyl, amino, aryloxy, halogen or phosphino, or R ¹ And R is ² 、R ² And R is ³ 、R ³ And R is ⁴ 、R ⁵ And R is ⁶ 、R ⁶ And R is ⁷ Or R is ⁷ And R is ⁸ One or more of which 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.

11. The catalyst compound of claim 10, wherein R ⁴ And R is ⁵ Independently C ₁ -C ₁₀ An alkyl group.

12. The catalyst compound of claim 11, wherein R ⁴ And R is ⁵ Is tert-butyl.

13. The catalyst compound of claim 10, wherein R ⁴ And R is ⁵ Is aryl.

14. The catalyst compound of claim 13, wherein R ⁴ And R is ⁵ Is phenyl or carbazole.

15. The catalyst compound of claim 10, wherein R ⁴ And R is ⁵ Is Et ₃ Si。

16. The catalyst compound of claim 10, wherein R ⁴ And R is ⁵ Is 3, 5-di-tert-butyl benzyl.

17. The catalyst compound of claim 10, wherein R ² And R is ⁷ Independently and separatelyIs C ₁ -C ₁₀ An alkyl group.

18. The catalyst compound of claim 10, wherein R ² And R is ⁷ Is methyl.

19. The catalyst compound of claim 7, wherein 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 is ¹⁹ Each independently is hydrogen or C ₁ -C ₁₀ An alkyl group.

20. The catalyst compound of claim 18, wherein 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 is ¹⁹ Independently is hydrogen, methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, or trimethylsilyl.

21. The catalyst compound of claim 20, wherein 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 is ¹⁹ Is hydrogen.

22. The catalyst compound of claim 1, wherein n is 2 and each X is independently chloro, benzyl or methyl.

23. The catalyst compound of claim 1, wherein the catalyst compound is selected from the group consisting of:

24. the catalyst compound of claim 1, wherein the catalyst compound is selected from the group consisting of:

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25. the catalyst compound of claim 1, wherein the catalyst compound is selected from the group consisting of:

26. a catalyst system comprising an activator and the catalyst compound of any one of claims 1 to 25.

27. The catalyst system of claim 26, further comprising a support material.

28. The catalyst system of claim 27, wherein the support material is selected from Al ₂ O ₃ 、ZrO ₂ 、SiO ₂ 、SiO ₂ /Al ₂ O ₃ 、SiO ₂ /TiO ₂ Silica clay, silica/clay, or mixtures thereof.

29. The catalyst system of claim 28, wherein the activator comprises a non-coordinating anion activator.

30. The catalyst system of claim 29, wherein the activator is represented by the formula:

(Z) _d ⁺ (A ^d- )

wherein Z is (L-H) or a reducible Lewis acid, L is a Lewis base, H is hydrogen, (L-H) ⁺ Is a Bronsted acid; a is that ^d- Is a non-coordinating anion having a charge d-; and d is an integer from 1 to 3.

31. The catalyst system of claim 29, wherein the activator is represented by formula (AI):

[R ¹ R ² R ³ EH] _d ⁺ [M ^k+ Q _n ] ^d- (AI)

wherein:

e is nitrogen or phosphorus;

d is 1, 2 or 3; k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6; n-k=d;

R ¹ 、R ² and R is ³ Each independently is hydrogen, optionally substituted C ₁ -C ₄₀ Alkyl, or optionally substituted C ₅ -C ₅₀ -an aryl group; wherein R is ¹ 、R ² And R is ³ Containing 15 or more carbon atoms in total;

m is an element selected from group 13 of the periodic Table; and

each Q is independently a hydrogen group, a bridged or unbridged dialkylamino group, a halo group, an alkoxy group, an aryloxy group, a hydrocarbyl group, a substituted hydrocarbyl group, a halocarbyl group, a substituted halocarbyl group, or a halogen substituted hydrocarbyl group.

32. The catalyst system of claim 29, wherein the activator is one or more of the following:

N-methyl-4-nonadecyl-N-octadecyl-anilinium tetrakis (perfluoronaphthalen-2-yl) borate,

N-methyl-4-nonadecyl-N-octadecyl-anilinium tetrakis (perfluorophenyl) borate,

n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,

dioctadecyl methyl ammonium tetrakis (pentafluorophenyl) borate,

octacosanyl methyl ammonium tetrakis (perfluoronaphthyl) borate,

triphenylcarbon tetrakis (pentafluorophenyl) borate

Trimethyl ammonium tetrakis (perfluoronaphthyl) borate,

triethylammonium tetrakis (perfluoronaphthyl) borate,

tripropylammonium tetrakis (perfluoronaphthyl) borate,

tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) borate,

tri (tert-butyl) ammonium tetrakis (perfluoronaphthyl) borate,

n, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate,

n, N-diethylanilinium tetrakis (perfluoronaphthyl) borate,

n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (perfluoronaphthyl) borate),

tetra (perfluoronaphthyl) boronic acid

Triphenylcarbon tetrakis (perfluoronaphthyl) borate

Triphenylborate tetrakis (perfluoronaphthyl)

Triethylsilane tetra (perfluoronaphthyl) borate

Benzene tetra (perfluoronaphthyl) borate (diazonium)

)，

Trimethyl ammonium tetrakis (perfluorobiphenyl) borate,

triethylammonium tetrakis (perfluorobiphenyl) borate,

Tripropylammonium tetrakis (perfluorobiphenyl) borate,

tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate,

tri (tert-butyl) ammonium tetrakis (perfluorobiphenyl) borate,

n, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate,

n, N-diethylanilinium tetrakis (perfluorobiphenyl) borate,

n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (perfluorobiphenyl) borate),

tetra (perfluorobiphenyl) boronic acid

Triphenylcarbon tetrakis (perfluorobiphenyl) borate

Triphenylborate tetrakis (perfluorobiphenyl)

Triethylsilane tetra (perfluorobiphenyl) borate

Benzene tetra (perfluorobiphenyl) borate (diazonium

)，

[ 4-tert-butyl-PhNMe ₂ H][(C ₆ F ₃ (C ₆ F ₅ ) ₂ ) ₄ B]，

The preparation method comprises the steps of carrying out trimethyl ammonium tetraphenyl borate,

triethylammonium tetraphenylborate, which is prepared from a mixture of water and a solvent,

tripropylammonium tetraphenylborate is used as a catalyst,

tri (n-butyl) ammonium tetraphenylborate,

tri (tert-butyl) ammonium tetraphenyl borate,

tetraphenylboronic acid N, N-dimethylanilinium,

tetraphenylboronic acid N, N-diethylanilinium,

tetraphenylboronic acid N, N-dimethyl- (2, 4, 6-trimethylanilinium),

tetraphenylboronic acid

Triphenylcarbon tetraphenyl borate

Triphenylboronic acid tetraphenyl salt

Triethylsilane tetraphenylborate

Tetraphenylboronic acid benzene (diazonium)

)，

Trimethyl ammonium tetrakis (pentafluorophenyl) borate,

triethylammonium tetrakis (pentafluorophenyl) borate,

tripropylammonium tetrakis (pentafluorophenyl) borate,

Tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate,

tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate,

n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,

n, N-diethylanilinium tetrakis (pentafluorophenyl) borate,

n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (pentafluorophenyl) borate,

tetrakis (pentafluorophenyl) borate

Triphenylcarbon tetrakis (pentafluorophenyl) borate

/>

Triphenylborate tetrakis (pentafluorophenyl)

Triethylsilane tetra (pentafluorophenyl) borate

Benzene tetra (pentafluorophenyl) borate (diazonium

)，

Trimethyl ammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,

triethylammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,

tripropylammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,

tri (n-butyl) ammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,

dimethyl (tert-butyl) ammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,

n, N-dimethylanilinium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,

n, N-diethylanilinium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,

n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate),

tetrakis (2, 3,4, 6-tetrafluorophenyl) borate

Triphenylcarbon tetrakis (2, 3,4, 6-tetrafluorophenyl) borate

Triphenyltetrakis (2, 3,4, 6-tetrafluorophenyl) borate

Triethylsilane tetrakis (2, 3,4, 6-tetrafluorophenyl) borate

Benzene tetrakis (2, 3,4, 6-tetrafluorophenyl) borate (diazonium

)，

Trimethylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

triethylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

tripropylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

tri (n-butyl) ammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

tri (tert-butyl) ammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

n, N-dimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

n, N-diethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate),

tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

Triphenylcarbon tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

Triphenyltetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

Triethylsilane tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

Benzene tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate (diazonium

)，

Di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate,

dicyclohexylammonium tetrakis (pentafluorophenyl) borate,

tris (o-tolyl) borate

Tris (2, 6-dimethylphenyl) tetrakis (pentafluorophenyl) borate

/>

Triphenylcarbon tetrakis (pentafluorophenyl) borate

1- (4- (tris (pentafluorophenyl) borate) -2,3,5, 6-tetrafluorophenyl) pyrrolidine

A tetrakis (pentafluorophenyl) borate salt, and a method of preparing the same,

4- (tris (pentafluorophenyl) boronic acid) -2,3,5, 6-tetrafluoropyridine, and

triphenylcarbon tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate

33. The catalyst system of claim 26, further comprising a metal hydrocarbenyl chain transfer agent represented by the formula:

Al(R') _3-v (R”) _v

wherein each R' is independently C ₁ -C ₃₀ A hydrocarbyl group; each R' is independently C having a terminal vinyl group ₄ -C ₂₀ A hydrocarbenyl group; and v is 0.1 to 3.

34. The catalyst system of any of claims 26, wherein the activator comprises an alkylaluminoxane.

35. The catalyst system of claim 34, wherein the aluminoxane is present in a molar ratio of aluminum to catalyst compound transition metal of 100:1 or greater.

36. A process for producing an ethylene-based polymer comprising: polymerizing ethylene by contacting ethylene with the catalyst system of claim 26 in one or more continuous stirred tank reactors or loop reactors in series or in parallel at a reactor pressure of from 0.05MPa to 1,500MPa and a reactor temperature of from 30 ℃ to 230 ℃.

37. The method of claim 36, wherein the ethylene-based polymer has a Mw of 1,000 to 3,000,000g/mol, a Mn of 1,000 to 2,000,000g/mol, a Mz of 1,000 to 10,000,000g/mol, and a PDI of 1 to 20.

38. The method of claim 37, wherein the ethylene-based polymer has a PDI of 1-5.

39. The method of claim 37, wherein the ethylene-based polymer has a PDI of 10-20.

40. The method of claim 36, wherein the ethylene-based polymer has a melting point of 100 ℃ to 140 ℃.

41. A process for producing a propylene-based polymer comprising: propylene is polymerized by contacting propylene with the catalyst system of claim 26 in one or more continuous stirred tank reactors or loop reactors in series or parallel at a reactor pressure of from 0.05MPa to 1,500MPa and a reactor temperature of from 30 ℃ to 230 ℃ to form a propylene-based polymer.

42. The method of claim 41, wherein the propylene-based polymer has a Mw of 500-150,000g/mol, a Mn of 500-100,000g/mol, a Mz of 2,000-400,000g/mol, and a PDI of 1-3.

43. The process of claim 41 wherein the propylene-based polymer has a melting point of from 50 ℃ to 170 ℃.

44. A process for producing an ethylene alpha-olefin copolymer comprising: by reacting ethylene and at least one C in one or more continuous stirred tank reactors or loop reactors in series or in parallel at a reactor pressure of from 0.05MPa to 1,500MPa and a reactor temperature of from 30℃to 230 DEG C ₃ -C ₂₀ Contacting an alpha-olefin with the catalyst system of claim 26, thereby polymerizing ethylene and at least one C ₃ -C ₂₀ Alpha-olefins to form ethylene alpha-olefin copolymers.

45. The method of claim 44, wherein the ethylene alpha-olefin copolymer has a Mw of from 5,000 to 1,500,000g/mol, a Mz of from 5,000 to 10,000,000g/mol, a Mn of from 2,000 to 400,000g/mol, and a PDI of from 1 to 40.

46. The process of claim 44 wherein the ethylene alpha-olefin copolymer has a PDI of from 1 to 5.

47. The process of claim 44 wherein the ethylene alpha olefin copolymer has a PDI of from 20 to 40.

48. The process of claim 44 wherein the ethylene alpha-olefin copolymer has a melting point of 40 ℃ to 140 ℃.

49. A transition metal compound comprising a tridentate dianionic ligand chelated with a group 4 transition metal, represented by formula (I) as defined in claim 1, wherein the tridentate ligand is complexed with the metal using two anionic oxygen donors and one neutral heterocyclic nitrogen donor to form a pair of octamembered metallocycle rings.

50. A catalyst system comprising an activator and the transition metal compound of claim 49.