Polyethylene compositions obtained using transition metal bis(phenolate) catalyst complexes and a homogeneous process for their production.

Abstract

The present invention relates to a homogeneous process for producing polyethylene compositions using dianionic tridentate transition metal complexes characterized by a central neutral heterocyclic Lewis base and two phenolate donors, where the tridentate ligands are coordinated to the metal center to form two eight-membered rings. Preferably, the bis(phenolate) complexes have the following formula (I): [Formula 1] TIFF2023513581000079.tif45150, where M, L, X, m, n, E, E', Q, R 1 , R 2 , R 3 , R 4 , R 1' , R 2' , R 3' , R 4' , A 1 , A 1' , [Case 2] TIFF2023513581000080.tif13150 is as described in this application, and A 1 QA 1’ is connected to A via a three-atom bridge. 2 A 2’ and Q is the central atom of the three-atom bridge.

Description

[Technical Field]

[0001] Inventor: Peijun Jiang, Jo Ann M. Canich, John R. Hagadorn Priority This application claims priority to and the benefit of U.S. Ser. No. 62 / 972,936, filed February 11, 2020. CROSS-REFERENCE TO RELATED APPLICATIONS: The present invention is related to the following applications: 1) USSN 16 / 788,022, filed February 11, 2020; 2) USSN 16 / 788,088, filed February 11, 2020; 3) USSN 16 / 788,124, filed February 11, 2020; 4) USSN 16 / 787,909, filed February 11, 2020; 5) USSN 16 / 787,837, filed February 11, 2020; 6) concurrently filed PCT Application No. PCT / US2020 / ____, entitled "Propylene Copolymers Obtained Using Transition Metal Bis(phenolate) Catalyst Complexes and Homogeneous Processes for the Production Thereof" (Attorney Docket No. 2020EM048); 7) concurrently filed PCT Application No. PCT / US2020 / ____, entitled "Propylene Polymers Obtained Using Transition Metal Bis(phenolate) Catalyst Complexes and Homogeneous Processes for the Production Thereof" (Attorney Docket No. 2020EM049); and 8) Concurrently filed PCT Application No. PCT / US2020 / ____, entitled "Polyethylene-Alpha Olefin-Diene Monomer Copolymers Obtained Using Transition Metal Bis(phenolate) Catalyst Complexes and Homogeneous Processes for the Production Thereof" (Attorney Docket No. 2020EM050). FIELD OF THE INVENTION The present invention relates to polyethylene compositions prepared with novel catalyst compounds comprising Group 4 bis(phenolate) complexes, compositions containing same, and processes for preparing said copolymers. [Background technology]

[0002] Background of the Invention Polyethylene resins are synthesized by copolymerizing ethylene with alpha-olefins, such as propylene, 1-butene, 1-hexene, or 1-octene. This copolymerization results in ethylene-based copolymers with many short-chain branches (SCBs) along the polymer backbone. For example, the incorporation of propylene, 1-butene, 1-hexene, or 1-octene copolymers results in methyl (1 carbon), ethyl (2 carbons), butyl (4 carbons), or hexyl (6 carbons) branches along the polymer backbone, respectively. The chain length of the short-chain branches affects end-use properties and processability. The effect of branching on PE properties is determined by the length and amount of branching. Short-chain branches (SCBs) of less than about 40 carbon atoms disrupt the formation of crystalline structure. Short branches primarily affect mechanical, thermal, and optical properties. Performance in applications such as blown film is also affected by the comonomer composition distribution (CCD) across the molecular weight distribution (MWD), often referred to as the short-chain branching distribution (SCBD). LLDPE has high impact resistance but is difficult to process, and therefore LLDPE could benefit from the addition of long-chain comonomers. Long-chain branching (LCB) structure is another attribute that has been explored for improvements to melt strength and processability.

[0003] Polyethylene (PE) and polyethylene-containing compositions are useful in many applications, such as films, fibers, molded or thermoformed articles, pipe coatings, etc. Improvements in both the polymeric materials used to make the products and the processability of the polymeric materials can synergistically make the end-use products more commercially attractive. However, optimal performance often means sacrificing one property for another. Many have been interested in modifying the structure of polyolefins to obtain new and better combinations of properties, such as melt strength, stiffness, shrinkage, and optical properties. Furthermore, high optical clarity, high melt strength, bubble stability, and good extrusion properties are important for blown films, such as heat-sealable blown films. However, a wide range of films made from polyethylene compositions still lack certain properties, such as high tensile and impact strength, puncture resistance, excellent optical properties, and excellent sealing properties. Improved strength properties, along with excellent durability, would enable downgauging in blown film applications (e.g., as bags).

[0004] Catalyst design, polymer reaction engineering, and polymer processing technologies are being explored to create new polyolefin materials to meet the demands of a highly diverse industry. Catalyst design plays a key role in manipulating the molecular structure of polyethylene and, therefore, the material's properties and processability. The polyethylene market is currently dominated by products prepared using Ziegler-Natta (ZN)-type catalysts and metallocene-type catalysts. Optimization of these polyethylene products often requires processes using multiple reactors and / or multiple catalysts. Both strategies tend to be complex and costly. Therefore, there is interest in identifying new catalyst systems that can enhance the commercial utility of catalysts and enable the production of polymers with improved properties.

[0005] Olefin polymerization catalysts can be based on bis(phenolate) complexes as catalyst precursors, which are typically activated with alumoxanes or non-coordinating anion-containing activators. Examples of bis(phenolate) complexes can be found in the following references: KR 2018-022137 (LG Chem.) describes transition metal complexes of bis(methylphenylphenolate)pyridine. US 7,030,256 B2 (Symyx Technologies, Inc.) describes a bridged biaromatic ligand, a catalyst, a polymerization process and the resulting polymer. US 6,825,296 (University of Hong Kong) describes transition metal complexes of a bis(phenolate) ligand that coordinates to the metal and has two six-membered rings. US 7,847,099 (California Institute of Technology) describes transition metal complexes of a bis(phenolate) ligand that coordinates to the metal and has two six-membered rings. WO 2016 / 172110 (Univation Technologies) describes complexes of tridentate bis(phenolate) ligands featuring acyclic ether or thioether donors. Other references of interest include: Baier, MC et al., "Post-Metallocenes in the Industrial Production of Polyolefins" Angew. Chem. Int. Ed. 2014, 53, 9722-9744; and Golisz and Bercaw, "Synthesis of Early Transition Metal Bisphenolate Complexes and Their Use as Olefin Polymerization Catalysts" Macromolecules 2009, 42, 8751-8762.

[0006] Furthermore, it is advantageous to conduct commercial solution polymerization reactions at elevated temperatures. Two major catalyst limitations that often prevent access to such high-temperature polymerizations are catalyst efficiency and molecular weight of the resulting polymer, both of which tend to decrease with increasing temperature. Typical metallocene catalysts suitable for use in producing polyethylene copolymers have relatively limited molecular weight possibilities and require low process temperatures to obtain the desired low melt flow rate products. The newly developed single-site catalysts described herein and related to U.S. Patent Application No. 16 / 787,909, filed February 11, 2020, entitled "Transition Metal Bis(phenolate) Complexes and Their Use as Catalysts for Olefin Polymerization" (Attorney Docket No. 2020EM045), have the ability to produce high molecular weight polymers at high polymerization temperatures. When paired with various types of activators and used in solution processes, these catalysts can produce polyethylene compositions with good molecular weight and plastomeric properties, such as low Tm, among others. Furthermore, the catalyst activity is high, facilitating its use under commercially relevant process conditions. This novel process provides novel copolymers with a wide melt flow rate range and can produce copolymers at high reactor throughput and higher polymerization temperatures during polymer production. Summary of the Invention

[0007] Summary of the Invention The present invention relates to polyethylene compositions, e.g., copolymers of ethylene and C3-C8 olefins, and blends comprising such copolymers, prepared in a solution process using a dianionic tridentate transition metal catalyst complex featuring a central neutral heterocyclic Lewis base and two phenolate donors, where the tridentate ligands are coordinated to the metal center to form two eight-membered rings. The polymer and copolymer compositions described herein preferably contain 20 mol % ethylene, with an optional C3 or higher alpha olefin comonomer content of up to 80 mol %. The present invention relates to polyethylene compositions, e.g., polyethylene and C3-C 12 Also directed to copolymers (e.g., ethylene-octene) copolymers, as well as blends comprising the copolymers, are polyethylene compositions prepared in a solution process using a bis(phenolate) complex represented by formula (I):

[0008] [ka]

[0009] During the ceremony: M is a Group 3-6 transition metal or a lanthanide; E and E' are each independently O, S, or NR 9 and R 9 are independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, or heteroatom-containing group; Q is a Group 14, 15, or 16 atom that forms a coordinate bond with the metal M; A 1 QA 1’ is connected to A via a three-atom bridge. 2 A 2’ and Q is the central atom of a three-atom bridge; A 1 and A 1' are independently C, N or C(R 22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl, C1-C 20 substituted hydrocarbyl;

[0010] [ka]

[0011] is connected to A via a two-atom bridge. 1 is a divalent group containing 2 to 40 non-hydrogen atoms that links to an E-linked aryl group;

[0012] [ka]

[0013] is connected to A via a two-atom bridge. 1' is a divalent group containing 2 to 40 non-hydrogen atoms that links to the E'-linked aryl group; L is a neutral Lewis base; X is an anionic ligand; n is 1, 2 or 3; m is 0, 1 or 2; n+m is less than or equal to 4; R 1 , R 2 , R 3 , R 4 , R 1' , R 2' , R 3' , and R 4' are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1' and R 2' , R 2’ and R 3' , R 3' and R 4' may combine 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, and where substituents on the rings may be joined to form additional rings; Any two L groups may be combined to form a bidentate Lewis base; The X group may be joined to the L group to form a monoanionic bidentate group; Any two X groups may be combined to form a dianionic ligand group.

[0014] The present invention also relates to a liquid phase process for polymerizing olefins comprising contacting a catalyst compound described herein with an activator, ethylene, and one or more comonomers. The present invention further relates to polyethylene compositions produced by the process described herein. DETAILED DESCRIPTION OF THE INVENTION

[0015] definition For purposes of the present invention and the claims thereto, the following definitions shall be used. The periodic table groups use the new numbering scheme as described in CHEMICAL AND ENGINEERING NEWS, 63(5), pg. 27 (1985). Thus, a "Group 4 metal" is an element in Group 4 of the periodic table, such as Hf, Ti, or Zr. "Catalyst productivity" is a measure of the mass of polymer produced using a known amount of polymerization catalyst. Typically, "catalyst productivity" is expressed in units such as kg of polymer per kg of catalyst or grams of polymer per mmol of catalyst. If no units are specified, "catalyst productivity" is in units of kg of polymer per gram of catalyst. Only the mass of the transition metal component of the catalyst is used to calculate the catalyst productivity (i.e., activator and / or cocatalyst are omitted). "Catalyst activity" is a measure of the mass of polymer produced per unit time using a known amount of polymerization catalyst for batch and semi-batch polymerizations. Typically, "catalyst activity" is expressed in units such as (g of polymer) / (mmol of catalyst) / hour or (kg of polymer) / (mmol of catalyst) / hour. If no units are specified, "catalyst activity" is in units of (g of polymer) / (mmol of catalyst) / hour.

[0016] "Conversion" is the percentage of monomer converted to polymer product in the polymerization, reported as a %, and calculated based on polymer yield, polymer composition, and the amount of monomer fed to the reactor. An "olefin," alternatively referred to as an "alkene," is a straight-chain, branched-chain, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended hereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in the polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the mer units in the copolymer are derived from ethylene in a polymerization reaction, and the derived units are present in an amount of 35 wt% to 55 wt%, based on the weight of the copolymer. A "polymer" has two or more identical or different mer units. A "homopolymer" is a polymer having identical mer units. A "copolymer" is a polymer having two or more different mer units. A "terpolymer" is a polymer having three different mer units. Thus, as used herein, the definition of copolymer includes terpolymers, etc. "Different" when used in reference to mer units means that the mer units differ from one another by at least one atom or are isomerically different. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer that contains at least 50 mol % ethylene-derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer that contains at least 50 mol % propylene-derived units, etc. A polyethylene composition comprises an ethylene polymer or ethylene copolymer. Ethylene shall be considered an alpha-olefin. Unless otherwise specified, the term "C n " means a hydrocarbon having n carbon atoms per molecule, where n is a positive integer.

[0017] The term "hydrocarbon" refers to a class of compounds containing hydrogen bonded to carbon and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds with different values ​​of n. Similarly, "C m -C y" group or compound refers to a group or compound containing a total number of carbon atoms in the range of m to y. Thus, C1-C 50 Alkyl refers to alkyl groups containing a total number of carbon atoms in the range of 1-50. The terms "group," "radical," and "substituent" may be used interchangeably. The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" may be used interchangeably and are defined to mean a group consisting solely of hydrogen and carbon atoms. Preferred hydrocarbyls are C-C radicals that may be straight-chain, branched-chain, or cyclic. 100 is a group, and when cyclic, may be aromatic or non-aromatic. Examples of such groups include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, and aryl groups such as phenyl, benzyl, naphthalenyl, and the like.

[0018] Unless otherwise indicated (e.g., in the definition of "substituted hydrocarbyl"), the term "substituted" means that at least one hydrogen atom has been replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom or heteroatom-containing group, such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group, such as -NR * 2, -OR * , -SeR * , -TeR * , -PR * 2, -AsR * 2, -SbR * 2, -SR * , -BR * 2, -SiR * 3. -GeR * 3. -SnR * 3. -PbR * 3. -(CH2) q -SiR * 3 means that q is 1 to 10, and each R *are independently hydrogen, hydrocarbyl, or halocarbyl groups, and two or more R * may be joined to form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or means that at least one heteroatom is inserted within the hydrocarbyl ring. The term "substituted hydrocarbyl" refers to a group in which at least one hydrogen atom of the hydrocarbyl group has been replaced with at least one heteroatom (e.g., a halogen, such as Br, Cl, F, or I) or heteroatom-containing group (e.g., a functional group, such as -NR * 2, -OR * , -SeR * , -TeR * , -PR * 2, -AsR * 2, -SbR * 2, -SR * , -BR * 2, -SiR * 3. -GeR * 3. -SnR * 3. -PbR * 3. -(CH2) q -SiR * 3rd class, q is 1 to 10, each R * are independently hydrogen, hydrocarbyl, or halocarbyl groups, and two or more R * may be attached to form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure) or at least one heteroatom is inserted within the hydrocarbyl ring.

[0019] The term "aryl" or "aryl group" refers to an aromatic ring (typically made of 6 carbon atoms) and its substituted variants, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Similarly, heteroaryl refers to an aryl group in which one ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O, or S. As used herein, the term "aromatic" also refers to pseudo-aromatic heterocycles, which are heterocyclic substituents that have similar properties and structure (nearly planar) as aromatic heterocyclic ligands, but which are by definition not aromatic. The term "substituted aromatic" means an aromatic group having one or more hydrogen radicals replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0020] A "substituted phenolate" is a phenolate in which at least 1, 2, 3, 4, or 5 hydrogen atoms at the 2-, 3-, 4-, 5-, and / or 6-positions are replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom or heteroatom-containing group, such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group, such as -NR * 2, -OR * , -SeR * , -TeR * , -PR * 2, -AsR * 2, -SbR * 2, -SR * , -BR * 2, -SiR * 3. -GeR * 3. -SnR * 3. -PbR * 3. -(CH2) q -SiR * 3, etc., q is 1 to 10, and each R * are independently hydrogen, hydrocarbyl, or halocarbyl groups, and two or more R * may be bonded to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, with the 1-position being a phenolate group (Ph-O-, Ph-S-, and Ph-N(R ^ )-group, and R ^is hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 Preferably, the "substituted phenolate" group of the catalyst compounds described herein is represented by the formula:

[0021] [ka]

[0022] In the formula, R 18 is hydrogen, C1-C 40 Hydrocarbyl (e.g., C1-C 40 alkyl) or C1-C 40 is a substituted hydrocarbyl, heteroatom or heteroatom-containing group, 17 is oxygen, sulfur, or NR 17 and R 17 , R 19 , R 20 , and R 21 are each independently hydrogen, C1-C 40 Hydrocarbyl (e.g., C1-C 40 alkyl) or C1-C 40 substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R 18 , R 19 , R 20 , and R 21 Two or more of these are combined to form C4-C 62 forming a cyclic or polycyclic ring structure, or combination thereof, and the wavy line indicates where the substituted phenolate group forms a bond to the remainder of the catalyst compound. An "alkyl-substituted phenolate" is an alkyl group in which at least 1, 2, 3, 4, or 5 hydrogen atoms at the 2, 3, 4, 5, and / or 6 positions are replaced by at least one alkyl group, e.g., C-C 40 , or C2-C 20 , or C3-C 12and phenolate groups substituted with alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantanyl, and the like, including substituted analogs thereof.

[0023] An "aryl substituted phenolate" is an aryl group in which at least 1, 2, 3, 4, or 5 hydrogen atoms at the 2-, 3-, 4-, 5-, and / or 6-positions are substituted with at least one aryl group, e.g., C-C 40 , or C2-C 20 , or C3-C 12 and phenolate groups substituted with aryl groups such as phenyl, 4-fluorophenyl, 2-methylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, mesityl, 2-ethylphenyl, naphthalenyl, and the like, including substituted analogs thereof. The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has 6 ring atoms and a tetrahydrofuran group has 5 ring atoms. Heterocyclic rings, also called heterocycles, are rings that have heteroatoms in the ring structure, as opposed to "heteroatom-substituted rings" in which hydrogen atoms on ring atoms are replaced with heteroatoms. For example, tetrahydrofuran is a heterocyclic ring, and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. A substituted heterocyclic ring refers to a heterocyclic ring having one or more hydrogen groups replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group. Substituted hydrocarbyl ring means a ring composed of carbon and hydrogen atoms with one or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0024] For purposes of this disclosure, with respect to catalyst compounds (e.g., substituted bis(phenolate) catalyst compounds), the term "substituted" means that a hydrogen group is replaced with a hydrocarbyl group, a heteroatom or heteroatom-containing group, such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group, such as -NR * 2, -OR * , -SeR * , -TeR * , -PR * 2, -AsR * 2, -SbR * 2, -SR * , -BR * 2, -SiR * 3. -GeR * 3. -SnR * 3. -PbR * 3. -(CH2) q -SiR * 3 means that q is 1 to 10, and each R * are independently hydrogen, hydrocarbyl, or halocarbyl groups, and two or more R * may be joined to form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or at least one heteroatom is inserted within the hydrocarbyl ring. A tertiary hydrocarbyl group has a carbon atom bonded to three other carbon atoms. When the hydrocarbyl group is an alkyl group, the tertiary hydrocarbyl group is also called a tertiary alkyl group. Examples of tertiary hydrocarbyl groups include tert-butyl, 2-methylbutan-2-yl, 2-methylhexan-2-yl, 2-phenylpropan-2-yl, 2-cyclohexylpropan-2-yl, 1-methylcyclohexyl, 1-adamantyl, bicyclo[2.2.1]heptan-1-yl, and the like. A tertiary hydrocarbyl group can be illustrated by Formula A below:

[0025] [ka]

[0026] In the formula, R A , R B and RC are hydrocarbyl or substituted hydrocarbyl groups which may optionally be bonded to each other, and the wavy line indicates where a tertiary hydrocarbyl group forms a bond to another group. A cyclic tertiary hydrocarbyl group is defined as a tertiary hydrocarbyl group that forms at least one alicyclic (non-aromatic) ring. A cyclic tertiary hydrocarbyl group is also called an alicyclic tertiary hydrocarbyl group. When the hydrocarbyl group is an alkyl group, the cyclic tertiary hydrocarbyl group is also called a cyclic tertiary alkyl group or an alicyclic tertiary alkyl group. Examples of cyclic tertiary hydrocarbyl groups include 1-adamantanyl, 1-methylcyclohexyl, 1-methylcyclopentyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclododecyl, bicyclo[3.3.1]nonan-1-yl, bicyclo[2.2.1]heptan-1-yl, bicyclo[2.3.3]hexan-1-yl, bicyclo(bicycle)[1.1.1]pentan-1-yl, bicyclo(bicycle)[2.2.2]octan-1-yl, etc. Cyclic tertiary hydrocarbyl groups can be illustrated by Formula B below:

[0027] [ka]

[0028] In the formula, R A is a hydrocarbyl group or a substituted hydrocarbyl group, and each R D are independently hydrogen or a hydrocarbyl or substituted hydrocarbyl group; w is an integer from 1 to about 30; R A , and one or more R D , and / or two or more R D may optionally be linked to each other to form a further ring. When the cyclic tertiary hydrocarbyl group contains more than one alicyclic ring, it may be referred to as a polycyclic tertiary hydrocarbyl group, or when the hydrocarbyl group is an alkyl group, it may be referred to as a polycyclic tertiary alkyl group. The terms "alkyl group" and "alkyl" are used interchangeably throughout this disclosure. For purposes of this disclosure, an "alkyl group" is a C-C alkyl group that may be straight-chained, branched-chained, or cyclic. 100 The term "alkyl" refers to a group in which at least one hydrogen atom of the alkyl group is substituted with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom or heteroatom-containing group, such as a halogen atom (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. -(CH2) q -SiR * 3, etc., and q is 1 to 10, and each R * are independently hydrogen, hydrocarbyl, or halocarbyl groups, and two or more R * may be joined to form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or at least one heteroatom is inserted within the hydrocarbyl ring.

[0029] Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), a reference to one member of the family (e.g., n-butyl) is intended to explicitly disclose the remaining isomers of the family (e.g., isobutyl, sec-butyl, and tert-butyl). Similarly, a reference to an alkyl, alkenyl, alkoxide, or aryl group (e.g., butyl) without specifying a particular isomer explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl). As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, Mz is z-average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol (g mol -1 )

[0030] The following abbreviations may be used herein: Me is methyl, Et is ethyl, Pr is propyl, cPr is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu is normal butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl, MAO is methylalumoxane, dme (also represented as DME) is 1,2-dimethoxyethane, p-tBu is para-tertiary. butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOA and TNOAL are tri(n-octyl)aluminum, p-Me is para-methyl, Bn is benzyl (i.e., CHPh), THF (also represented as thf) is tetrahydrofuran, RT is room temperature (and 23° C. unless otherwise indicated), tol is toluene, EtOAc is ethyl acetate, Cbz is carbazole, Cy is cyclohexyl, h is hour, and min is minute.

[0031] A "catalyst system" is a combination comprising at least one catalyst compound and at least one activator. When "catalyst system" is used to describe such a pair prior to activation, it refers to the unactivated catalyst complex (pre-catalyst) along with the activator and, optionally, a co-activator. When "catalyst system" is used to describe such a pair after activation, it refers to the activated complex and activator or other charge-balancing moiety. The transition metal compound may be neutral, as in a pre-catalyst, or may be a charged species with a counterion, as in an activated catalyst system. For purposes of this invention and the claims thereto, when a catalyst system is described as comprising the neutral stable form of a component, those skilled in the art will appreciate that the ionic form of the component is the form that reacts with a monomer to produce a polymer. A polymerization catalyst system is a catalyst system capable of polymerizing a monomer into a polymer. In the description herein, the catalyst may be referred to as a catalyst, catalyst precursor, pre-catalyst compound, catalyst compound, or transition metal compound, and these terms are used interchangeably.

[0032] An "anionic ligand" is a negatively charged ligand that donates one or more electron pairs to a metal ion. The term "anionic donor" is used interchangeably with "anionic ligand." Examples of anionic donors in the context of the present invention include, but are not limited to, methyl, chloride, fluoride, alkoxide, aryloxide, alkyl, alkenyl, thiolate, carboxylate, amide, methyl, benzyl, hydride, amidinate, amidate, and phenyl. Two anionic donors may combine to form a dianionic group. A "neutral Lewis base" or "neutral donor group" is an uncharged (i.e., neutral) group that donates one or more electron pairs to a metal ion. Non-limiting examples of neutral Lewis bases include ethers, thioethers, amines, phosphines, ethyl ethers, tetrahydrofuran, dimethyl sulfide, triethylamine, pyridine, alkenes, alkynes, allenes, and carbenes. Lewis bases may also combine to form bidentate or tridentate Lewis bases. For purposes of this invention and the claims thereto, phenolate donors include Ph-O-, Ph-S-, and Ph-N(R ^ )-group, where R^ is hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, heteroatom or heteroatom-containing group, and Ph is an optionally substituted phenyl.

[0033] Detailed Description The present invention relates to a solution process using a novel catalyst family comprising a dianionic tridentate transition metal complex characterized by a central neutral donor group and two phenolate donors, where the tridentate ligands are coordinated to the metal center to form two eight-membered rings, and polyethylene compositions produced using the catalyst family. In this type of complex, the central neutral donor is advantageously a heterocyclic group. It is particularly advantageous for the heterocyclic group to lack a hydrogen atom alpha to the heteroatom. In this type of complex, the phenolate is also advantageously substituted with one or more cyclic tertiary alkyl substituents. The use of cyclic tertiary alkyl-substituted phenolates demonstrates improved ability of these catalysts to produce high molecular weight polymers. Complexes of substituted bis(phenolate) ligands (e.g., adamantanyl-substituted bis(phenolate) ligands) useful herein, when combined with an activator, such as a non-coordinating anion or an alumoxane activator, form active olefin polymerization catalysts. Useful bis(arylphenolate)pyridine complexes include tridentate bis(arylphenolate)pyridine ligands that coordinate to a Group 4 transition metal to form two eight-membered rings.

[0034] The present invention also relates to a solution process for producing polyethylene compositions utilizing a metal complex comprising a metal selected from a Group 3 to Group 6 metal or a Lanthanide metal, and a tridentate dianionic ligand containing two anionic donor groups and a neutral Lewis base donor, wherein the neutral Lewis base donor is covalently bonded between the two anionic donors, and the metal-ligand complex is characterized by a pair of eight-membered metallacycle rings. The present invention relates to a catalyst system for use in a solution process for preparing a polyethylene composition, comprising an activator as described herein and one or more catalyst compounds. The present invention also relates to a solution process for polymerizing olefins (preferably at elevated temperatures) using the catalyst compounds described herein, comprising contacting ethylene and one or more olefin comonomers with a catalyst system comprising an activator and a catalyst compound described herein.

[0035] The present disclosure also relates to catalyst systems comprising the transition metal compounds and activator compounds described herein, the use of the activator compounds to activate the transition metal compounds in the catalyst systems to polymerize ethylene and olefin comonomers, and a process for polymerizing said olefins, comprising contacting ethylene and one or more olefin comonomers under polymerization conditions with a catalyst system comprising a transition metal compound and an activator compound, wherein an aromatic solvent such as toluene is absent (e.g., present at zero mol % or present at less than 1 mol % relative to the moles of activator, and preferably the catalyst system, the polymerization reaction, and / or the resulting polymer are free of detectable aromatic hydrocarbon solvents, such as toluene. The polyethylene compositions produced herein preferably contain 0 ppm (alternatively less than 1 ppm, alternatively less than 100 ppm, alternatively less than 500 ppm) aromatic hydrocarbons, such as toluene. Preferably, the polyethylene compositions produced herein contain 0 ppm (alternatively less than 1 ppm) toluene. The catalyst systems used herein preferably contain 0 ppm (alternatively less than 1 ppm) aromatic hydrocarbons. Preferably, the catalyst systems used herein contain 0 ppm (alternatively less than 1 ppm) toluene.

[0036] catalyst compound The terms "catalyst," "compound," "catalyst compound," and "complex" can be used interchangeably to describe a transition metal or lanthanide metal complex that, when combined with an appropriate activator, forms an olefin polymerization catalyst. The catalyst complexes of the present invention comprise a metal selected from Group 3, 4, 5, or 6 metals of the Periodic Table of the Elements or a Lanthanide metal, and a tridentate dianionic ligand containing two anionic donor groups and a neutral heterocyclic Lewis base donor, where the heterocyclic donor is covalently bonded between the two anionic donors. Preferably, the dianionic tridentate ligand features a central heterocyclic donor group and two phenolate donors, with the tridentate ligand coordinating to the metal center to form two eight-membered rings.

[0037] The metal is preferably selected from elements of Groups 3, 4, 5, or 6. Preferably, the metal M is a Group 4 metal. Most preferably, the metal M is zirconium or hafnium. Preferably, the heterocyclic Lewis base donor is characterized by a nitrogen or oxygen donor atom. Preferred heterocyclic groups include pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and derivatives thereof, and their substituted variants. Preferably, the heterocyclic Lewis base lacks a hydrogen atom in the alpha position relative to the donor atom. Particularly preferred heterocyclic Lewis base donors include pyridine, trisubstituted pyridine, and tetrasubstituted pyridine. The anionic donor of the dianionic tridentate ligand can be an arylthiolate, phenolate, or anilide. A preferred anionic donor is phenolate. Preferably, the dianionic tridentate ligand coordinates to the metal center to form a complex lacking a mirror plane of symmetry. Preferably, the dianionic tridentate ligand coordinates to the metal center to form a complex with a two-fold axis of symmetry; only the metal and the dianionic tridentate ligand are considered (i.e., the remaining ligands are ignored) when determining the symmetry of a bis(phenolate) complex.

[0038] Bis(phenolate) ligands useful in the present invention include dianionic multidentate ligands featuring two anionic phenolate donors. Preferably, the bis(phenolate) ligand is a dianionic tridentate ligand that coordinates to the metal M in a manner that forms a pair of eight-membered metallacycle rings. Preferred bis(phenolate) ligands wrap around the metal to form complexes with a two-fold axis, thereby imparting C2 symmetry to the complex. The C2 geometry and the eight-membered metallacycle ring are characteristics of these complexes that make them effective catalytic components for the production of polyolefins, particularly isotactic poly(alphaolefins). The ligands allow the complexes to be mirror-faced (C s If the catalyst is coordinated to a metal in a manner with α- and β- symmetry, the catalyst is expected to produce only atactic poly(alphaolefins); these symmetry-reactivity rules are summarized by Bercaw in Macromolecules 2009, 42, 8751-8762. The pair of eight-membered metallacycle rings of the inventive complexes is also a notable feature that favors catalytic activity, thermal stability, and equiselectivity of monomer enchainment. Related Group 4 complexes featuring smaller six-membered metallacycle rings (Macromolecules 2009, 42, 8751-8762) have been used in olefin polymerization to produce only C2 and C3 poly(alphaolefins). s It is known to be less suitable for producing highly isotactic poly(alpha olefins) due to the formation of mixtures of symmetric complexes.

[0039] The bis(phenolate) ligands containing oxygen donor groups in the present invention (i.e., E = E' = oxygen in formula (I)) are preferably substituted with alkyl, substituted alkyl, aryl, or other groups. Advantageously, each phenolate group is substituted at the ring position adjacent to the oxygen donor atom. The substituent adjacent to the oxygen donor atom is preferably an alkyl group containing 1 to 20 carbon atoms. The substituent adjacent to the oxygen donor atom is preferably a non-aromatic cyclic alkyl group having one or more 5- or 6-membered rings. The substituent adjacent to the oxygen donor atom is preferably a cyclic tertiary alkyl group. It is highly preferred that the substituent adjacent to the oxygen donor atom is adamantan-1-yl or substituted adamantan-1-yl. The neutral heterocyclic Lewis base donor is covalently linked between the two anionic donors via a "linker group" that connects the heterocyclic Lewis base to the phenolate group. The "linker group" is the group represented by (A 3 A 2 ) and (A 2’ A 3’ ) The selection of each linker group can affect the catalytic performance, for example, the stereoregularity of the poly(alphaolefin) produced. Each linker group is typically two atoms long, C2-C 40 It is a divalent group. One or both linker groups may independently be phenylene, substituted phenylene, heteroaryl, vinylene, or an acyclic two-carbon long linker group. When one or both linker groups are phenylene, alkyl substituents on the phenylene group may be selected to optimize catalytic performance. Typically, one or both phenylenes may be unsubstituted or may be C-C 20 It may be independently substituted with alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or an isomer thereof, such as isopropyl. The present invention further relates to catalyst compounds represented by the following formula (I), and catalyst systems containing said compounds:

[0040] [ka]

[0041] During the ceremony: M is a Group 3, 4, 5, or 6 transition metal or a lanthanide (e.g., Hf, Zr, or Ti); E and E' are each independently O, S, or NR 9 and R 9 are independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 a substituted hydrocarbyl, or heteroatom-containing group, preferably O, where preferably both E and E' are O; Q is a Group 14, 15, or 16 atom that forms a coordinate bond with the metal M, preferably Q is C, O, S, or N, more preferably Q is C, N, or O, and most preferably Q is N; A 1 QA 1’ is connected to A via a three-atom bridge. 2 A 2’ and Q is the central atom of a three-atom bridge (A 1 QA 1’ is A 1 and A 1’ (Together with the curve connecting the two, this represents a heterocyclic Lewis base), A 1 and A 1' are independently C, N, or C(R 22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl, and C1-C 20 substituted hydrocarbyl, preferably A 1 and A 1' is C;

[0042] [ka]

[0043] is connected to A via a two-atom bridge. 1 to the E-linked aryl group, such as ortho-phenylene, substituted ortho-phenylene, ortho-arene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene, 1,2-ethylene (—CHCH—), substituted 1,2-ethylene, 1,2-vinylene (—HC═CH—), or substituted 1,2-vinylene, preferably

[0044] [ka]

[0045] is a divalent hydrocarbyl group;

[0046] [ka]

[0047] is connected to A via a two-atom bridge. 1' to the E'-linked aryl group, such as ortho-phenylene, substituted ortho-phenylene, ortho-arene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene, 1,2-ethylene (-CH2CH2-), substituted 1,2-ethylene, 1,2-vinylene (-HC=CH-), or substituted 1,2-vinylene, preferably

[0048] [ka]

[0049] is a divalent hydrocarbyl group; each L is independently a Lewis base; each X is independently an anionic ligand; n is 1, 2 or 3; m is 0, 1, or 2; n+m is less than or equal to 4; R 1 , R 2 , R 3 , R 4 , R 1' , R 2' , R 3' , and R 4' are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 substituted hydrocarbyl, heteroatom or heteroatom-containing group (preferably R 1' and R 1 are independently a cyclic group, e.g., a cyclic tertiary alkyl group), or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1' and R 2' , R 2’ and R 3' , R 3' and R 4' may combine 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, and where substituents on the rings may be joined to form additional rings; Any two L groups may be combined to form a bidentate Lewis base; The X group may be joined to the L group to form a monoanionic bidentate group; Any two X groups may be combined to form a dianionic ligand group. The present invention further relates to a catalyst compound represented by the following formula (II), and a catalyst system comprising said compound:

[0050] [ka]

[0051] During the ceremony: M is a Group 3, 4, 5, or 6 transition metal or lanthanide (e.g., Hf, Zr, or Ti); E and E' are each independently O, S, or NR 9 and R 9 are independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 a substituted hydrocarbyl, or heteroatom-containing group, preferably O, where preferably both E and E' are O; each L is independently a Lewis base; each X is independently an anionic ligand; n is 1, 2 or 3; m is 0, 1, or 2; n+m is less than or equal to 4; R 1 , R 2 , R 3 , R 4 , R 1' , R 2' , R 3' , and R 4' are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1' and R 2' , R 2’ and R 3' , R 3' and R 4' may combine 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, and where substituents on the rings may be joined to form additional rings; Any two L groups may be combined to form a bidentate Lewis base; The X group may be joined to the L group to form a monoanionic bidentate group; Any two X groups may be combined to form a dianionic ligand group; R 5 , R 6 , R 7, R 8 , R 5’ , R 6’ , R 7’ , R 8’ , R 10 , R 11 , and R 12 are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 5’ and R 6’ , R 6’ and R 7’ , R 7’ and R 8’ , R 10 and R 11 , or R 11 and R 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, and where substituents on the rings may be joined to form additional rings.

[0052] The metal M is preferably selected from elements of Groups 3, 4, 5 or 6, more preferably from elements of Group 4. Most preferably, the metal M is zirconium or hafnium. The donor atom Q of the neutral heterocyclic Lewis base (in formula (I)) is preferably nitrogen, carbon, or oxygen. A preferred Q is nitrogen. Non-limiting examples of neutral heterocyclic Lewis base groups include derivatives of pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and substituted variants thereof. Preferred heterocyclic Lewis base groups include derivatives of pyridine, pyrazine, thiazole, and imidazole. A of the heterocyclic Lewis base (in formula (I)) 1 and A 1 are each independently C, N, or C(R22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl, and C1-C 20 substituted hydrocarbyl. Preferably, A 1 and A 1' is carbon. When Q is carbon, A 1 and A 1’ is nitrogen and C(R 22 When Q is nitrogen, A 1 and A 1’ is preferably carbon. Q=nitrogen and A 1 =A 1’ When Q is nitrogen or oxygen, the heterocyclic Lewis base in formula (I) is preferably A 1 or A 1’ It is preferred not to have any hydrogen atoms attached to the atoms, as it is believed that hydrogens at those positions may undergo undesired decomposition and reduce the stability of the catalytically active species. A 1 and A 1’ Together with the curve that connects 1 QA 1’ The heterocyclic Lewis base (of formula (I)) represented by 23 Groups include hydrogen, heteroatoms, C1-C 20 Alkyl, C1-C 20 Alkoxides, C1-C 20 Amides and C1-C 20 substituted alkyl.

[0053] [ka]

[0054] In formula (I) or (II), E and E′ are each oxygen or NR 9 Selected from R 9 are independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40E and E' are preferably oxygen. E and / or E' are preferably NR 9 When R 9 is C1-C 20 Preferably, E and E' are selected from hydrocarbyl, alkyl, or aryl. In one embodiment, E and E' are each selected from O, S, or N(alkyl) or N(aryl), with alkyl preferably being C1-C6. 20 Alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.; aryl, for example, C-C 40 Aryl groups include, for example, phenyl, naphthalenyl, benzyl, methylphenyl, and the like. In an embodiment,

[0055] [ka]

[0056] are independently divalent hydrocarbyl groups, e.g., C-C 12 It is a hydrocarbyl group. In the complexes of formula (I) or (II), when E and E′ are oxygen, each phenolate group is located at the position adjacent to the oxygen atom (i.e., R 1 and R 1’ ) is advantageously substituted. Thus, when E and E' are oxygen, R 1 and R 1' are C1-C 40 Hydrocarbyl, C1-C 40 Preferably, R is a substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group. More preferably, R 1 and R 1' are each independently a non-aromatic cyclic alkyl group having one or more 5- or 6-membered rings (e.g., cyclohexyl, cyclooctyl, adamantanyl, 1-methylcyclohexyl, or substituted adamantanyl), most preferably a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantanyl, or substituted adamantanyl). In some embodiments of the present invention according to formula (I) or (II), R 1 and R 1' are each independently a tertiary hydrocarbyl group. In another embodiment of the present invention according to formula (I) or (II), R 1 and R 1' are each independently a cyclic tertiary hydrocarbyl group. In another embodiment of the present invention according to formula (I) or (II), R 1 and R 1' are each independently a polycyclic tertiary hydrocarbyl group. In some embodiments of the present invention according to formula (I) or (II), R 1 and R 1' are each independently a tertiary hydrocarbyl group. In another embodiment of the present invention according to formula (I) or (II), R 1 and R 1' are each independently a cyclic tertiary hydrocarbyl group. In another embodiment of the present invention according to formula (I) or (II), R 1 and R 1' are each independently a polycyclic tertiary hydrocarbyl group. The linker group (i.e.,

[0057] [ka]

[0058] are each preferably part of an ortho-phenylene group, preferably a substituted ortho-phenylene group. 7 and R 7’ positions are hydrogen or C1-C 20 Preferably, R is alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or an isomer thereof, such as isopropyl. In applications where a polymer having high stereoregularity is desired, R in formula (II) 7 and R 7’ Rank C1-C 20Preferably, R is alkyl. 7 and R 7’ Most preferably, both are C1-C3 alkyl. In the embodiments of formula (I) herein, Q is C, N or O, preferably Q is N. In embodiments of formula (I) herein, A 1 and A 1' are independently carbon, nitrogen, or C(R 22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl, C1-C 20 substituted hydrocarbyl. Preferably, A 1 and A 1’ is carbon. In an embodiment of formula (I) herein, A in formula (I) 1 QA 1’ is part of a heterocyclic Lewis base such as pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or substituted versions thereof. In embodiments of formula (I) herein, A 1 QA 1’ is connected to A via a three-atom bridge. 2 A 2’ and Q is the central atom of a three-atom bridge. 1 and A 1' are carbon atoms, and A 1 QA 1’ The fragment forms part of a group or a substituted variant of a pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or a substituted variant thereof. In one embodiment of formula (I) herein, Q is carbon and A 1 and A 1' are N or C(R 22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl, C1-C 20In this embodiment, A is selected from the group consisting of a substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group. 1 QA 1’ The fragment forms part of a cyclic carbene, an N-heterocyclic carbene, a cyclic aminoalkylcarbene, or a substituted variant thereof, or a substituted variant thereof. In embodiments of formula (I) herein,

[0059] [ka]

[0060] is connected to A via a two-atom bridge. 1 is a divalent group containing 2 to 20 non-hydrogen atoms that links

[0061] [ka]

[0062] is a straight chain alkyl or forms part of a cyclic group (eg an optionally substituted ortho-phenylene group or an ortho-arylene group) or substituted variants thereof.

[0063] [ka]

[0064] is connected to A via a two-atom bridge. 1' is a divalent group containing 2 to 20 non-hydrogen atoms that links

[0065] [ka]

[0066] is a straight chain alkyl or forms part of a cyclic group (eg an optionally substituted ortho-phenylene group or an ortho-arylene group) or substituted variants thereof. In an embodiment of the invention herein, in formulas (I) and (II), M is a Group 4 metal, such as Hf or Zr. In an embodiment of the invention herein, E and E' are O in formulas (I) and (II). In an embodiment of the invention herein, in formulas (I) and (II), R 1 , R 2 , R 3 , R 4 , R 1' , R 2' , R 3' , and R 4' are independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1' and R 2' , R 2’ and R 3' , R 3' and R 4' 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, and where substituents on the rings may be joined to form further rings, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof.

[0067] In an embodiment of the invention herein, in formulas (I) and (II), R 1 , R 2 , R 3 , R 4 , R 1' , R 2' , R 3' , R 4' , and R 9are independently selected from 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, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

[0068] In an embodiment of the invention herein, in formulas (I) and (II), R 4 and R 4' are independently hydrogen or C1-C3 hydrocarbyl, such as methyl, ethyl, or propyl. In an embodiment of the invention herein, in formulas (I) and (II), R 9 is hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 A substituted hydrocarbyl or heteroatom-containing group, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof. Preferably, R 9 is methyl, ethyl, propyl, butyl, C1-C6 alkyl, phenyl, 2-methylphenyl, 2,6-dimethylphenyl, or 2,4,6-trimethylphenyl. In an embodiment of the invention herein, in formulas (I) and (II), each X is independently selected from the group consisting of a hydrocarbyl group (e.g., alkyl or aryl) having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, alkylsulfonate, and combinations thereof (two or more X may form a fused ring or ring system), preferably each X is independently selected from a halide, aryl, and a C1-C5 alkyl group, preferably each X is independently hydride, dimethylamido, diethylamido, methyltrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl, fluoro, iodo, bromo, or chloro group. Alternatively, each X can independently be a halide, hydride, alkyl group, alkenyl group, or arylalkyl group.

[0069] In embodiments of the invention herein, in formulas (I) and (II), each L is a Lewis base independently selected from the group consisting of ethers, thioethers, amines, nitriles, imines, pyridines, halocarbons, and phosphines, preferably ethers and thioethers, and combinations thereof, and optionally two or more L may form part of a fused ring or ring system, preferably each L is independently selected from ether and thioether groups, and preferably each L is an ethyl ether, tetrahydrofuran, dibutyl ether, or dimethyl sulfide group. In an embodiment of the invention herein, in formulas (I) and (II), R 1 and R 1’ are independently a cyclic tertiary alkyl group. In an embodiment of the invention herein, in formulas (I) and (II), n is 1, 2 or 3, typically 2. In an embodiment of the invention herein, in formulas (I) and (II), m is 0, 1 or 2, typically 0. In an embodiment of the invention herein, in formulas (I) and (II), R 1 and R 1' is not hydrogen.

[0070] In an embodiment of the invention herein, in formulas (I) and (II), M is Hf or Zr, E and E′ are O; R 1 and R 1’ are C1-C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, heteroatom or heteroatom-containing group, R 2 , R 3 , R 4 , R 2' , R 3' , and R 4' are each independently hydrogen, C1-C 20 Hydrocarbyl, C1-C 20 is a substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1' and R 2' , R 2’ and R 3' , R 3' and R 4' may combine 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, and where substituents on the rings may be bonded to form additional rings; each X is independently selected from the group consisting of a hydrocarbyl group (e.g., alkyl or aryl) having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, and combinations thereof (two or more X may form part of a fused ring or ring system); each L is independently selected from the group consisting of an ether, a thioether, and a halocarbon (two or more L may form part of a fused ring or ring system).

[0071] In an embodiment of the invention herein, in formula (II), R 5 , R 6 , R 7 , R 8 , R 5' , R 6' , R 7' , R8' 、 R 10 , R 11 and R 12 are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 may be substituted hydrocarbyl, heteroatom or heteroatom-containing group, or one or more adjacent R groups may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and where substituents on the rings may be joined to form additional rings. In an embodiment of the invention herein, in formula (II), R 5 , R 6 , R 7 , R 8 , R 5' , R 6' , R 7' , R 8' , R 10 , R 11 and R 12 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof. In an embodiment of the invention herein, in formula (II), R 5 , R 6 , R 7 , R 8 , R 5' , R 6' , R 7' , R 8' , R 10 , R 11 and R 12are each independently selected from 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, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

[0072] In an embodiment of the invention herein, in formula (II), M is Hf or Zr, E and E′ are O; R 1 and R 1' are C1-C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, heteroatom or heteroatom-containing group; R 1 , R 2 , R 3 , R 4 , R 1' , R 2' , R 3' , and R 4' are each independently hydrogen, C1-C 20 Hydrocarbyl, C1-C 20 is a substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1' and R 2' , R 2’ and R 3' , R 3' and R 4'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, and where substituents on the rings may be joined to form additional rings; R 9 is hydrogen, C1-C 20 Hydrocarbyl, C1-C 20 substituted hydrocarbyl, or heteroatom-containing groups such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof; Each X is independently selected from the group consisting of a hydrocarbyl group (e.g., alkyl or aryl) having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, a diene, an amine, a phosphine, an ether, and combinations thereof, (two or more X may form part of a fused ring or ring system); n is 2; m is 0; and R 5 , R 6 , R 7 , R 8 , R 5' , R 6' , R 7' , R 8' 、 R 10 , R 11 and R 12 are each independently hydrogen, C1-C 20 Hydrocarbyl, C1-C 20 may be substituted hydrocarbyl, heteroatom or heteroatom-containing group, or one or more adjacent R groups may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may be joined to form additional rings, e.g., R 5 , R 6 , R 7 , R 8 , R 5' , R 6' , R 7' , R 8' , R 10 , R 11 and R 12are each independently selected from 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, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

[0073] A preferred embodiment of formula (I) is where M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both E and E are carbons ’ Both are oxygen and R 1 and R 1’ Both are C4-C 20 It is a cyclic tertiary alkyl. A preferred embodiment of formula (I) is where M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both E and E are carbons ’ Both are oxygen and R 1 and R 1’ are both adamantan-1-yl or substituted adamantan-1-yl. A preferred embodiment of formula (I) is where M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both E and E are carbons ’ are oxygen, X is methyl or chloro, and n is 2. A preferred embodiment of formula (II) is where M is Zr or Hf, and E and E ’ Both are oxygen and R 1 and R 1’ Both are C4-C 20 It is a cyclic tertiary alkyl. A preferred embodiment of formula (II) is where M is Zr or Hf, and E and E ’Both are oxygen and R 1 and R 1’ are both adamantan-1-yl or substituted adamantan-1-yl. A preferred embodiment of formula (II) is where M is Zr or Hf, and E and E ’ Both are oxygen and R 1 , R 1’ , R 3 and R 3’ are each adamantan-1-yl or substituted adamantan-1-yl. A preferred embodiment of formula (II) is where M is Zr or Hf, and E and E ’ Both are oxygen and R 1 and R 1’ Both are C4-C 20 is a cyclic tertiary alkyl, and R 7 and R 7’ Both C1-C 20 It is alkyl.

[0074] Catalyst compounds particularly useful in the present invention include one or more of the following: dimethylzirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)], dimethylhafnium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate], dimethylzirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate], dimethylhafnium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1, 1'-biphenyl]-2-olate)], dimethylzirconium [6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-adamantan-1-yl)-4-methylphenolate)], dimethylhafnium [6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-adamantan-1-yl)-4-methylphenolate] ], dimethylzirconium [2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-olate)], dimethylhafnium [2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-olate)], dimethyl Zirconium [2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-olate)], dimethylhafnium [2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-olate)]. Catalyst compounds particularly useful in the present invention include those represented by one or more of the following formulas:

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] In some embodiments, two or more different catalyst compounds are present in the catalyst system used herein. In some embodiments, two or more different catalyst compounds are present in the reaction zone where the processes described herein occur. While it is preferred to use the same activator for the transition metal compound, two different activators can be used in combination, such as a non-coordinating anion activator and an alumoxane. If one or more transition metal compounds contain an X group that is not hydride, hydrocarbyl, or substituted hydrocarbyl, the alumoxane can be contacted with the transition metal compound before the addition of the non-coordinating anion activator. The two transition metal compounds (pre-catalysts) may be used in any ratio. Preferred molar ratios of (A) transition metal compound to (B) transition metal compound are (A:B) 1:1000-1000:1, alternatively 1:100-500:1, alternatively 1:10-200:1, alternatively 1:1-100:1, alternatively 1:1-75:1, alternatively 5:1-50:1. The specific ratio selected will depend on the exact pre-catalyst selected, the activation method, and the desired end product. In certain embodiments, when two pre-catalysts, both activated with the same activator, are used, useful mole percentages are, based on the molecular weight of the pre-catalyst, 10-99.9% A to 0.1-90% B, alternatively 25-99% A to 0.5-50% B, alternatively 50-99% A to 1-25% B, alternatively 75-99% A to 1-10% B.

[0080] Method for preparing catalyst compounds Ligand synthesis Bis(phenol) ligands can be prepared using the general method shown in Scheme 1. Coupling of Compound A with Compound B to form a bis(phenol) ligand (Method 1) can be achieved by known Pd and Ni catalyzed couplings, such as the Negishi, Suzuki, or Kumada coupling. Coupling of Compound C with Compound D to form a bis(phenol) ligand (Method 2) can also be achieved by known Pd and Ni catalyzed couplings, such as the Negishi, Suzuki, or Kumada coupling. Compound D can be prepared by reacting Compound E with an organolithium reagent or magnesium metal followed by a typical metal halide (e.g., ZnCl) or a boron-based reagent (e.g., B(O i Pr)3, i Compound E can be prepared from Compound E by optional reaction with PrOB(pin)). Compound E can be prepared without catalyst by the reaction of an aryllithium or aryl Grignard reagent (Compound F) with a dihalogenated arene (Compound G), such as 1-bromo-2-chlorobenzene. Compound E may also be prepared by Pd or Ni catalyzed reaction by the reaction of an arylzinc or aryl-boron reagent (Compound F) with a dihalogenated arene (Compound G). Scheme 1.

[0081] [ka]

[0082] [ka]

[0083] wherein M' is a Group 1, 2, 12, or 13 element or substitute, such as Li, MgCl, MgBr, ZnCl, B(OH), B(pinacolato), P is a protecting group, such as methoxymethyl (MOM), tetrahydropyranyl (THP), t-butyl, allyl, ethoxymethyl, trialkylsilyl, t-butyldimethylsilyl, or benzyl, and R is a C-C 40alkyl, substituted alkyl, aryl, tertiary alkyl, cyclic tertiary alkyl, adamantanyl, or substituted adamantanyl; and X′ and X are each halogen, such as Cl, Br, F, or I. Bis(phenol) ligands and intermediates used in the preparation of bis(phenol) ligands are preferably prepared and purified without the use of column chromatography. This can be achieved by a variety of methods, including distillation, precipitation and washing, formation of insoluble salts (e.g., by reaction of pyridine derivatives with organic acids), and liquid-liquid extraction. Preferred methods include those described in "Practical Process Research and Development—A Guide for Organic Chemists" by Neal C. Anderson (ISBN: 1493300125X).

[0084] Synthesis of carbene bis(phenol) ligands A general synthetic method for generating carbene bis(phenol) ligands is shown in Scheme 2. Substituted phenols can be ortho-brominated and then protected with known phenol protecting groups, such as MOM, THP, t-butyldimethylsilyl (TBDMS), benzyl (Bn), etc. This bromide is then converted to a boronate ester (compound I) or boronic acid that can be used in Suzuki couplings with bromoanilines. Biphenylanilines (compound J) can be crosslinked by reaction with dibromoethane or condensation with oxalaldehyde and then deprotected (compound K). Reaction with triethyl orthoformate forms an iminium salt, which can be deprotonated to yield the carbene. Scheme 2.

[0085] [ka]

[0086] To a substituted phenol (Compound H) dissolved in methylene chloride is added an equivalent of N-bromosuccinimide and 0.1 equivalents of diisopropylamine. After stirring at ambient temperature until completion, the reaction is quenched with a 10% solution of HCl. The organic portion is washed with brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give the bromophenol, typically as a solid. The substituted bromophenol, methoxymethyl chloride, and potassium carbonate are dissolved in dry acetone and stirred at ambient temperature until the reaction is complete. The solution is filtered, and the filtrate is concentrated to give the protected phenol (Compound I). Alternatively, a substituted bromophenol and an equivalent of dihydropyran are dissolved in methylene chloride and cooled to 0°C. A catalytic amount of para-toluenesulfonic acid is added, and the reaction is stirred for 10 minutes before being quenched with trimethylamine. The mixture is washed with water and brine, then dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give the tetrahydropyran-protected phenol.

[0087] The aryl bromide (Compound I) is dissolved in THF and cooled to -78°C. n-Butyllithium is slowly added, followed by trimethoxyborate. The reaction is stirred at ambient temperature until completion. The solvent is removed, and the solid boronic ester is washed with pentane. Boronic acids can be prepared from the boronic ester by treatment with HCl. The boronic ester or boronic acid is dissolved in toluene with an equivalent of ortho-bromoaniline and a catalytic amount of palladium tetrakistriphenylphosphine. Aqueous sodium carbonate is added, and the reaction is heated to reflux overnight. Upon cooling, the layers are separated, and the aqueous layer is extracted with ethyl acetate. The combined organics are washed with brine, dried (MgSO4), filtered, and concentrated under reduced pressure. The coupled product (Compound J) is typically purified using column chromatography. Aniline (compound J) and dibromoethane (0.5 equivalents) are dissolved in acetonitrile and heated at 60°C overnight. The reaction is filtered and concentrated to give the ethylene-bridged dianiline. The protected phenol is deprotected by reaction with HCl to give the bridged bisamino(biphenyl)ol (compound K). The diamine (compound K) is dissolved in triethyl orthoformate. Ammonium chloride is added and the reaction is heated to reflux overnight. The resulting precipitate is collected by filtration and washed with ether to yield the iminium salt. The iminium chloride is suspended in THF and treated with lithium or sodium hexamethyldisilylamide. Upon completion, the reaction is filtered and the filtrate is concentrated to yield the carbene ligand.

[0088] Preparation of bis(phenolate) complexes The present invention utilizes a transition metal or lanthanide metal bis(phenolate) complex as a catalyst component for olefin polymerization. The terms "catalyst" and "catalyst complex" are used interchangeably. The preparation of the transition metal or lanthanide metal bis(phenolate) complex can be achieved by reacting a bis(phenol) ligand with a metal reactant containing an anionic basic leaving group. Typical anionic basic leaving groups include dialkylamide, benzyl, phenyl, hydride, and methyl. In this reaction, the role of the basic leaving group is to deprotonate the bis(phenol) ligand. Suitable metal reactants for this type of reaction include, but are not limited to, HfBn4 (Bn = CH2Ph), ZrBn4, TiBn4, ZrBn2Cl2(OEt2), HfBn2Cl2(OEt2), Zr(NMe2)2Cl2 (dimethoxyethane), Zr(NEt2)2Cl2 (dimethoxyethane), Hf(NEt2)2Cl2 (dimethoxyethane), Hf(NMe2)2Cl2 (dimethoxyethane), Hf(NMe2)4, Zr(NMe2)4, and Hf(NEt2)4. Suitable metal reagents also include ZrMe4, HfMe4, and other Group 4 alkyls that can be formed in situ and used without isolation.

[0089] A second method for the preparation of transition metal or lanthanide bis(phenolate) complexes involves the reaction of a bis(phenol) ligand with an alkali metal or alkaline earth metal base (e.g., Na, BuLi, iAfter generating a deprotonated ligand by reaction with a metal halide (e.g., HfCl4, ZrCl4), a bis(phenolate) complex is formed. Bis(phenolate) metal complexes containing metal halide, alkoxide, or amide leaving groups can be alkylated by reaction with organolithium, Grignard, and organoaluminum reagents. In the alkylation reaction, an alkyl group is transferred to the bis(phenolate) metal center and the leaving group is removed. Reagents typically used for alkylation reactions include, but are not limited to, MeLi, MeMgBr, AlMe3, Al( i Examples of suitable alkylating reagents include (Bu), AlOct, and PhCHMgCl. Typically, 2 to 20 molar equivalents of alkylating reagent are added to the bis(phenolate) complex. The alkylation is generally carried out in an ethereal or hydrocarbon solvent or solvent mixture, typically at temperatures ranging from -80°C to 120°C.

[0090] activator The terms "cocatalyst" and "activator" are used interchangeably. The catalyst systems described herein typically include a catalyst complex, such as the transition metal or lanthanide bis(phenolate) complexes described above, and an activator, such as an alumoxane or a non-coordinating anion. These catalyst systems can be formed by combining the catalyst components described herein with an activator in any manner known in the literature. The catalyst system may be added to or produced in a solution or bulk polymerization (monomer state). 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 capable of activating any one of the catalyst compounds described above by converting a neutral metal compound to a catalytically active metal compound cation. Non-limiting activators include, for example, alumoxanes, ionizing activators, which may be neutral or ionic, and conventional cocatalysts. Preferred activators typically include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that remove reactive metal ligands to render the metal compound cationic and provide a charge-balancing non-coordinating or weakly coordinating anion, e.g., a non-coordinating anion.

[0091] Alumoxane Activator The catalyst systems described herein utilize an alumoxane activator. Alumoxanes generally have the structure -Al(R 1 )-O-subunits, and R 1 is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable catalyst activators, especially when the removable ligand is an alkyl, halide, alkoxide, or amide. Mixtures of different alumoxanes and modified alumoxanes may be used. The use of visually clear methylalumoxane may be preferred. Cloudy or gelled alumoxanes can be filtered to produce a clear solution, or the clear alumoxane can be decanted from the cloudy solution. A useful alumoxane is modified methylalumoxane (MMAO) cocatalyst type 3A (protected under Patent No. 5,041,584 and commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A). Another useful alumoxane is solid polymethylaluminoxane, as described in US 9,340,630; US 8,404,880; and US 8,975,209.

[0092] When the activator is an alumoxane (modified or unmodified), typically the maximum amount of activator is up to a 5,000-fold molar excess of Al / M relative to the catalyst compound (per metal catalytic site). The minimum activator to catalyst compound is a 1:1 molar ratio. Alternative preferred ranges include 1:1 to 500:1, alternatively 1:1 to 200:1, alternatively 1:1 to 100:1, alternatively 1:1 to 50:1. In alternative embodiments, little or no alumoxane is used in the polymerization processes described herein. Preferably, the alumoxane is present at zero mole percent, or the alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal of less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1:1.

[0093] Ionizing / Non-Coordinating Anion Activators The term "noncoordinating anion" (NCA) refers to an anion that does not coordinate to a cation or coordinates only weakly to a cation and therefore remains sufficiently unstable to be displaced by a neutral Lewis base. Furthermore, the anion will not transfer an anionic substituent or fragment to the cation, resulting in the formation of a neutral transition metal compound and neutral by-products from the anion. Noncoordinating anions useful in accordance with the present invention are noncoordinating anions that are compatible, in the sense that they balance their ionic charge at +1, stabilize the transition metal cation, and yet retain sufficient lability to allow displacement during polymerization. The term NCA is also defined to include multicomponent NCA-containing activators containing an acidic cationic group and a noncoordinating anion, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by removal of the anionic group. Any metal or metalloid capable of forming a compatible, weakly coordinating complex may be used or included 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. It is within the scope of the present invention to use neutral or ionic ionizing activators, either alone or in combination with alumoxane or alumoxane activators.

[0094] In an embodiment of the present invention, the activator is represented by formula (III): (Z)d + (A d- ) (III) wherein Z is (LH) or a reducing Lewis acid, L is a neutral Lewis base; H is hydrogen; (LH) + is a Bronsted acid; A d- is a non-coordinating anion having a charge d-; d is an integer from 1 to 3 (e.g., 1, 2, or 3), and preferably Z is (ArC + ), where Ar is aryl or heteroatom-substituted aryl, C-C 40 Hydrocarbyl or substituted C1-C 40 Anionic component A is a hydrocarbyl. d- has the formula [M k+ Q n ] d- where k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4); nk=d; M is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum; and Q is independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halo-substituted hydrocarbyl group, said Q having up to 40 carbon atoms (optionally, provided that in one or fewer occurrences, Q is a halide). Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 40 (e.g., 1 to 20) carbon atoms, more preferably each Q is a fluorinated aryl group, such as a perfluoroaryl group, and most preferably each Q is a pentafluorylaryl group or a perfluoronaphthalenyl group. Suitable A d- Examples also include the diboron compounds disclosed in US Pat. No. 5,447,895, which is incorporated herein by reference in its entirety.

[0095] When Z is an activating cation (LH), it can be a Bronsted acid capable of donating a proton to a transition metal catalyst precursor, resulting in a transition metal cation including ammonium, oxonium, phosphonium, sulfonium, and mixtures thereof, such as ammonium from methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, N-methyl-4-nonadecyl-N-octadecylaniline, N-methyl-4-octadecyl-N-octadecylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, dioctadecylmethylamine, triethylphosphine, triphenylphosphine, and diphenylphosphine; oxonium from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane; sulfonium from thioethers such as diethylthioether, tetrahydrothiophene, and mixtures thereof.

[0096] In particularly useful embodiments of the present invention, the activator is soluble in a non-aromatic hydrocarbon solvent, such as an aliphatic solvent. In one or more embodiments, a mixture of 20 wt % activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear homogeneous solution at 25° C., and preferably a mixture of 30 wt % activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear homogeneous solution at 25° C. In embodiments of the invention, the activators described herein have a solubility of greater than 10 mM (or greater than 20 mM, or greater than 50 mM) in methylcyclohexane at 25° C. (stirring for 2 hours). In an embodiment of the invention, the activators described herein have a solubility of greater than 1 mM (or greater than 10 mM, or greater than 20 mM) in isohexane at 25° C. (stirring for 2 hours). In an embodiment of the invention, the activators described herein have a solubility of greater than 10 mM (or greater than 20 mM, or greater than 50 mM) in methylcyclohexane at 25° C. (stirring for 2 hours) and greater than 1 mM (or greater than 10 mM, or greater than 20 mM) in isohexane at 25° C. (stirring for 2 hours).

[0097] In a preferred embodiment, the activator is a non-aromatic hydrocarbon soluble activator compound. Non-aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (V): [R 1' R 2' R 3' EH] d+ [Mt k+ Q n ] d- (V) During the ceremony: 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; nk=d (preferably d is 1, 2, or 3; k is 3; and n is 4, 5, or 6); R 1' , R 2' , and R 3' are independently C-C groups optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups. 50 is a hydrocarbyl group, R 1' , R 2' , and R 3' contains a total of 15 or more carbon atoms; Mt is an element selected from Group 13 of the Periodic Table of the Elements, for example B or Al; and Each Q is independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halo-substituted hydrocarbyl group.

[0098] Non-aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (VI): [R 1' R 2' R 3' EH] + [BR 4' R 5' R 6' R 7' ] - (VI) During the ceremony: E is nitrogen or phosphorus; R 1' is a methyl group; R 2' and R 3' are independently C-C groups optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups. 50 is a hydrocarbyl group, R 2' and R 3' contains a total of 14 or more carbon atoms; B is boron; and R 4' , R 5' , R 6' , and R 7' is independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halo-substituted hydrocarbyl group. Non-aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (VII) or formula (VIII):

[0099] [ka]

[0100] During the ceremony: N is nitrogen; R 2' and R 3' are independently C-C groups optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups. 40 is a hydrocarbyl group, R 2' and R 3'(if present) contain a total of 14 or more carbon atoms; R 8' , R 9' , and R 10' are independently C4-C 30 Hydrocarbyl or substituted C4-C 30 is a hydrocarbyl group; B is boron; And R 4' , R 5' , R 6' , and R 7' is independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halo-substituted hydrocarbyl group.

[0101] Optionally, in any of formulas (V), (VI), (VII), or (VIII) herein, R 4' , R 5' , R 6' , and R 7' is pentafluorophenyl. Optionally, in any of formulas (V), (VI), (VII), or (VIII) herein, R 4' , R 5' , R 6' , and R 7' is pentafluoronaphthalenyl. Optionally, in any embodiment of formula (VIII) herein, R 8' and R 10' is hydrogen and R 9' is a C4-C alkyl group optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups; 30 It is a hydrocarbyl group. Optionally, in any embodiment of formula (VIII) herein, R 9' is a C-C alkyl group optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups; 22 It is a hydrocarbyl group. Optionally, in any embodiment of formula (VII) or (VIII) herein, R 2' and R 3' are independently C 12 -C 22 It is a hydrocarbyl group.

[0102] In some cases, R 1' , R 2' and R 3' contains a total of 15 or more carbon atoms (e.g., 18 or more carbon atoms, for example, 20 or more carbon atoms, for example, 22 or more carbon atoms, for example, 25 or more carbon atoms, for example, 30 or more carbon atoms, for example, 35 or more carbon atoms, for example, 38 or more carbon atoms, for example, 40 or more carbon atoms, for example, 15 to 100 carbon atoms, for example, 25 to 75 carbon atoms). In some cases, R 2' and R 3' contains a total of 15 or more carbon atoms (e.g., 18 or more carbon atoms, for example, 20 or more carbon atoms, for example, 22 or more carbon atoms, for example, 25 or more carbon atoms, for example, 30 or more carbon atoms, for example, 35 or more carbon atoms, for example, 38 or more carbon atoms, for example, 40 or more carbon atoms, for example, 15 to 100 carbon atoms, for example, 25 to 75 carbon atoms). In some cases, R 8' , R 9' , and R 10' contains a total of 15 or more carbon atoms (e.g., 18 or more carbon atoms, for example, 20 or more carbon atoms, for example, 22 or more carbon atoms, for example, 25 or more carbon atoms, for example, 30 or more carbon atoms, for example, 35 or more carbon atoms, for example, 38 or more carbon atoms, for example, 40 or more carbon atoms, for example, 15 to 100 carbon atoms, for example, 25 to 75 carbon atoms).

[0103] Optionally, when Q is a fluorophenyl group, R 2' is C1-C 40 Not a straight chain alkyl group (or R 2' is optionally substituted C1-C 40 (not a straight-chain alkyl group). In some cases, R 4' , R 5' , R 6' , and R 7' are each an aryl group (e.g., phenyl or naphthalenyl), and R 4' , R 5' , R 6' , and R 7' At least one of R is substituted with at least one fluorine atom, preferably R 4' , R 5' , R 6' , and R 7' are each a perfluoroaryl group (e.g., perfluorophenyl or perfluoronaphthalenyl). Optionally, each Q is an aryl group (e.g., phenyl or naphthalenyl) and at least one Q is substituted with at least one fluorine atom, preferably each Q is a perfluoroaryl group (e.g., perfluorophenyl or perfluoronaphthalenyl). In some cases, R 1' is a methyl group; R 2' is C6-C 50 is an aryl group; and R 3' are C1-C independently 40 Straight chain alkyl or C5-C 50 It is an aryl group. In some cases, R 2' and R 3' are each independently unsubstituted or halide, C-C 35 Alkyl, C5-C 15 Aryl, C6-C 35 Aryl alkyl, C6-C 35 substituted with at least one of alkylaryl and R 2 and R 3 contains a total of 20 or more carbon atoms.

[0104] Optionally, each Q is independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halo-substituted hydrocarbyl group, with the proviso that when Q is a fluorophenyl group, R 2' is C1-C 40 It is not a linear alkyl group, and preferably R 2' is an optionally substituted C1-C 40 If Q is not a straight chain alkyl group (or if Q is a substituted phenyl group, R 2' is C1-C 40 It is not a linear alkyl group, and preferably R 2' is an optionally substituted C1-C 40 (It is not a straight chain alkyl group.) In some cases, when Q is a fluorophenyl group (or when Q is a substituted phenyl group), R 2' is a meta- and / or para-substituted phenyl group, the meta and para substituents being independently optionally substituted C-C 40 Hydrocarbyl groups (e.g., C6-C 40 Aryl group or linear alkyl group, C 12 -C 30 Aryl group or straight chain alkyl group, or C 10 -C 20 Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, more preferably each Q is a fluorinated aryl (e.g., phenyl or naphthalenyl) group, and most preferably each Q is a perfluoroaryl (e.g., phenyl or naphthalenyl) group. k+ Q n ] d-Examples of Q include the diboron compounds disclosed in U.S. Patent No. 5,447,895, which is incorporated herein by reference in its entirety. Optionally, at least one Q is not a substituted phenyl. Optionally, all Q are not a substituted phenyl. Optionally, at least one Q is not a perfluorophenyl. Optionally, all Q are not a perfluorophenyl.

[0105] In some embodiments of the present invention, R 1' is not methyl, R 2' is C 18 Not alkyl, R 3' is C 18 Not alkyl or R 1' is not methyl, R 2' is C 18 Not alkyl, R 3' is C 18 is not alkyl, and at least one Q is not substituted phenyl, and optionally all Q are not substituted phenyl. Useful cationic moieties in formulas (III) and (V)-(VIII) include those represented by the following formulae:

[0106] [ka]

[0107] Useful cationic moieties in formulas (III) and (V)-(VIII) include those represented by the following formula:

[0108] [ka]

[0109] The anion component of the activators described herein includes a compound of the formula [Mt k+ Q n ] -where k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4) (preferably k is 3; n is 4, 5, or 6, preferably when M is B, n is 4); Mt is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum; and Q is independently hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halo-substituted hydrocarbyl groups, said Q having up to 20 carbon atoms, with the proviso that in one or fewer occurrences Q is a halide. Preferably, each Q is a fluorinated hydrocarbyl group, optionally having from 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a perfluoroaryl group. Preferably at least one Q is not a substituted phenyl, such as perfluorophenyl, and preferably all Q are not substituted phenyl, such as perfluorophenyl.

[0110] In one embodiment, the borate activator comprises tetrakis(heptafluoronaphth-2-yl)borate. In one embodiment, the borate activator comprises tetrakis(pentafluorophenyl)borate. Anions for use in the non-coordinating anion activators described herein include those represented by Formula 7:

[0111] [ka]

[0112] During the ceremony: M * is a group 13 atom, preferably B or Al, preferably B; Each R 11 are independently a halide, preferably a fluoride; Each R 12 are independently halide, C6-C 20a substituted aromatic hydrocarbyl group or a group of the formula -O-Si-R a where R a is C1-C 20 is a hydrocarbyl or hydrocarbylsilyl group, preferably R 12 is a fluoride or perfluorophenyl group; Each R 13 Halide, C6-C 20 a substituted aromatic hydrocarbyl group or a group of the formula -O-Si-R a where R a is C1-C 20 is a hydrocarbyl or hydrocarbylsilyl group, preferably R 13 is a fluoride or C6 perfluoroaromatic hydrocarbyl group; R 12 and R 13 can form one or more saturated or unsaturated, substituted or unsubstituted rings, preferably R 12 and R 13 forms a perfluorophenyl ring. Preferably the anion has a molecular weight greater than 700 g / mol and preferably M * At least three of the substituents on the atom each have a molar volume greater than 180 cubic angstroms.

[0113] "Molar volume" is used herein as an approximation of the spatial steric volume of an activator molecule in solution. When comparing substituents with different molar volumes, the substituent with the smaller molar volume can be considered "less bulky" than the substituent with the larger molar volume. Conversely, the substituent with the larger molar volume can be considered "bulkier" than the substituent with the smaller molar volume. Molar volume can 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, Vol. 71, November 1994, pp. 962-964. Molar volume (MV) in cubic angstroms is calculated using the formula: MV = 8.3V s is calculated using V s is the scaled volume. V s is the sum of the relative volumes of the constituent atoms, calculated from the molecular formula of the substituents using the relative volumes in Table A below. For fused rings, V s The calculated total MV of an anion is the sum of the MVs per substituent, e.g., the MV of perfluorophenyl is 183 Å. 3 and the calculated total MV for tetrakis(perfluorophenyl)borate is 183 Å 3 4 times, or 732 Å 3 is.

[0114] [Table 1]

[0115] Exemplary anions useful herein and their respective scaled volumes and molar volumes are shown below in Table B. The dashed bond indicates a bond to boron.

[0116] [Table 2]

[0117] For example, an activator may be added to the polymerization in the form of an ion pair using [MHTH] + [NCA] -, where the di(hydrogenated tallow)methylamine ("MHTH") cation reacts with a basic leaving group on the transition metal complex to form the transition metal complex cation and [NCA] -. Alternatively, the transition metal complex may be reacted with a neutral NCA precursor, such as B(CF) , which removes the anionic group from the complex to form the activated species. Useful activators include di(hydrogenated tallow)methylammonium [tetrakis(pentafluorophenyl)borate] (i.e., [MHTH]B(CF) ) and di(octadecyl)tolylammonium [tetrakis(pentafluorophenyl)borate] (i.e., [DOdTH]B(CF) ).

[0118] Activator compounds particularly useful in the present invention include one or more of the following: N,N-di(hydrogenated tallow)methylammonium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-hexadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-tetradecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-dodecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-decyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-octyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-hexyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-butyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-octadecyl-N-decylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate], N-ethyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dihexadecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-ditetradecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-didodecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-didecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dioctylammonium [tetrakis(perfluorophenyl)borate], N-ethyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate], N,N-di(octadecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(hexadecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(tetradecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(dodecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-tetradecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-tetradecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-dodecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-decylanilinium [tetrakis(perfluorophenyl)borate], and N-Methyl-N-octylanilinium [tetrakis(perfluorophenyl)borate].

[0119] Additional useful activators and syntheses of non-aromatic hydrocarbon soluble activators are described in U.S. Ser. No. 16 / 394,166, filed April 25, 2019, U.S. Ser. No. 16 / 394,186, filed April 25, 2019, and U.S. Ser. No. 16 / 394,197, filed April 25, 2019, which are incorporated herein by reference. Similarly, particularly useful activators include dimethylanilinium tetrakis(pentafluorophenyl)borate and dimethylanilinium tetrakis(heptafluoro-2-naphthalenyl)borate. For a more detailed description of useful activators, see WO 2004 / 026921, pages 72-81, paragraph

[0119] to

[0151] . A list of further particularly useful activators that can be used in the practice of the present invention can be found in WO 2004 / 046214, pages 72-74, paragraph

[0177] to

[0178] . See US 8,658,556 and US 6,211,105 for a description of useful activators.

[0120] Preferred activators for use herein include N-methyl-4-nonadecyl-N-octadecylbenzeneaminium tetrakis(pentafluorophenyl)borate, N-methyl-4-nonadecyl-N-octadecylbenzeneaminium tetrakis(perfluoronaphthalenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthalenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthalenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [MeNH + ][B(C6F5)4 - 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium; and tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

[0121] In a preferred embodiment, the activator comprises a triarylcarbenium (e.g., triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthalenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate). In another embodiment, the activator is selected from the group consisting of trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(perfluoronaphthalenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthalenyl)borate, N,N-dialkyl and di(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, wherein alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl.

[0122] Typical activator to catalyst ratios, e.g., all NCA activator to catalyst ratios, are about 1:1 molar ratio. Alternative preferred ranges include 0.1:1 to 100:1, alternatively 0.5:1 to 200:1, alternatively 1:1 to 500:1, alternatively 1:1 to 1000:1. A particularly useful range is 0.5:1 to 10:1, preferably 1:1 to 5:1. It is also within the scope of the present disclosure that the catalyst compound can be used in combination with alumoxanes and NCAs (see, e.g., U.S. Pat. No. 5,153,157; ​​U.S. Pat. No. 5,453,410; EP 0 573 120 B1; WO 1994 / 007928; and WO 1995 / 014044, the disclosures of which are incorporated herein by reference in their entireties, which disclose the use of alumoxanes in combination with ionizing activators).

[0123] Optional scavengers, coactivators, chain transfer agents In addition to the activator compound, a scavenger or co-activator may be used. Scavengers are compounds typically added to promote polymerization by removing impurities. Some scavengers can also act as activators and are sometimes called co-activators. A co-activator that is not a scavenger may be used in combination with an activator to form an active catalyst. In some embodiments, the co-activator may be premixed with the transition metal compound to form an alkylated transition metal compound. Examples of co-activators include alumoxanes, such as methylalumoxane, modified alumoxanes, such as modified methylalumoxane, and aluminum alkyls, such as trimethylaluminum, triisobutylaluminum, triethylaluminum, and triisopropylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, or tri-n-dodecylaluminum. When the precatalyst is not a dihydrocarbyl or dihydride complex, the co-activator is typically used in combination with a Lewis acid activator and an ionic activator. The co-activator may also be used as a scavenger to inactivate impurities in the feedstock or reactor.

[0124] Aluminum alkyl or organoaluminum compounds which may be utilized as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and dialkylzincs such as diethylzinc. A chain transfer agent may be used in the compositions and / or processes described herein. Useful chain transfer agents are typically hydrogen, alkylalumoxanes, compounds represented by the formula AlR3, ZnR2 (each R is independently a C1-C8 aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, or an isomer thereof), or combinations thereof, such as diethylzinc, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof.

[0125] Polymerization Process The polymerization reactions disclosed herein can be carried out using a solution polymerization process in any suitable manner known to those skilled in the art. In certain embodiments, the polymerization process can be carried out in a continuous polymerization process. The term "batch" refers to a process in which the entire reaction mixture is removed from the polymerization reactor at the end of the polymerization reaction. In contrast, in a continuous polymerization process, one or more reactants are continuously introduced into the reactor, and a solution containing the polymer product is simultaneously or nearly simultaneously removed. Solution polymerization refers to a polymerization process in which the resulting polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer, or a blend thereof. Solution polymerization is typically homogeneous. Homogeneous polymerization is a polymerization in which the polymer product is dissolved in the polymerization medium. The system is preferably not turbid, as described in J. Vladimir Oliveira, C. Dariva and JC Pinto, Ind. Eng. Chem. Res. v.29, 2000, pg. 4627.

[0126] In a typical solution process, catalyst components, solvent, monomer, and hydrogen (if used) are fed under pressure to one or more reactors. Temperature control within the reactor is generally achieved by balancing the heat of polymerization and by reactor jacket or cooling coils to cool the reactor contents, auto-refrigeration, pre-cooled feed, reactor cooling by vaporization of the liquid medium (diluent, monomer, or solvent), or a combination of all three. Adiabatic reactors with pre-cooled feeds can also be used. Monomers are dissolved / dispersed in a solvent or dissolved in the reaction mixture before being fed to the first reactor. Solvents and monomers are generally purified to remove potential catalyst poisons before entering the reactor. Feedstocks may be heated or cooled before being fed to the first reactor. Additional monomer and solvent may be added to the second reactor, which may be heated or cooled. Catalyst / activator may be fed to the first reactor or split between the two reactors. In solution polymerization, the product polymer melts and remains dissolved in the solvent under reactor conditions, forming a polymer solution (also called the effluent).

[0127] The solution polymerization process of the present invention employs a stirred tank reactor system containing one or more stirred polymerization reactors. The reactors should generally be operated under conditions that provide thorough mixing of the reactants. In a multi-reactor system, the first polymerization reactor preferably operates at a lower temperature. The residence time in each reactor will depend on the reactor design and capacity. The catalyst / activator can be fed only to the first reactor or split between the two reactors. In alternative embodiments, loop reactors and plug flow reactors can be utilized for the present invention. The polymer solution is then discharged from the reactor as an effluent stream, and the polymerization reaction is typically quenched to prevent further polymerization with a coordinating polar compound. Upon leaving the reactor system, the polymer solution passes through a heat exchanger system on route to a devolatilization system and a polymer finishing process. The dilute phase and volatiles removed downstream of the liquid phase separation can be recycled and become part of the polymerization feedstock. The polymer can be recovered from the reactor effluent or mixed effluent by separating it from the other components of the effluent. Conventional separation means may be utilized. For example, the polymer can be recovered from the effluent by coagulation with a non-solvent such as isopropyl alcohol, acetone, or n-butyl alcohol, or by thermal and vacuum stripping of the solvent or other medium with heat or steam. One or more conventional additives, such as antioxidants, can be incorporated into the polymer during the recovery procedure. Other recovery methods, such as by liquefaction after use of a lower critical solution temperature (LCST), are also contemplated.

[0128] Suitable diluents / solvents for carrying out the polymerization reaction include non-coordinating, inert liquids. In certain embodiments, the reaction mixture for the solution polymerization reaction disclosed herein may contain at least one hydrocarbon solvent. Examples include linear and branched chain 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 those commercially available (Isopar™); halogenated and perhalogenated hydrocarbons, such as perfluoro C4-C 10 Examples of suitable hydrocarbon solvents include alkanes, chlorobenzene, and mixtures thereof; and aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene, ethylbenzene, xylene, and mixtures thereof. Mixtures of any of the aforementioned hydrocarbon solvents may also be used. Suitable solvents also include liquid olefins, which may serve as monomers or comonomers, such as ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In another embodiment, the solvent is not aromatic, and preferably aromatic compounds are present in the solvent at less than 1 wt %, preferably less than 0.5 wt %, and preferably less than 0 wt %, based on the weight of the solvent.

[0129] The polymerization methods and solution polymerization conditions disclosed herein can be used to polymerize any olefin feedstock. Suitable olefin feedstocks include any C2-C olefins that may be straight or split chain, cyclic or acyclic, and may optionally contain terminal or non-terminal heteroatom substitution. 40 Alkenes are also included. In more specific embodiments, the olefin feedstock is C-C 20 Alkenes, particularly linear alpha-olefins such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, or 1-dodecene, may be included. Other suitable olefin monomers include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or non-conjugated dienes, polyenes, vinyl monomers, and cyclic olefins. Non-limiting olefin monomers also include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl-substituted styrenes, ethylidene norbornene, dicyclopentadiene, cyclopentene, and cyclohexene. Any single olefin monomer or any mixture of olefin monomers may be polymerized according to the present disclosure.

[0130] Preferred diolefin monomers useful in the present invention include any hydrocarbon structure, preferably C5-C6, having at least two unsaturated bonds that can be readily incorporated into a polymer to form a crosslinked polymer. 30Examples of such polyenes include α,ω-dienes (e.g., butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, and 1,13-tetradecadiene) and certain polycyclic alicyclic fused and bridged ring dienes (e.g., tetrahydroindene; divinylbenzene, norbornadiene; methyl-tetrahydroindene; dicyclopentadiene; bicyclo-(2.2.1)-heptadiene; -2,5-dienes; and alkenylnorbornenes, alkylidenenorbornenes, cycloalkenylnorbornenes, and cycloalkylienenorbornenes, including, for example, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propentyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene. Alternatively, the copolymers produced herein are free of dienes.

[0131] Preferred polymerizations can proceed at any temperature and / or pressure suitable to obtain the desired polymer. Solution polymerization conditions suitable for use in the polymerization processes disclosed herein include temperatures ranging from about 0°C to about 300°C, or from about 50°C to about 250°C, or from about 70°C to about 200°C, or from about 90°C to about 180°C, or from about 90°C to about 140°C, or from about 120°C to about 140°C. Pressures can range from about 0.1 MPa to about 15 MPa, or from about 0.2 MPa to about 12 MPa, or from about 0.5 MPa to about 10 MPa, or from about 1 MPa to about 7 MPa. Polymerization run times (residence times) can range up to about 300 minutes, particularly from about 5 minutes to about 250 minutes, or from about 10 minutes to about 120 minutes. To improve control of melt index and / or molecular weight distribution, small amounts of hydrogen, for example, 1 to 5,000 parts per million (ppm) by mass, based on the total solution fed to the reactor, may be added to one or more of the feed streams of the reactor system. In some embodiments, hydrogen may be included in the reaction vessel in a solution polymerization process. According to various embodiments, the concentration of hydrogen gas in the reaction mixture may range from up to about 5,000 ppm, or up to about 4,000 ppm, or up to about 3,000 ppm, or up to about 2,000 ppm, or up to about 1,000 ppm, or up to about 500 ppm, or up to about 400 ppm, or up to about 300 ppm, or up to about 200 ppm, or up to about 100 ppm, or up to about 50 ppm, or up to about 10 ppm, or up to about 1 ppm. In some or other embodiments, hydrogen gas may be present in the reaction vessel at a partial pressure of about 0.007 to 345 kPa, or about 0.07 to 172 kPa, or about 0.7 to 70 kPa. In some embodiments, the process excludes the addition of hydrogen.

[0132] In a preferred embodiment, the polymerization is carried out 1) at a temperature of 100°C or higher (preferably 120°C or higher, preferably 140°C or higher); 2) at atmospheric pressure up to 18 MPa (preferably 0.35 to 18 MPa, preferably 0.35 to 10 MPa, preferably 0.45 to 6 MPa, preferably 0.5 to 4 MPa); 3) in an aliphatic hydrocarbon solvent (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, e.g., cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof). preferably, aromatics (e.g., toluene) are present in the solvent at less than 1 wt. %, preferably less than 0.5 wt. %, preferably less than 0.1 wt. %, preferably 0 wt. %, based on the weight of the solvent; 4) ethylene is present in the polymerization reactor at a concentration of 6 moles / liter or less; 5) polymerization preferably occurs in one reaction zone; and 6) the productivity of the catalyst compound is 50,000 kg or more of polymer per kg of catalyst (preferably 100,000 kg or more of polymer per kg of catalyst, e.g., 150,000 kg or more of polymer per kg of catalyst, e.g., 200,000 kg or more of polymer per kg of catalyst).

[0133] In more specific embodiments, the one or more olefin monomers present in the reaction mixture disclosed herein comprise at least ethylene and one alpha-olefin, such as butene, hexene, and octene. In even more specific embodiments, the one or more olefin monomers can comprise ethylene and a C4-C8 alpha-olefin. In even more specific embodiments, the one or more olefin monomers can comprise a mixture of ethylene and an alpha-olefin. The molecular weight distribution of polymers made by solution processes can be advantageously controlled by preparing the polymer in multiple reactors operated under different conditions, most often at different temperatures and / or monomer concentrations. These conditions determine the molecular weight and density of the polymer fractions produced. The relative amounts of the different fractions are controlled by adjusting the process conditions in each reactor. Typical process conditions used include the type and concentration of catalyst in each reactor and the reactor residence time. In one embodiment, the polymerization process includes at least two reactors connected in either a series or parallel configuration.

[0134] In embodiments herein, the present invention relates to a polymerization process in which a monomer (e.g., ethylene), and optionally a comonomer, are contacted with a catalyst system comprising an activator as described above and at least one catalyst compound. The catalyst compound and activator may be combined in any order, and are typically combined before contact with the monomer. In one embodiment, the catalyst and activator can be fed to the polymerization reactor in the form of a dry powder or slurry, without the need to prepare a homogeneous catalyst solution by dissolving the catalyst in a carrying solvent. The polymerization process of the present invention can be carried out in any manner known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process known in the art can be utilized. The process can be carried out in batch, semi-batch, or continuous mode. Homogeneous polymerization processes are preferred (homogeneous polymerization processes are preferably those in which at least 90 wt. % of the product is soluble in the reaction medium). In a useful embodiment, the process is a solution process.

[0135] A "reaction zone," also called a "polymerization zone," is a vessel in which polymerization occurs, e.g., a batch reactor. When multiple reactors are used in a series or parallel configuration, each reactor is considered a separate polymerization zone. For multi-stage polymerizations in both batch and continuous reactors, each polymerization stage is considered a separate polymerization zone. In a preferred embodiment, polymerization occurs in one reaction zone. In one embodiment, multiple reactors are used in the polymerization process. Optionally, other additives may be used in the polymerization, such as, for example, one or more scavengers, hydrogen, aluminum alkyls, silanes, or chain transfer agents (e.g., alkylalumoxanes, compounds represented by the formula AlR or ZnR, where each R is independently a C-C aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, or an isomer thereof, or combinations thereof, such as diethylzinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof).

[0136] Using the process of the present invention, for example, about 0.900 to 0.970 g / cm 3 , especially 0.915~0.965g / cm 3 Ethylene homopolymers and copolymers of ethylene and alpha-olefins can be prepared having densities ranging from about 0.1 to 200 dg / min, particularly from about 0.5 to 120 dg / min. The polymers can have melt indices, as measured by the method of ASTM D-1238, ranging from about 0.1 to 200 dg / min, and particularly from about 0.5 to 120 dg / min. The polymers can be produced with narrow or broad molecular weight distributions. For example, the polymers can have MWDs ranging from about 1.5 to 10, and particularly from about 2 to 7. The process of the present invention is believed to be particularly useful for producing polymers with narrow molecular weight distributions. Using the process of the present invention, for example, about 0.84 to 0.970 g / cm 3 , especially 0.88 to 0.965 g / cm 3 Homopolymers of ethylene and copolymers of ethylene and alpha olefins can be prepared having densities ranging from 0.1 dg / min or less, and from about 0.5 to 120 dg / min, as measured by the method of ASTM D-1238.

[0137] Polyolefin Products The present invention also relates to compositions produced by the methods described herein. The processes described herein may be utilized to produce polymers of olefins or mixtures of olefins. Polymers that can be prepared include ethylene and C3-C20 Copolymers of olefins, and ethylene and C3-C 20 Terpolymers of olefins are included. Preferably, the polyethylene compositions, such as the ethylene copolymers produced herein, are free of dienes. In a preferred embodiment, the process described herein provides a polyethylene composition, e.g., an ethylene-alpha olefin (preferably C3-C6) having a Mw of 50,000 g / mol or more, preferably 100,000 g / mol or more, more preferably 150,000 g / mol or more, and a Mw / Mn of between 1 and 20 (preferably 2-15, preferably 2-10, preferably 2-8). 20 ) copolymers (e.g., ethylene-hexene copolymers or ethylene-octene copolymers). In preferred embodiments, the polymers produced herein have a unimodal or polymodal molecular weight distribution as determined by gel permeation chromatography (GPC). "Unimodal" means that the GPC chromatograph has one peak or inflection point. "Polymodal" means that the GPC chromatograph has at least two peaks or inflection points. An inflection point is the point at which the second derivative of the curve changes sign (e.g., from negative to positive or vice versa).

[0138] In embodiments, the polymers produced herein contain 0-70 mol % (alternatively 0-65 mol %, alternatively 0.5-50 mol %, alternatively 1-25 mol %, alternatively 20-40 mol %, alternatively 0.1-10 mol %, alternatively 0.1-65 mol %, preferably 3-15 mol %) of one or more C3-C 20 Olefin comonomers (preferably C3-C 12 Copolymers of ethylene with an alpha olefin, preferably propylene, butene, hexene, octene, decene, dodecene, more preferably butene, hexene, octene. In embodiments, the polymers produced herein are polymers comprising ethylene and one or more C3-C 20The copolymer is an olefin comonomer, wherein the polymer has a composition of greater than 35 mol% ethylene (alternatively 35.1-99.9 mol%, alternatively 50-85 mol%, alternatively 60-80 mol%, alternatively 60-99.9 mol%, alternatively 50-99.9 mol%, preferably 60-99 mol%). The mol% of monomer A in a copolymer of monomers A and B is equal to ((100)(moles of monomer A)) / ((moles of monomer A)+(moles of monomer B)). The mol% of monomer A in a terpolymer of monomers A, B, and C is equal to ((100)(moles of monomer A)) / ((moles of monomer A)+(moles of monomer B)+(moles of monomer C)). The mol% of monomer A in a tetrapolymer of monomers A, B, C, and D is equal to ((100)(moles of monomer A)) / ((moles of monomer A)+(moles of monomer B)+(moles of monomer C)+(moles of monomer D)).

[0139] In a preferred embodiment, the polymers produced herein preferably contain 0-25 mol % (alternatively 0.5-20 mol %, alternatively 1-15 mol %, preferably 3-15 mol %) of one or more C3-C 20 Olefin comonomers (preferably C3-C 12 Copolymers of ethylene with an alpha olefin, preferably propylene, butene, hexene, octene, decene, dodecene, more preferably butene, hexene, octene. Preferably, the copolymers produced herein are copolymers of ethylene with 5 to 35 wt % (alternatively 10 to 32 wt %, alternatively 11 to 25 wt %) of one, two, three, four or five or more of propylene, butene, hexene, octene, decene, dodecene, preferably ethylene, butene, hexene, and octene. In a preferred embodiment, the monomer is ethylene and the comonomer is hexene, preferably 1 to 20 mol %, alternatively 1 to 15 mol % hexene.

[0140] In one embodiment, the polyethylene composition has a heterogeneous comonomer distribution across the molecular weight. Preferably, the comonomer content is higher at the lower molecular weight end and lower at the higher molecular weight end. The composition distribution across the molecular weight range can be determined using size exclusion chromatography, as described below. In one embodiment, the polyethylene composition has a viscosity of, for example, about 0.900 to 0.970 g / cm 3 , especially 0.915~0.965g / cm 3 The polymers may have a melt index, as measured by the method of ASTM D-1238, in the range of about 0.1 to 200 dg / min, particularly about 0.5 to 120 dg / min. The polymers may be produced with narrow or broad molecular weight distributions. For example, the polymers may have an MWD in the range of about 1.5 to 10, particularly about 2 to 7. In one embodiment, the polyethylene composition preferably has a viscosity of 0.850 or 0.870 g / cm 3 to 0.900 or 0.910 g / cm 3 The density ranges from

[0141] Although the properties of the polyethylene composition may vary depending on the exact process used to make it, preferably the polyethylene composition has the following measurable characteristics. Specific GPC measurable characteristics include: weight average molecular weight (Mw) preferably in the range of from 50,000 or 60,000 or 80,000 g / mol to 150,000 or 180,000 or 250,000 or 300,000 or 400,000 or 500,000 g / mol; number average molecular weight (Mn) preferably in the range of from 10,000 or 15,000 or 20,000 g / mol to 30,000 or 50,000 or 100,000 or 150,000 or 200,000 g / mol. The z-average molecular weight (Mz) is preferably greater than 200,000 or 300,000 or 400,000 or 500,000 g / mol, more preferably in the range of from 150,000 or 200,000 or 300,000 g / mol to 500,000 or 600,000 or 800,000 or 1,000,000 or 1,500,000 or 2,000,000 g / mol. The polyethylene composition has a molecular weight distribution (Mw / Mn) in the range of from 2.0 or 2.5 to 7.0 or 8.0 or 10.0 or 12.0.

[0142] Specific DSC measurable properties include the following: The polyethylene composition preferably has a melting point temperature (T m The polyethylene composition preferably has a crystallization temperature (T) in the range of from 5 or 10, or 20, or 30, or 40, or 50, or 60, or 70, or 80, or 85, or 90° C. to 110, or 115, or 120, or 125° C. c The polyethylene composition preferably also has a heat of fusion (H) in the range of from 10 or 20 or 30 or 40 or 50 or 60 or 75 or 80 J / g to 90 or 120 or 200 or 250 or 300 J / g. fAlternatively, the polyethylene composition preferably also has a melting point temperature (T) of 50°C or more, alternatively 60°C or more, alternatively 70°C or more, alternatively 80°C or more, alternatively 90°C or more, alternatively 95°C or more, alternatively 100°C or more. m Alternatively, the polyethylene composition preferably has a melting point temperature (T m )

[0143] The polymers produced herein may have a melt index (I2, ASTM 1238, 2.16 kg, 190°C) from a low of about 0.1 dg / min, about 0.2 dg / min, about 0.5 dg / min, about 1 dg / min, about 15 dg / min, about 30 dg / min, or about 45 dg / min to a high of about 200 dg / min, about 300 dg / min, about 500 dg / min, or about 1500 dg / min. Specific melt flow properties of the polyethylene composition include the following: the polyethylene composition preferably has a melt index (190°C / 2.16 kg, "I2") in the range of 400 g / 10 min or less, 300 g / 10 min or less, 200 g / 10 min or less, or 100 g / 10 min or less, more preferably 0.10 or 0.20 or 0.30 or 0.80 or 1.0 g / 10 min to 40 or 80 or 120 or 200 g / 10 min. The polyethylene composition may have a wide range of high load melt index (I 21 ), but preferably has a high load melt index (190°C / 2.16kg, "I") of 200g / 10min or less, or 100g / 10min or less, or 50g / 10min or less. 21 The polyethylene composition has a melt index ratio (I ) in the range of from 10 or 20 or 30 to 70 or 75 or 80 or 85 or 90. 21 / I2).

[0144] Specific dynamic properties of the polyethylene composition include the following: the polyethylene composition preferably has a complex viscosity in the range of 20,000, or 50,000, or 100,000, or 150,000 Pa·s to 300,000, or 350,000, or 400,000, or 450,000, or 1,000,000 Pa·s at a frequency of 0.1 rad / s and a temperature of 190° C. The polyethylene composition preferably has a complex viscosity in the range of 200 or 500 Pa·s to 5,000, or 8,000, or 10,000, or 15,000 Pa·s at a frequency of 128 rad / s and a temperature of 190° C. The polyethylene composition also preferably has a complex modulus of 500,000 Pa and a phase angle in the range of 10° to 60°, or 10° to 50°, or 10° to 40°, or 20° to 31°, or 15° to 40°, or 20° to 60°, or 15° to 36° (or from 10 or 15 or 20 or 25° to 45 or 50 or 55 or 60°), when the complex shear rheology is measured at a temperature of 190°C. The polyethylene composition has a long chain branched structure, and the branching level can be determined by measuring the branching index (g' vis ) is measured by g'. vis A smaller value of g' means a higher branching level. vis The value of g' is preferably less than 0.98 or 0.95 or 0.92 or 0.90 or 0.88, or in the range of 0.60 or 0.70 to 0.90 or 0.95 or 0.97, for example 0.60-0.90, or 0.70-0.90, or 0.80-0.90, or 0.81-0.87, or 0.70-0.95. When the polyethylene has no long chain branches, the polyethylene is "linear" and typically has a g' of 0.98 or greater. vis It has.

[0145] Shear thinning is observed for polyethylene compositions and is a property used to describe them. Shear thinning is a characteristic of branched polymers due to chain entanglement and long relaxation times. Shear thinning is also used as a measure of the level of branching. The melt index ratio, or I 21 / I2, and shear thinning ratio (defined as the ratio of the complex shear viscosity at a frequency of 0.245 rad / sec to the complex shear viscosity at a frequency of 128 rad / sec) are properties used to describe the inventive polyethylene compositions. Preferred values ​​of the shear thinning ratio are greater than 30 or 40 or 50 or 60 or 70 or 80 or 100, while I 21 A preferred value of / I2 is greater than 10, 20, or 30. A more preferred value of the shear thinning ratio is 50 to 200, or 60 to 180, or 70 to 160, or 75 to 150. More particularly, the shear thinning ratio is in the range of 5, 10, or 20 to 40, 50, 60, 70, 100, 200, or 300, and I 21 / I2 ranges from 20 or 30 or 40 to 100 or 200 or 250 or 300 or 400. For some desirable materials, the I2 value may be too low to be measured, in which case I 21 Note that / I2 is either very high or not recorded. Alternatively, the polyethylene composition has a shear thinning ratio (e.g., the ratio of the complex viscosity at a frequency of 0.245 rad / sec to the complex viscosity at a frequency of 128 rad / sec), when the complex viscosity is measured using an RPA according to the procedure described in the Test Methods section below, of 30 or greater, more preferably 40 or greater, and even more preferably 50 or greater.

[0146] blend In another embodiment, the polyethylene compositions produced herein are combined with one or more additional polymers before being formed into a film, molded part, or other article. Other useful polymers include polyethylene, polypropylene, random copolymers of propylene and ethylene, and / or butene, and / or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, copolymers of ethylene vinyl acetate, ethylene methyl acetate, acrylic acid, polymethyl methacrylate, or any other polymer polymerizable by a high-pressure free radical process, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resin, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymers, styrene block copolymers, polyamide, polycarbonate, PET resin, cross-linked 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.

[0147] In a preferred embodiment, the polymer produced herein is present in the blend at 10 to 99 wt%, preferably 20 to 95 wt%, more preferably at least 30 to 90 wt%, more preferably at least 40 to 90 wt%, more preferably at least 50 to 90 wt%, more preferably at least 60 to 90 wt%, and more preferably at least 70 to 90 wt%, based on the weight of the polymer in the blend. The blends may be produced by mixing the polymers of the present invention with one or more polymers (as described above), by connecting reactors in series to create a reactor blend, or by using multiple catalysts to produce multiple polymers in the same reactor. The polymers may be mixed prior to entering the extruder or may be mixed in the extruder. Alternatively, the blends may be produced by mixing the polymers of the present invention with one or more polymers (as described above), by connecting reactors in parallel or series to create a reactor blend.

[0148] The blends may be formed utilizing conventional equipment and methods, for example, by dry blending the individual components followed by melt mixing in a mixer, or by directly mixing the components in a mixer such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or by directly mixing the components in 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 resin powders or pellets in the hopper of a film extruder). Additionally, additives may be included in the blend, one or more components of the blend, and / or in the product, e.g., a film, formed from the blend, if desired. Such additives are well known in the art and include, for example, fillers; antioxidants (e.g., hindered phenols such as IRGANOX™ 1010 or IRGANOX™ 1076 available from BASF); phosphites (e.g., IRGAFOS™ 168 available from BASF); anti-cling additives; tackifiers such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; antiblocking agents; mold release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; talc, and the like.

[0149] film In particular, any of the aforementioned polymers, such as the aforementioned polyethylene polymers or blends thereof, can be used in a wide variety of end uses. Such uses include, for example, monolayer or multilayer blown, extruded, and / or shrink films. These films can be formed by any number of well-known extrusion or coextrusion techniques, such as blown bubble film processing. In this technique, the composition is extruded in a molten state through an annular die and expanded to form a uniaxially or biaxially oriented melt, which is then cooled to form a tubular blown film, which can then be axially slit and expanded to form a flat film. The film can then be unoriented, uniaxially oriented, or biaxially oriented to the same or different degrees. One or more of the layers of the film can be oriented in the transverse or longitudinal directions to the same or different degrees. Uniaxial orientation can be achieved using typical cold or hot stretching methods. Biaxial orientation can be achieved using a tenter frame apparatus or a double bubble process and can occur before or after the individual layers are assembled. For example, a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene or polyethylene layer, or the polyethylene and polypropylene can be coextruded into a film and then oriented. Similarly, an oriented polypropylene copolymer could be laminated to oriented polyethylene, or oriented polyethylene could be coated onto polypropylene, and then this combination could optionally be further oriented. Typically, the film is oriented in the machine direction (MD) at a ratio of up to 15, preferably between 5 and 7, and in the transverse direction (TD) at a ratio of up to 15, preferably 7 to 9. However, in other film embodiments, the film is oriented to the same degree in both the MD and TD directions.

[0150] Films may vary in thickness depending on the intended use; however, films having a thickness of 1 to 50 μm are usually suitable. Films intended for packaging are usually 10 to 50 μm thick. The thickness of the sealing layer is typically 0.2 to 50 μm. There may be a sealing layer on both the inner and outer surfaces of the film, or the sealing layer may be present only on the inner or only on the outer surface. In other embodiments, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave. In a preferred embodiment, one or both of the surface layers are modified by corona treatment.

[0151] Any of the aforementioned polymers and compositions, combined with optional additives (see, e.g., U.S. Patent Application Publication No. 2016 / 0060430, paragraphs

[0082] -

[0093] ), can be used in a wide variety of end uses. Such end uses can be produced by methods known in the art. End uses include polymeric products and specialty end-use products. Typical end uses are films, film-based products, diaper backsheets, housewraps, wire and cable coating compositions, articles formed by molding techniques such as injection molding or blow molding, extrusion coating, forming, casting, and combinations thereof. End uses also include products made from the films, such as bags, packaging, and personal care films, pouches, and medical supplies, such as medical films and intravenous (IV) bags.

[0152] Lubricants and viscosity modifiers The present invention also provides lubricant compositions and lubricating oils comprising blends of the ethylene-olefin copolymers described herein. Preferably, the ethylene-olefin copolymers have a branching index (g') of 0.98 or less, and preferably 0.90 or less. vis ). The long-chain branched ethylene copolymer is soluble in the lubricating oil at the application concentration at temperatures between -40 and 150°C. The concentration of the long-chain branched ethylene copolymer in the lubricating oil is 5 wt% or less. The branched ethylene copolymer in the lubricating oil has a shear stability index (at 30 cycles) of about 10% to about 60%, and a kinematic viscosity at 100°C of about 5 cSt to about 20 cSt. The shear stability index (SSI) is determined using a Kurt Orbahn diesel injection apparatus at 30 cycles according to ASTM D6278. The kinematic viscosity (KV) is determined according to ASTM D445.

[0153] In another embodiment, the invention relates to the following paragraphs: 1. In a homogeneous phase, ethylene and C3-C 40 and an optional comonomer selected from alpha olefins, an activator, and a copolymer of formula (I):

[0154] [ka]

[0155] (In the formula: M is a Group 3, 4, 5, or 6 transition metal or a lanthanide; E and E' are each independently O, S, or NR 9 and R 9 are independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl or heteroatom-containing group; Q is a Group 14, 15, or 16 atom that forms a coordinate bond with the metal M; A 1 QA 1’ is connected to A via a three-atom bridge. 2 A 2’ Q is the central atom of a three-atom bridge; A is a part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms linked to 1 and A 1' are independently C, N, or C(R 22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl, C1-C 20 substituted hydrocarbyl;

[0156] [ka]

[0157] is connected to A via a two-atom bridge. 1 is a divalent group containing 2 to 40 non-hydrogen atoms that links to an E-linked aryl group;

[0158] [ka]

[0159] is connected to A via a two-atom bridge. 1' is a divalent group containing 2 to 40 non-hydrogen atoms that links to the E'-linked aryl group; L is a Lewis base; X is an anionic ligand; n is 1, 2, or 3; m is 0, 1, or 2; and n+m is 4 or less; R 1 , R 2 , R 3 , R 4 , R 1' , R 2' , R 3' , and R 4' are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, heteroatom or heteroatom-containing group; R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1' and R 2' , R 2’ and R 3' , R 3' and R 4' may combine 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, and where substituents on the rings may be joined to form additional rings; Any two L groups may be combined to form a bidentate Lewis base; The X group may be joined to the L group to form a monoanionic bidentate group; Any two X groups may be combined to form a dianionic ligand group. and contacting the catalyst system with a catalyst compound represented by A polymerization process comprising: 2. The catalyst compound is represented by the following formula (II):

[0160] [ka]

[0161] (In the formula: M is a Group 3, 4, 5, or 6 transition metal or a lanthanide; E and E' are each independently O, S, or NR 9 and R 9 are independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, or heteroatom-containing group; each L is independently a Lewis base; each X is independently an anionic ligand; n is 1, 2, or 3; m is 0, 1, or 2; n+m is 4 or less; R 1 , R 2 , R 3 , R 4 , R 1' , R 2' , R 3' , and R 4' are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1' and R 2' , R 2’ and R 3' , R 3' and R 4' may combine 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, and where substituents on the rings may be joined to form additional rings; any two L groups may combine to form a bidentate Lewis base; The X group may be joined to the L group to form a monoanionic bidentate group; Any two X groups may be combined to form a dianionic ligand group; R 5 , R 6 , R 7 , R 8 , R 5’ , R 6’ , R 7’ , R 8’ , R 10 , R 11 , and R 12 are each independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 5’ and R 6’ , R 6’ and R 7’ , R 7’ and R 8’ , R 10 and R 11 , or R 11 and R 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, and where substituents on the rings may be joined to form additional rings. 2. The process of paragraph 1, represented by:

[0162] 3. The process of paragraph 1 or 2, wherein M is Hf, Zr, or Ti. 4. The process of paragraph 1, 2 or 3, wherein E and E' are each O. 5. R 1 and R 1’ However, independently C4-C 40 5. The process of paragraph 1, 2, 3, or 4, wherein the hydrocarbyl group is a tertiary hydrocarbyl group. 6. R 1 and R 1’ However, independently C4-C 40 5. The process of paragraph 1, 2, 3, or 4, wherein the cyclic tertiary hydrocarbyl group is a cyclic tertiary hydrocarbyl group. 7. R 1 and R 1’ However, independently C4-C 40 5. The process of paragraph 1, 2, 3, or 4, wherein the group is a polycyclic tertiary hydrocarbyl group. 8. The process of any one of paragraphs 1-7, wherein each X is independently selected from the group consisting of a substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, and combinations thereof (two X may form part of a fused ring or ring system). 9. The process of any one of paragraphs 1-8, wherein each L is independently selected from the group consisting of ethers, thioethers, amines, phosphines, ethyl ethers, tetrahydrofuran, dimethyl sulfide, triethylamine, pyridine, alkenes, alkynes, allenes, and carbenes, and combinations thereof, and optionally two or more L may form part of a fused ring or ring system. 10. M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both E and E are carbons ’ Both are oxygen and R 1 and R 1’ Both are C4-C 20 2. The process of paragraph 1, wherein the alkyl group is a cyclic tertiary alkyl. 11. M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both E and E are carbons ’ Both are oxygen and R 1 and R 1’ 10. The process of paragraph 1, wherein both of are adamantan-1-yl or substituted adamantan-1-yl. 12. M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both E and E are carbons ’ 10. The process of paragraph 1, wherein both of are oxygen, X is methyl or chloro, and n is 2. 13. Q is nitrogen and A 1 and A1’ are both carbons and R 1 and R 1’ Both E and E are hydrogen ’ Both are NR 9 and R 9 is C1-C 40 Hydrocarbyl, C1-C 40 10. The process of paragraph 1, wherein the alkyl group is selected from a substituted hydrocarbyl, or heteroatom-containing group. 14. Q is carbon and A 1 and A 1’ are both nitrogen, and E and E ’ 2. The process of paragraph 1, wherein both of 15. Q is carbon and A 1 is nitrogen and A 1’ is C(R 22 ) and E and E ’ Both are oxygen and R 22 is hydrogen, C1-C 20 Hydrocarbyl, C1-C 20 10. The process of paragraph 1, wherein the alkyl group is selected from the group consisting of substituted hydrocarbyls. 16. A heterocyclic Lewis base having the formula:

[0163] [ka]

[0164] (In the formula, each R 23 is hydrogen, C1-C 20 Alkyl and C1-C 20 substituted alkyl) 2. The process of paragraph 1, wherein the compound is selected from the group represented by 17. M is Zr or Hf, and E and E ’ Both are oxygen and R 1 and R 1’ Both are C4-C 20 3. The process of paragraph 2, wherein the alkyl group is a cyclic tertiary alkyl. 18. M is Zr or Hf, and E and E ’ Both are oxygen and R1 and R 1’ 3. The process of paragraph 2, wherein both of are adamantan-1-yl or substituted adamantan-1-yl. 19. M is Zr or Hf, and E and E ’ Both are oxygen and R 1 , R 1’ , R 3 and R 3’ 3. The process of paragraph 2, wherein each is adamantan-1-yl or substituted adamantan-1-yl. 20. M is Zr or Hf, and E and E ’ Both are oxygen and R 1 and R 1’ Both are C4-C 20 is a cyclic tertiary alkyl, and R 7 and R 7’ Both C1-C 20 3. The process of paragraph 2, wherein the alkyl is alkyl. 21. M is Zr or Hf, and E and E ’ Both are O and R 1 and R 1’ Both are C4-C 20 is a cyclic tertiary alkyl, and R 7 and R 7’ Both C1-C 20 3. The process of paragraph 2, wherein the alkyl is alkyl. 22. M is Zr or Hf, and E and E ’ Both are O and R 1 and R 1’ Both are C4-C 20 is a cyclic tertiary alkyl, and R 7 and R 7’ 3. The process of paragraph 2, wherein both of are C1-C3 alkyl. 23. The catalyst compound has the formula:

[0165] [ka]

[0166] [ka]

[0167] [ka]

[0168] 2. The process of paragraph 1, represented by one or more of: 24. The process of paragraph 23, wherein the catalyst compound is any one or more of complexes 1-6. 25. The process of any one of paragraphs 1 to 24, wherein the activator comprises an alumoxane or a noncoordinating anion. 26. The process of any one of paragraphs 1 to 25, wherein the activator is soluble in a non-aromatic hydrocarbon solvent. 27. The process of any one of paragraphs 1 to 26, wherein the catalyst system does not contain an aromatic solvent. 28. The activator has the formula: (Z) d + (A d- ) wherein Z is (LH) or a reducing Lewis acid, L is a neutral Lewis base; H is hydrogen; (LH) + is a Bronsted acid; A d- is a non-coordinating anion having a charge d-; d is an integer from 1 to 3. 28. The process of any one of paragraphs 1 to 27, represented by: 29. The activator has the formula: [R 1' R 2' R 3' EH] d+ [Mt k+ Q n ] d- (V) (In the formula: 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; nk=d; R 1' , R 2', and R 3' are independently C-C groups optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups. 50 is a hydrocarbyl group, R 1' , R 2' , and R 3' contains a total of 15 or more carbon atoms; Mt is an element selected from Group 13 of the Periodic Table of the Elements; and Each Q is independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halo-substituted hydrocarbyl group. 28. The process of any one of paragraphs 1 to 27, represented by: 30. The activator has the formula: (Z) d + (A d- ) is represented by In the formula, A d- is a non-coordinating anion having a charge d-; d is an integer from 1 to 3, and (Z) d + 2. The process of paragraph 1, wherein is represented by one or more of the following formulas:

[0169] [ka]

[0170] 31. The activator is: N-methyl-4-nonadecyl-N-octadecylbenzeneaminium tetrakis(pentafluorophenyl)borate, N-methyl-4-nonadecyl-N-octadecylbenzeneaminium tetrakis(perfluoronaphthalenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, Dioctadecylmethylammonium tetrakis(perfluoronaphthalenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(perfluoronaphthalenyl)borate, triethylammonium tetrakis(perfluoronaphthalenyl)borate, tripropylammonium tetrakis(perfluoronaphthalenyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthalenyl)borate, tri(t-butyl)ammonium tetrakis(perfluoronaphthalenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthalenyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthalenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthalenyl)borate, tropylium tetrakis(perfluoronaphthalenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthalenyl)borate, triphenylphosphonium tetrakis(perfluoronaphthalenyl)borate, triethylsilylium tetrakis(perfluoronaphthalenyl)borate, benzene(diazonium)tetrakis(perfluoronaphthalenyl)borate, trimethylammonium tetrakis(perfluorobiphenyl)borate, triethylammonium tetrakis(perfluorobiphenyl)borate, tripropylammonium tetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate, tri(t-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, tropylium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylphosphonium tetrakis(perfluorobiphenyl)borate, triethylsilylium tetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, [4-t-butyl-PhNMe2H][(C6F3(C6F5)2)4B], trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, tropylium tetraphenylborate, triphenylcarbenium tetraphenylborate, triphenylphosphonium tetraphenylborate, triethylsilylium tetraphenylborate, Benzene(diazonium)tetraphenylborate, trimethylammonium 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, tropylium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, triethylsilylium tetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammonium 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(t-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, tropylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, 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(t-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, tropylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, and Triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate 30. The process of any one of paragraphs 1 to 29, wherein the process is one or more of:

[0171] 32. The process of any one of paragraphs 1 to 31, wherein the process is a solution process. 33. The process of any one of paragraphs 1 to 32, wherein the process occurs at a temperature of about 80°C to about 300°C, a pressure in the range of about 0.35 MPa to about 15 MPa, and a residence time of up to 300 minutes. 34. The process of any one of paragraphs 1 to 33, wherein the process is a continuous process. 35. The process of any one of paragraphs 1 to 34, further comprising obtaining a polyethylene composition, e.g., an ethylene copolymer, preferably having an ethylene content of 20 mol % or more. 36. The method further comprising obtaining an ethylene copolymer, the copolymer having a shear thinning ratio greater than 30 and an I greater than 10. 21 35. The process of any one of paragraphs 1 to 34, having / I2.

[0172] 37. A copolymer comprising ethylene and a comonomer selected from propylene, butene, hexene, and octene, the copolymer having a melt index of 400 g / 10 min or less. 38. A polymer produced by the process of any one of paragraphs 1 to 36, comprising ethylene and one or more comonomers selected from propylene, butene, hexene, and octene, the copolymer having an ethylene content of 30 to 50 mol%. 39. A polymer produced by the process of any one of paragraphs 1 to 36, comprising ethylene and one or more comonomers selected from propylene, butene, hexene, and octene, the copolymer having an ethylene content of 50 to 70 mol%. 40. A polymer produced by the process of any one of paragraphs 1 to 36, comprising ethylene and one or more comonomers selected from propylene, butene, hexene, and octene, the copolymer having an ethylene content of 70 to 90 mol%. 41. A polymer produced by the process of any one of paragraphs 1 to 36, comprising ethylene and one or more comonomers selected from propylene, butene, hexene, and octene, the copolymer having an ethylene content of 90 mol% or greater. 42. A polymer produced by the process of any one of paragraphs 1 to 36, comprising ethylene and one or more comonomers selected from propylene, butene, hexene, and octene, the copolymer having a branching index of 0.98 or less.

[0173] 43. A copolymer produced by a polymerization process comprising contacting, in a homogeneous phase, ethylene and propylene with a catalyst system comprising an activator and a Group 4 bis(phenolate) catalyst compound, the polymerization process occurring at a temperature of 90°C or greater in the absence of added hydrogen, and having the following properties: 65-80 mol% ethylene; shear thinning ratio (measured at 125°C) of 70-150; phase angle (measured at 125°C) of less than 50° @ complex modulus G * = 500 kPa; Mooney Large Viscosity (measured at 125°C) of 80 to 120 mu; and Mooney Relaxation Area (measured at 125°C) of 550 to 3200 mu.sec. 44. A copolymer produced by a polymerization process comprising contacting, in a homogeneous phase, ethylene and propylene with a catalyst system comprising an activator and a Group 4 bis(phenolate) catalyst compound, the polymerization process occurring at a temperature of 120°C or greater in the presence of added hydrogen, and having the following properties: 50 to 65 mol% ethylene; g' of 0.8 to 0.9. vis ; A copolymer that produces a polymer having a Mooney Large Viscosity (measured at 125°C) of 35-40 mu.sec; a Mooney Relaxation Area (measured at 125°C) of 300-400 mu.sec.

[0174] Test Method Molecular weight and composition distribution (GPC-IR): Molecular weight distributions and moments (Mw, Mn, Mw / Mn, etc.) and comonomer distributions (C2, C3, C6, etc.) were measured by high-temperature gel permeation chromatography (PolymerChar GPC-IR) equipped with a multichannel band filter based on the infrared detector Ensemble IR5. A broadband channel was used to measure polymer concentration, while two narrowband channels were used to characterize composition. Polymer separation was achieved using three Agilent PLgel 10 μm Mixed-B LS columns. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) containing 300 ppm of the antioxidant butylated hydroxytoluene (BHT) was used as the mobile phase. The TCB mixture was filtered through a 0.1 μm Teflon filter and degassed with an online degasser before entering the GPC instrument. The nominal flow rate was 1.0 mL / min, and the nominal injection volume was 200 μL. The entire system, including the transfer line, column, and detector, is housed in an oven maintained at 145°C. A given amount of polymer sample is weighed and sealed in a standard vial with 10 μL of flow marker (heptane). The vial is then loaded into the autosampler, and the polymer is automatically dissolved in the instrument with 8 mL of TCB solvent. The polymer is dissolved at 160°C with continuous shaking for approximately 1 hour for most PE samples and 2 hours for PP samples. The TCB density used for concentration calculations is 1.463 g / ml at room temperature and 1.284 g / ml at 145°C. The sample solution concentration ranges from 0.2 to 2.0 mg / ml, with lower concentrations being used for higher molecular weight samples.

[0175] The concentration c of each point in the chromatogram was calculated from the baseline subtracted IR5 broadband signal I by the following formula: c=αI Calculate using: α is the mass constant determined for PE standard NBS 1475. Calculate mass recovery from the ratio of the integrated area of ​​the concentration chromatogram over the elution volume to the injected mass, which is equal to the given concentration multiplied by the injection loop volume. Molecular weights are determined by combining a universal calibration relationship with column calibration performed with a series of monodisperse polystyrene (PS) standards. The following formula is used to calculate the molecular weight at each elution volume:

[0176]

number

[0177] where K and α are coefficients of the Mark-Houwink equation. Variables with the subscript "X" represent the test sample, while variables with the subscript "PS" represent polystyrene. In this method, α PS =0.67 and K PS =0.000175, and α X and K. X is determined based on the composition of linear ethylene / propylene copolymers and linear ethylene-propylene-diene terpolymers using standard calibration procedures. The comonomer composition is determined by the ratio of the IR detector intensities corresponding to the CH2 and CH3 channels, calibrated with a series of PE and PP homopolymer / copolymer standards whose nominal values ​​have been previously determined by NMR. The LS detector was an 18-angle Wyatt Technology High Temperature DAWN HELEOS II. The LS molecular weight (M) of each point in the chromatogram was calculated by applying the LS output to the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, MB, Ed.; Academic Press, 1972):

[0178]

number

[0179] where ΔR(θ) is the excess Rayleigh scattering intensity measured at scattering angle θ, c is the polymer concentration determined from IR analysis, A2 is the second virial coefficient, P(θ) is the monodisperse random coil form factor, and Ko is the following system:

[0180]

number

[0181] are optical constants for A is Avogadro's number, and (dn / dc) is the refractive index increment of the system. For TCB, the refractive index n=1.500 at 145°C and λ=665 nm. To analyze polyethylene homopolymer, ethylene-hexene copolymer, and ethylene-octene copolymer, dn / dc=0.1048 ml / mg and A2=0.0015; to analyze ethylene-butene copolymer, dn / dc=0.1048*(1-0.00126*w2) ml / mg and A2=0.0015, where w2 is the weight percent of butene comonomer. Specific viscosity is measured using a high-temperature Agilent (or Viscotek Corporation) viscometer with four capillaries arranged in a Wheatstone bridge configuration containing two pressure transducers. One transducer measures the total pressure drop across the detector, and the other transducer, located between the two sides of the bridge, measures the differential pressure. From their outputs, the specific viscosity, η, is calculated for the solution flowing through the viscometer. s The intrinsic viscosity [η] of each point in the chromatogram is calculated using the formula [η] = η S / c, where c is the concentration, determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as follows:

[0182]

number

[0183] In the formula, α ps is 0.67, and K PS is 0.000175. Branching index (g' vis) is calculated using the output of the GPC-IR5-LS-VIS method as follows: Average intrinsic viscosity [η] of the sample avg is calculated by the following formula:

[0184]

number

[0185] where the summation is over all of the chromatographic slices i between the integration limits. Branching index g' vis is the following:

[0186]

number

[0187] where M v is the viscosity average molecular weight based on molecular weights determined by LS analysis, and K and α are relative to reference linear polymers; for the purposes of this disclosure, α=0.695 and K=0.000579 for linear ethylene polymers, α=0.705 and K=0.0002288 for linear propylene polymers, and for linear butene polymers, α is 0.695 and K is 0.000579*(1-0.0087*w2b+0.000018*(w2b)^2). where w2b is the bulk weight percent of the butene comonomer, and for ethylene-hexene copolymers, α is 0.695, K is 0.000579*(1-0.0075*w2b), where w2b is the bulk weight percent of the hexene comonomer, and for ethylene-octene copolymers, α is 0.695, K is 0.000579*(1-0.0077*w2b), where w2b is the bulk weight percent of the octene comonomer. Concentrations are in g / cm unless otherwise noted. 3 where w2b is the viscosity of the polymer, w2b is the molecular weight in g / mol, and w2b is the intrinsic viscosity (hence K in the Mark-Houwink equation) in dL / g. The calculation of w2b is as described above.

[0188] Details of the experiments and analyses not mentioned above, including the detector calibration method and the calculation method of the composition dependence of the Mark-Houwink parameters and the second virial coefficient, are described by T. Sun, P. Brant, R.R. Chance, and W.W. Graessley (Macromolecules, 2001, Vol. 34(19), pp. 6812-6820). The comonomer content of butene, hexene, and octene is determined according to ASTM D3900( 13 The copolymer mass percentage is determined by FTIR measurements (calibrated against C NMR) according to the following: A thin homogeneous film of the polymer pressed at a temperature of about 150°C was mounted on a Perkin Elmer Spectrum 2000 infrared spectrophotometer. The mass percentage of the copolymer was determined by the following method (calibrated against C NMR): -1 The peak height of this band is determined by measuring the methyl deformation band at 4321 cm. -1 Normalize by the bond and overtone bands in C and correct for path length differences. The content of other comonomers is C. 13 The content of other dienes, if present, can be determined using NMR. 13 This can be obtained using NMR. The comonomer content and sequence distribution of the polymer are 13 C nuclear magnetic resonance (NMR) can be used to measure ethylene content by methods well known to those skilled in the art. See U.S. Pat. No. 6,525,157, which contains further details on determining ethylene content by NMR. Comonomer content of individual molecular weights can be measured using methods well known to those skilled in the art, including Fourier transform infrared spectroscopy (FTIR) in conjunction with GPC samples, as described in Wheeler and Willis, Applied Spectroscopy, 1993, v. 47, pp. 1128-1130.

[0189] The peak melting temperature (Tm) (also referred to as melting point), peak crystallization temperature (Tc) (also referred to as crystallization temperature), glass transition temperature (Tg), heat of fusion (ΔHf or Hf), and percent crystallinity were determined in accordance with ASTM D3418-03 using the following DSC procedure. Differential scanning calorimetry (DSC) data were obtained using a TA Instruments Model Q200 instrument. Samples weighing approximately 5-10 mg were sealed in aluminum hermetic sample pans. DSC data were recorded by first gradually heating the sample to 200°C at a rate of 10°C / min. The sample was held at 200°C for 2 minutes, then cooled to -90°C at a rate of 10°C / min, held isothermally for 2 minutes, and heated to 200°C at 10°C / min. Thermal events were recorded for both the first and second cycles. The area under the endothermic peak was measured and used to determine the heat of fusion and percent crystallinity. The percent crystallinity is calculated using the formula [area under the melting peak (Joules / gram) / B (Joules / gram)] * 100, where B is the heat of fusion for a 100% crystalline homopolymer of the major monomer component. These values ​​for B can be obtained from the Polymer Handbook published by John Wiley and Sons (4th Edition, New York 1999), provided that a value of 189 J / g (B) is used for the heat of fusion for 100% crystalline polypropylene and a value of 290 J / g is used for the heat of fusion for 100% crystalline polyethylene. The melting and crystallization temperatures reported herein were obtained during the second heating / cooling cycle unless otherwise noted.

[0190] For polymers exhibiting multiple endothermic and exothermic peaks, all peak crystallization temperatures and peak melting temperatures were reported. The heat of fusion for each endothermic peak was calculated individually. The percent crystallinity was calculated using the sum of the heats of fusion from all endothermic peaks. Some resulting polymer blends exhibit secondary melting / cooling peaks that overlap with the main peak; these peaks are collectively considered a single melting / cooling peak. The highest point of these peaks is considered the peak melting temperature / crystallization point. For amorphous polymers with relatively low levels of crystallinity, the melting temperature is typically measured and reported during the first heating cycle. Prior to DSC measurement, samples were aged or annealed (typically by holding at ambient temperature for 2 days) to maximize the level of crystallinity.

[0191] Rubber Process Analyzer (RPA): Dynamic shear melt rheology data were measured using an ATD® 1000 Rubber Process Analyzer from Alpha Technologies. Samples weighing approximately 4.5 gm were mounted between the parallel plates of the ATD® 1000. A stream of nitrogen was circulated throughout the sample oven during the experiment. The test temperature was 125°C for ethylene-propylene copolymers containing 60-80 wt% ethylene and 190°C for all other ethylene copolymers. The applied strain was 14%, and the frequency was varied from 0.1 rad / s to 385 rad / s. At each frequency, the complex modulus (G * ), complex viscosity (η *) and phase angle (δ). A sinusoidal shear strain is applied to the material. If the strain amplitude is small enough, the material will behave linearly. As those skilled in the art will appreciate, the resulting steady-state stress will also oscillate sinusoidally at the same frequency, but will be shifted by a phase angle δ relative to the strain wave. For a perfectly elastic material, δ = 0° (stress is in phase with the strain), and for a perfectly viscous material, δ = 90°. For viscoelastic materials, 0 < δ < 90. Small amplitude oscillatory shear testing provides the complex viscosity, loss modulus (G"), and storage modulus (G') as a function of frequency. Kinematic viscosity is also called complex viscosity or dynamic shear viscosity. The phase angle or loss angle (δ) is the inverse tangent of the ratio of G" (shear loss modulus) to G' (shear storage modulus).

[0192] Shear Thinning Ratio: Shear thinning is the rheological response of a polymer melt in which the resistance to flow (viscosity) decreases as the shear rate increases. The complex shear viscosity is generally constant at low shear rates (Newtonian region) and decreases with increasing shear rate. In the low shear rate region, viscosity is called the zero shear viscosity and is often difficult to measure for polydisperse and / or LCB polymer melts. At higher shear rates, polymer chains orient in the shear direction, reducing the number of chain entanglements compared to their undeformed state. This reduction in chain entanglements results in lower viscosity. Shear thinning is characterized by a sinusoidal decrease in complex kinematic viscosity with increasing frequency of applied shear. The shear thinning ratio is defined as the ratio of the complex shear viscosity at a frequency of 0.245 rad / s to the complex shear viscosity at a frequency of 128 rad / s.

[0193] Mooney Large Viscosity (ML) and Mooney Relaxation Area (MLRA): ML and MLRA are measured using a Mooney viscometer according to ASTM D-1646, modified as detailed in the description below. The sample is placed on either side of the rotor. The upper platen is lowered air-pressure to fill the cavity. The upper and lower platens are electrically heated and controlled at 125°C. The torque to rotate the rotor at 2 rpm is measured with a torque transducer. 2 seconds-1 Run the Mooney Viscometer at an average shear rate of 1 / 2000. After closing the platens, preheat the sample for 1 minute. Then start the motor and record the torque for 4 minutes. Report the results as ML(1+4)@125°C, where M is the Mooney viscosity number, L means large rotor, 1 is the preheat time in minutes, 4 is the sample run time in minutes after starting the motor, and 125°C is the test temperature.

[0194] The torque limit of the Mooney viscometer is approximately 100 Mooney units. Mooney viscosity values ​​greater than approximately 100 Mooney units generally cannot be measured under these conditions. In this case, a non-standard rotor design is utilized by altering the Mooney scale, allowing the Mooney viscometer to be used for more viscous polymers. This rotor, which is smaller in diameter and thinner than the standard Mooney Large (ML) rotor, is called the MST (Mooney Small Thin). Typically, when utilizing an MST rotor, tests are also performed at different times and temperatures. The preheat time is changed from the standard 1 minute to 5 minutes, and the test is performed at 200°C instead of the standard 125°C. Therefore, values ​​are reported as MST(5+4)@200°C. Note that the 4-minute run time, at the end of which the Mooney is measured, remains the same as the standard conditions. According to EP 1 519 967, if MST is measured at (5+4@200°C) and ML is measured at (1+4@125°C), one MST point is approximately 5 ML points. The MST rotor should be prepared as follows: a. The rotor should have a diameter of 30.48 + / - 0.03 mm and a thickness of 2.8 + / - 0.03 mm (serrated top) and a shaft no larger than 11 mm in diameter. b. The rotor should have a serrated face and edge with square grooves 0.8mm wide and 0.25-0.38mm deep cut on 1.6mm centers. The serrated face and edge will consist of two sets of grooves at right angles to each other (forming a square crosshatch pattern). The rotor shall be centered in the die cavity so that the centerline of the rotor disc is coincident with the centerline of the die cavity within a tolerance of + / - 0.25mm. Spacers or shims may be used to raise the shaft to the midpoint. d. The wear spot (the cone-shaped protuberance in the center of the top surface of the rotor) should be machined flush with the rotor surface.

[0195] MLRA data are obtained from Mooney viscosity measurements as the rubber relaxes after the rotor has stopped. MLRA is the integrated area under the Mooney torque-relaxation time curve from 1 to 100 seconds. MLRA is a measure of chain relaxation in a molten polymer and can be considered a stored energy term, suggesting that longer or branched chains can store more energy and require longer time to relax after removal of the applied strain. Therefore, the MLRA values ​​of bimodal rubbers (presence of distinct polymer fractions with ultra-high molecular weight and different compositions) or long-chain branched rubbers are greater than those of broad or narrow molecular weight rubbers when compared at the same Mooney viscosity value. The Mooney relaxation area is dependent on the Mooney viscosity of the polymer and increases as the Mooney viscosity increases. To remove the dependence on the Mooney viscosity of the polymer, the corrected MLRA (cMLRA) parameter is used to normalize the MLRA of the polymer to a standard of 80 Mooney viscosity. The formula for cMLRA is provided below:

[0196]

number

[0197] where MLRA and ML are the Mooney relaxation area and Mooney viscosity of the polymer sample measured at 125°C. The melt index (I2) was measured according to ASTM D1238 at a temperature of 190°C and a load of 2.16 kg. 21 ) was determined according to ASTM D1238 at a temperature of 190°C using a load of 21.6 kg. Density was measured according to ASTM D1505, after cooling slowly (i.e., over a period of 10 minutes) to room temperature and measuring ±0.001 g / cm 3 The density gradient column is determined using compression molded specimens that have been aged for a sufficient period of time to be constant within 100%. Shore hardness was measured using a durometer at 23°C according to ISO 868. Stress-strain properties such as ultimate tensile strength, ultimate elongation, and 100% modulus were measured according to ISO 37 using an Instron testing machine at 23°C on 2mm thick compression molded plaques. [Example]

[0198] experiment Cat-Hf (complex 5) and Cat-Zr (complex 6) and complex 33 were prepared as follows. Starting materials 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Aldrich), 2,6-dibromopyridine (Aldrich), 2-bromoiodobenzene (Acros), 2.5 M in hexane nBuLi (Chemetall GmbH), Pd(PPh3)4 (Aldrich), methoxymethyl chloride (Aldrich), NaH (60% wt. in mineral oil, Aldrich), THF (Merck), ethyl acetate (Merck), methanol (Merck), toluene (Merck), hexane (Merck), dichloromethane (Merck), HfCl4 (<0.05% Zr, Strem), ZrCl4 (Strem), Cs2CO3 (Merck), K2CO3 (Merck), Na2SO4 (Akzo Nobel), silica gel 60 (40-63 μm; Merk), and CDCl3 (Deutero GmbH) were used as received. Benzene-d6 (Deutero GmbH) and dichloromethane-d2 (Deutero GmbH) were dried over MS 4A prior to use. THF for organometallic syntheses was freshly distilled from sodium benzophenone ketyl. Toluene and hexane for organometallic synthesis were dried over MS 4 A. 2-(adamantan-1-yl)-4-(tert-butyl)phenol was prepared from 4-tert-butylphenol (Merck) and adamantanol-1 (Aldrich) as described in Organic Letters, 2015, 17(9), 2242-2245.

[0199] 2-(adamantan-1-yl)-6-bromo-4-(tert-butyl)phenol [ka]

[0200] To a solution of 57.6 g (203 mmol) of 2-(adamantan-1-yl)-4-(tert-butyl)phenol in 400 mL of chloroform was added a solution of 10.4 mL (203 mmol) of bromine in 200 mL of chloroform dropwise over 30 minutes at room temperature. The resulting mixture was diluted with 400 mL of water. The resulting mixture was extracted with dichloromethane (3 × 100 mL), and the combined organic extracts were washed with 5% NaHCO₃, dried over Na₂SO₄, and evaporated to dryness. Yield 71.6 g (97%) of a white solid. 1H NMR (CDCl3, 400 MHz): δ 7.32 (d, J = 2.3 Hz, 1 H), 7.19 (d, J = 2.3 Hz, 1 H), 5.65 (s, 1 H), 2.18 - 2.03 (m, 9 H), 1.78 (m, 6 H), 1.29 (s, 9 H). 13 C NMR (CDCl3, 100 MHz): δ 148.07, 143.75, 137.00, 126.04, 123.62, 112.11, 40.24, 37.67, 37.01, 34.46, 31.47, 29.03.

[0201] (1-(3-bromo-5-(tert-butyl)-2-(methoxymethoxy)phenyl)adamantane [ka]

[0202] To a solution of 71.6 g (197 mmol) of 2-(adamantan-1-yl)-6-bromo-4-(tert-butyl)phenol in 1,000 mL of THF was added 8.28 g (207 mmol, 60% wt. in mineral oil) of sodium hydride portionwise at room temperature. To the resulting suspension was added 16.5 mL (217 mmol) of methoxymethyl chloride dropwise over 10 min at room temperature. The resulting mixture was stirred overnight and then poured into 1,000 mL of water. The resulting mixture was extracted with dichloromethane (3 × 300 mL), and the combined organic extracts were washed with 5% NaHCO₃, dried over Na₂SO₄, and evaporated to dryness. Yield: 80.3 g (nearly quantitative) of a white solid. 1 H NMR (CDCl3, 400 MHz): δ 7.39 (d, J = 2.4 Hz, 1 H), 7.27 (d, J = 2.4 Hz, 1 H), 5.23 (s, 2 H), 3.71 (s, 3 H), 2.20 - 2.04 (m, 9 H), 1.82 - 1.74 (m, 6 H), 1.29 (s, 9 H). 13C NMR (CDCl3, 100 MHz): δ 150.88, 147.47, 144.42, 128.46, 123.72, 117.46, 99.53, 57.74, 41.31, 38.05, 36.85, 34.58, 31.30, 29.08.

[0203] (2-(3-adamantan-1-yl)-5-(tert-butyl)-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ka]

[0204] A solution of 22.5 g (55.0 mmol) of (1-(3-bromo-5-(tert-butyl)-2-(methoxymethoxy)phenyl)adamantane in 300 mL of dry THF was added to 23.2 mL (57.9 mmol, 2.5 M) of hexane. n BuLi was added dropwise over 20 min at -80 °C. The reaction mixture was stirred at this temperature for 1 h, after which 14.5 mL (71.7 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The resulting suspension was stirred at room temperature for 1 h and then poured into 300 mL of water. The resulting mixture was extracted with dichloromethane (3 × 300 mL), and the combined organic extracts were dried over NaSO and evaporated to dryness. Yield 25.0 g (nearly quantitative) of a colorless viscous oil. 1 H NMR (CDCl3, 400 MHz): δ 7.54 (d, J = 2.5 Hz, 1 H), 7.43 (d, J = 2.6 Hz, 1 H), 5.18 (s, 2 H), 3.60 (s, 3 H), 2.24 - 2.13 (m, 6 H), 2.09 (br. s., 3 H), 1.85 - 1.75 (m, 6 H), 1.37 (s, 12 H), 1.33 (s, 9 H). 13C NMR (CDCl3, 100 MHz): δ 159.64, 144.48, 140.55, 130.58, 127.47, 100.81, 83.48, 57.63, 41.24, 37.29, 37.05, 34.40, 31.50, 29.16, 24.79.

[0205] 1-(2'-Bromo-5-(tert-butyl)-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane [ka]

[0206] To a solution of 25.0 g (55.0 mmol) of (2-(3-adamantan-1-yl)-5-(tert-butyl)-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane in 200 mL of dioxane was subsequently added 15.6 g (55.0 mmol) of 2-bromoiodobenzene, 19.0 g (137 mmol) of potassium carbonate, and 100 mL of water. The resulting mixture was purged with argon for 10 minutes, after which 3.20 g (2.75 mmol) of Pd(PPh3)4 was added. The resulting mixture was stirred at 100 °C for 12 hours, then cooled to room temperature and diluted with 100 mL of water. The resulting mixture was extracted with dichloromethane (3 × 100 mL), and the combined organic extracts were dried over Na2SO4 and evaporated to dryness. The residue was purified by silica gel 60 flash chromatography (40-63 μm, eluent: hexane-dichloromethane=10:1, vol.) to give a white solid (yield: 23.5 g, 88%). 1H NMR (CDCl3, 400 MHz): δ 7.68 (dd, J = 1.0, 8.0 Hz, 1 H), 7.42 (dd, J = 1.7, 7.6 Hz, 1 H), 7.37 - 7.32 (m, 2 H), 7.20 (dt, J = 1.8, 7.7 Hz, 1 H), 7.08 (d, J = 2.5 Hz, 1 H), 4.53 (d, J = 4.6 Hz, 1 H), 4.40 (d, J = 4.6 Hz, 1 H), 3.20 (s, 3 H), 2.23 - 2.14 (m, 6 H), 2.10 (br. s., 3 H), 1.86 - 1.70 (m, 6H), 1.33 (s, 9 H). 13 C NMR (CDCl3, 100 MHz): δ 151.28, 145.09, 142.09, 141.47, 133.90, 132.93, 132.41, 128.55, 127.06, 126.81, 124.18, 123.87, 98.83, 57.07, 41.31, 37.55, 37.01, 34.60, 31.49, 29.17.

[0207] 2-(3'-(adamantan-1-yl)-5'-(tert-butyl)-2'-(methoxymethoxy)-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ka]

[0208] A solution of 30.0 g (62.1 mmol) of 1-(2'-bromo-5-(tert-butyl)-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane in 500 mL of dry THF was added to 25.6 mL (63.9 mmol, 2.5 M) of hexane. nBuLi was added dropwise over 20 min at -80 °C. The reaction mixture was stirred at this temperature for 1 h, after which 16.5 mL (80.7 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The resulting suspension was stirred at room temperature for 1 h and then poured into 300 mL of water. The resulting mixture was extracted with dichloromethane (3 × 300 mL), and the combined organic extracts were dried over NaSO and evaporated to dryness. Yield 32.9 g (nearly quantitative) of a colorless glassy solid. 1 H NMR (CDCl3, 400 MHz): δ 7.75 (d, J = 7.3 Hz, 1 H), 7.44 - 7.36 (m, 1 H), 7.36 - 7.30 (m, 2 H), 7.30 - 7.26 (m, 1 H), 6.96 (d, J = 2.4 Hz, 1 H), 4.53 (d, J = 4.7 Hz, 1 H), 4.37 (d, J = 4.7 Hz, 1 H), 3.22 (s, 3 H), 2.26 - 2.14 (m, 6 H), 2.09 (br. s., 3 H), 1.85 - 1.71 (m, 6 H), 1.30 (s, 9H), 1.15 (s, 6H), 1.10 (s, 6 H). 13 C NMR (CDCl3, 100 MHz): δ 151.35, 146.48, 144.32, 141.26, 136.15, 134.38, 130.44, 129.78, 126.75, 126.04, 123.13, 98.60, 83.32, 57.08, 41.50, 37.51, 37.09, 34.49, 31.57, 29.26, 24.92, 24.21.

[0209] (2',2'''-(pyridin-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) [ka]

[0210] To a solution of 32.9 g (62.0 mmol) of 2-(3'-(adamantan-1-yl)-5'-(tert-butyl)-2'-(methoxymethoxy)-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane in 140 mL of dioxane was added 7.35 g (31.0 mmol) of 2,6-dibromopyridine, 50.5 g (155 mmol) of cesium carbonate, and 70 mL of water. The resulting mixture was purged with argon for 10 minutes, after which 3.50 g (3.10 mmol) of Pd(PPh3)4 was added. The mixture was stirred for 12 hours at 100 °C, then cooled to room temperature and diluted with 50 mL of water. The resulting mixture was extracted with dichloromethane (3 × 50 mL), and the combined organic extracts were dried over Na2SO4 and evaporated to dryness. To the resulting oil, 300 mL of THF, 300 mL of methanol, and 21 mL of 12 N HCl were subsequently added. The reaction mixture was stirred overnight at 60 °C and then poured into 500 mL of water. The resulting mixture was extracted with dichloromethane (3 × 350 mL), and the combined organic extracts were washed with 5% NaHCO 3 , dried over Na 2 SO 4 , and evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate = 10:1, vol.). The resulting glassy solid was triturated with 70 mL of n-pentane, and the resulting precipitate was filtered off, washed with 2 × 20 mL of n-pentane, and dried in vacuo. Yield: 21.5 g (87%) of a mixture of two isomers as a white powder. 1 H NMR (CDCl3, 400 MHz): δ 8.10 + 6.59 (2s, 2H), 7.53 - 7.38 (m, 10H), 7.09 + 7.08 (2d, J = 2.4 Hz, 2H), 7.04 + 6.97 (2d, J = 7.8 Hz, 2H), 6.95 + 6.54 (2d, J = 2.4 Hz), 2.03 - 1.79 (m, 18H), 1.74 - 1.59 (m, 12H), 1.16 + 1.01 (2s, 18H). 13 C NMR (CDCl3, 100 MHz, minor isomer shifts *(shown in ): δ 157.86, 157.72 * , 150.01, 149.23 * , 141.82 * , 141.77, 139.65 * , 139.42, 137.92, 137.43, 137.32 * , 136.80, 136.67 * , 136.29 * , 131.98 * , 131.72, 130.81, 130.37 * , 129.80, 129.09 * , 128.91, 128.81 * , 127.82 * , 127.67, 126.40, 125.65 * , 122.99 * , 122.78, 122.47, 122.07 * , 40.48, 40.37 * , 37.04, 36.89 * , 34.19 * , 34.01, 31.47, 29.12, 29.07 * .

[0211] Dimethylhafnium (2',2'''-(pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)) (Cat-Hf; Complex 5) [ka]

[0212] To a suspension of 3.22 g (10.05 mmol) of hafnium tetrachloride (<0.05% Zr) in 250 mL of dry toluene was added 14.6 mL (42.2 mmol, 2.9 M) of MeMgBr in diethyl ether in one portion via syringe at 0 °C. The resulting suspension was stirred for 1 min, and 8.00 g (10.05 mmol) of (2',2'''-(pyridin-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) was added in portions over 1 min. The reaction mixture was stirred for 36 h at room temperature and then evaporated to near dryness. The resulting solid was extracted with 2 × 100 mL of hot toluene, and the combined organic extracts were filtered through a thin pad of Celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 50 mL of n-hexane and the resulting precipitate was filtered off (G3), washed with 20 mL of n-hexane (2 x 20 mL) and then dried in vacuo. Yield 6.66 g (61%, approximately 1:1 solvate with n-hexane) of a pale beige solid. 59 H 69 HfNO2×1.0(C6H 14 ) Calculated: C, 71.70; H, 7.68; N, 1.29. Found: C 71.95; H, 7.83; N 1.18. 1 H NMR (C6D6, 400 MHz): δ 7.58 (d, J = 2.6 Hz, 2 H), 7.22 - 7.17 (m, 2 H), 7.14 - 7.08 (m, 4 H), 7.07 (d, J = 2.5 Hz, 2 H), 7.00 - 6.96 (m, 2 H), 6.48 - 6.33 (m, 3 H), 2.62 - 2.51 (m, 6H), 2.47 - 2.35 (m, 6H), 2.19 (br.s, 6H), 2.06 - 1.95 (m, 6H), 1.92 - 1.78 (m, 6H), 1.34 (s, 18 H), -0.12 (s, 6 H). 13C NMR (C6D6, 100 MHz): δ 159.74, 157.86, 143.93, 140.49, 139.57, 138.58, 133.87, 133.00, 132.61, 131.60, 131.44, 127.98, 125.71, 124.99, 124.73, 51.09, 41.95, 38.49, 37.86, 34.79, 32.35, 30.03.

[0213] Dimethylzirconium (2',2'''-(pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)) (Cat-Zr; Complex 6) [ka]

[0214] To a suspension of 2.92 g (12.56 mmol) of zirconium tetrachloride in 300 mL of dry toluene was added 18.2 mL (52.7 mmol, 2.9 M) of MeMgBr in diethyl ether via syringe at 0 °C in one portion. To the resulting suspension was added 10.00 g (12.56 mmol) of (2',2'''-(pyridin-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) in one portion immediately. The reaction mixture was stirred for 2 h at room temperature and then evaporated to near dryness. The resulting solid was extracted with 2 × 100 mL of hot toluene, and the combined organic extracts were filtered through a thin pad of Celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 50 mL of n-hexane, and the resulting precipitate was filtered off (G3), washed with n-hexane (2 x 20 mL), and then dried in vacuo. Yield 8.95 g (74%, approximately 1:0.5 solvate with n-hexane) of a beige solid. 59 H 69 ZrNO2×0.5(C6H 14 ) Calculated: C, 77.69; H, 7.99; N, 1.46. Found: C 77.90; H, 8.15; N 1.36. 1H NMR (C6D6, 400 MHz): δ 7.56 (d, J = 2.6 Hz, 2 H), 7.20 - 7.17 (m, 2 H), 7.14 - 7.07 (m, 4 H), 7.07 (d, J = 2.5 Hz, 2 H), 6.98 - 6.94 (m, 2 H), 6.52 - 6.34 (m, 3H), 2.65 - 2.51 (m, 6H), 2.49 - 2.36 (m, 6H), 2.19 (br.s., 6H), 2.07 - 1.93 (m, 6H), 1.92 - 1.78 (m, 6H), 1.34 (s, 18 H), 0.09 (s, 6 H). 13 C NMR (C6D6, 100 MHz): δ 159.20, 158.22, 143.79, 140.60, 139.55, 138.05, 133.77, 133.38, 133.04, 131.49, 131.32, 127.94, 125.78, 124.65, 124.52, 42.87, 41.99, 38.58, 37.86, 34.82, 32.34, 30.04.

[0215] (3-(adamantan-1-yl)-2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)lithium [ka]

[0216] Hexane (100 mL) was added to 1-(2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)adamantane (12.15 g, 31.59 mmol) to form a clear, pale yellow solution. BuLi (12.69 mL, 31.59 mmol) was added dropwise to form a yellow solution. DME (3.284 mL, 31.59 mmol) was added rapidly. After stirring overnight, the white solid was collected on a frit and washed with hexane (3 x 10 mL). The solid was dried under reduced pressure. HNMR analysis indicated the presence of 0.88 equivalents of DME. Used without further purification. Yield: 8.36 g, 56.3%.

[0217] 1-(2'-Bromo-2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-3-yl)adamantane [ka]

[0218] Toluene (120 mL) was dissolved in (3-(adamantan-1-yl)-2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)lithium (DME). 0.88 (8.36 g, 17.79 mmol) to form a suspension. A solution of 1-bromo-2-chlorobenzene (3.747 g, 19.57 mmol) in toluene (25 mL) was added dropwise over 3.5 h. After stirring overnight, the cloudy mixture was transferred to a separatory funnel and extracted with water (5 x 50 mL) and then brine (2 x 10 mL). The organics were dried over MgSO4, filtered, and evaporated to give a pale yellow oil. HNMR indicates the presence of 0.5 equivalents of toluene in the crude product. Used without further purification. Yield: 9.92 g, 95.2%.

[0219] 2-(3'-(adamantan-1-yl)-2'-(methoxymethoxy)-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ka]

[0220] Hexane (200 mL) was added to 1-(2'-bromo-2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-3-yl)adamantane (9.92 g, 16.94 mmol) to form a clear solution. The mixture was cooled to -40 °C, and BuLi (6.84 mL, 17.79 mmol) was added dropwise. After stirring for 20 minutes, the mixture was removed from the cold bath and allowed to warm to about ambient temperature over 25 minutes. The mixture was then cooled to -40 °C, and a cold hexane solution (2 mL) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.964 g, 26.68 mmol) was added in one portion. The mixture was allowed to slowly warm to ambient temperature and then stirred at ambient temperature. After 1 h, the cloudy mixture was poured into a separatory funnel and extracted with water (6 x 100 mL) until the aqueous layer was neutral. The organics were extracted with brine (2 x 20 mL). The organics were dried over MgSO4, filtered, and dried under vacuum for several days to give the product as an amorphous solid, which was used without further purification. Yield: 9.197 g, 92.6%.

[0221] 2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-(2,4,4-trimethylpentan-2-yl)-[1'',1''-biphenyl]-2-ol) [ka]

[0222] A 500 mL round-bottom flask was charged with 2-(3'-(adamantan-1-yl)-2'-(methoxymethoxy)-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9.197 g, 15.68 mmol), 2,6-dibromopyridine (1.783 g, 7.525 mol), Na2CO3 (4.154 g, 39.19 mmol), dioxane (180 mL), and water (90 mL). The mixture was sparged with nitrogen for 50 minutes before adding solid Pd(PPh3)4 (0.906 g, 0.784 mmol). The mixture was sparged with nitrogen for an additional 40 minutes, then rapidly stirred and heated in an oil bath maintained at 100 °C. After 20 h, the volatiles were evaporated to give a yellow foamy solid. The solid was triturated and stirred with water (200 mL) for several minutes. The solid was then collected on a frit and washed with water (3 × 200 mL). This yellow solid was then dried under reduced pressure. Methanol (100 mL), thf (100 mL), and concentrated HCl (7 mL) were added and the mixture was heated to 60 °C overnight. The volatiles were then evaporated, and the residue was extracted with ether (200 mL) and charged to a separatory funnel. The organics were extracted with dilute NaHCO (100 mL), water (4 × 150 mL), and then brine (20 mL). The organics were dried over MgSO and evaporated to give a foamy yellow solid (8.4 g). The crude product was purified on SiO eluting with 1–5% EtOAc in isohexane. Yield: 4.92 g, 72.0%.

[0223] Dichlorozirconium (2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-(2,4,4-trimethylpentan-2-yl)-[1'',1'''-biphenyl]-2-olate)) (complex 33-dichloride) [ka]

[0224] Benzene (4 mL) was added to ZrCl2(NMe2)2(dme) (0.0374 g, 0.110 mmol) to form a slightly cloudy solution. 2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-(2,4,4-trimethylpentan-2-yl)-[1'',1'''-biphenyl]-2-ol) (0.0998 g, 0.110 mmol) and a small amount of toluene (2 mL) were then added, and the mixture was stirred at 35 °C. After 30 min, an aliquot was removed and analyzed by H NMR, which showed fairly clean formation of the presumed dichloride. The solution was then heated to 80 °C for 25 min. The volatiles were evaporated, and the residue was dried under reduced pressure. The residue was extracted with hot isohexane (8 mL) and filtered. The volatiles were evaporated to give a white solid which was dried under vacuum at 80° C. for about 5 minutes. Yield: 0.0948 g, 80.7%.

[0225] Dimethylzirconium (2',2''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-(2,4,4-trimethylpentan-2-yl)-[1'',1''-biphenyl]-2-olate)) (Complex 33) [ka]

[0226] Toluene (6 mL) was added to complex 33-dichloride (0.0948 g, 0.0887 mmol) to form a clear, colorless solution. The mixture was cooled to -15 °C, and MeMgBr (0.0995 mL, 0.326 mmol) was added. The mixture was allowed to warm to ambient temperature over approximately 15 minutes. After 1 hour, the solution was evaporated to a residue, and a small amount of isohexane (1 mL) was added. The mixture was stirred and evaporated. A small amount of isohexane (1 mL) was added to dissolve the residue, and the volatiles were then evaporated again. The residue was then dried under reduced pressure. The residue was then extracted with isohexane (10 mL), filtered through Celite 503, and evaporated to a residue that was dried under reduced pressure. The vial was scraped to give complex 33 as a light brown solid. Yield: 0.0819 g, 90.0%.

[0227] polymerization Polymerizations were carried out in a continuous stirred tank reactor system. The 1-liter autoclave reactor was equipped with an agitator, pressure controller, and water / steam heating element and temperature controller. The reactor was operated at liquid-fill conditions, with the reactor pressure exceeding the bubble point pressure of the reactant mixture, maintaining the reactants in the liquid phase. Pulsa feed pumps delivered propylene (optional) and isohexane to the reactor, and octene (optional) was fed under N2 head pressure in a holding tank. Coriolis mass flow controllers (Quantim series from Brooks) were used to control all liquid flow rates. Ethylene and hydrogen flowed as gases through Brooks flow controllers under their own pressure. The ethylene, hydrogen, and alpha-olefin feeds were combined into a single stream and then mixed with a pre-chilled isohexane stream cooled to at least 0°C. The mixture was then fed to the reactor via a single line. A solution of tri(n-octyl)aluminum (TNOA) was added to the mixed solvent and monomer streams just before they entered the reactor. The catalyst solution was fed to the reactor via a separate line using an ISCO syringe pump. Isohexane (used as solvent) and monomers (e.g., ethylene, octene, and propylene) were purified over alumina and molecular sieve beds. Toluene for preparing the catalyst solution was also purified by the same technique.

[0228] Complex Cat-Zr (Complex 6) was used in Examples 1-17. The catalyst solution was prepared by combining complex Cat-Zr (approximately 20 mg) with N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in approximately 1:1 molar ratio in approximately 900 ml of toluene. A solution of tri-n-octylaluminum (TNOA) (25 wt% in hexane, Sigma Aldrich) was prepared by dissolving 2.7 × 10 in isohexane. -3 Further dilutions were made to moles / liter concentrations. The polymer produced in the reactor exited through a backpressure control valve, which reduced the pressure to atmospheric pressure. This allowed the unconverted monomer in solution to flow into the vapor phase, which was discharged from the top of the gas-liquid separator. The liquid phase, primarily containing polymer and solvent, was collected for polymer recovery. The collected samples were first air-dried in a hood to evaporate most of the solvent, and then dried in a vacuum oven at a temperature of about 90°C for about 12 hours. The vacuum oven-dried samples were weighed to obtain yields. Detailed process conditions and some characterization data for the ethylene-octene copolymers for Examples 1-10 are listed in Table 2 below. Detailed process conditions and some characterization data for the ethylene-propylene copolymers for Examples 11-17 are listed in Table 3 below.

[0229] [Table 3]

[0230] [Table 4]

[0231] [Table 5]

[0232] [Table 6]

[0233] [Table 7]

[0234] All documents cited herein, including any priority documents and testing procedures, are incorporated herein by reference to the extent they do not contradict this text. While aspects of the invention have been illustrated and described, as is apparent from the foregoing general description and specific embodiments, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, no limitation of the invention is intended. Similarly, the term "comprising" is considered synonymous with the term "including." Similarly, whenever a composition, element, or group of elements precedes the transitional phrase "comprising," it should be understood that we also contemplate the same composition or group of elements having the transitional phrase "consisting essentially of," "consisting of," "selected from the group of consisting of," or "is" preceding the recitation of the composition, element, or group of elements, and vice versa. Another aspect of the present invention may be as follows. [1] In a homogeneous phase, ethylene and C 3 -C 40 and an optional comonomer selected from alpha olefins, an activator, and a copolymer of formula (I): TIFF0007757293000068.tif51150 (In the formula: M is a Group 3, 4, 5, or 6 transition metal or a lanthanide; E and E' are each independently O, S, or NR 9 and R 9 are independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 is a substituted hydrocarbyl or heteroatom-containing group; Q is a Group 14, 15, or 16 atom that forms a coordinate bond with the metal M; A 1 QA 1’ is connected to A via a three-atom bridge. 2 A 2’ Q is the central atom of the three-atom bridge; A is a part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms linked to 1 and A 1' are independently C, N, or C(R 22 ) and R 22 is hydrogen, C 1 -C 20 Hydrocarbyl, C 1 -C 20 substituted hydrocarbyl; TIFF0007757293000069.tif1028 is connected to A via a two-atom bridge. 1 is a divalent group containing 2 to 40 non-hydrogen atoms that links to an E-linked aryl group; TIFF0007757293000070.tif1029 is connected to A via a two-atom bridge. 1' is a divalent group containing 2 to 40 non-hydrogen atoms that links to the E'-linked aryl group; 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 less than or equal to 4; R 1 、R 2 、R 3 、R 4 、R 1' 、R 2' 、R 3' , and R 4' are independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 is a substituted hydrocarbyl, heteroatom or heteroatom-containing group; R 1 and R 2 、R 2 and R 3 、R 3 and R 4、R 1' and R 2' 、R 2’ and R 3' 、R 3' and R 4' may combine 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, and where substituents on the rings may be joined to form additional rings; Any two L groups may be combined to form a bidentate Lewis base; The X group may be joined to the L group to form a monoanionic bidentate group; Any two X groups may be combined to form a dianionic ligand group. and a catalyst system comprising a catalyst compound represented by: and obtaining a polymer containing more than 35 mol % ethylene. A polymerization process comprising: [2] The catalyst compound is represented by the following formula (II): TIFF0007757293000071.tif69170 (In the formula: M is a Group 3, 4, 5, or 6 transition metal or a lanthanide; E and E' are each independently O, S, or NR 9 and R 9 are independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 is a substituted hydrocarbyl, or heteroatom-containing group; each L is independently a Lewis base; each X is independently an anionic ligand; n is 1, 2 or 3; m is 0, 1, or 2; n+m is less than or equal to 4; R 1 、R 2 、R 3 、R 4 、R 1' 、R 2' 、R 3' , and R 4' are independently hydrogen, C 1 -C40 Hydrocarbyl, C 1 -C 40 is a substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 、R 2 and R 3 、R 3 and R 4 、R 1' and R 2' 、R 2’ and R 3' 、R 3' and R 4' may combine 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, and where substituents on the rings may be joined to form additional rings; any two L groups may combine to form a bidentate Lewis base; The X group may be joined to the L group to form a monoanionic bidentate group; Any two X groups may be combined to form a dianionic ligand group; R 5 、R 6 、R 7 、R 8 、R 5’ 、R 6’ 、R 7’ 、R 8’ 、R 10 、R 11 , and R 12 are independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 is a substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 5 and R 6 、R 6 and R 7 、R 7 and R 8 、R 5’ and R6’ 、R 6’ and R 7’ 、R 7’ and R 8’ 、R 10 and R 11 , or R 11 and R 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, and where substituents on the rings may be joined to form additional rings. The process described in [1] above, wherein the process is represented by: [3] The process according to [1] or [2] above, wherein M is Hf, Zr, or Ti. [4] The process according to [1], [2] or [3], wherein E and E' are each O. 〔5〕R 1 and R 1’ But independently C 4 -C 40 The process according to [1], [2], [3], or [4], wherein the group is a tertiary hydrocarbyl group. 〔6〕R 1 and R 1’ But independently C 4 -C 40 The process according to [1], [2], [3], or [4], wherein the cyclic tertiary hydrocarbyl group is a cyclic tertiary hydrocarbyl group. 〔7〕R 1 and R 1’ But independently C 4 -C 40 The process according to [1], [2], [3], or [4], wherein the tertiary hydrocarbyl group is a polycyclic tertiary hydrocarbyl group. [8] The process according to any one of [1] to [7] above, wherein each X is independently selected from the group consisting of a substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, and combinations thereof (two Xs may form part of a fused ring or ring system). [9] The process according to any one of [1] to [8] above, wherein each L is independently selected from the group consisting of ethers, thioethers, amines, phosphines, ethyl ethers, tetrahydrofuran, dimethyl sulfide, triethylamine, pyridine, alkenes, alkynes, allenes, and carbenes, and combinations thereof, and optionally two or more L may form part of a fused ring or ring system.

[10] M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both E and E are carbons ’ Both are oxygen and R 1 and R 1’ Both are C 4 -C 20 The process according to [1] above, wherein the alkyl group is a cyclic tertiary alkyl.

[11] M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both E and E are carbons’ Both are oxygen and R 1 and R 1’ The process according to [1] above, wherein both of are adamantan-1-yl or substituted adamantan-1-yl.

[12] M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both E and E are carbons ’ and n is 2.

[13] Q is nitrogen and A 1 and A 1’ are both carbons and R 1 and R 1’ Both E and E are hydrogen ’ Both are NR 9 and R 9 is C 1 -C 40 Hydrocarbyl, C 1 -C 40 The process according to [1] above, wherein the alkyl group is selected from the group consisting of substituted hydrocarbyl, substituted hydrocarbyl, and heteroatom-containing groups.

[14] Q is carbon and A 1 and A 1’ are both nitrogen, and E and E ’ The process according to [1] above, wherein both of are oxygen.

[15] Q is carbon and A 1 is nitrogen and A 1’ is C(R 22 ) and E and E ’ Both are oxygen and R 22 is hydrogen, C 1 -C 20 Hydrocarbyl, C 1 -C 20 The process according to [1] above, wherein the alkyl group is selected from the group consisting of substituted hydrocarbyls.

[16] The heterocyclic Lewis base is represented by the following formula: TIFF0007757293000072.tif8892 (In the formula, each R 23 is hydrogen, C 1 -C 20 Alkyl, and C 1 -C20 substituted alkyl) The process according to [1] above, wherein the compound is selected from the group represented by

[17] M is Zr or Hf, and E and E ’ Both are oxygen and R 1 and R 1’ Both are C 4 -C 20 The process according to [2] above, wherein the alkyl group is a cyclic tertiary alkyl.

[18] M is Zr or Hf, and E and E ’ Both are oxygen and R 1 and R 1’ The process according to [2] above, wherein both of are adamantan-1-yl or substituted adamantan-1-yl.

[19] M is Zr or Hf, and E and E ’ Both are oxygen and R 1 、R 1’ 、R 3 and R 3’ and each is adamantan-1-yl or substituted adamantan-1-yl.

[20] M is Zr or Hf, and E and E ’ Both are oxygen and R 1 and R 1’ Both are C 4 -C 20 is a cyclic tertiary alkyl, and R 7 and R 7’ Both are C 1 -C 20 The process according to [2] above, wherein the alkyl is alkyl.

[21] M is Zr or Hf, and E and E ’ Both are O and R 1 and R 1’ Both are C 4 -C 20 is a cyclic tertiary alkyl, and R 7 and R 7’ Both are C 1 -C 20 The process according to [2] above, wherein the alkyl is alkyl.

[22] M is Zr or Hf, and E and E ’ Both are O and R 1 and R 1’ Both are C 4 -C 20 is a cyclic tertiary alkyl, and R 7 and R 7’ Both are C 1 -C 3 The process according to [2] above, wherein the alkyl is alkyl.

[23] The catalyst compound is represented by the following formula: TIFF0007757293000073.tif90154 TIFF0007757293000074.tif230170 TIFF0007757293000075.tif226170 The process described in [1] above, represented by one or more of the following:

[24] The process according to [1], wherein the catalyst compound is one or more of the following: TIFF0007757293000076.tif107167

[25] The process according to any one of [1] to

[24] above, wherein the activator comprises an alumoxane or a non-coordinating anion.

[26] The process according to any one of [1] to

[24] above, wherein the activating agent is soluble in a non-aromatic hydrocarbon solvent.

[27] The process according to any one of [1] to

[24] above, wherein the catalyst system does not contain an aromatic solvent.

[28] The activator is represented by the following formula: (Z) d + (A d- ) wherein Z is (LH) or a reducing Lewis acid, L is a neutral Lewis base; H is hydrogen; (LH) + is a Bronsted acid; A d- is a non-coordinating anion having a charge d-; d is an integer from 1 to 3. The process according to any one of [1] to

[27] above, wherein the process is represented by the following formula:

[29] The activator is represented by the following formula: [R 1' R 2' R 3' EH] d+ [Mt k+ Q n ]d- (V) (In the formula: 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; nk=d; R 1' 、R 2' , and R 3' C, which may be independently optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups; 1 -C 50 is a hydrocarbyl group, R 1' 、R 2' , and R 3' contains a total of 15 or more carbon atoms; Mt is an element selected from Group 13 of the Periodic Table of the Elements; and Each Q is independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halo-substituted hydrocarbyl group. The process according to any one of [1] to

[27] above, wherein the process is represented by the following formula:

[30] The activator is represented by the following formula: (Z) d + (A d- ) is represented by In the formula, A d- is a non-coordinating anion having a charge d-; d is an integer from 1 to 3, and (Z) d + The process according to any one of [1] to

[27] above, wherein the process is represented by one or more of the following: TIFF0007757293000077.tif204161

[31] The activator is selected from the group consisting of: N-methyl-4-nonadecyl-N-octadecylbenzeneaminium tetrakis(pentafluorophenyl)borate, N-methyl-4-nonadecyl-N-octadecylbenzeneaminium tetrakis(perfluoronaphthalenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, Dioctadecylmethylammonium tetrakis(perfluoronaphthalenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(perfluoronaphthalenyl)borate, triethylammonium tetrakis(perfluoronaphthalenyl)borate, tripropylammonium tetrakis(perfluoronaphthalenyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthalenyl)borate, tri(t-butyl)ammonium tetrakis(perfluoronaphthalenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthalenyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthalenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthalenyl)borate, tropylium tetrakis(perfluoronaphthalenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthalenyl)borate, triphenylphosphonium tetrakis(perfluoronaphthalenyl)borate, triethylsilylium tetrakis(perfluoronaphthalenyl)borate, benzene(diazonium)tetrakis(perfluoronaphthalenyl)borate, trimethylammonium tetrakis(perfluorobiphenyl)borate, triethylammonium tetrakis(perfluorobiphenyl)borate, tripropylammonium tetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate, tri(t-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, tropylium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylphosphonium tetrakis(perfluorobiphenyl)borate, triethylsilylium tetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, [4-t-butyl-PhNMe 2 H][(C 6 F 3 (C 6 F 5 ) 2 ) 4 B]、 trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, tropylium tetraphenylborate, triphenylcarbenium tetraphenylborate, triphenylphosphonium tetraphenylborate, triethylsilylium tetraphenylborate, Benzene(diazonium)tetraphenylborate, trimethylammonium 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, tropylium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, triethylsilylium tetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammonium 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(t-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, tropylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, 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(t-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, tropylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, and Triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate The process according to any one of [1] to

[27] above, wherein the process is one or more of the following:

[32] The process according to any one of [1] to

[31] above, wherein the process is a solution process.

[33] The process according to any one of [1] to

[32] , wherein the process occurs at a temperature of about 80°C to about 300°C, a pressure in the range of about 0.35 MPa to about 10 MPa, and a residence time of up to 300 minutes.

[34] The process according to any one of [1] to

[33] above, wherein the process is a continuous process.

[35] The process according to any one of [1] to

[34] above, further comprising obtaining a polyethylene composition having an ethylene content of at least 20 mol%.

[36] The method further comprises obtaining an ethylene copolymer, wherein the copolymer has a composition of at least 20 mol% ethylene, a shear thinning ratio of greater than 30, and an I of greater than 10. 21 / I 2 The process according to any one of [1] to

[34] above, comprising:

[37] A polymer comprising ethylene and a comonomer selected from propylene, butene, hexene, and octene, the copolymer having a composition of at least 20 mol% ethylene and a melt index of 400 g / 10 min or less.

[38] A polymer produced by the process according to any one of [1] to

[36] above, comprising ethylene and one or more comonomers selected from propylene, butene, hexene, and octene, the copolymer having an ethylene content of 30 to 50 mol%.

[39] A polymer produced by the process according to any one of [1] to

[36] above, comprising ethylene and one or more comonomers selected from propylene, butene, hexene, and octene, the copolymer having an ethylene content of 50 to 70 mol%.

[40] A polymer produced by the process according to any one of [1] to

[36] above, comprising ethylene and one or more comonomers selected from propylene, butene, hexene, and octene, the copolymer having an ethylene content of 70 to 90 mol%.

[41] A polymer produced by the process according to any one of [1] to

[36] above, comprising ethylene and one or more comonomers selected from propylene, butene, hexene, and octene, the copolymer having an ethylene content of 90 mol% or more.

[42] A polymer produced by the process according to any one of [1] to

[34] above, comprising ethylene and one or more comonomers selected from propylene, butene, hexene, and octene, the copolymer having a branching index of 0.98 or less.

[43] A copolymer produced by a polymerization process comprising contacting, in a homogeneous phase, ethylene and propylene with a catalyst system comprising an activator and a Group 4 bis(phenolate) catalyst compound, said polymerization process being conducted at a temperature of 90°C or greater in the absence of added hydrogen, and comprising: (i) 65-80 mol% ethylene; (ii) shear thinning ratio of 70 to 150 (measured at 125°C); (iii) Phase angle less than 50° (measured at 125°C) @ complex modulus G * = 500 kPa; (iv) a Mooney Large viscosity of 80 to 120 mu (measured at 125°C); and (v) Mooney relaxation area of ​​550 to 3200 mu.sec (measured at 125°C) The copolymer produces a polymer having the formula:

[44] A copolymer produced by a polymerization process comprising contacting, in a homogeneous phase, ethylene and propylene with a catalyst system comprising an activator and a Group 4 bis(phenolate) catalyst compound, said polymerization process being carried out at a temperature of 120°C or greater in the presence of added hydrogen, and comprising: (i) 50-65 mol% ethylene; (ii) g' of 0.8 to 0.9 vis ; (iii) Mooney Large viscosity of 35-40 mu (measured at 125°C); (iv) Mooney relaxation area of ​​300-400 mu.sec (measured at 125°C) The copolymer produces a polymer having the formula:

Claims

1. In a homogeneous phase, ethylene and C 3 -C 40 and an optional comonomer selected from alpha olefins, with an activator and a compound of formula (I): 【Chemical 1】 (In the formula: M is a Group 3, 4, 5, or 6 transition metal or a lanthanide; E and E' are each independently O, S, or NR 9 and R 9 are independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 is a substituted hydrocarbyl or heteroatom-containing group; Q is a Group 14, 15, or 16 atom that forms a coordinate bond with the metal M; A 1 QA 1’ is connected to A via a three-atom bridge. 2 A 2’ Q is the central atom of the three-atom bridge; A 1 and A 1' are independently C, N, or C(R 22 ) and R 22 is hydrogen, C 1 -C 20 Hydrocarbyl, C 1 -C 20 substituted hydrocarbyl; 【Chemistry 2】 is connected to A via a two-atom bridge. 1 to the E-linked aryl group, ortho-phenylene, substituted ortho-phenylene, ortho-arene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene, 1,2-ethylene (-CH 2 CH 2 -), substituted 1,2-ethylene, 1,2-vinylene (-HC=CH-), or substituted 1,2-vinylene; 【Chemistry 3】 is connected to A via a two-atom bridge. 1' ortho-phenylene, substituted ortho-phenylene, ortho-arene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene, 1,2-ethylene (-CH 2 CH 2 -), substituted 1,2-ethylene, 1,2-vinylene (-HC=CH-), or substituted 1,2-vinylene; 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 less than or equal to 4; R 1 , R 2 , R 3 , R 4 , R 1' , R 2' , R 3' , and R 4' are independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 is a substituted hydrocarbyl, heteroatom or heteroatom-containing group; R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1' and R 2' , R 2’ and R 3' , R 3' and R 4' 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, and where substituents on the rings may be joined to form additional rings; Any two L groups may be combined to form a bidentate Lewis base; The X group may be joined to the L group to form a monoanionic bidentate group; Any two X groups may be combined to form a dianionic ligand group. and a catalyst system comprising a catalyst compound represented by: and obtaining a polymer containing more than 35 mol % ethylene. A polymerization process comprising:

2. The catalyst compound is represented by the following formula (II): 【Chemistry 4】 (In the formula: M is a Group 3, 4, 5, or 6 transition metal or a lanthanide; E and E' are each independently O, S, or NR 9 and R 9 are independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 is a substituted hydrocarbyl, or heteroatom-containing group; each L is independently a Lewis base; each X is independently an anionic ligand; n is 1, 2 or 3; m is 0, 1, or 2; n+m is less than or equal to 4; R 1 , R 2 , R 3 , R 4 , R 1' , R 2' , R 3' , and R 4' are independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 is a substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1' and R 2' , R 2’ and R 3' , R 3' and R 4' may combine 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, and where substituents on the rings may be joined to form additional rings; any two L groups may combine to form a bidentate Lewis base; The X group may be joined to the L group to form a monoanionic bidentate group; Any two X groups may be combined to form a dianionic ligand group; R 5 , R 6 , R 7 , R 8 , R 5’ , R 6’ , R 7’ , R 8’ , R 10 , R 11 , and R 12 are independently hydrogen, C 1 -C 40 Hydrocarbyl, C 1 -C 40 is a substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 5’ and R 6’ , R 6’ and R 7’ , R 7’ and R 8’ , R 10 and R 11 , or R 11 and R 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, and where substituents on the rings may be joined to form additional rings.

2. The process of claim 1, wherein:

3. 3. The process of claim 1 or 2, wherein M is Hf, Zr or Ti.

4. 3. The process of claim 1 or 2, wherein E and E' are each O.

5. R 1 and R 1’ But independently C 4 -C 40 Tertiary hydrocarbyl groups, C 4 -C 40 Cyclic tertiary hydrocarbyl groups and C 4 -C 40 3. The process of claim 1 or 2, wherein the aryl group is selected from the group consisting of polycyclic tertiary hydrocarbyl groups.

6. 10. The process of claim 1, wherein each X is independently selected from the group consisting of a substituted or unsubstituted hydrocarbyl group having from 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, and combinations thereof, wherein two Xs may form part of a fused ring or ring system.

7. 10. The process of claim 1, wherein each L is independently selected from the group consisting of ethers, thioethers, amines, phosphines, ethyl ethers, tetrahydrofuran, dimethyl sulfide, triethylamine, pyridine, alkenes, alkynes, allenes, and carbenes, and combinations thereof, and optionally two or more L may form part of a fused ring or ring system.

8. M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both E and E are carbons ’ Both are oxygen and R 1 and R 1’ Both are independently C 4 -C 20 2. The process of claim 1, wherein the cyclic tertiary alkyl is selected from the group consisting of adamantan-1-yl and substituted adamantan-1-yl.

9. M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both E and E are carbons ’ are oxygen, X is methyl or chloro, and n is 2.

10. Q is nitrogen and A 1 and A 1’ are both carbons and R 1 and R 1’ Both E and E are hydrogen ’ Both are NR 9 and R 9 is C 1 -C 40 Hydrocarbyl, C 1 -C 40 10. The process of claim 1, wherein the alkyl group is selected from a substituted hydrocarbyl, or heteroatom-containing group.

11. Q is carbon and A 1 and A 1’ are both nitrogen, and E and E ’ 2. The process of claim 1, wherein both of said oxygen atoms are oxygen.

12. Q is carbon and A 1 is nitrogen and A 1’ is C(R 22 ) and E and E ’ Both are oxygen and R 22 is hydrogen, C 1 -C 20 Hydrocarbyl, C 1 -C 20 2. The process of claim 1, wherein the alkyl group is selected from the group consisting of substituted hydrocarbyls.

13. The process of any one of claims 1 to 12, wherein the process is a solution process.

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