Ring-containing polymer compositions obtained using transition metal bis(phenolate) catalyst complexes and methods for their preparation

Abstract

The present invention relates to a method for preparing a cyclic olefin-containing polymer composition using a dianionic tridentate transition metal complex characterized by a central neutral heterocyclic Lewis base and two phenolate donors, wherein the tridentate ligands coordinate to the metal center to form two eight-membered rings. Preferably, the bis(phenolate) complex has the formula (I): 1 , R 2 , R 3 , R 4 , R 1’ , R 2’ , R 3’ , R 4’ , A 1 , A 1’ ,A 3 =A 2 , and qA 2’ =A 3’ is in the same position as described in the specification, and A 1 QA 1’ is a three-atom bridge, 2 and A 2’ where Q is the central atom of a three-atom bridge. TIFF2023538006000173.tif4199

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 065344, filed August 13, 2020, the disclosure of which is incorporated herein by reference.

[0002] The present invention relates to the following: 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) PCT application number PCT / US2020 / 045819, filed August 11, 2020; 7) PCT application number PCT / US2020 / 045820, filed August 11, 2020; and 8) PCT Application No. PCT / US2020 / 045822, filing date: August 11, 2020

[0003] FIELD OF THEINVENTION The present invention relates to polymer compositions containing cyclic monomers prepared using novel catalyst compounds comprising Group 4 bis(phenolate) complexes, compositions containing same, and methods for making such copolymers. [Background technology]

[0004] There has been interest in modifying the structure of polyolefins in the hope of obtaining new and better combinations of properties such as melt strength, stiffness, shrinkage, and optical properties. In addition, high optical clarity, excellent 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 excellent tensile and impact strength, puncture resistance, excellent optical properties, and best sealing properties. Improved strength properties, along with excellent stretchability, allow downgauging in blown film applications (e.g., as bags).

[0005] Catalyst design, polymer reaction engineering, and polymer process technology have been investigated to produce novel polyolefin materials that meet the diversified industrial demands. Catalyst design plays a key role in controlling the molecular structure of polyethylene and therefore the material properties and processability. The polymer market is currently dominated by products prepared with Ziegler-Natta (ZN) type catalysts and metallocene type catalysts. Optimization of these polyethylene products most often involves multiple reactor and / or multiple catalyst processes. Both strategies tend to be complex and expensive. Therefore, there is interest in finding novel catalyst systems that can enhance the commercial utility of catalysts and enable the production of polymers with improved properties.

[0006] Catalysts for olefin polymerization are based on bis(phenolate) complexes as catalyst precursors and are typically activated by activators containing alumoxanes or non-coordinating anions. Examples of bis(phenolate) complexes are described in the following documents:

[0007] KR2018-022137 (LG Chem.) describes transition metal complexes of bis(methylphenylphenolate)pyridine.

[0008] US 7,030,256 B2 (Symyx Technologies, Inc.) describes bridged diaromatic ligands, catalysts, polymerization processes, and polymers therefrom.

[0009] US 6,825,296 (University of Hong Kong) describes transition metal complexes of metal-coordinating bis(phenolate) ligands having two six-membered rings.

[0010] US 7,847,099 (California Institute of Technology) describes transition metal complexes of metal-coordinating bis(phenolate) ligands having two six-membered rings.

[0011] WO2016 / 172110 (Univation Technologies) describes complexes of tridentate bis(phenolate) ligands featuring acyclic ether or thioether donors.

[0012] Other references include: Baier, MC et al. "Post-Metallocenes in the Industrial Production of Polyolefins" Angew. Chem. Int. Ed. 2014, 53, 9722-9744; Golisz and Bercaw "Synthesis of Early Transition Metal Bisphenolate Complexes and their use as Olefin Polymerization Catalysts" Macromolecules 2009, 42, 8751-8762.

[0013] In addition, it is advantageous to carry out commercial solution polymerization reactions at elevated temperatures. Two major catalyst limitations that often prevent access to such high temperature polymerizations are catalyst efficiency and the molecular weight of the polymer produced, both of which decrease with increasing temperature. Typical metallocene catalysts suitable for use in the production of polyethylene copolymers have relatively limited molecular weight capabilities that require low process temperatures to achieve the desired low melt flow rate products.

[0014] The newly developed single-site catalysts described in related U.S. patent application Ser. No. 16 / 787,909, filed Feb. 11, 2020, have the ability to produce high molecular weight polymers at high polymerization temperatures. These catalysts, when used in solution processes in combination with various types of activators, can produce polymer compositions with superior properties, especially lower Tm with superior molecular weight. Furthermore, the catalyst activity is high, facilitating its use in commercially relevant process conditions. The novel process provides novel polymers with an extended melt flow rate range, increasing throughput in the reactor and allowing production at higher polymerization temperatures during polymer production. Summary of the Invention [Means for solving the problem]

[0015] The present invention relates to a cyclic olefin and ethylene and / or propylene and / or one or more C4-C 12The present invention relates to polymer compositions comprising cyclic olefins, such as copolymers with alpha olefins, and blends comprising such copolymers, the polymer compositions being produced in a solution process using transition metal catalyst complexes of bis(phenolate) ligands. Preferably, the bis(phenolate) ligands are dianionic tridentate ligands featuring a central neutral heterocyclic Lewis base and two phenolate donors, which coordinate to the metal center to form two eight-membered rings. The polymer and copolymer compositions described herein preferably contain greater than 0.1 mole % of cyclic olefins, ethylene and / or propylene, any C4 or higher alpha olefin comonomer.

[0016] The present invention relates to a cyclic olefin and ethylene and / or propylene, and / or any C4-C 12 With respect to polymer compositions, such as copolymers containing alpha-olefin comonomers, as well as blends containing such copolymers, the polymer compositions are prepared in a solution process using a bis(phenolate) complex, preferably a bis(phenolate) complex represented by formula (I): TIFF0007629985000001.tif47143 [In formula: M is a Group 3-6 transition metal or lanthanide; E and E' are each independently O, S or NR 9 where R 9 are independently hydrogen, C1 to C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl or heteroatom-containing group; Q is an atom of Group 14, 15, or 16 that forms a coordinate bond with the metal M; A 1 QA 1’ is a three-atom bridge, 2 and A 2’ A is a part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms linking 1 and A1’ are independently C, N, or C(R 22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl, C1-C 20 substituted hydrocarbyl; TIFF0007629985000002.tif1128 is a 2-atom bridge resulting in A 1 and an E-linked aryl group; TIFF0007629985000003.tif1128 shows A by 2-atom bridge. 1’ and E' is a divalent group containing 2 to 40 non-hydrogen atoms linking the 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 each independently hydrogen, C1 to 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’one or more of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, where substitutions on a ring 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 linked to the L group to form a monoanionic bidentate group; Any two X groups may be combined to form a dianionic ligand. A process for polymerization comprising contacting a catalyst system comprising a catalyst compound represented by

[0017] The present invention also provides a process for the preparation of a catalyst compound as described herein, comprising reacting the catalyst compound with an activator, a cyclic olefin, and optionally ethylene and / or propylene, and one or more C4-C 10 The present invention further relates to a liquid phase process for polymerizing cyclic olefins comprising contacting the cyclic olefins with an alpha-olefin comonomer.The present invention further relates to a polymer composition comprising the cyclic olefins produced by the process described herein.

[0018] definition For purposes of the present invention and the claims, the following definitions shall be used.

[0019] The new numbering scheme for the Periodic Table Groups is used as set forth in Chemical and Engineering News, v. 63(5), pg. 27 (1985). Thus, a "Group 4 metal" is an element in Group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.

[0020] "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 millimole of catalyst. If no units are specified, "catalyst productivity" is in units of grams of polymer per gram of catalyst. To calculate catalyst productivity, only the weight of the transition metal component of the catalyst is used (i.e., excluding activators and / or cocatalysts). "Catalyst activity" is a measure of the mass of polymer produced using a known amount of polymerization catalyst per unit time for batch and semi-batch polymerizations. Typically, "catalyst activity" is expressed in units such as (g of polymer) / (mmole of catalyst) / hour or (kg of polymer) / (mmole of catalyst) / hour. If no units are specified, "catalyst activity" is (g of polymer) / (mmole of catalyst) / hour.

[0021] "Conversion" is the percentage of monomer that is converted to polymer product in a polymerization, reported as a percentage, and calculated based on the polymer yield, polymer composition, and amount of monomer fed to the reactor.

[0022] An "olefin" (also called an "alkene") is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. In this specification and the appended claims, when a polymer or copolymer is referred to as containing an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is described as having an "ethylene" content of 35% to 55% by weight, 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% to 55% by weight, based on the weight of the copolymer. A "polymer" has two or more of the same or different mer units. A "homopolymer" is a polymer having the same mer units. A "copolymer" is a polymer having two or more mer units that are different from each other. A "terpolymer" is a polymer having three mer units that are different from each other. Thus, the definition of copolymer used herein includes terpolymers, etc. "Different" as used in referring to mer units indicates that the mer units differ from each other by at least one atom, or are isomeric. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer that contains at least 50 mol% of units derived from ethylene, and a "propylene polymer" or "propylene copolymer" is a polymer or copolymer that contains at least 50 mol% of units derived from propylene. A polyethylene composition comprises an ethylene polymer or an ethylene copolymer.

[0023] Ethylene is also considered an alpha-olefin.

[0024] Unless otherwise specified, the term "C n " means a hydrocarbon having n carbon atoms per molecule, where n is a positive integer.

[0025] The term "hydrocarbon" refers to a class of compounds containing hydrogen bonded to carbon and includes (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. m -C y A group or compound refers to a group or compound containing a total number of carbon atoms in the range of m to y. Thus, a C1-C50 alkyl group refers to an alkyl group containing a total number of carbon atoms in the range of 1 to 50.

[0026] The terms "group," "radical," and "substituent" can be used interchangeably.

[0027] 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 those having a C1-C 100 The radical may be linear, branched, or cyclic, and if cyclic, may be aromatic or non-aromatic. Examples of such radicals 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, octylcyclopropyl, etc., aryl groups such as cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc., phenyl, benzylnaphthalen-2-yl, etc.

[0028] Unless otherwise specified (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 -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 In this case, q is 1 to 10, and R * are each independently hydrogen, a hydrocarbyl or a halocarbyl radical, and two or more R * may be taken together to form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic ring, or polycyclic ring structure, or mean that at least one heteroatom is inserted within the hydrocarbyl ring.

[0029] The term "substituted hydrocarbyl" refers to a group in which at least one hydrogen atom of a hydrocarbyl radical has been replaced with at least one heteroatom (such as a halogen, e.g., Br, Cl, F, or I) or heteroatom-containing group (such as a functional group, e.g., -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., where q is 1 to 10 and R * are each independently hydrogen, a hydrocarbyl, or a halocarbyl radical, and two or more R * may be attached to form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic structure), or at least one heteroatom is inserted within the hydrocarbyl ring.

[0030] The term "aryl" or "aryl group" refers to an aromatic ring (typically consisting of six carbon atoms) and substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Similarly, heteroaryl refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) is replaced with a heteroatom such as N, O, or S. As used herein, it also refers to pseudoaromatic, which is a heterocyclic substituent having similar properties and structure (nearly planar) as aromatic heterocyclic ligands, but which is not aromatic by definition.

[0031] 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.

[0032] A "substituted phenolate" is one 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, e.g., a hydrocarbyl group, a heteroatom or heteroatom-containing group, e.g., a halogen (such as Br, Cl, F, or I), or at least one functional group (-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 where q is 1 to 10, and R * are each independently hydrogen, a hydrocarbyl or a halocarbyl radical, and two or more R *may together form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic or polycyclic ring structure, in which the 1-position is a phenolate group (Ph-O-, Ph-S-, and Ph-N(R^)- group, where R^ is hydrogen, C1--C 40 Hydrocarbyl, C1-C 40 A substituted hydrocarbyl, heteroatom or heteroatom-containing group. Preferably, the "substituted phenolate" group in the catalyst compounds described herein has the formula: TIFF0007629985000004.tif3644[where, R 18 is hydrogen, C1-C 40 Hydrocarbyl (C1-C 40 Alkyl, etc.) or C1-C 40 is a substituted hydrocarbyl, heteroatom or heteroatom-containing group, E 17 is oxygen, sulfur, or NR 17 and R 17 , R 19 , R 20 , and R 21 are independently hydrogen, C1 to C 40 Hydrocarbyl (C1-C 40 Alkyl, etc.) or C1-C 40 substituted hydrocarbyl, a heteroatom or a 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 is attached to the remainder of the catalyst compound.] It is expressed as:

[0033] 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-, and / or 6-positions are substituted with at least one alkyl group, e.g., C1-C 40 , C2~C 20 , or C3~C 12and phenolate groups substituted with alkyl, such as methyl, ethyl, 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, and substituted analogs thereof.

[0034] 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-, and / or 6-positions are replaced by at least one aryl group, e.g., C1-C 40 , C2~C 20 , or C3~C 12 Aryl, e.g. phenyl 、 Phenolate groups substituted with 4-fluorophenyl, 2-methylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, mesityl, 2-ethylphenyl, naphthalen-2-yl, and their substituted analogues.

[0035] The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has 6 ring atoms and a tetrahydrofuran has 5 ring atoms.

[0036] A heterocyclic ring (also called heterocyclic) is a ring that has a heteroatom in the ring structure, in contrast to a "heteroatom-substituted ring" in which hydrogen on a ring atom is replaced with a heteroatom. For example, tetrahydrofuran is a heterocyclic ring, and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Substituted heterocyclic ring refers to a heterocyclic ring that has one or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0037] Substituted hydrocarbyl ring means a ring composed of carbon and hydrogen atoms having one or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing group.

[0038] For purposes of this disclosure, with respect to catalyst compounds (e.g., substituted bis(phenolate) catalyst compounds), the term "substituted" refers to a hydrogen group being replaced with a hydrocarbyl group, a heteroatom or a heteroatom-containing group, such as a halogen (Br, Cl, F, I, etc.) or -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 In this case, q is 1 to 10, and R * are each independently hydrogen, a hydrocarbyl or a halocarbyl group, and two or more R * may be linked to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or at least one heteroatom may be inserted within the hydrocarbyl ring.

[0039] Tertiary hydrocarbyl groups have a carbon atom bonded to three other carbon atoms. When the hydrocarbyl group is an alkyl group, the tertiary hydrocarbyl group is also referred to as 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. Tertiary hydrocarbyl groups are represented by the formula A: TIFF0007629985000005.tif2020[where, R A , R B and R Care hydrocarbyl or substituted hydrocarbyl groups which may be bonded to each other, and the wavy lines indicate where the tertiary hydrocarbyl groups form bonds to other groups. It can be shown by:

[0040] 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 referred to as an alicyclic tertiary hydrocarbyl group. When the hydrocarbyl group is an alkyl group, the cyclic tertiary hydrocarbyl group is also referred to as 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[1.1.1]pentan-1-yl, bicyclo[2.2.2]octan-1-yl, and the like. A cyclic tertiary hydrocarbyl group is represented by the formula B: TIFF0007629985000006.tif4145[where, R A is a hydrocarbyl group or a substituted hydrocarbyl group, R D are each independently hydrogen or a hydrocarbyl group or a 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 joined together to form an additional ring. It can be shown by:

[0041] When a cyclic tertiary hydrocarbyl group contains two or more alicyclic rings, it may be referred to as a polycyclic tertiary hydrocarbyl group, and when the hydrocarbyl group is an alkyl group, it may be referred to as a polycyclic tertiary alkyl group.

[0042] The terms "alkyl radical" and "alkyl" are used interchangeably throughout this disclosure. For the purposes of this disclosure, an "alkyl radical" is a C1-C6 alkyl group that may be linear, branched, or cyclic. 100 The term "alkyl" refers to a group of radicals that are defined as alkyl. Examples of such radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and substituted analogs thereof. Substituted alkyl radicals are defined as radicals in which at least one hydrogen atom of the alkyl radical has been replaced with at least one non-hydrogen atom, such as a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, such as a halogen (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 where q is 1 to 10 and R * are each independently hydrogen, a hydrocarbyl or a halocarbyl group, and two or more R * may be linked to form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic ring or polycyclic structure, or at least one heteroatom may be inserted within the hydrocarbyl ring.

[0043] Where isomers of a specified alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), a reference to one member of the group (e.g., n-butyl) expressly discloses the remaining isomers within the family (e.g., isobutyl, sec-butyl, and tert-butyl). Similarly, a reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl).

[0044] 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 called 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 (gmol- 1 ).

[0045] 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 called DME) is 1,2-dimethoxyethane, p-tBu is para-tert-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., CH2Ph), THF (also called thf) is tetrahydrofuran, RT is room temperature (23 °C unless otherwise specified), tol is toluene, EtOAc is ethyl acetate, Cbz is carbazole, Cy is cyclohexyl, cP is cyclopentene, NB is 2-norbornene, h is hour, and min is minute. Micromole may be abbreviated as umol or μmol. Microliter may be abbreviated as uL or μL.

[0046] A "catalyst system" is a combination that includes at least one catalyst compound and at least one activator. When "catalyst system" is used to describe such a pair before activation, it means the unactivated catalyst complex (precatalyst) together with the activator and optionally coactivator. When used to describe such a pair after activation, it means the activated complex and the activator or other charge-balancing moiety. The transition metal compound can be neutral, as in the precatalyst, or a charged species with a counterion, as in the activated catalyst system. For the purposes of the present invention and claims, when a catalyst system is described as including the neutral stable form of a component, it is well understood by those skilled in the art 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 that can polymerize a monomer into a polymer.

[0047] In the description herein, the catalyst may be described as a catalyst, a catalyst precursor, a pre-catalyst compound, a catalyst compound or a transition metal compound, and these terms are used interchangeably.

[0048] 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 anion donors may combine to form a dianionic group.

[0049] 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, dimethylsulfide, triethylamine, pyridine, alkenes, alkynes, arenes, and carbenes. Lewis bases may combine to form bidentate or tridentate Lewis bases.

[0050] For purposes of this invention and the claims thereto, phenolate donors include Ph-O-, Ph-S-, and Ph-N(R^)- groups, where R^ is hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, and Ph is an optionally substituted phenyl. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0051] Detailed Description The present invention relates to a polymer composition comprising a cyclic monomer prepared using a solution process and a novel family of catalysts comprising transition metal complexes of a dianionic tridentate ligand, preferably a bis(phenolate) ligand, characterized by a central neutral donor group and two phenolate donors, wherein the tridentate ligand coordinates to the metal center and forms two eight-membered rings. In this type of complex, it is advantageous for the central neutral donor to be a heterocyclic group. It is particularly advantageous for the heterocyclic group to lack a hydrogen in the alpha position to the heteroatom. It is also advantageous for this type of complex to have the phenolate substituted with one or more cyclic tertiary alkyl substituents. The use of cyclic tertiary alkyl substituted phenolates is demonstrated to improve the ability of these catalysts to produce high molecular weight polymers.

[0052] Complexes of substituted bis(phenolate) ligands useful herein (e.g., adamantanyl-substituted bis(phenolate) ligands) when combined with a non-coordinating anion or an activator, such as an alumoxane activator, form active olefin polymerization catalysts. Useful bis(arylphenolate)pyridine complexes include tridentate bis(arylphenolate)pyridine ligands coordinated to a Group 4 transition metal by forming two eight-membered rings.

[0053] The present invention also relates to a solution process for producing polymer compositions comprising cyclic monomers utilizing a metal complex comprising a metal selected from Groups 3-6 or Lanthanide metals and a tridentate dianionic ligand comprising two anionic donor groups and a neutral Lewis base donor, where 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 metallocyclic rings.

[0054] The present invention relates to a catalyst system for use in a solution process for preparing a cyclic monomer-containing polymer composition comprising an activator and one or more catalyst compounds as described herein.

[0055] The present invention also relates to a solution process for polymerizing olefins (preferably at higher temperatures) using the catalyst compounds described herein, which comprises contacting a cyclic monomer and, optionally, one or more olefin comonomers with a catalyst system comprising an activator and catalyst compound described herein.

[0056] The present disclosure also relates to catalyst systems comprising the transition metal compound and activator compound described herein, an activator for activating the transition metal compound in a catalyst system for polymerizing a cyclic monomer and, optionally, one or more olefin comonomers, and a method for polymerizing said olefins, the method comprising contacting one or more olefin comonomers with a catalyst system comprising a transition metal compound and an activator compound under polymerization conditions, wherein no aromatic solvent such as toluene is present (e.g., present at zero mole % or present at less than 1 mole % relative to the moles of activator, preferably the catalyst system, the polymerization reaction and / or the polymer produced does not contain detectable aromatic hydrocarbon solvents such as toluene).

[0057] The cyclic olefin-containing polymer compositions produced herein preferably contain 0 ppm (alternatively less than 1 ppm, alternatively less than 100 ppm, alternatively less than 500 ppm) of aromatic hydrocarbons such as toluene. Preferably, the polyethylene compositions produced herein contain 0 ppm (alternatively less than 1 ppm) of toluene.

[0058] The catalyst systems used herein preferably contain 0 ppm (alternatively less than 1 ppm) of aromatic hydrocarbons. Preferably, the catalyst systems used herein contain 0 ppm (alternatively less than 1 ppm) of toluene.

[0059] catalyst compound The terms "catalyst," "compound," "catalyst compound," and "complex" can be used interchangeably to refer to transition metal or lanthanide metal complexes that, when combined with an appropriate activator, form olefin polymerization catalysts.

[0060] The catalyst complex of the present invention comprises a metal or lanthanide metal selected from group 3, 4, 5 or 6 of the periodic table of elements, a tridentate dianionic ligand comprising two anion donor groups, and a neutral heterocyclic Lewis base donor, where the heterocyclic donor is covalently bonded between the two anionic donors.Preferably, the catalyst complex comprises a dianionic tridentate ligand featuring a central heterocyclic donor group and two phenolate donors, where the tridentate ligand coordinates to the metal center to form two eight-membered rings.Also preferably, the catalyst complex comprises a tridentate dianionic ligand featuring a central heterocyclic donor bonded to two phenolate donors, where the central heterocyclic ring is linked to each phenolate donor by a 1,2-arylene bridge (e.g., 1,2-phenylene).

[0061] The metal is preferably selected from the 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.

[0062] Preferably, the heterocyclic Lewis base donor features a nitrogen or oxygen donor atom.Preferred heterocyclic ring groups include pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and derivatives of their substituted variants.Preferably, the heterocyclic Lewis base lacks a hydrogen atom alpha to the donor atom.Particularly preferred heterocyclic Lewis base donors include pyridine, 3-substituted pyridine, and 4-substituted pyridine.

[0063] The anion donor of the tridentate dianionic ligand can be an arylthiolate, phenolate, or anilide. The preferred anion donor is phenolate. It is preferred that the tridentate dianionic ligand coordinates to the metal center to form a complex that lacks a mirror plane of symmetry. It is preferred that the tridentate dianionic ligand coordinates to the metal center to form a complex that has a double rotation axis of symmetry. When determining the symmetry of a bis(phenolate) complex, only the metal and the dianionic tridentate ligand are considered (i.e., the remaining ligands are ignored).

[0064] Bis(phenolate) ligands useful in the present invention include dianionic polydentate (e.g., bidentate, tridentate, or tetradentate) ligands featuring two anionic phenolate donors. Preferably, the bis(phenolate) ligands are tridentate dianionic ligands that coordinate to the metal M such that a pair of eight-membered metallocyclic rings are formed. Preferred bis(phenolate) ligands wrap around the metal to form complexes with a two-fold axis, thus giving the complex C2 symmetry. The C2 geometry and the eight-membered metallocyclic ring are characteristic of these complexes that are effective catalyst components for the production of polyolefins, particularly isotactic poly(alphaolefins). The ligands allow the complexes to have a mirror (C2) symmetry. s ) symmetry, the catalyst is expected to produce only atactic poly(alpha olefins). These symmetric reactivity rules are summarized in Bercaw's Macromolecules 2009, v.42, pp. 8751-8762. The pair of eight-membered metallocyclic rings of the complexes of the present invention is also a notable feature that favors catalytic activity, temperature stability, and equiselectivity of monomer binding. Related Group 4 complexes featuring smaller six-membered metallocyclic rings show excellent catalytic activity in the polymerization of C2 and C3 olefins. sの It is known to form mixtures of symmetrical complexes and thus is poorly suited for the preparation of highly isotactic poly(alpha olefins) (Macromolecules 2009, v.42, pp. 8751-8762).

[0065] The bis(phenolate) ligands of the present invention containing an oxygen donor group (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 a ring position adjacent to the oxygen donor atom. The substitution at the position adjacent to the oxygen donor atom is preferably an alkyl group having 1 to 20 carbon atoms. The substitution at the position adjacent to the oxygen donor atom is preferably a non-aromatic cyclic alkyl group having one or more 5- or 6-membered rings. The substitution at the position adjacent to the oxygen donor atom is preferably a cyclic tertiary alkyl group. The substitution at the position adjacent to the oxygen donor atom is highly preferably an adamantan-1-yl or substituted adamantan-1-yl.

[0066] 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 represented by (A 3 A 2 ) and (A 2’ A 3’ The selection of each linker group can affect the performance of the catalyst, including the stereoregularity of the poly(alphaolefin) produced. Each linker group is typically two atoms in length, C2-C 40 It is a divalent group. One or both linker groups can be independently phenylene, substituted phenylene, heteroaryl, vinylene, or acyclic two carbon long linker groups. When one or both linker groups are phenylene, alkyl substituents on the phenylene group can be selected to optimize catalytic performance. Typically, one or both phenylenes can be unsubstituted or can be a C1-C6 alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, e.g., isopropyl. 10 It may be substituted with an alkyl group, or an isomer thereof.

[0067] The present invention further relates to catalyst compounds of formula (I) and catalyst systems comprising such compounds. TIFF0007629985000007.tif41101[In formula: 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 where R 9 are independently hydrogen, C1 to C 40 Hydrocarbyl, C1-C 40 A substituted hydrocarbyl or heteroatom-containing group, preferably O, and preferably both E and E' are O; Q is an atom of Group 14, 15, or 16 which 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 a three-atom bridge, 2 and A 2’ A is a part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms linking 1 QA 1’ A 1 and A 1’ A is connected by a curved line to represent a heterocyclic Lewis base. 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, preferably A 1 and A 1’ is C; TIFF0007629985000008.tif1128 is bridged by two atoms to form A 1and a divalent group containing 2 to 40 non-hydrogen atoms linking the E-bonded aryl group, such as orthophenylene, substituted orthophenylene, orthoarene, 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 TIFF0007629985000009.tif1130 is a divalent hydrocarbyl group; TIFF0007629985000010.tif1231 is bridged by two atoms to form A 1’ and the E'-linked aryl group, a divalent group containing 2 to 40 non-hydrogen atoms, such as orthophenylene, substituted orthophenylene, orthoarene, 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 TIFF0007629985000011.tif1231 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 to C 40 Hydrocarbyl, C1-C 40substituted hydrocarbyl, heteroatom, or heteroatom-containing group (preferably R 1’ and R 1 are independently a cyclic group, such as a cyclic tertiary alkyl 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’ one or more of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, where substitutions on a ring 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 linked to the L group to form a monoanionic bidentate group; Any two X groups may be combined to form a dianionic ligand.

[0068] The present invention further relates to catalyst compounds and catalyst systems comprising such compounds, represented by formula (II): TIFF0007629985000012.tif52140 [In formula: 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 where R 9 are independently hydrogen, C1 to C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl or heteroatom-containing group, preferably O, and preferably both E and E' are O; Each L is independently a Lewis base; 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 to 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 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, where substitutions on a ring 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 linked to the L group to form a monoanionic bidentate group; Any two X groups may combine to form a dianionic ligand; 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 to C 40 Hydrocarbyl, C1-C 40is a substituted hydrocarbyl, heteroatom or heteroatom-containing group; 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, where substitutions on a ring may be joined to form additional rings.

[0069] The metal M is preferably selected from elements of groups 3, 4, 5 or 6, more preferably from group 4. Most preferably, the metal M is zirconium or hafnium.

[0070] The donor atom Q of the neutral heterocyclic Lewis base (in formula (I)) is preferably nitrogen, carbon or oxygen. A preferred Q is nitrogen.

[0071] 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.

[0072] A of the heterocyclic Lewis base (in formula I) 1 and A 1’ are each independently C, N, or C(R 22 ) and R 22is hydrogen, C1-C 20 Hydrocarbyl, and C1-C 20 substituted hydrocarbyl. 1 and A 1’ is carbon. If Q is carbon, then A 1 and A 1’ However, 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 to have no hydrogen atoms attached to the atoms, as it is believed that hydrogen at these positions may undergo undesirable decomposition reactions that reduce the stability of the catalytically active species.

[0073] (in formula (I)) A 1 and A 1’ Combined with the curve connecting 1 QA 1’ The heterocyclic Lewis base represented by the formula: 23 The group can be hydrogen, heteroatoms, C1-C 20 Alkyl, C1-C 20 Alkoxides, C1-C 20 Amides, and C1-C 20 substituted alkyl. TIFF0007629985000013.tif103108

[0074] In formula (I) or (II), E and E′ are each oxygen or NR 9 Selected from R 9 are independently hydrogen, C1 to C 40 Hydrocarbyl, C1-C 40 E and E' are preferably oxygen. E and / or E' are preferably NR9 If 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), where alkyl is preferably a C1-C aryl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, etc. 20 Alkyl is C6-C such as phenyl, naphthalene-2-yl, benzyl, and methylphenyl. 40 It is an aryl group.

[0075] In an embodiment, TIFF0007629985000014.tif13150 is C1~C 12 The aryl group is a divalent hydrocarbyl group, such as a hydrocarbyl group.

[0076] In the complexes represented by formula (I) or (II), when E and E′ are oxygen, each phenolate group is located 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’ Each of these is independently C1 to C 40 Hydrocarbyl, C1-C 40 It is preferred that 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, or 1-methylcyclohexyl, or substituted adamantanyl), most preferably a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantanyl, or substituted adamantanyl).

[0077] 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.

[0078] 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.

[0079] Linker group (i.e., the group shown below in formula (I)) Each of R in formula (II) is preferably a part of an orthophenylene group, preferably a substituted orthophenylene group. 7 and R 7’ C1-C alkyl groups such as hydrogen or isomers thereof, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or isopropyl. 20 In applications targeting polymers with high stereoregularity, R in formula (II) is preferably 7 and R 7 'th place is C1~C 20It is preferably alkyl. 7 and R 7’ It is most preferable that both are C1-C3 alkyl.

[0080] In an embodiment of formula (I) herein, Q is C, N or O, preferably Q is N.

[0081] In the 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. 1 and A 1’ is carbon.

[0082] 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 variants thereof.

[0083] In the embodiments of formula (I) herein, A 1 QA 1’ is a 3-atom bridge, 2 and A 2’ and Q is the central atom of the three-atom bridge. 1 and A 1’ is a carbon atom, and A 1 QA 1’ The fragment may form part of a pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or a substituted variant thereof, or a substituted variant thereof.

[0084] In one embodiment of formula (I) herein, Q is carbon and each A 1 and A 1’ is N or C(R 22 ), where R 22 is hydrogen, C1-C 20 Hydrocarbyl, C1-C 20 In this embodiment, A is selected from the group consisting of a substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group. 1 QA 1’ The fragments form part of, or are part of, cyclic carbenes, N-heterocyclic carbenes, cyclic aminoalkylcarbenes, or substituted variants of that group.

[0085] In an embodiment of formula (I) of the specification, TIFF0007629985000016.tif1129 is a divalent group containing 2 to 20 non-hydrogen atoms, and is linked to A by two-atom bridges. 1 is attached to the E-linked aryl group. TIFF0007629985000017.tif411 is a straight chain alkyl group or forms part of a cyclic group (eg an optionally substituted ortho-phenylene group, or an ortho-arylene group) or substituted variants thereof.

[0086] TIFF0007629985000018.tif1129 is a divalent group containing 2 to 20 non-hydrogen atoms and is linked by a two-atom bridge to form A 1’ is attached to the E' linked aryl group. TIFF0007629985000019.tif1130 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.

[0087] In an embodiment of the invention, in formula (I) or (II), M is a Group 4 metal, such as Hf or Zr.

[0088] In an embodiment of the invention, E and E' are O in formulae (I) and (II).

[0089] In an embodiment of the present invention, 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 to C 40 Hydrocarbyl, C1-C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 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 having 5, 6, 7, or 8 ring atoms, respectively, where substitutions on a ring, when joined to form an additional ring, may preferably be hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.

[0090] In an embodiment of the present invention, in formulas (I) and (II), R 1 , R 2 , R 3 , R 4 , R 1’ , R 2’ , R 3’ , R 4’ 、 and R 9is 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, dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalen-2-yl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

[0091] In an embodiment of the present invention, in formulas (I) and (II), R 4 and R 4’は are independently hydrogen or a C1 to C3 hydrocarbyl such as methyl, ethyl or propyl.

[0092] In an embodiment of the invention herein, in formula (I) and (II), R 9 is hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 R is a substituted hydrocarbyl or heteroatom-containing group, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof. 9 is preferably methyl, ethyl, propyl, butyl, C1 to C6 alkyl, phenyl, 2-methylphenyl, 2,6-dimethylphenyl, or 2,4,6-trimethylphenyl.

[0093] In an embodiment of the invention, in formulas (I) and (II), X is independently selected from hydrocarbyl groups having 1 to 20 carbon atoms (e.g., alkyl or aryl), hydrides, amides, alkoxides, sulfides, phosphides, halides, alkylsulfonates, and combinations thereof (two or more X may form part of a fused ring or ring system). X is preferably independently selected from halides, aryls, and C1-C5 alkyl groups. X is preferably independently selected from hydride, dimethylamide, diethylamide, methyltrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl, fluoro, iodo, bromo, or chloro groups.

[0094] Alternatively, each X may independently be a halide, a hydride, an alkyl group, an alkenyl group, or an arylalkyl group.

[0095] In an embodiment of the invention, in formulae (I) and (II), L is each independently a Lewis base 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, L is preferably each independently selected from ether and thioether groups, and L is preferably an ethyl ether, tetrahydrofuran, dibutyl ether, or dimethyl sulfide group, respectively.

[0096] In an embodiment of the invention herein, in formula (I) and (II), R 1 and R 1’ is independently a cyclic tertiary alkyl group.

[0097] In an embodiment of the invention, in formulae (I) and (II), n is 1, 2 or 3, typically 2.

[0098] In an embodiment of the present invention, in formulae (I) and (II), m is 0, 1 or 2, and is typically 0.

[0099] In an embodiment of the present invention, in formulas (I) and (II), R 1 and R 1’ is not hydrogen.

[0100] In an embodiment of the invention, in formulas (I) and (II), M is Hf or Zr, E and E' are O; R 1 and R 1’ are each independently C1 to C 40 Hydrocarbyl, C1-C 40 R is a substituted hydrocarbyl, heteroatom or heteroatom-containing group; 2 , R 3 , R 4 , R 2’ , R 3’ , and R 4’ , each independently hydrogen, C1-C 20 Hydrocarbyl, C1-C 20 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, unsubstituted hydrocarbyl, or substituted or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, or substituents on the rings may combine to form additional rings. Each X is independently selected from the group consisting of a hydrocarbyl radical (e.g., alkyl or aryl) having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, and combinations thereof (two or more Xs 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 Ls may form part of a fused ring or ring system).

[0101] 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, C1 to C 40 Hydrocarbyl, C1-C 40 may be substituted hydrocarbyl, heteroatom or heteroatom-containing group, or one or more adjacent R groups may join to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic, or unsubstituted heterocyclic rings having 5, 6, 7, or 8 ring atoms, respectively, and substitutions on the rings may be joined to form additional rings.

[0102] 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, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.

[0103] 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 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, dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalen-2-yl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

[0104] 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 each independently C1 to C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, a heteroatom or a 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 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, unsubstituted hydrocarbyl, or substituted heterocyclic rings, 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 a substituted hydrocarbyl, or heteroatom-containing group, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof; X are each independently 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; 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 to C 20 Hydrocarbyl, C1-C 20R may be a substituted hydrocarbyl, heteroatom or heteroatom-containing group, or one or more adjacent R groups may combine 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 substitutions on the rings may combine 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 12 are 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, dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

[0105] A preferred embodiment of formula (I) is where M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both are carbon, and E and E ’ Both are oxygen and R 1 and R 1’ Both are C4~C 20 It is a cyclic tertiary alkyl.

[0106] A preferred embodiment of formula (I) is where M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both are carbon, and E and E ’Both are oxygen and R 1 and R 1’ are both adamantan-1-yl or substituted adamantan-1-yl.

[0107] A preferred embodiment of formula (I) is where M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ are carbon, both E and E' are oxygen, X is methyl or chloro, and n is 2.

[0108] 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.

[0109] 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.

[0110] 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’ is adamantan-1-yl or substituted adamantan-1-yl.

[0111] 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 Cyclic tertiary alkyl, R 7 and R 7’ Both are C1-C 20 It is an alkyl.

[0112] Particularly useful catalytic compounds in the present invention are dimethylzirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-oleate], dimethylhafnium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-oleate], ate)], 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)], dimethyl hafnium [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)].

[0113] Particularly useful catalyst compounds in the present invention include compounds represented by one or more of the following formulas: TIFF0007629985000020.tif134144 TIFF0007629985000021.tif41137 TIFF0007629985000022.tif140147 TIFF0007629985000023.tif46133 TIFF0007629985000024.tif140147 TIFF0007629985000025.tif4193 TIFF0007629985000026.tif41114 TIFF0007629985000027.tif3692 TIFF0007629985000028.tif3682 TIFF0007629985000029.tif35126 TIFF0007629985000030.tif51152 TIFF0007629985000031.tif46139 TIFF0007629985000032.tif46142 TIFF0007629985000033.tif46142 TIFF0007629985000034.tif46142 TIFF0007629985000035.tif46142 TIFF0007629985000036.tif4199 TIFF0007629985000037.tif57119 TIFF0007629985000038.tif36109 TIFF0007629985000039.tif3561

[0114] 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 in which the process described herein occurs. Although it is preferable 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 a hydride, hydrocarbyl, or substituted hydrocarbyl, the alumoxane can be contacted with the transition metal compound before the addition of the non-coordinating anion activator.

[0115] The two transition metal compounds (pre-catalysts) can be used in any ratio. Preferred molar ratios of (A) transition metal compound to (B) transition metal compound (A:B) fall within the range of 1:1000-1000:1, or 1:100-500:1, or 1:10-200:1, or 1:1-100:1, or 1:1-75:1, or 5:1-50:1. The particular ratio selected will depend on the exact pre-catalyst selected, the method of activation, and the desired end product. In certain embodiments, when using two pre-catalysts, both of which are activated with the same activator, useful mole percentages based on the molecular weight of the pre-catalysts are 10-99.9% A: 0.1-90% B, or 25-99% A: 0.5-50% B, or 50-99% A: 1-25% B, or 75-99% A: 1-10% B.

[0116] Method for producing catalyst compound Ligand synthesis Bis(phenol) ligands can be prepared using the general methodology 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 Negishi coupling, Suzuki coupling, Kumada coupling, etc. Coupling of compound C with compound D to form a bis(phenol) ligand (Method 2) can be achieved by known Pd- and Ni-catalyzed couplings, such as Negishi coupling, Suzuki coupling, Kumada coupling, etc. Compound D can be prepared from compound E by reaction of compound E with an organolithium reagent or magnesium metal, followed by reaction with a main group metal halide (e.g., ZnCl2) or a boron-based reagent (e.g., B(O i Pr)3, i Compound E can be prepared by any reaction with PrOB(pin)). Compound E can be prepared by a non-catalyzed reaction by the reaction of an aryl lithium or aryl Grignard reagent (compound F) with a dihalogenated arene (compound G), such as 1-bromo-2-chlorobenzene. Compound E can also be prepared by a Pd or Ni catalyzed reaction by the reaction of an aryl zinc or aryl boron reagent (compound F) with a dihalogenated arene (compound G). Scheme 1 TIFF0007629985000040.tif51123 TIFF0007629985000041.tif92123 [wherein M' is an element of group 1, 2, 12, or 13, or Li, MgCl, MgBr, ZnCl, B(OH) 2 , 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 C1-C 40alkyl, substituted alkyl, aryl, tertiary alkyl, cyclic tertiary alkyl, adamantanyl, or substituted adamantanyl, and X′ and X are each a halogen, such as Cl, Br, F, or I.

[0117] 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 accomplished 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).

[0118] Synthesis of carbene bis(phenol) ligands. A general synthetic method for the synthesis of carbene bis(phenol) ligands is shown in Scheme 2. Substituted phenols are ortho-brominated and then protected with known phenol protecting groups, such as methoxymethyl ether (MOM), tetrahydropyranyl ether (THP), t-butyldimethylsilyl (TBDMS), benzyl (Bn), etc. The bromides are then converted to boronic esters (compound I) or boronic acids that can be used in Suzuki coupling with bromoanilines. Biphenylanilines (compound J) are crosslinked and deprotected by reaction with dibromoethane or condensation with oxalaldehyde (compound K). Reaction with triethyl orthoformate forms iminium salts, which are then deprotected to carbenes. Scheme 2 TIFF0007629985000042.tif134147

[0119] To the substituted phenol (compound H) dissolved in methylene chloride is added an equivalent of N-bromosuccinimide and 0.1 equivalent of diisopropylamine. After stirring at ambient temperature until complete, the reaction is quenched with 10% HCl solution. 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, the substituted bromophenol and an equivalent of dihydropyran are dissolved in methylene chloride and cooled to 0° C. A catalytic amount of paratoluenesulfonic acid is added and the reaction is stirred for 10 minutes and then 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.

[0120] 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 boronic esters by treatment with HCl. The boronic ester or acid is dissolved in toluene with an equivalent amount of orthobromoaniline and a catalytic amount of palladium tetrakistriphenylphosphine. An aqueous solution of sodium carbonate is added and the reaction is heated to reflux overnight. After cooling, the layers are separated and the aqueous layer is extracted with ethyl acetate. The combined organic portions are washed with brine, dried (MgSO4), filtered and concentrated under reduced pressure. Column chromatography is typically used to purify the coupled product (compound J).

[0121] The aniline (compound J) and dibromoethane (0.5 equiv.) 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).

[0122] The diamine (compound K) is dissolved in triethyl orthoformate. Ammonium chloride is added and the reaction is heated to reflux overnight. A precipitate forms which is collected by filtration and washed with ether to give the iminium salt. The iminium chloride is suspended in THF and treated with lithium or sodium hexamethyldisilylamide. Once complete, the reaction is filtered and the filtrate is concentrated to give the carbene ligand.

[0123] Preparation of bis(phenolate) complexes A transition metal or lanthanide metal bis(phenolate) complex is used as a catalyst component for olefin polymerization in the present invention. The terms "catalyst" and "catalyst complex" are used interchangeably. The preparation of a transition metal or lanthanide metal bis(phenolate) complex can be achieved by the reaction of a bis(phenol) ligand with a metal reactant that contains 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. Metal reactants suitable for this type of reaction include, but are not limited to, HfBn4 (Bn=CH2Ph), ZrBn4, TiBn4, ZrBn2Cl2(OEt2), HfBn2Cl2(OEt2)2, Zr(NMe2)2Cl2(dimethoxyethane), Zr(NEt2)2Cl2(dimethoxyethane), Hf(NEt2)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 may be formed in situ and used without isolation. Preparation of transition metal bis(phenolate) complexes is typically carried out in an ether or hydrocarbon solvent or solvent mixture, typically at temperatures ranging from -80°C to 120°C.

[0124] A second method for preparing transition metal or lanthanide bis(phenolate) complexes involves coupling the bis(phenol) ligand with an alkali metal or alkaline earth metal base (e.g., Na, BuLi, iBis(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, the 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 alkylating reagents include bis(phenolate) complexes, such as bis(phenyl)amine, bis(phenyl)amine, bis(phenyl)amine, and bis(phenyl)amine. Typically, 2-20 molar equivalents of alkylating reagent are added to the bis(phenolate) complex. The alkylation is generally carried out in an ether or hydrocarbon solvent or solvent mixture, typically at temperatures ranging from -80°C to 120°C.

[0125] Activator The terms "cocatalyst" and "activator" are used interchangeably herein.

[0126] 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 systems can also be added to or formed in solution or bulk polymerization (in monomer). The catalyst systems of the present disclosure can 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 above catalyst compounds by converting a neutral metal compound to a catalytically active metal compound cation. Non-limiting activators include, for example, alumoxanes, ionizing activators, which can be neutral or ionic, and conventional cocatalysts. Preferred activators typically include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract reactive metal ligands, cationize the metal compound, and provide a non-coordinating or weakly coordinating anion, such as a non-coordinating anion, to balance the charge.

[0127] Alumoxane Activator Alumoxane activators are utilized as activators in the catalyst systems described herein. Alumoxanes are generally of the formula -Al(R 99 )-O-subunit (wherein R 99is an oligomeric compound containing an alkyl group). Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, especially when the abstractable ligand is an alkyl, halide, alkoxide, or amide. Mixtures of different alumoxanes and modified alumoxanes can also be used. It is preferred to use visually clear methylalumoxane. Cloudy or gelled alumoxanes can be filtered to produce a clear solution, or clear alumoxane can be decanted from the cloudy solution. A useful alumoxane is modified methylalumoxane (MMAO) catalyst type 3A (covered in U.S. Pat. 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, which is described in US Pat. No. 9,340,630; US Pat. No. 8,404,880; and US Pat. No. 8,975,209.

[0128] When the activator is an alumoxane (modified or unmodified), typically the maximum amount of activator is up to a 5000-fold molar excess of Al / M relative to the catalyst compound (per metal catalytic site). The minimum molar ratio of activator to catalyst compound is 1:1. Alternative preferred ranges include 1:1 to 500:1, or 1:1 to 200:1, or 1:1 to 100:1, or 1:1 to 50:1.

[0129] In another embodiment, 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 transition metal of the catalyst compound of less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1:1.

[0130] Ionizing / Non-Coordinating Anion Activators The term "non-coordinating anion" (NCA) refers to an anion that does not coordinate to a cation or that only weakly coordinates to a cation, thereby remaining sufficiently unstable to be displaced by a neutral Lewis base. Furthermore, the anion does not transfer an anionic substituent or fragment to the cation to form a neutral transition metal compound and a neutral by-product from the anion. Useful non-coordinating anions of the present invention are those that are compatible and stabilize the transition metal cation in the sense of balancing the ionic charge with +1, yet retain sufficient lability to allow for displacement during polymerization. The term NCA is also defined to include multi-component NCA-containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, which contain an acidic cationic group and a non-coordinating anion. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, which can react with the catalyst to form an activated species by abstraction of an anionic group. Any metal or metalloid capable of forming a compatible weakly coordinating complex can 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.

[0131] It is within the scope of the present invention to use neutral or ionic ionizing activators, either alone or in combination with alumoxane or modified alumoxane activators.

[0132] In an embodiment of the present invention, the activator is represented by formula (III). TIFF0007629985000043.tif15115 wherein Z is (LH) or a reducible Lewis acid, L is a neutral Lewis base; H is hydrogen; (LH) + is a Brønsted 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, C1-C 40 Hydrocarbyl or substituted C1-C 40 Anion component A is a hydrocarbyl. d - has the formula [M k+ Q n ] d -, in which 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; Q is independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halo-substituted hydrocarbyl group, with Q having up to 40 carbon atoms (optionally, but not more than one occurrence of Q being 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 pentafluoroaryl group or a perfluoronaphthalene-2-yl group. Suitable A d Examples of - include the diboron compounds disclosed in US Pat. No. 5,447,895, which is incorporated herein by reference in its entirety.

[0133] When Z is an activating cation (LH), it may be a Bronsted acid capable of donating a proton to a transition metal catalyst precursor to generate a transition metal cation, including ammonium compounds, oxonium compounds, phosphonium compounds, sulfonium compounds, and mixtures thereof, such as ammonium compounds derived 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, ammonium compounds derived from methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, dioctadecylmethylamine, phosphonium compounds derived from triethylphosphine, triphenylphosphine, diphenylphosphine, oxonium compounds derived from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, and sulfonium compounds derived from thioethers such as sulfonium diethylthioether, tetrahydrothiophene, and mixtures thereof.

[0134] In particularly useful embodiments of the present invention, the activator is soluble in a non-aromatic hydrocarbon solvent, such as an aliphatic solvent.

[0135] In one or more embodiments, a 20% by weight mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear homogeneous solution at 25° C., and preferably, a 30% by weight mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear homogeneous solution at 25° C.

[0136] In an embodiment of the invention, the activators described herein have a solubility in methylcyclohexane at 25° C. (stirring for 2 hours) of greater than 10 mM (or greater than 20 mM, or greater than 50 mM).

[0137] In an embodiment of the invention, the activators described herein have a solubility in isohexane at 25° C. (stirring for 2 hours) of greater than 1 mM (or greater than 10 mM, or greater than 20 mM).

[0138] In an embodiment of the invention, the activators described herein have a solubility in methylcyclohexane at 25° C. (stirring for 2 hours) of greater than 10 mM (or greater than 20 mM, or greater than 50 mM) and a solubility in isohexane at 25° C. (stirring for 2 hours) of greater than 1 mM (or 10 mM or more, or 20 mM or more).

[0139] In a preferred embodiment, the activator is a non-aromatic hydrocarbon soluble activator compound.

[0140] Non-aromatic hydrocarbon soluble activator compounds useful herein include compounds represented by formula (V): TIFF0007629985000044.tif15110 [In 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 (preferably, d is 1, 2, or 3; k is 3; and n is 4, 5, or 6); R 1’ , R 2’ , and R 3’ is a C1-C substituted or unsubstituted alkyl group, optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups; 50 is a hydrocarbyl group; Here, 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 (e.g., B or Al); Each Q is independently a hydride, a bridged or unbridged dialkylamide, a halide, an alkoxide, an aryloxide, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, or a halo-substituted hydrocarbyl group.

[0141] Non-aromatic hydrocarbon soluble activator compounds useful herein include compounds represented by formula (VI): TIFF0007629985000045.tif16149 [wherein E is nitrogen or phosphorus; R 1’ is a methyl group; R 2’ and R 3’ is a C4-C alkyl group which may be independently substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups. 50 is a hydrocarbyl group, where R 2’ and R 3’ together contain 14 or more carbon atoms; B is boron; R 4’ , R 5’ , R 6’ and R 7’ are independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halo-substituted hydrocarbyl radical.

[0142] Non-aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (VII) or formula (VIII): TIFF0007629985000046.tif26143 and TIFF0007629985000047.tif31130 [In formula: N is nitrogen, R 2’ and R 3’ is a C6-C alkyl group which may be independently substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups; 40 is a hydrocarbyl group, R2’ and R 3’ (when present) together contain 14 or more carbon atoms; R 8’ , R 9’ and R 10’ are independent, C4~C 30 Hydrocarbyl or substituted C4-C 30 is a hydrocarbyl group; B is boron; R 4’ , R 5’ , R 6’ and R 7’ are independently a hydride, a bridged or unbridged dialkylamide, a halide, an alkoxide, an aryloxide, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, or a halo-substituted hydrocarbyl group.

[0143] Optionally, in any of formulas (V), (VI), (VII), or (VIII) herein, R 4’ , R 5’ , R 6’ and R 7’ is pentafluorophenyl.

[0144] Optionally, the compound represented by formula (V), (VI), (VII), or (VIII)R 4’ In any of the above, R 4’ , R 5’ , R 6’ and R 7’ is pentafluoronaphthalene-2-yl.

[0145] Optionally, in the embodiment of formula (VIII) herein, R 8’ and R 10’ is a hydrogen atom, 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.

[0146] Optionally, in the embodiment of formula (VIII) herein, R9’ is a C8-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.

[0147] Optionally, in embodiments of formula (VII) or (VIII) herein, R 2’ and R 3’ is independently 12 ~C 22 It is a hydrocarbyl group.

[0148] Optionally, R 1’ , R 2’ and R 3’ together contain 15 or more carbon atoms (e.g., 18 or more carbon atoms, 20 or more carbon atoms, 22 or more carbon atoms, 25 or more carbon atoms, 30 or more carbon atoms, 35 or more carbon atoms, 38 or more carbon atoms, 40 or more carbon atoms, 15 to 100 carbon atoms, 25 to 75 carbon atoms).

[0149] Optionally, R 2’ and R 3’ together contain 15 or more carbon atoms (e.g., 18 or more carbon atoms, 20 or more carbon atoms, 22 or more carbon atoms, 25 or more carbon atoms, 30 or more carbon atoms, 35 or more carbon atoms, 38 or more carbon atoms, 40 or more carbon atoms, 15 to 100 carbon atoms, 25 to 75 carbon atoms).

[0150] Optionally, R 8’ , R 9’ and R 10’ together contain 15 or more carbon atoms (e.g., 18 or more carbon atoms, 20 or more carbon atoms, 22 or more carbon atoms, 25 or more carbon atoms, 30 or more carbon atoms, 35 or more carbon atoms, 38 or more carbon atoms, 40 or more carbon atoms, 15 to 100 carbon atoms, 25 to 75 carbon atoms).

[0151] Optionally, when Q is a fluorophenyl group, R 2’ is C1~C40 Not a straight chain alkyl group (or R 2’ is optionally substituted C1-C 40 (not a straight chain alkyl group).

[0152] Optionally, R 4’ , R 5’ , R 6’ and R 7’ are each an aryl group (e.g., phenyl or naphthalene-2-yl), 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 (eg, perfluorophenyl or perfluoronaphthalen-2-yl).

[0153] Optionally, Q is each an aryl group (e.g., phenyl or naphthalene-2-yl) and at least one Q is substituted with at least one fluorine atom, preferably Q is each a perfluoroaryl group (e.g., perfluorophenyl or perfluoronaphthalene-2-yl).

[0154] Optionally, R 1’ is a methyl group; R 2’ is C6~C 50 is an aryl group; R 3’ are independent, C1~C 40 Straight chain alkyl or C5-C 50 -aryl group.

[0155] Optionally, R 2’ and R 3’ are each independently unsubstituted or a halide, C35 Alkyl, C5~ C15 Aryl, C6-C 35 Aryl alkyl, C6~ C35is substituted with at least one of alkylaryl, R 2’ and R 3’ contains 20 or more carbon atoms.

[0156] Optionally, Q is independently a hydride, a bridged or unbridged dialkylamide, a halide, an alkoxide, an aryloxide, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, or a halo-substituted hydrocarbyl radical, provided that when Q is a fluorophenyl group, R 2’ is C1-C 40 It is not a straight chain alkyl group, and preferably R 2’ is not an optionally substituted C1-C40 linear alkyl group (or, if Q is a substituted phenyl group, R 2’ is C1-C 40 It is not a straight chain alkyl group, and preferably R 2’ is not an optionally substituted C1-C40 straight chain alkyl group). Optionally, 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 C1-C 40 Hydrocarbyl groups (e.g., C6-C 40 Aryl or linear alkyl group, C 12 ~C 30 Aryl or linear alkyl group, C 10 ~C 20 aryl or straight chain alkyl groups), optionally substituted alkoxy groups, or optionally substituted silyl groups. Optionally, Q is a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, more preferably Q is a fluorinated aryl group (e.g., phenyl or naphthalene-2-yl, etc.), and most preferably Q is a perfluoroaryl group (e.g., phenyl or naphthalene-2-yl). Suitable [Mt k+ Q n ] dExamples of - also 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.

[0157] In some embodiments of the present invention, R 1’ is not methyl, but R 2’ is C 18 R, not alkyl 3’ is C 18 Not alkyl, or R 1’ is not methyl, but R 2’ is C 18 R, not alkyl 3’ is C 18 is not alkyl, at least one Q is not substituted phenyl, and optionally all Q are not substituted phenyl.

[0158] Useful cationic moieties in formula (III) and formulas (V)-(VIII) include those represented by the following formula: TIFF0007629985000048.tif179164

[0159] Useful cationic moieties in formula (III) and formulas (V)-(VIII) include those represented by the following formula: The anion component of the activator described herein has the formula [Mt k+ Q n ] d-, wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4), (preferably k is; 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 radicals, with Q having up to 20 carbon atoms, provided that in not more than one occurrence Q is a halide. Preferably, Q is a fluorinated hydrocarbyl group, each of which may have 1 to 20 carbon atoms, more preferably Q is a fluorinated aryl group, and most preferably Q is a perfluoroaryl group. Preferably, at least one Q is not a substituted phenyl, such as perfluorophenyl, and preferably all of Q are not substituted phenyl, such as perfluorophenyl.

[0160] In one embodiment, the borate activator comprises tetrakis(heptafluoronaphth-2-yl)borate.

[0161] In one embodiment, the borate activator comprises tetrakis(pentafluorophenyl)borate.

[0162] Anions for use in the non-coordinating anion activators described herein include those represented by Formula 7: TIFF0007629985000050.tif88143 [In formula: M * is a group 13 atom, preferably B or Al, preferably B; R 11 are each independently a halide, preferably a fluoride; R 12 are each independently a halide, C6 to C 20Substituted aromatic hydrocarbyl groups, or groups 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; R 13 are halides, C6-C 20 Substituted aromatic hydrocarbyl groups, or groups 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; Here, R 12 and R 13 may form one or more saturated or unsaturated, substituted or unsubstituted rings, preferably R 12 and R 13 forms a perfluorinated phenyl ring. Preferably, the anion has a molecular weight greater than 700 g / mol, and preferably M * At least three substituents on the atom each have a molecular volume greater than 180 cubic Å.

[0163] "Molecular volume" is used herein as an approximation of the spatial steric volume of an activator molecule in solution. When comparing substituents with different molecular volumes, the substituent with the smaller molecular volume is considered to be "less bulky" compared to the substituent with the larger molecular volume. Conversely, the substituent with the larger molecular volume can be considered to be "more bulky" than the substituent with the smaller molecular volume.

[0164] Molecular volume can be calculated as described 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(11), Nov. 1994, pp. 962-964. Molecular volume (MV) in cubic angstroms is calculated using the formula: MV = 8.3V s It is calculated using, where V s is the scaled volume. V s is the sum of the relative volumes of the constituent atoms and is calculated from the molecular formula of the substituents using Table A of relative volumes below. s decreases by 7.5% for each fused ring. The calculated total MV of the anion is the sum of the MVs per substituent. For example, the MV of perfluorophenyl is 183 Å. 3 and the calculated total MV of tetrakis(perfluorophenyl)borate is 183 Å. 3 4 times, or 732 Å 3 It is. TIFF0007629985000051.tif51111 TIFF0007629985000052.tif197164

[0165] The activator is, for example, [M2HTH] +[NCA]- can be added to the polymerization in the form of an ion pair using di(hydrogenated tallow)methylamine ("M2HTH") cation, which 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 can be reacted with a neutral NCA precursor, such as B(C6F5)3, to abstract an anionic group from the complex to form an activated species. Useful activators include di(hydrogenated tallow)methylammonium [tetrakis(pentafluorophenyl)borate] (i.e. [M2HTH]B(C6F5)4) and di(octadecyl)tolylammonium [tetrakis(pentafluorophenyl)borate] (i.e. [DOdTH]B(C6F5)4).

[0166] Activator compounds particularly useful in the present invention include one or more of the following compounds: 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]

[0167] Additional useful activators and synthetic non-aromatic hydrocarbon soluble activators are described in USSN 16 / 394,166, filed April 25, 2019, USSN 16 / 394,186, filed April 25, 2019, and USSN 16 / 394,197, filed April 25, 2019, which are incorporated herein by reference.

[0168] Similarly, particularly useful activators include dimethylanilinium tetrakis(pentafluorophenyl)borate and dimethylanilinium tetrakis(heptafluoronaphthalene-2-yl)borate. For a more detailed description of useful activators, see WO2004 / 026921, page 72, paragraph

[0119] to page 81, paragraph

[0151] . A list of further useful activators that can be used in the practice of the present invention can be found in WO2004 / 046214, page 72, paragraph

[0177] to page 74, paragraph

[0178] .

[0169] For a description of useful activators, see US Pat. No. 8,658,556 and US Pat. No. 6,211,105.

[0170] Preferred activators for use herein include N-methyl-4-nonadecyl-N-octadecylbenzeneaminium tetrakis(pentafluorophenyl)borate, N-methyl-4-nonadecyl-N-octadecylbenzeneaminium tetrakis(perfluoronaphthalen-2-yl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthalen-2-yl)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(perfluoronaphthalen-2-yl)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; tetrakis(pentafluorophenyl)borate, including 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

[0171] 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(perfluoronaphthalen-2-yl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

[0172] In other embodiments, the activator is one or more of trialkylammonium pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(perfluoronaphthalene-2-yl)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(perfluoronaphthalene-2-yl)borate, N, including N-dialkylanilinium tetrakis(perfluoronaphthalen-2-yl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, where alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl.

[0173] Typical activator to catalyst ratios, including all NCA activator to catalyst ratios, are about 1:1 molar ratio. Alternative preferred ranges include 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to 500:1, or 1:1 to 1000:1. Particularly useful ranges are 0.5:1 to 10:1, preferably 1:1 to 5:1.

[0174] It is also within the scope of the present disclosure that the catalyst compound can be combined with a combination of an alumoxane and an NCA (see, for example, US 5,153,157; ​​US 5,453,410; EP 0573120 B1; WO 1994 / 007928; and WO 1995 / 014044, which describe the use of an alumoxane in combination with an ionizing activator), the disclosures of which are incorporated herein by reference in their entireties.

[0175] Optional scavengers, coactivators, and chain transfer agents In addition to the activator compound, a scavenger or coactivator can be used. Scavenger is a compound that is typically added to remove impurities and promote polymerization. Some scavengers can also function as activators and are also called coactivators. Coactivators that are not scavengers can also be used in combination with activators to form active catalysts. In some embodiments, the coactivator can be premixed with the transition metal compound to form an alkylated transition metal compound.

[0176] Coactivators include alumoxanes such as methylalumoxane, modified alumoxanes such as modified methylalumoxane, and alkylaluminums such as trimethylaluminum, triisobutylaluminum, triethylaluminum, and triisopropylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, or tri-n-dodecylaluminum. Coactivators are typically used in combination with Lewis acid activators and ionic activators when the precatalyst is not a dihydrocarbyl or dihydride complex. Coactivators are also often used as scavengers to inactivate impurities in the feed or reactor.

[0177] Aluminum alkyl or organoaluminum compounds which can be used as scavengers or coactivators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and dialkylzincs, such as diethylzinc.

[0178] Chain transfer agents can be used in the compositions and / or processes described herein. Useful chain transfer agents are typically hydrogen, alkylalumoxanes, of the formula AlR3, ZnR2, where each R is independently a C1-C8 aliphatic radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or isomers thereof, or combinations thereof, such as diethylzinc, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof.

[0179] 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 complete reaction mixture is removed from the polymerization reaction vessel at the end of the polymerization reaction. In contrast, in a continuous polymerization process, one or more reactants are continuously introduced into the reaction vessel and a solution containing the polymer product is simultaneously or nearly simultaneously removed. Solution polymerization refers to a polymerization process in which the polymer produced is soluble in a liquid polymerization medium, such as an inert solvent or monomer or a blend thereof. Solution polymerizations are typically homogeneous. Homogeneous polymerizations are those in which the polymer product is dissolved in the polymerization medium. Such systems are described in J. Vladimir Oliveira, et al., Ind. Eng. Chem. Res., v.29, 2000, pg. 4627.

[0180] In a typical solution process, catalyst components, solvent, monomer, and hydrogen (if used) are fed under pressure to one or more reactors. Temperature control in the reactor is generally obtained by a balance between the heat of polymerization and reactor cooling by reactor jacket or cooling coils to cool the reactor contents, autocooling, pre-cooled feed, reactors cooled by liquid media (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 before being fed to the first reactor or dissolved in the reaction mixture. Solvents and monomers are generally purified to remove potential catalyst poisons before entering the reactors. The feedstock can be heated or cooled before being fed to the first reactor. Additional monomer and solvent can be added to the second reactor, which can be heated or cooled. The catalyst / activator can be fed to the first reactor or split between the two reactors. In solution polymerization, the polymer produced melts and remains dissolved in the solvent under reactor conditions, forming a polymer solution (also called the effluent).

[0181] The solution polymerization process of the present invention employs a stirred tank reactor system comprising one or more stirred polymerization reactors. In general, the reactors should be operated under conditions that achieve thorough mixing of the reactants. In a multiple reactor system, the first polymerization reactor preferably operates at a lower temperature. The residence time of each reactor depends on the design and capacity of the reactor. The catalyst / activator can be fed only to the first reactor or split between the two reactors. In another embodiment, loop reactors and plug flow reactors can be used in the present invention.

[0182] The polymer solution is then discharged from the reactor as an effluent stream and the polymerization reaction is typically quenched with a coordinating polar compound to prevent further polymerization. Upon exiting the reactor system, the polymer solution passes through a heat exchanger system and is sent to a devolatilization system and a polymer finishing process. The dilute phase and volatiles removed downstream of the liquid phase separation can be recycled as part of the polymerization feed.

[0183] The polymer can be recovered from the reactor effluent or mixed effluent by separating the polymer from other components of the effluent. Conventional separation means can be used. 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 the polymer can be recovered by thermal and vacuum stripping 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 the use of a lower critical solution temperature (LCST) followed by devolatilization, are also contemplated.

[0184] 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 include at least one hydrocarbon solvent. Examples include straight 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-C6 10 alkanes, chlorobenzene, and mixtures thereof; aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene, ethylbenzene, xylene, and mixtures thereof. Mixtures of any of the aforementioned hydrocarbon solvents can also be used. Suitable solvents include 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 aromatics are present in the solvent at less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0% by weight, based on the weight of the solvent.

[0185] The polymerization methods and solution polymerization conditions disclosed herein can be used to polymerize any olefin feed. Suitable olefin feeds include any C2-C olefin that contains at least one cyclic or substituted cyclic olefin, optionally containing heteroatom substitution, and that may be linear or branched, cyclic or acyclic, and terminal or non-terminal. 40 In a more specific embodiment, the olefin feed may comprise an alkene. 20 Alkenes, particularly linear alpha olefins such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, or 1-dodecene, in combination with cyclic olefins such as, but not limited to, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclononene, cyclodecene, and 2-norbornene. Other suitable olefin monomers may include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or non-conjugated dienes, polyenes, and vinyl monomers. Non-limiting olefin monomers may also include norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl-substituted styrenes, ethylidene norbornene, and dicyclopentadiene. A single olefin monomer or any mixture of olefin monomers may be polymerized according to the disclosure herein.

[0186] In one embodiment, the cyclic olefin is a substituted or unsubstituted C-C 20 The cyclic olefin is selected from cycloolefins, preferably containing at least one C4-C8 cyclic structure. In one embodiment, the cyclic olefin is selected from cyclopentene or C1-C 10 Alkyl-substituted cyclopentene, preferably with the substitution being sp 2 Not on a carbon atom.

[0187] In some embodiments, the cyclic olefin is a substituted or unsubstituted C-C olefin, including a bicyclic olefin, which is a cyclic olefin containing a bridged hydrocarbon group that forms multiple rings throughout the structure. 20In some embodiments, the cyclic olefin is norbornene or a C1-C 10 Alkyl-substituted norbornenes, where the substitution is preferably sp 2 Not on a carbon atom.

[0188] Preferred cyclic olefins include cyclopentene and 2-norbornene.

[0189] Preferred diolefin monomers useful in the present invention are 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. 30 Examples 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, 1,13-tetradecadiene) and certain polycyclic alicyclic fused and bridged ring dienes (e.g., tetrahydroindene, divinylbenzene, norbornadiene, methyltetrahydroindene; dicyclopentadiene, bicyclo-(2.2.1)-hepta-2,5-diene; and alkenyl-, alkylidene-, cycloalkenyl-, and cycloalkylenenorbornenes, 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.

[0190] Separately, dienes are not present in the copolymers produced herein.

[0191] Monomer combinations useful herein include ethylene and a cyclic olefin, propylene with a cyclic olefin; ethylene and propylene with a cyclic olefin.

[0192] Preferred polymerizations can be carried out 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 times (residence times) range up to about 300 minutes, particularly from about 5 minutes to about 250 minutes, or from about 10 minutes to about 120 minutes.

[0193] Small amounts of hydrogen, e.g., 1 to 5,000 parts by weight per million (ppm) based on the total solution fed to the reactor, can be added to one or more of the feed streams of the reactor system to improve control of melt index and / or molecular weight distribution. In some embodiments, hydrogen can be included in the reaction vessel in a solution polymerization process. According to various embodiments, the concentration of hydrogen gas in the reaction mixture can 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.

[0194] In a preferred embodiment, the polymerization is: 1) carried out at a temperature of 100°C or higher (preferably 120°C or higher, preferably 140°C or higher); 2) carried out at a pressure of atmospheric pressure 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) carried out in an aliphatic hydrocarbon solvent (e.g., 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; preferably, aromatics (such as toluene) are preferably present in the solvent, less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0.1% by weight, preferably 0% by weight, based on the weight of the solvent); 4) if used, ethylene is present in the polymerization reactor at a concentration of 6 moles / liter or less). 5) the polymerization preferably occurs in one reaction zone. 6) The productivity of the catalyst compound is 50,000 kg of polymer per kg of catalyst or more (preferably 100,000 kg of polymer per kg of catalyst or more, 150,000 kg of polymer per kg of catalyst or more, 200,000 kg of polymer per kg of catalyst or more, etc.).

[0195] In more specific embodiments, the one or more olefin monomers present in the reaction mixture disclosed herein include at least one cyclic olefin, optionally ethylene and / or propylene, and optionally one or more alpha olefins, such as butene, hexene, and octene. In even more specific embodiments, the one or more olefin monomers may include a cyclic olefin and ethylene and / or propylene. In even more specific embodiments, the one or more olefin monomers may include ethylene and one or more cyclic olefins, such as cyclopentene and / or 2-norbornene. In even more specific embodiments, the one or more olefin monomers may include propylene and one or more cyclic olefins, such as cyclopentene and / or 2-norbornene.

[0196] The molecular weight distribution of polymers produced by solution processes can be advantageously controlled by producing the polymer in multiple reactors that are controlled 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. Process conditions typically used include the type and concentration of catalyst in each reactor, and the residence time of the reactor. In one embodiment, the polymerization process includes at least two reactors connected in either a series or parallel configuration.

[0197] In an embodiment herein, the present invention relates to a polymerization process in which a monomer, and optionally a comonomer, is contacted with a catalyst system comprising an activator and at least one catalyst compound, as described above. The catalyst compound and the activator can be combined in any order, and are typically combined before contacting with the monomer. In one embodiment, the catalyst and the activator can be fed to the polymerization reactor in the form of a dry powder or a slurry, without the need to prepare a homogeneous catalyst solution by dissolving the catalyst in a support solvent.

[0198] 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 used. Such processes can be run in batch, semi-batch, or continuous mode. Homogeneous polymerization processes are preferred. (Homogeneous polymerization processes are preferably those in which at least 90% by weight of the product is dissolved in the reaction medium.) In a useful embodiment, the process is a solution process.

[0199] A "reaction zone" (also referred to as 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 to be a separate polymerization zone. In multi-stage polymerizations, both in batch and continuous reactors, each polymerization stage is considered to be 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.

[0200] Optionally, one or more scavengers, hydrogen, aluminum alkyls, silanes, or chain transfer agents (e.g., alkylalumoxanes, formula AlR3 or ZnR2, where 、 Each R is independently a C1 to C8 aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyloctyl or an isomer thereof, or other additives such as diethylzinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof may be used.

[0201] The process of the invention can be used to prepare homopolymers of cyclic olefins, and copolymers of ethylene and cyclic olefins, and propylene and cyclic olefins, having a molecular weight of, for example, about 0.900 to 0.970 g / cm 3 , especially 0.915~0.965g / cm 3 The polymer may include an alpha-olefin to produce a polymer having a density of about 0.1 to 200 dg / min, particularly about 0.5 to 120 dg / min, as measured by the method of ASTM D-1238. The polymer may be produced with narrow or broad molecular weight distribution. For example, the polymer may have an MWD in the range of about 1.5 to 10, particularly about 2 to 7. The process of the present invention is believed to be particularly useful for producing polymers with narrow molecular distribution.

[0202] The method of the present invention is, for example, about 0.84 to 0.970 g / cm 3 , especially 0.88~0.965g / cm3 The copolymers can be used to prepare cyclic olefin copolymers of ethylene and / or propylene, and copolymers of cyclic olefins with ethylene and / or propylene and additional alpha-olefins, having a density of 0.1 or less, in the range of about 0.5 to 120 dg / min, as measured by the method of ASTM D-1238.

[0203] Polyolefin Products The present invention also relates to compositions produced by the methods described herein. The methods described herein can be used to make polymers and copolymers of cyclic olefins. Polymers that can be prepared include homopolymers of cyclic monomers, and copolymers of cyclic olefins and C2-C 20 The polymers that can be prepared herein include copolymers of cyclic olefins and ethylene with any C4-C 20 Copolymers with olefins; cyclic olefins and propylene with any C4-C 20 Copolymers with olefins; cyclic olefins, ethylene, and propylene with any C4-C 20 Includes copolymers with olefins.

[0204] Preferably, dienes are absent from the polymer compositions produced herein.

[0205] In preferred embodiments, the polymer obtained by the methods described herein may comprise 0.1 mol% or more cyclic olefin monomer, or 0.2 mol% or more cyclic olefin monomer, or 0.5 mol% or more cyclic olefin monomer, or 1.0 mol% or more cyclic olefin monomer, or 2.0 mol% or more cyclic olefin monomer, or 3.0 mol% or more cyclic olefin monomer, or 5 mol% or more cyclic olefin monomer, or 10 mol% or more cyclic olefin monomer, or 15 mol% or more cyclic olefin monomer, or 20 mol% or more cyclic olefin monomer, or 30 mol% or more cyclic olefin monomer, or 40 mol% or more cyclic olefin monomer, or 50 mol% or more cyclic olefin monomer, or 60 mol% or more cyclic olefin monomer, or 70 mol% or more cyclic olefin monomer, or 80 mol% or more cyclic olefin monomer, or 90 mol% or more cyclic olefin monomer, or 100 mol% cyclic olefin.

[0206] Molecular weights (weight average molecular weight (Mw), number average molecular weight (Mn), z-average molecular weight (Mz)) and molecular weight distributions (PDI=MWD=Mw / Mn), also called polymer polydispersity (PDI), are measured by gel permeation chromatography against linear polystyrene standards as described below.

[0207] In a preferred embodiment, the process described herein produces a copolymer comprising ethylene and a cyclic olefin, the cyclic olefin being a C5-C 20Cyclic olefins, preferably cyclopentene and / or 2-norbornene, the copolymers having Mn of 3,000 g / mol or more, alternatively 5,000 g / mol or more, alternatively 10,000 g / mol or more, alternatively 50,000 g / mol or more, alternatively 75,000 g / mol or more, alternatively 100,000 g / mol or more, alternatively 200,000 g / mol or more, Mw / Mn between 1.0-10, alternatively 1.5-5.0, alternatively 1.8-3.0, and the cyclic olefin content may be 0.05-99 mol%, alternatively 0.1-50 mol%, alternatively 0.2-40 mol%, alternatively 0.3-30 mol%, alternatively 0.5-20 mol%. The cyclic olefin may be incorporated through 1,2 bonds (across the double bond) or 1,3 bonds (by rearrangement), or a combination of both.

[0208] In a preferred embodiment, the process described herein comprises the step of producing ethylene, a cyclic olefin, and one or more additional C-C 12 It produces copolymers containing alpha olefins and cyclic olefins ranging from C5 to C 20 Cyclic olefins, preferably cyclopentene and / or 2-norbornene, the copolymers have Mn of 3,000 g / mol or more, alternatively 5,000 g / mol or more, alternatively 10,000 g / mol or more, alternatively 50,000 g / mol or more, alternatively 75,000 g / mol or more, alternatively 100,000 g / mol or more, alternatively 200,000 g / mol or more, and Mw / Mn between 1.0-10, alternatively 1.5-5.0, alternatively 1.8-3.0, and the cyclic olefin content can be 0.05-99 mol%, alternatively 0.1-50 mol%, alternatively 0.2-40 mol%, alternatively 0.3-30 mol%, alternatively 0.5-20 mol%. The cyclic olefins can be incorporated by 1,2 bonds (across the double backbone) or 1,3 bonds (by rearrangement), or a combination of both.

[0209] In some embodiments, the ethylene cyclopentene copolymers have a Mn of from about 2,000 to 2,000,000 g / mol, alternatively from about 5,000 to 1,500,000 g / mol, alternatively from about 10,000 to 1,000,000 g / mol, alternatively from about 50,000 to 800,000, alternatively from about 100,000 to 500,000 g / mol.

[0210] In some embodiments, the ethylene cyclopentene copolymers have a Mw from about 5,000 to 4,000,000 g / mol, alternatively from about 10,000 to 3,000,000 g / mol, alternatively from about 20,000 to 2,000,000 g / mol, alternatively from about 100,000 to 1,500,000 g / mol, alternatively from about 200,000 to 1,000,000 g / mol.

[0211] In some embodiments, the ethylene cyclopentene copolymer has a Mz from about 100,000 to 10,000,000 g / mol, alternatively from about 200,000 to 8,000,000 g / mol, alternatively from about 300,000 to 6,000,000 g / mol, alternatively from about 400,000 to 3,000,000 g / mol, or alternatively from about 500,000 to 2,000,000 g / mol.

[0212] In some embodiments, the ethylene cyclopentene copolymers have a Mw / Mn from about 1.0 to 10, alternatively from about 1.5 to 5.0, alternatively from about 1.8 and 3.0, alternatively from about 2.0 to 4.0.

[0213] In some embodiments, the ethylene cyclopentene copolymer has a cyclopentene content of about 0.05-99 mol%, alternatively about 0.1-50 mol%, alternatively about 0.2-40 mol%, alternatively about 0.3-30 mol%, alternatively about 0.5 mol%-20 mol%. In some embodiments, the ethylene cyclopentene copolymer has a cyclopentene content less than 50 mol%, alternatively less than 45 mol%, alternatively less than 40 mol%.

[0214] Cyclopentene monomers may be incorporated through 1,2 bonds (across the double backbone) or 1,3 bonds (by rearrangement), or a combination of both. In some embodiments, the ethylene cyclopentene copolymer has predominantly 1,2 bonds. Preferably, the 1,2 bonds are 90% or more, alternatively 95% or more, alternatively 98% or more, alternatively 99% or more of the total cyclopentene incorporated into the ethylene backbone. In some embodiments, the ethylene cyclopentene copolymer has 5% or less, alternatively 3% or less, alternatively 2% or less, alternatively 1% or less, alternatively 0.5% or less of 1,3 bonds. In some embodiments, the triad sequence distribution (ccc, ece, and cce) has a percentage of ccc of 12% or more, alternatively 15% or more, alternatively 20% or more, alternatively 30% or more, indicating clustering of cyclopentene units. In some embodiments, the triad sequence distribution has a percentage of ece of 86% or less, alternatively 84% or less, alternatively 80% or less, alternatively 70% or less, alternatively 60% or less, or alternatively 50% or less, indicating isolated cyclopentene units.

[0215] In some embodiments of the invention, the ethylene cyclopentene copolymers have a cyclopentene content greater than 5 mole percent, 1,2-linkages greater than or equal to 90%, a ccc sequence distribution greater than or equal to 12%, and an ece sequence distribution less than or equal to 86%.

[0216] In some embodiments of the invention, the ethylene cyclopentene copolymers have a cyclopentene content of less than 50 mole percent, 1,2-linkages of 90% or more, a ccc sequence distribution of 12% or more, and an ece sequence distribution of 86% or less.

[0217] In a preferred embodiment, the ethylene cyclopentene copolymer is: a. Mn greater than 5,000 g / mol, alternatively greater than 10,000 g / mol, alternatively greater than 100,000 g / mol, alternatively greater than 150,000 g / mol; b. Mw greater than 10,000 g / mol, alternatively greater than 20,000 g / mol, alternatively greater than 200,000 g / mol, alternatively greater than 300,000 g / mol; c. Mw / Mn from about 1 to 10, alternatively from about 1.5 to 5.0, alternatively from about 1.8 to 3.0, alternatively from about 2.0 to 4.0; d. a cyclopentene content of 0.1 mol% or more and up to 50 mol% or less, or up to 45 mol% or less; e. Approximately 90% or more of the total cyclopentene units incorporated into the polymer are cyclopentene 1,2 bonds. has.

[0218] In some embodiments, the ethylene norbornene copolymer is from about 2,000 to 1,500,000 g / mol, alternatively from about 5,000 to 1,000,000 g / mol, alternatively from about 10,000 to 800,000 g / mol, alternatively from about 20,000 to 500,000, alternatively from about 30,000 to 300,000 g / mol.

[0219] In some embodiments, the ethylene norbornene copolymer has a Mw from about 5,000 to 3,000,000 g / mol, alternatively from about 10,000 to 2,000,000 g / mol, alternatively from about 20,000 to 1,000,000 g / mol, alternatively from about 50,000 to 800,000 g / mol, alternatively from about 100,000 to 500,000 g / mol.

[0220] In some embodiments, the ethylene norbornene copolymer has a Mz from about 10,000 to 3,000,000 g / mol, alternatively from about 20,000 to 2,000,000 g / mol, alternatively from about 50,000 to 1,000,000 g / mol, alternatively from about 100,000 to 800,000 g / mol, alternatively from about 200,000 to 500,000 g / mol.

[0221] In some embodiments, the ethylene norbornene copolymers have a Mw / Mn from about 1.0 to 10, alternatively from about 1.2 to 5.0, alternatively from about 1.5 to 4.0, alternatively from about 2.0 to 3.0.

[0222] In some embodiments, the ethylene norbornene copolymer has a norbornene content of about 0.1-80 mol%, alternatively about 1-70 mol%, alternatively about 2-60 mol%, alternatively about 2-50 mol%, alternatively about 50 mol%, alternatively about 3-50 mol%, alternatively about 3-45 mol%, alternatively about 4-40 mol%.

[0223] In some embodiments, the ethylene norbornene copolymer has a norbornene content of 10 mol% or more, alternatively 20 mol% or more, alternatively 30 mol% or more, alternatively 40 mol% or more, up to an upper limit of 90 mol% or less, alternatively 80 mol% or less.

[0224] In some embodiments, the norbornene units in the polymer may be independent, alternating, or block. Preferably, the norbornene units are 10-80% independent, 10-80% alternating, and 1-50% block, with the sum of independent, alternating, and block being 100%. Alternatively, the norbornene units may be 20-80% independent, 20-80% alternating, and 1-45% block.

[0225] In some embodiments of the invention, the ethylene norbornene copolymer has a norbornene content of 20 mol% or more, alternatively 40 mol% or more, alternatively 45 mol% or more, alternatively 50 mol% or more, alternatively 60 mol% or more, alternatively 70 mol% or more.

[0226] In some embodiments, the ethylene norbornene copolymer has a norbornene content of from about 10 mol % to about 90 mol %, alternatively from about 15 mol % to about 80 mol %, alternatively from about 20 mol % to about 70 mol %, alternatively from about 20 mol % to about 60 mol %.

[0227] In some embodiments, the ethylene norbornene copolymer has a Tg (°C) of 30°C or greater, alternatively 40°C or greater, alternatively 50°C or greater, alternatively 60°C or greater, up to 200°C.

[0228] In a preferred embodiment, the ethylene norbornene copolymer is: a. Mn greater than 50,000 g / mol, alternatively greater than 100,000 g / mol, alternatively greater than 150,000 g / mol, alternatively greater than 200,000 g / mol; b. Mw greater than 100,000 g / mol, or greater than 200,000 g / mol, or greater than 300,000 g / mol, or greater than 400,000 g / mol; c. Mw / Mn of about 1.2-5.0, alternatively about 1.5-4.0, alternatively about 2.0-3.0; d. a norbornene content of 20 mol% or more and up to 80 mol% or less; e. Norbornene units that are 10-80% independent, 10-80% alternating, and 1-50% blocked, with the sum of independent, alternating, and blocked being 100%; has.

[0229] In a preferred embodiment, the process described herein produces a copolymer comprising propylene and a cyclic olefin, where the cyclic olefin is a C5-C 20 The cyclic olefin is preferably cyclopentene and / or 2-norbornene, and the copolymer has a Mn of 3,000 g / mol or more, alternatively 5,000 g / mol or more, alternatively 10,000 g / mol or more, alternatively 50,000 g / mol or more, alternatively 75,000 g / mol or more, alternatively 100,000 g / mol or more, has a Mw / Mn of 1.0-10, alternatively 1.5-5.0, alternatively 1.8-3.0, and has a cyclic olefin content of 0.05-99 mol%, alternatively 0.1-50 mol%, alternatively 0.2-40 mol%, alternatively 0.3-30 mol%, alternatively 0.5-20 mol%. The cyclopentene may be incorporated through 1,2 or 1,3 bonds or a combination of both.

[0230] In a preferred embodiment, the process described herein comprises the step of producing a propylene-based cyclic olefin, optionally with one or more additional C-C 12 The cyclic olefin further comprises an alpha olefin, and the cyclic olefin is a C5-C 20The cyclic olefin is preferably cyclopentene and / or 2-norbornene, and the copolymer has a Mn of 3,000 g / mol or more, alternatively 5,000 g / mol or more, alternatively 10,000 g / mol or more, alternatively 50,000 g / mol or more, alternatively 75,000 g / mol or more, alternatively 100,000 g / mol or more, and a Mw / Mn of 1.0-10, alternatively 1.5-5.0, alternatively 1.8-3.0, and a cyclic olefin content of 0.05-99 mol%, alternatively 0.1-50 mol%, alternatively 0.2-40 mol%, alternatively 0.3-30 mol%, alternatively 0.5-20 mol%. The cyclopentene may be incorporated through 1,2 or 1,3 bonds or a combination of both.

[0231] In some embodiments, the propylene cyclopentene copolymer has a Mn of about 1,000-1,000,000 g / mol, alternatively about 2,000-800,000 g / mol, alternatively about 3,000-500,000 g / mol, alternatively about 4,000-100,000, alternatively about 5,000-50,000 g / mol.

[0232] In some embodiments, the propylene cyclopentene copolymer has a Mw of about 2,000-2,000,000 g / mol, alternatively about 4,000-1,500,000 g / mol, alternatively about 5,000-2,000,000 g / mol, alternatively about 8,000-500,000 g / mol, or alternatively about 10,000-200,000 g / mol.

[0233] In some embodiments, the propylene cyclopentene copolymer has a Mz of about 5,000-4,000,000 g / mol, alternatively about 10,000-2,000,000 g / mol, alternatively about 20,000-1,000,000 g / mol, alternatively about 25,000-500,000 g / mol, or alternatively about 30,000-200,000 g / mol.

[0234] In some embodiments, the propylene cyclopentene copolymer has a Mw / Mn from about 1.0 to 10, alternatively from about 1.5 to 5.0, alternatively from about 1.8 to 3.0, alternatively from about 2.0 to 4.0.

[0235] In some embodiments, the propylene cyclopentene copolymer has a cyclopentene content of about 0.05-99 mol%, alternatively about 0.1-50 mol%, alternatively about 0.2-40 mol%, alternatively about 0.3-30 mol%, alternatively about 0.5-20 mol%, alternatively about 1.0 mol% to about 10 mol%. The cyclopentene monomers may be incorporated through 1,2 bonds (across the double bond) or 1,3 bonds (by rearrangement), or a combination of both. In some embodiments, the propylene cyclopentene copolymer has predominantly 1,2 bonds. Preferably, the 1,2 bonds are 90% or more, alternatively 95% or more, alternatively 98% or more, alternatively 99% or more of the total cyclopentene incorporated into the propylene backbone. In some embodiments, the propylene cyclopentene copolymer has 5% or less, alternatively 3% or less, alternatively 2% or less, alternatively 1% or less, alternatively 0.5% or less of 1,3 bonds.

[0236] In a preferred embodiment, the propylene cyclopentene copolymer is: a. Mn greater than 3,000 g / mol, alternatively greater than 5,000 g / mol, alternatively greater than 10,000 g / mol; b. Mw greater than 6,000 g / mol, or greater than 10,000 g / mol, or greater than 20,000 g / mol; c. Mw / Mn from about 1 to 10, alternatively from about 1.5 to 5.0, alternatively from about 1.8 to 3.0, alternatively from about 2.0 to 4.0; d. a cyclopentene content of 0.1 mol% or more and up to 50 mol% or less, or up to 45 mol% or less; e. greater than about 90% of the total cyclopentene units incorporated into the polymer are cyclopentene 1,2 bonds; has.

[0237] In some embodiments, the propylene norbornene copolymer has a Mn of about 1,000 to 1,000,000 g / mol, alternatively about 2,000 to 800,000 g / mol, alternatively about 3,000 to 500,000 g / mol, alternatively about 4,000 to 200,000, alternatively about 5,000 to 100,000 g / mol.

[0238] In some embodiments, the propylene norbornene copolymer has a Mw of about 2,000-2,000,000 g / mol, alternatively about 4,000-1,500,000 g / mol, alternatively about 5,000-1,000,000 g / mol, alternatively about 8,000-500,000 g / mol, or alternatively about 10,000-300,000 g / mol.

[0239] In some embodiments, the propylene norbornene copolymer has a Mz of about 4,000-3,000,000 g / mol, alternatively about 5,000-2,000,000 g / mol, alternatively about 6,000-1,500,000 g / mol, alternatively about 10,000-800,000 g / mol, alternatively about 10,000-500,000 g / mol.

[0240] In some embodiments, the propylene norbornene copolymers have a Mw / Mn of from about 1.0 to 10, alternatively from about 1.2 to 5.0, alternatively from about 1.5 and 4.0, alternatively from about 2.0 to 3.0.

[0241] In some embodiments, the propylene norbornene copolymer has a norbornene content of about 0.1-60 mol %, alternatively about 1-50 mol %, alternatively about 2-40 mol %, alternatively about 3-35 mol %, alternatively about 4-30 mol %.

[0242] In some embodiments, the propylene norbornene copolymer has a Tm (° C.) of about 90 to about 130° C. In other embodiments, the propylene norbornene copolymer is amorphous and does not exhibit polymer crystallinity.

[0243] In a preferred embodiment, the propylene norbornene copolymer is a. Mn greater than 3,000 g / mol, alternatively greater than 5,000 g / mol, alternatively greater than 10,000 g / mol; b. Mw greater than 6,000 g / mol, or greater than 10,000 g / mol, or greater than 20,000 g / mol; c. Mw / Mn of about 1.2-5.0, alternatively about 1.5-4.0, alternatively about 2.0-3.0; d. Norbornene content of 1 mol% or more and up to 50 mol% or less has.

[0244] In some embodiments, the polymer produced is a homopolymer of cyclopentene (polycyclopentene) having a Mn of about 100-5,000 g / mol, alternatively about 200-2,000 g / mol, alternatively about 250-1,200 g / mol, alternatively about 300-1,000 g / mol.

[0245] In some embodiments, the polymer produced is a homopolymer of cyclopentene having a Mw of about 200-10,000 g / mol, alternatively about 300-5,000 g / mol, alternatively about 350-2,000 g / mol, alternatively about 300-1,000 g / mol.

[0246] In some embodiments, the polymer produced is a homopolymer of cyclopentene having a Mz of about 400-20,000 g / mol, alternatively about 500-10,000 g / mol, alternatively about 600-5,000 g / mol, alternatively about 700-1,000 g / mol.

[0247] In some embodiments, the Mn of the polycyclopentene is less than 1000 g / mol, alternatively less than 800 g / mol, alternatively less than 600 g / mol, alternatively less than 500 g / mol, and the Mn is 200 g / mol or more, alternatively 250 g / mol or more, alternatively 300 g / mol or more.

[0248] In a preferred embodiment, the polymers produced herein have a unimodal or multimodal molecular weight distribution as determined by gel permeation chromatography (GPC). "Unimodal" means that the GPC chromatograph has one peak or inflection point. "Multimodal" means that the GPC chromatograph has at least two peaks or inflection points. An inflection point is a point where the sign of the second derivative of the curve changes (e.g., from negative to positive or from negative to positive).

[0249] blend In another embodiment, the polymer 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, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethyl methacrylate or other polymers polymerizable by high pressure free radical processes, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resins, ethylene propylene rubber (EPR), vulcanized EPR, EPDM, block copolymers, styrenic block copolymers, polyamides, polycarbonates, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetals, polyvinylidene fluoride, polyethylene glycol, and / or polyisobutylene.

[0250] In a preferred embodiment, the polymer produced herein is present in said blend at 10-99% by weight, preferably 20-95% by weight, even more preferably at least 30-90% by weight, even more preferably at least 40-90% by weight, even more preferably at least 50-90% by weight, even more preferably at least 60-90% by weight, and even more preferably at least 70-90% by weight, based on the weight of polymer in the blend.

[0251] The above blends can be made by mixing the polymer of the present invention with one or more polymers (mentioned above), by connecting reactors in series to make a reactor blend, or by using two or more catalysts to produce multiple polymer species in the same reactor. The polymers can be mixed together prior to entering the extruder or can be mixed in the extruder. Alternatively, the above blends can be made by mixing the polymer of the present invention with one or more polymers (mentioned above) and connecting reactors in parallel or series to make a reactor blend.

[0252] The blends can be formed using conventional equipment and methods, such as by dry blending the individual components followed by melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin screw extruder, which may include compounding extruders and side arm extruders used immediately downstream of the polymerization process, which may include blending resin powders or pellets in the hopper of a film extruder. Additionally, additives can be included in the blend, one or more components of the blend, and / or in products formed from the blend, such as films, as needed. Such additives are well known in the art and can include, for example: antioxidants (e.g., IRGANOX, available from BASF, TM 1010 or IRGANOX TM1076); phosphites (e.g., IRGAFOSTM 168 available from BASF); anti-blocking additives; tackifiers such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; antiblocking agents; release agents; antistatic agents; pigments; colorants; dyes; waxes; silicas; fillers; talc, and the like.

[0253] film In particular, any of the aforementioned polymers, such as the aforementioned polymers or blends thereof, can be used in a variety of end-use applications. Such applications include, for example, monolayer or multilayer blown, extruded, and / or shrunk films. These films can be formed by any number of well-known extrusion or coextrusion techniques, such as blown bubble film processing techniques, in which the composition is extruded in a molten state through an annular die and then expanded to form a tubular blown film before the uniaxially or biaxially oriented melt is cooled. It is then axially slit and unfolded to form a flat film. The film can subsequently be unstretched, uniaxially stretched, or biaxially stretched to the same or different degrees. One or more layers of the film can be oriented to the same or different degrees in the transverse and / or longitudinal directions. Uniaxial orientation can be obtained using typical cold or hot stretching methods. Biaxial orientation can be achieved using a tenter frame apparatus or a double bubble process, and can be achieved before or after the individual layers are brought together. For example, a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer, or polyethylene and polypropylene can be coextruded together into a film and then oriented. Similarly, oriented polypropylene can be laminated to oriented polyethylene, or oriented polyethylene can be coated onto polypropylene, and optionally the combination can be further oriented. Typically, the film is oriented in the machine direction (MD) by a ratio of up to 15, preferably 5-7, and in the transverse direction (TD) by a ratio of up to 15, preferably 7-9. In another embodiment, the film is oriented to the same extent in both the MD and TD directions.

[0254] The thickness of the film varies depending on the application. However, a film having a thickness of 1 to 50 μm is usually suitable. The thickness of the film for packaging is usually 10 to 50 μm. 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 outer surface.

[0255] In another embodiment, one or more layers can 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.

[0256] Any of the aforementioned polymers and compositions in combination with any additives (see, for example, U.S. Patent Application Publication No. 2016 / 0060430, paragraphs

[0082] -

[0093] ) can be used in a variety of end-use applications. Such end-use applications can be produced by methods known in the art. End-use applications include polymer products and products with specific end-use applications. Exemplary end-use applications can be films, film-based products, diaper backsheets, house wraps, wire and cable coating compositions, articles formed by molding techniques, such as injection or blow molding, extrusion coating, foaming, casting, and combinations thereof. End-use applications also include products made from films, such as bags, packaging, personal care films, pouches, medical products, such as medical films and intravenous (IV) bags.

[0257] Lubricants and Viscosity Modifiers The present invention also provides a lubricant composition comprising a blend of the ethylene-cyclic monomer copolymer described herein and a lubricating oil. The concentration of the ethylene cyclic monomer copolymer in the lubricating oil is 5% by weight or less. The branched ethylene copolymer has a shear stability index (30 cycles) in the lubricating oil 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 according to ASTM D6278 at 30 cycles using a Kurt Orbahn diesel injection device. The kinematic viscosity (KV) is measured according to ASTM D445.

[0258] The present invention relates to the following: 1. Cyclic olefin monomers and C2-C 20An optional comonomer selected from an alpha olefin is reacted with an activator and a copolymer of formula (I): TIFF0007629985000053.tif47143 [In formula: M is a Group 3, 4, 5, or 6 transition metal or lanthanide; E and E' are each independently O, S or NR 9 where R 9 are independently hydrogen, C1 to C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl or heteroatom-containing group; Q is an atom of Group 14, 15, or 16 that forms a coordinate bond with the metal M; A 1 QA 1’ is a three-atom bridge, 2 and A 2’ A is a part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms linking 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; TIFF0007629985000054.tif1128 shows A by 2-atom bridge. 1 and an E-linked aryl group; TIFF0007629985000055.tif1230 shows A by 2-atom bridge. 1’ and E' is a divalent group containing 2 to 40 non-hydrogen atoms linking the 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 each independently hydrogen, C1 to 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’ one or more of may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, where substitutions on a ring 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 linked to the L group to form a monoanionic bidentate group; Any two X groups may be combined to form a dianionic ligand. A process for polymerization comprising contacting a catalyst system comprising a catalyst compound represented by 2. The catalyst compound has the formula (II): TIFF0007629985000056.tif52140 [In formula: M is a Group 3, 4, 5, or 6 transition metal or lanthanide; E and E' are each independently O, S or NR 9 where R 9 are independently hydrogen, C1 to C 40 Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl or heteroatom-containing group; Each L is independently a Lewis base; 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 to 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 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, where substitutions on a ring 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 linked to the L group to form a monoanionic bidentate group; Any two X groups may combine to form a dianionic ligand; 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 to C 40Hydrocarbyl, C1-C 40 is a substituted hydrocarbyl, heteroatom or heteroatom-containing group; 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, where substitutions on a ring may be joined to form additional rings. The method according to item 1, represented by: 3. The method according to item 1 or 2, wherein M is Hf, Zr or Ti. 4. The method of any one of items 1, 2 and 3, wherein E and E' are each O. 5. R 1 and R 1’ are each independently C4~C 40 The method of claim 1, 2, 3, or 4, wherein the hydrocarbyl group is a tertiary hydrocarbyl group. 6. R 1 and R 1’ are each independently, C4~ C40 The method of claim 1, 2, 3, or 4, wherein the cyclic tertiary hydrocarbyl group is a cyclic tertiary hydrocarbyl group. 7. R 1 and R 1’ are each independently C4~C 40 The method of claim 1, 2, 3, or 4, wherein the moiety is a polycyclic tertiary hydrocarbyl group. 8. The method according to any one of items 1 to 7, wherein each X is independently a substituted or unsubstituted hydrocarbyl radical 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 method of any one of items 1 to 8, wherein each L is independently an ether, a thioether, an amine, a phosphine, an ethyl ether, tetrahydrofuran, dimethylsulfide, triethylamine, pyridine, an alkene, an alkyne, an allene, and a carbene, and combinations thereof (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 are carbon, E and E ’ Both are oxygen and R 1 and R 1’ Both are C4~C 20 Item 3. The method according to item 1, wherein the alkyl group is a cyclic tertiary alkyl group. 11. M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both are carbon, E and E ’ Both are oxygen and R 1 and R 1’ The method of claim 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 are carbon, E and E ’ The method according to claim 1, wherein both of the formula (I) and (II) are oxygen, X is methyl or chloro, and n is 2. 13. Q is nitrogen and A is 1 and A 1’ Both are carbon and R 1 and R 1’ Both are hydrogen, and E and E ’ Both are NR 9 and R 9 is C1~C40 Hydrocarbyl, C1-C 40 Item 10. The method of claim 1, wherein the alkyl group is selected from the group consisting of a substituted hydrocarbyl, ... or a heteroatom-containing group. 14. Q is carbon and A is 1 and A 1’ Both are nitrogen, and E and E ’ The method according to claim 1, wherein both of said are oxygen. 15. Q is carbon and A is 1 is nitrogen, and A 1’ is C(R 22 ), where E and E ’ Both are oxygen and R 22 is hydrogen, C1-C 20 Hydrocarbyl, or C1-C 20 Item 10. The method of claim 1, wherein the aryl group is selected from the group consisting of substituted hydrocarbyls. 16. A heterocyclic Lewis base has the formula: TIFF0007629985000057.tif98102[where, R 23 are each independently hydrogen, C1 to C 20 Alkyl, and C1-C 20 substituted alkyl.] Item 3. The method according to item 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 Item 3. The method according to item 2, wherein the alkyl group is a cyclic tertiary alkyl group. 18. M is Zr or Hf, and E and E ’ Both are oxygen and R 1 and R 1’ The method according to item 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’Each of 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~ C20 Cyclic tertiary alkyl, R 7 and R 7’ Both are C1~C 20 Item 3. The method according to item 2, wherein the alkyl group 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 Cyclic tertiary alkyl, R 7 and R 7’ Both are C1~C 20 Item 3. The method according to item 2, wherein the alkyl group 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 Cyclic tertiary alkyl, R 7 and R 7’ and wherein both of are C1-C3 alkyl. 23. The catalyst compound has the formula: TIFF0007629985000058.tif88148 TIFF0007629985000059.tif93148 TIFF0007629985000060.tif88142 TIFF0007629985000061.tif103147 TIFF0007629985000062.tif93152 TIFF0007629985000063.tif82149 TIFF0007629985000064.tif3035 TIFF0007629985000065.tif3069 TIFF0007629985000066.tif36123 TIFF0007629985000067.tif46136 TIFF0007629985000068.tif46140 TIFF0007629985000069.tif41126 TIFF0007629985000070.tif46141 TIFF0007629985000071.tif41125 TIFF0007629985000072.tif41126 TIFF0007629985000073.tif4199 TIFF0007629985000074.tif51108 TIFF0007629985000075.tif35109 The method of claim 1, wherein the compound is one or more of the groups represented by TIFF0007629985000076.tif3561. 24. The catalyst compound has the formula: The method of claim 1, wherein the compound is one or more of the groups represented by TIFF0007629985000077.tif165164. 25. The method of any one of paragraphs 1 to 24, wherein the activator comprises an alumoxane or a non-coordinating anion. 26. The method according to any one of items 1 to 24, wherein the activating agent is soluble in a non-aromatic hydrocarbon solvent. 27. The method of any one of paragraphs 1 to 24, wherein the catalyst system does not contain an aromatic solvent. 28. The activator has the formula: TIFF0007629985000078.tif1438 [wherein Z is (LH) or a reducible Lewis acid, L is a neutral Lewis base; H is hydrogen; (LH) + is a Brønsted acid; A d - is a non-coordinating anion having a charge d-; d is an integer from 1 to 3. The method according to any one of items 1 to 27, wherein the compound is represented by the formula: 29. The activator has the formula: TIFF0007629985000079.tif15110 [In 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’ is a C1-C substituted or unsubstituted alkyl group, optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups; 50 is a hydrocarbyl group; Here, 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; Each Q is independently a hydride, a bridged or unbridged dialkylamide, a halide, an alkoxide, an aryloxide, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, or a halo-substituted hydrocarbyl group. The method according to any one of items 1 to 27, wherein the compound is represented by the formula: 30. The activator has the formula: TIFF0007629985000080.tif1438[where A d - is a non-coordinating anion having a charge d-; d is an integer from 1 to 3; (Z) d + teeth, TIFF0007629985000081.tif183164] The method according to any one of items 1 to 27, wherein the compound is represented by the formula: 31. Activators are: N-methyl-4-nonadecyl-N-octadecylbenzeneaminium tetrakis(pentafluorophenyl)borate, N-methyl-4-nonadecyl-N-octadecylbenzeneaminium tetrakis(perfluoronaphthalen-2-yl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(perfluoronaphthalen-2-yl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(perfluoronaphthalen-2-yl)borate, Triethylammonium tetrakis(perfluoronaphthalen-2-yl)borate, tripropylammonium tetrakis(perfluoronaphthalen-2-yl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthalen-2-yl)borate, tri(t-butyl)ammonium tetrakis(perfluoronaphthalen-2-yl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthalen-2-yl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthalen-2-yl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthalen-2-yl)borate, tropylium tetrakis(perfluoronaphthalen-2-yl)borate, triphenylcarbenium tetrakis(perfluoronaphthalen-2-yl)borate, triphenylphosphonium tetrakis(perfluoronaphthalen-2-yl)borate, Triethylsilylium tetrakis(perfluoronaphthalen-2-yl)borate, benzene(diazonium)tetrakis(perfluoronaphthalen-2-yl)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-tetrafluoro-phenyl)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 28. The method according to any one of items 1 to 27, wherein the method is one or more of the following: 32. The method according to any one of items 1 to 31, which is a solution method. 33. The method according to any one of items 1 to 32, which is carried out 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 300 minutes or less. 34. The method of any one of paragraphs 1 to 33, which is a continuous process. 35. The method of any one of paragraphs 1 to 34, wherein the polymer contains at least 0.1 mol % of a cyclic olefin. 36. The method of any one of paragraphs 1 to 34, wherein the polymer comprises at least 1 mol % of a cyclic olefin. 37. The method of any one of paragraphs 1 to 34, wherein the polymer comprises at least 10 mol % of a cyclic olefin. 38. The method of any one of paragraphs 1 to 37, wherein the polymer comprises at least 1 mol % cyclic olefin and at least 20 mol % ethylene. 39. The method of any one of paragraphs 1 to 37, wherein the polymer comprises at least 1 mol % cyclic olefin and at least 20 mol % propylene. 40. A polymer produced by the method according to any one of paragraphs 1 to 40, comprising one or more cyclic olefin monomers selected from substituted or unsubstituted cyclopentene and substituted or unsubstituted 2-norbornene. 41. A polymer produced by the method of any one of paragraphs 1 to 40, comprising one or more cyclic monomers selected from substituted or unsubstituted cyclopentene. 42. A polymer produced by the method according to any one of items 1 to 39, comprising one or more cyclic monomers selected from substituted or unsubstituted 2-norbornene. 43. The method of any one of paragraphs 1 to 33, wherein the polymer is a homopolymer of substituted or unsubstituted cyclopentene. 44. The method of claim 43, wherein the polymer is a homopolymer of cyclopentene. 45. Polymers are: a. Mn greater than 5,000 g / mol, alternatively greater than 10,000 g / mol, alternatively greater than 100,000 g / mol, alternatively greater than 150,000 g / mol; b. Mw greater than 10,000 g / mol, alternatively greater than 20,000 g / mol, alternatively greater than 200,000 g / mol, alternatively greater than 300,000 g / mol; c. Mw / Mn from about 1 to 10, alternatively from about 1.5 to 5.0, alternatively from about 1.8 to 3.0, alternatively from about 2.0 to 4.0; d. a cyclopentene content of 0.1 mol% or more, up to an upper limit of 50 mol% or less, alternatively 45 mol% or less; e. Approximately 90% or more of the total cyclopentene units incorporated into the polymer are cyclopentene 1,2 bonds. Item 41. The method according to any one of items 1 to 40, wherein the copolymer is an ethylene cyclopentene copolymer having the formula: 46. ​​Polymers are: a. Mn greater than 50,000 g / mol, alternatively greater than 100,000 g / mol, alternatively greater than 150,000 g / mol, alternatively greater than 200,000 g / mol; b. Mw greater than 100,000 g / mol, or greater than 200,000 g / mol, or greater than 300,000 g / mol, or greater than 400,000 g / mol; c. Mw / Mn of about 1.2-5.0, alternatively about 1.5-4.0, alternatively about 2.0-3.0; d. a norbornene content of 20 mol% or more and up to 80 mol% or less; e. Norbornene units that are 10-80% independent, 10-80% alternating, and 1-50% blocked, with the sum of independent, alternating, and blocked equal to 100%. Item 41. The method according to any one of items 1 to 40, wherein the copolymer is an ethylene norbornene copolymer. 47. Polymers are: a. Mn greater than 3,000 g / mol, alternatively greater than 5,000 g / mol, alternatively greater than 10,000 g / mol; b. Mw greater than 6,000 g / mol, or greater than 10,000 g / mol, or greater than 20,000 g / mol; c. Mw / Mn from about 1 to 10, alternatively from about 1.5 to 5.0, alternatively from about 1.8 to 3.0, alternatively from about 2.0 to 4.0; d. a cyclopentene content of 0.1 mol% or more, up to an upper limit of 50 mol% or less, alternatively 45 mol% or less; e. Approximately 90% or more of the total cyclopentene units incorporated into the polymer are cyclopentene 1,2 bonds. Item 41. The method according to any one of items 1 to 40, wherein the copolymer is a propylene cyclopentene copolymer having the formula: 48. Polymers are: a. Mn greater than 3,000 g / mol, alternatively greater than 5,000 g / mol, alternatively greater than 10,000 g / mol; b. Mw greater than 6,000 g / mol, or greater than 10,000 g / mol, or greater than 20,000 g / mol; c. Mw / Mn of about 1.2-5.0, alternatively about 1.5-4.0, alternatively about 2.0-3.0; d. Norbornene content of 1 mol% or more and up to 50 mol% or less Item 41. The method according to any one of items 1 to 40, wherein the copolymer is a propylene norbornene copolymer having the formula:

[0259] Test methods for large scale polymerization Molecular weight and composition distribution (GPC-IR): The distribution and moments of molecular weights (e.g., Mn, Mw, Mz) and comonomer distribution (C2, C3, C6, etc.) are measured by high temperature gel permeation chromatography (PolymerChar GPC-IR) equipped with a multi-channel band filter-based infrared detector ensemble IR5. Here, a broadband channel is used to measure the polymer concentration and two narrowband channels to characterize the composition. Three Agilent PLgel 10 μm Mixed-B LS columns are used to separate the polymers. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300 ppm of the antioxidant butylated hydroxytoluene (BHT) is used as the mobile phase. The TCB mixture is filtered through a 0.1 micrometer Teflon filter and degassed with an online degasser before being loaded into the GPC instrument. The nominal flow rate is 1.0 mL / min and the nominal injection volume is 200 microliters. The entire system, including the transfer line, columns, and detectors, is placed in an oven maintained at 145 °C. A given amount of polymer sample is weighed and sealed in a standard vial with the addition of 10 microliters of flow marker (heptane). After loading the vial into the autosampler, the polymer is dissolved automatically in the instrument by adding 8 mL of TCB solvent. The polymer is dissolved at 160 °C with continuous shaking for approximately 1 h for most PE samples and 2 h for PP samples. The TCB density used to calculate the concentration is 1.463 g / ml at room temperature and 1.284 g / ml at 145 °C. The concentration of the sample solution is 0.2-2.0 mg / ml, with lower concentrations being used for samples with higher molecular weights.

[0260] The concentration c at each point in the chromatogram is calculated from the baseline-subtracted IR5 broadband signal I using the following formula: c=αI where α is the mass constant as determined by PE standard NBS 1475. Mass recovery is calculated from the ratio of the integrated area of ​​the concentrated chromatography over the elution volume to the injected mass, which is equal to the given concentration multiplied by the injection loop volume.

[0261] Molecular weights are determined by combining a column calibration performed with a series of monodisperse polystyrene (PS) standards with a universal calibration relationship. Molecular weights are calculated at each elution volume using the following formula: TIFF0007629985000082.tif1585 where K and α are coefficients in the Mark-Houwink equation. The variables with the subscript "X" represent the test sample, and the 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 IR detector intensities corresponding to the CH2 and CH3 channels calibrated with a series of PE and PP homo / copolymer standards.

[0262] The LS detector is an 18-corner Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model of static light scattering (Light Scattering from Polymer Solutions; Huglin, MB, Ed.; Academic Press, 1972.).

[0263] TIFF0007629985000083.tif1861 where δR(θ) is the excess Rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined from IR5 analysis, A2 is the second virial coefficient, and P(θ) is the monodisperse random coil form factor. K o are the optical constants of the system. TIFF0007629985000084.tif2264 formula, N Ais Avogadro's number and (dn / dc) is the increment in the refractive index of the system. The refractive index of TCB at 145°C and λ=665 nm is n=1.500. For the analysis of polyethylene homopolymer, ethylene-hexene copolymer, and ethylene-octene copolymer, dn / dc=0.1048 ml / mg, A2=0.0015; for the analysis of ethylene-butene copolymer, dn / dc=0.1048 * (1-0.00126 * w2) ml / mg, A2 = 0.0015 (w2 is the weight percent of butene comonomer).

[0264] A high temperature Agilent (or Viscotek Corporation) with four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers is used to determine viscosity. One transducer measures the pressure drop across the detector, and the other transducer is placed between the two sides of the bridge and measures the differential pressure. The specific viscosity, η, of the solution passing through the viscometer s is calculated from these outputs. The intrinsic viscosity [η] at 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: TIFF0007629985000085.tif1157 In the formula, α ps is 0.67, and K PS is 0.000175.

[0265] Branching index (g' vis ) is calculated using the output of the GPC-IR5-LS-VIS method as follows: The average intrinsic viscosity [η]avg of the sample is calculated as follows: TIFF0007629985000086.tif2148 where the sum is over chromatographic slice i between the integration limits.

[0266] Branching index g' vis is defined as follows: TIFF0007629985000087.tif2541 where Mv is the viscosity average molecular weight based on molecular weight determined by LS analysis, K and α are values ​​for reference linear polymers, which for the purposes of this disclosure are: for linear ethylene, α=0.695 and K=0.000579; for linear propylene polymers, α=0.705 and K=0.0002288; for linear butene polymers, α=0.695 and K=0.000181; and for ethylene-butene copolymers, 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; 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; 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 stated. 3 where the molecular weight is in g / mole and the intrinsic viscosity (K in the Mark-Houwink equation) is in dL / g. The calculation of w2b value is as above.

[0267] Experimental and analytical details not described above, including the detector calibration method, the composition dependence of the Mark-Houwink parameters, and the calculation method of the second virial coefficient, can be found in T. Sun, P. Brant, RR Chance, and WW Graessley (Macromolecules, 2001, v.34(19), pp. 6812-6820).

[0268] The peak melting point 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 are determined using the following DSC procedure in accordance with ASTM D3418-03. Differential scanning calorimetry (DSC) data was obtained using a TA Instruments model DSC2500 machine. Samples weighing approximately 5-10 mg were sealed in aluminum hermetic sample pans. DSC data was 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, followed by isothermalization for 2 minutes and heating to 200°C at 10°C / min. Thermal events from both the first and second cycles were recorded. The area under the endothermic peak was measured and used to determine the heat of fusion and percent crystallinity. 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 of a 100% crystalline homopolymer of the major monomeric component. These B values ​​are taken from the Polymer Handbook, Fourth Edition, published by John Wiley and Sons, New York 1999, except that a value of 189 J / g(B) is used for the heat of fusion of 100% crystalline polypropylene and a value of 290 J / g is used for the heat of fusion of 100% crystalline polyethylene. Melting and crystallization temperatures reported here were obtained during the second heating / cooling cycle unless otherwise noted.

[0269] For polymers that exhibit 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 separately. Percent crystallinity is calculated using the sum of the heats of fusion from all endothermic peaks. Some of the polymer blends produced exhibit secondary melting / cooling peaks that overlap with the main peak. These peaks are considered as a single melting / cooling peak. The highest point of these peaks is considered as the peak melting temperature / crystallization point. For amorphous polymers with relatively low crystallinity, the melting temperature is usually measured during the first heating cycle. Prior to DSC measurements, samples were aged (usually held at ambient temperature for 2 days) or annealed to maximize crystallinity.

[0270] The melt index (I2) was measured according to ASTM D1238 using a load of 2.16 kg at a temperature of 190°C. The melt index under high load conditions (I 21 ) was measured according to ASTM D1238 using a load of 21.6 kg at a temperature of 190°C.

[0271] Density is measured as specified in ASTM D1505 by slowly cooling to room temperature (i.e., over 10 minutes) and measuring to a density of + / - 0.001 g / cm 3 It is determined in accordance with ASTM D1505 using a density gradient column on compression molded specimens that have been aged for a sufficient time to be constant within

[0272] experiment The catalysts used in the polymerizations reported herein were synthesized according to the procedures reported in US2020-0255553, USSN62 / 972953, USSN62 / 972936, US2020-0255555, US2020-0254431, and US2020-0255556.

[0273] Cat-Hf (complex 5), Cat-Zr (complex 6), and complex 66 were prepared as follows.

[0274] Starting materials 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Aldrich) 2,6-Dibromopyridine (Aldrich), 2-bromoiodobenzene (Acros), 2.5M in hexane n BuLi (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; Merck), and CDCl3 (Deutero GmbH) were used as received. Benzene-d6 (Deutero GmbH) and dichloromethane-d2 (Deutero GmbH) were dried with MS 4A before use. THF for organometallic syntheses was freshly distilled from sodium benzophenone ketyl. Toluene and hexane for organometallic synthesis were dried with MS 4A. 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.

[0275] 2-(adamantan-1-yl)-6-bromo-4-(tert-butyl)phenol TIFF0007629985000088.tif314257.6 g (203 mmol) of 2-(adamantan-1-yl)-4-(tert-butyl)phenol in 400 mL of chloroform was added dropwise over 30 min at room temperature to a solution of 10.4 mL (203 mmol) of bromine in 200 mL of chloroform. 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 then evaporated to dryness. Yield 71.6 g (97%) of a white solid. 1 H 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.

[0276] 1-(3-bromo-5-(tert-butyl)-2-(methoxymethoxy)phenyl)adamantane TIFF0007629985000089.tif37347A solution of 1.6 g (197 mmol) of 2-(adamantan-1-yl)-6-bromo-4-(tert-butyl)phenol in 1000 mL of THF and 8.28 g (207 mmol, 60 wt% in mineral oil) of sodium hydride was added portionwise at room temperature. To the resulting suspension, 16.5 mL (217 mmol) of methoxymethyl chloride was added 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 x 300 mL) and the combined organic extracts were washed with 5% NaHCO3, dried over Na2SO4, and then evaporated to dryness. Yield 80.3 g (~quant) of white solid. 1H 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). 13 C 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.

[0277] (2-(3-adamantan-1-yl)-5-(tert-butyl)-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane TIFF0007629985000090.tif37402A solution of 2.5 g (55.0 mmol) of 1-(3-bromo-5-(tert-butyl)-2-(methoxymethoxy)phenyl)adamantane in 300 mL of dry THF was mixed with 23.2 mL (57.9 mmol, 2.5 M) of n A solution of BuLi in hexane was added dropwise at -80°C for 20 min. The reaction mixture was stirred at this temperature for 1 h, followed by the addition of 14.5 mL (71.7 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. 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 x 300 mL) and the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. Yield 25.0 g (~quant) of a colorless viscous oil. 1H 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. 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.

[0278] 1-(2'-Bromo-5-(tert-butyl)-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane 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, 15.6 g (55.0 mmol) of 2-bromoiodobenzene, 19.0 g (137 mmol) of potassium carbonate, and 100 mL of water were subsequently added. The resulting mixture was purged with argon for 10 min, followed by the addition of 3.20 g (2.75 mmol) of Pd(PPh3)4. The resulting mixture was stirred at 100 °C for 12 h, 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 then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, by volume). Yield 23.5 g (88%) of a white solid. 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, 6 H), 1.33 (s, 9 H). 13C 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.

[0279] 2-(3'-(adamantan-1-yl)-5'-(tert-butyl)-2'-(methoxymethoxy)-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane TIFF0007629985000092.tif3748To 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 dropwise at -80 °C for 20 min with 25.6 mL (63.9 mmol, 2.5 M) of nBuLi in hexane. The reaction mixture was stirred at this temperature for 1 h, followed by the addition of 16.5 mL (80.7 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. 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 x 300 mL) and the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. Yield: 32.9 g (~quant.) of a colorless glassy solid. 1H 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, 9 H), 1.15 (s, 6 H), 1.10 (s, 6 H). 13C 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.

[0280] (2',2''-(pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol)) TIFF0007629985000093.tif43632-(3'-(adamantan-1-yl)-5-(tert-butyl)-2'-(methoxymethoxy)-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (32.9 g (62.0 mmol) 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, followed by 70 mL of water. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 3.50 g (3.10 mmol) of Pd(PPh3)4. The mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The resulting mixture was extracted with dichloromethane (3×50 mL), the combined organic extracts were dried over Na2SO4, and then evaporated to dryness. To the resulting oil, 300 mL of THF, 300 mL of methanol, and 21 mL of 12N HCl were successively added. The reaction mixture was stirred at 60° C. overnight and then poured into 500 mL of water. The resulting mixture was extracted with dichloromethane (3×350 mL), the combined organic extracts were washed with 5% NaHCO3, dried over Na2SO4, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, by volume). 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 vacuum. Yield 21.5 g (87%) of the mixture of the two isomers as a white powder. 1H 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 labeled with *): 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*.

[0281] Dimethylhafnium (2',2''-(pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-oleate)) (Cat-Hf; Complex 5) TIFF0007629985000094.tif43632To a suspension of 3.22 g (10.05 mmol) of hafnium tetrachloride (<0.05% Zr) in 50 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'''-(pyridine-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 at room temperature for 36 h and then evaporated to dryness. The resulting solid was extracted with 2 x 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 (2×20 mL) and then dried under vacuum. Yield 6.66 g (61%, ∼1:1 solvate with n-hexane) of a light beige solid. C 59 H 69 HfNO2×1.0(C6H 14 ) Calculated values: C, 71.70; H, 7.68; N, 1.29. Found values: 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.

[0282] Dimethylzirconium (2',2''-(pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-oleate)) (Cat-Zr; Complex 6) TIFF0007629985000095.tif4567To 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 in one portion via syringe at 0 °C. To the resulting suspension was added 10.00 g (12.56 mmol) of (2',2'''-(pyridine-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 at room temperature for 2 h and then evaporated to near dryness. The resulting solid was extracted with 2 x 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 (2×20 mL) and then dried under vacuum. Yield 8.95 g (74%, ∼1:0.5 solvate with n-hexane) of a beige solid. C 59 H 69 ZrNO2×0.5(C6H 14 ) Calculated values: C, 77.69; H, 7.99; N, 1.46. Found values: 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.

[0283] (3-(adamantan-1-yl)-2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)lithium TIFF0007629985000096.tif4636Hexane (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 quickly. After stirring overnight, a white solid was collected on a frit and washed with hexane (3 x 10 mL). The solid was dried under reduced pressure. H NMR analysis indicated the presence of 0.88 equivalents of DME. Used without further purification. Yield: 8.36 g, 56.3%.

[0284] 1-(2'-Bromo-2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-3-yl)adamantane. TIFF0007629985000097.tif4643Toluene (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) then brine (2 x 10 mL). The organics were dried over MgSO4, filtered and evaporated to give a pale yellow oil. H NMR indicated the presence of 0.5 equivalents of toluene in the crude product. Used without further purification. Yield: 9.92 g, 95.2%.

[0285] 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. TIFF0007629985000098.tif4650 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 min, the mixture was removed from the cold bath and allowed to warm to near ambient temperature over 25 min. 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. The mixture was allowed to warm slowly 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 (6×100 mL) until the aqueous layer was neutral. The organics were extracted with brine (2×20 mL). The organics were dried over MgSO4, filtered, and dried under vacuum for several days to give the product as an amorphous solid. Used without further purification. Yield: 9.197 g, 92.6%.

[0286] 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). 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 min and then solid Pd(PPh3)4 (0.906 g, 0.784 mmol) was added. The mixture was sparged for a further 40 min, 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 broken up and stirred with water (200 mL) for several minutes. The solid was then collected on a frit and washed with water (3 x 200 mL). The 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 placed in a separatory funnel. The organics were extracted with dilute NaHCO3 (100 mL), water (4 x 150 mL), and then brine (20 mL). The organics were dried over MgSO4 and then evaporated to give a foamy yellow solid (8.4 g). The crude product was purified on SiO2, eluting with 1-5% EtOAc in isohexane. Yield: 4.92g, 72.0%.

[0287] Dichloroziconium (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 66-dichloride). TIFF0007629985000100.tif3566Benzene (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 taken for H NMR analysis, 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%.

[0288] Dimethylziconium (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-oleate)) (complex 66). TIFF0007629985000101.tif3566Toluene (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 min. After 1 h, 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 evaporated again. The residue was then dried under reduced pressure. The residue was then extracted with isohexane (10 mL), filtered through Celite 503, evaporated to a residue and dried under reduced pressure. The vial was scraped to give complex 33 as a light brown solid. Yield: 0.0819 g, 90.0%.

[0289] The following complexes were used in small and large scale polymerization experiments. The complex numbers shown correspond to the Cat-ID numbers. TIFF0007629985000102.tif133164

[0290] The following comparative complexes were used in the following small scale polymerization experiments, where C-# indicates the catalyst ID (Cat-ID). TIFF0007629985000103.tif162164

[0291] Small scale polymerization example Polymerization grade toluene and / or isohexane as solvents were obtained from ExxonMobil Chemical Company and purified through a series of columns: two 500 cm in series from Labclear (Oakland, California); 3 An Oxyclear cylinder was then used, followed by two 500 cm in series packed with dry 3 Å molecular sieves (8 mesh-12 mesh; Aldrich Chemical Company). 3 column, and two 500 cm in series packed with dry 5 Å molecular sieves (8-12 mesh; Aldrich Chemical Company). 3 column.

[0292] 2-Norbornene (NB, Aldrich Chemical Company) was diluted with toluene, sparged with nitrogen, and passed through a column of Brockmann basic alumina (Aldrich Chemical Company). The final solution concentration was 42 wt% or 78 wt% in toluene. Cyclopentene (cP, Aldrich Chemical Company) was purged with nitrogen, passed through a column of neutral alumina, and stored over molesieves. Tri(n-octyl)aluminum (TNOA or TnOAl) was purchased from Aldrich Chemical Company or Akzo Nobel and used as received.

[0293] Polymerization grade ethylene was further purified by passage through a series of columns: Labclear (Oakland, California) 500 cm 3 An Oxyclear cylinder was then used, followed by a 500 cm cylinder packed with dry 3 Å molecular sieves (8 mesh-12 mesh; Aldrich Chemical Company). 3 The column was packed with dried 5 Å molecular sieves (8 mesh to 12 mesh; Aldrich Chemical Company) at 500 cm 3 column.

[0294] The polymerization grade propylene was further purified by passing it through a series of columns: Labclear 2,250 cm 3 An Oxyclear cylinder was then used, followed by a 2,250 cm column packed with 3 Å molecular sieves (8 mesh-12 mesh; Aldrich Chemical Company). 3 The column was then filled with 50 Å molecular sieves (8 mesh-12 mesh; Aldrich Chemical Company). 0cm 3 Column: 500 cm packed with SelexsorbCD (BASF) 3 The column was filled with Selexsorb COS (BASF) at the end, and the 500 cm 3 column.

[0295] N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate was purchased from Boulder Scientific or W.R. Grace. N,N-Dimethylanilinium tetrakis(perfluoronaphthalen-2-yl)borate was purchased from W.R. Grace. All complexes and activators were added to the reactor as dilute solutions in toluene. The concentrations of activator, scavenger, and complex solutions added to the reactor were selected to ensure accurate delivery, between 40 microliters and 200 microliters of solution were added to the reactor.

[0296] Reactor description and preparation Polymerizations were carried out in an autoclave in an inert atmosphere (N2) drybox. The autoclave was equipped with an external heater for temperature control, a glass insert (internal reactor volume = 23.5 mL for runs with C2 and 22.5 mL for runs with C3), a septum inlet to regulate the nitrogen, ethylene, and propylene feeds, and a disposable polyetheretherketone mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110°C or 115°C for 5 hours, then at 25°C for 5 hours.

[0297] Ethylene polymerization (PE), ethylene / cyclic olefin copolymerization (E - cP or E - NB) and cyclic olefin homopolymerization (p - cP) The reactor was prepared as above and then purged with ethylene or, in the case of reactors not using ethylene, with nitrogen. Isohexane (solvent unless otherwise noted) and cyclic comonomer were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to process temperature (typically 100° C.) and charged with ethylene (if used) while stirring at 800 RPM. A scavenger solution (e.g., TNOA in isohexane or toluene) was then added via syringe to the reactor at process conditions. A non-coordinating activator (e.g., N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate) solution (in toluene) was added via syringe to the reactor at process conditions, followed by the addition of the pre-catalyst (i.e., complex or catalyst identified by CatID). The solution (in toluene) was injected via syringe into the reactor at process conditions. If used, ethylene was admitted to the autoclave (using a computer-controlled solenoid valve) to maintain the gauge pressure of the reactor (+ / - 2 psi) during polymerization. The reactor temperature was monitored and typically maintained within ±1°C. Polymerization was stopped by adding a compressed dry air mixture at about 50 psi to the autoclave for about 30 seconds. Polymerization was quenched after the addition of a predetermined cumulative amount of ethylene (if used) or during the maximum minutes of polymerization time. The reactor was cooled and vented. The polymer was isolated after removing the solvent in vacuum. The reported yield includes the total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer per millimole of transition metal compound per hour of reaction time (g / mmol / hr). "C#" indicates a comparative example. Microliters (μl or μL) may be reported as uL or ul in the tables below.

[0298] Propylene polymerization (PP) and propylene / cyclic olefin copolymerization (P - cP or P - N.B. The reactor was prepared as described above, then heated to 40°C and purged with propylene gas at atmospheric pressure. Isohexane (solvent unless otherwise noted), cyclic comonomer, and liquid propylene were added via syringe. The reactor was then heated to process temperature (typically 100°C) with stirring at 800 RPM. A scavenger solution (e.g., TNOA in isohexane or toluene) was then added to the reactor at process conditions via syringe. A non-coordinating activator (e.g., N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate or N,N-dimethylanilinium tetrakis(perfluoronaphthalen-2-yl)borate) solution (in toluene) was then added to the reactor at process conditions via syringe. Subsequently, a precatalyst (i.e., complex or catalyst identified by catalyst ID) solution (in toluene) was injected into the reactor at process conditions via syringe. The reactor temperature was monitored and typically maintained within ±1°C. Polymerizations were stopped by adding a compressed dry air (alternatively, CO2, if mentioned) gas mixture at about 50 psi to the autoclave for about 30 seconds unless otherwise noted. Polymerizations were quenched based on a predetermined pressure drop of about 8 psi (unless otherwise noted) or based on a maximum polymerization time of 30 minutes (unless otherwise noted). The reactor was cooled and evacuated. The polymer was isolated after removing the solvent in vacuum. The reported yield includes the total weight of polymer and residual catalyst. Catalyst activity can usually be reported as grams of polymer per mmol of transition metal compound per hour of reaction time (g / mmol / hr).

[0299] Quench time (s, seconds) is the actual time of polymerization, determined by the maximum uptake (quench value) or maximum quench time shown. Quench value (psi) is the setpoint for ethylene uptake in polymerizations with ethylene, or the total pressure loss in polymerizations without ethylene. Maximum reaction (rxn) time is the setpoint for the maximum time that polymerization can run if not already quenched by uptake.

[0300] Small scale polymer characterization For analytical testing, the polymers were prepared by dissolving in 1,2,4-trichlorobenzene (TCB, from Aldrich, 99+%) containing 2,6-di-tert-butyl-4-methylphenol (BHT, from Aldrich, 99%) for approximately 3 hours in a shaker oven at 165 °C. Typical concentrations of polymer in solution were 0.1-0.9 mg / mL with a BHT concentration of 1.25 mg BHT / mL of TCB. Samples were cooled to 135 °C for testing.

[0301] High temperature size exclusion chromatography was performed using an automated "Rapid GPC" system as described in U.S. Patent Nos. 6,491,816; 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388; each of which is incorporated herein by reference. Molecular weights (weight average (Mw), number average (Mn), z-average (Mz)) and molecular weight distributions (PDI = MWD = Mw / Mn), also referred to as polymer polydispersity (PDI), were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector (ELSD) and calibrated with polystyrene standards (Polymer Laboratories: Polystill Calibration Kit SM-10: Mp (peak Mw) 5,000-3,390,000). Alternatively, samples were measured by gel permeation chromatography using a Symyx Technology GPC equipped with a dual wavelength infrared detector and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) 580-3,039,000). Samples (250 μL of polymer solution in TCB injected into the system) were analyzed using three Polymer Laboratories: PLgel 10 μm Mixed-B300x7.5 mm columns in series at an eluent flow rate of 2.0 ml / min (sample temperature 135° C., oven / column 165° C.). No column diffusion correction was performed. Numerical analysis was performed using Epoch® software available from Symyx Technologies or Automation Studio software available from Freeslate. Molecular weights obtained are relative to linear polystyrene standards. Molecular weight data are reported in the following tables in Mn, Mw, Mz, and PDI as defined above.

[0302] Differential scanning calorimetry (DSC) measurements were performed using a TA-Q100 instrument to determine the melting points of the polymers. The samples were pre-annealed at 220°C for 15 minutes (first melt) and then cooled to room temperature overnight. The samples were then heated to 220°C at a rate of 100°C / min (second melt) and then cooled at a rate of 50°C / min. Melting points were collected during the heating period. The reported value is the peak melting temperature, also referred to as the second melt for the purposes of this disclosure. The results are reported as T m are reported in the table below.

[0303] Ethylene-cyclopentene copolymer 1 H NMR measurement: Unless otherwise stated, 1 Ethylene-cyclopentene (E-Cp) samples for H NMR spectroscopy were dissolved in 1,1,2,2-tetrachloroethane-d2 (tc-d2) at a concentration of 30 mg / mL at 140 °C. Samples were measured using a Bruker NMR spectrometer at 120 °C. NMR measurements were performed using a 600 MHz or higher NMR spectroscopy. 1 H NMR was performed using a 10 mm cryoprobe with a 30° pulse, at least 512 scans, and a 5 s delay. E-Cp chemical shifts were referenced to the solvent tc-d2 at 5.98 ppm. TIFF0007629985000104.tif4594 TIFF0007629985000105.tif41164E=Ethylene, Cp=Cyclopentene, 1000C=1000 main chain carbons This calculation is used for the 1,2 addition of Cp.

[0304] Polycyclopentene 1 H NMR measurement: Unless otherwise noted, 1 Polycyclopentene (polyCp) samples for H NMR spectroscopy were dissolved in 1,1,2,2-tetrachloroethane-d2 (tc-d2) at a concentration of 30 mg / mL at 140 °C. Samples were measured using a Bruker NMR spectrometer at 120 °C. NMR measurements were performed using a 500 MHz or higher NMR spectrometer. 1H NMR was performed at 1 H NMR frequency, 30° pulse, at least 512 scans, and 5 s delay. Chemical shifts of polyCp were referenced to the solvent tc-d2 at 5.98 ppm. TIFF0007629985000106.tif79164

[0305] Ethylene-norbornene (E-MB) polymer 1 H NMR measurement: Unless otherwise stated, 1 Ethylene-norbornene copolymer (E-NB) samples for H NMR spectroscopy were dissolved in 1,1,2,2-tetrachloroethane-d2 at a concentration of 30 mg / mL at 140 °C. Samples were measured at 120 °C using a Bruker NMR spectrometer. NMR measurements were performed using a 600 MHz or higher NMR spectrometer. 1 H NMR was performed at 3° pulse frequency, 512 scans, and a 15 second delay. TIFF0007629985000107.tif64164

[0306] Copolymer 13 C NMR measurement: Unless otherwise stated, 13 Copolymer samples for C NMR spectroscopy (E-Cp, PP-Cp, E-NB, and PP-NB) were dissolved in 1,1,2,2-tetrachloroethane-d2 (TC-D2) at 140 °C to concentrations ranging from 33 to 67 mg / mL. Samples were measured using a Bruker NMR spectrometer at 120 °C. NMR measurements were performed using a 150 MHz or higher NMR spectrometer. 13 A 10 mm cryoprobe with gated decoupling at C frequency, 90° pulses, and at least 512 transients with a 10 s delay were used. For ethylene-based polymers, chemical shifts were referenced to the main PE peak at 29.98 ppm, and for propylene-based polymers, chemical shifts were referenced to the main isotactic CH3 peak at 21.83 ppm.

[0307] Ethylene-cyclopentene copolymer (E-Cp): Assignments and base calculations for the 1,3 cis and 1,3 trans additions of cyclopentene, and the 1,2 additions of cyclopentene in ethylene-cyclopentene copolymers were taken from M. Napoli et.al. "Copolymerization of Ethylene with Cyclopentene or 2-butene with Half Titanocenes-Based Catalysts" Journal of Polymer Science A: Polymer Chemistry, v.46, pp. 4725-4733, (2008).

[0308] The assignments and nomenclature of the 1,2 additions of cyclopentene-ethylene copolymers are taken from A. Jerschow et.al. "Nuclear Magnetic Resonance Evidence for a new Microstructure in Ethene-Cyclopentene Copolymers" Macromolecules, v.28, pp. 7095-7099, (1995). c=Cp, e=ethylene TIFF0007629985000108.tif82164

[0309] 1,2 addition sequence distribution where triad distribution is denoted by ccc, ece, and cce. TIFF0007629985000109.tif51164

[0310] Propylene-cyclopentene copolymer (P-Cp): The assignments and nomenclature of propylene-cyclopentene (P-Cp) are based on N. Naga, Y. Imanishi, "Structure of cyclopentene unit in the copolymer with propylene obtained by stereospecific zirconocene catalysts" Polymer, v.43, pp. 2133-2139, (2002). These assignments are for 1,2 addition only. TIFF0007629985000110.tif41134 TIFF0007629985000111.tif89164

[0311] Ethylene-norbornene copolymer (E-NB): Calculation of E-NB (ethylene-norbornene) composition (mol%) and assignment and quantification of composition distribution (isolated, alternating, block-like) are based on Bergstrom et.al. "Influence of Polymerization Conditions on Microstructure of Norbornene-Ethylene Copolymers Made Using Metallocene Catalysts and MAO" Journal of Applied Polymer Science, v.63, pp. 1071-1076, (1997). TIFF0007629985000112.tif3028 TIFF0007629985000113.tif68164

[0312] Propylene-norbornene copolymer (P-NB): The assignment and numbering of P-NB (propylene-norbornene) is based on I. Tritto et.al. "Propene-Norbornene Copolymers: Synthesis and Analysis of Polymer Structure by 13C NMR Spectroscopy and ab Initio Chemical Shift Computations" Macromolecules, v.36, pp. 882-890 (2003). The composition (mol%) was calculated as follows: TIFF0007629985000114.tif5576 TIFF0007629985000115.tif68164

[0313] large scale polymerization

[0314] Polymerizations were carried out in a continuous stirred tank reactor system. A 1 liter autoclave reactor was fitted with a water cooling / steam heating element with an agitator, pressure controller, and temperature controller. The reactor was operated in a liquid-filled state with the reactor pressure above the boiling point pressure of the reactant mixture to maintain the reactants in the liquid phase. Isohexane was pumped into the reactor by a Pulsa feed pump and its flow rate was controlled using a Coriolis mass flow controller (Quantim series from Brooks). Norbornene (Sigma Aldrich) was dissolved in toluene to form a solution of approximately 85.3 wt.%. The solution was fed to the reactor using a metering pump. Ethylene flowed as a gas under its own pressure through a Brooks flow controller. The monomers (e.g., ethylene and norbornene) were combined into one stream and then mixed with the isohexane stream. The mixture was then fed to the reactor through a single line. A scavenger solution was added to the combined solvent and monomer stream just before the reactor to further reduce catalyst poisons. Similarly, the catalyst solution was fed to the reactor through a separate line using an ISCO syringe pump. Isohexane (used as solvent), as well as the norbornene solution and ethylene, were purified over an alumina bed and molecular sieves. Toluene for preparing the catalyst solution was similarly purified. Unless otherwise stated, all reactions were carried out at a pressure of approximately 2.4 MPa / g.

[0315] A solution of tri-n-octylaluminum (TNOA) in isohexane (25 wt% in hexane, Sigma Aldrich) was used as the scavenger solution. Catalyst solutions were prepared by mixing precatalysts (complex 6 or comparative complex C-7) with N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (A1) in a molar ratio of about 1:1 in 900 ml of toluene or with (hydrogenated tallow alkyl)methylammonium tetra(pentafluorophenyl)borate (A2, 10 wt% in methylcyclohexane) in a molar ratio of about 1:1 in 900 ml of toluene. Both activators are available from Boulder Scientific Company.

[0316] The polymer produced in the reactor was discharged through a back pressure control valve that reduced the pressure to atmospheric pressure. This caused the unconverted monomers in the solution to evaporate into the vapor phase, which was discharged from the top of the gas-liquid separator. The liquid phase, which mainly contained the polymer and the solvent, was collected to recover the polymer. The collected samples were first precipitated using isopropyl alcohol and stabilized using IRGANOX1076 (available from BASF), 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 the yield. Tg was measured using DSC, and norbornene content was measured using proton NMR as described above. The detailed polymerization conditions for Examples G1-G20 are shown in Tables 8-10 below. TIFF0007629985000116.tif230161 TIFF0007629985000117.tif24199 TIFF0007629985000118.tif237159 TIFF0007629985000119.tif235161 TIFF0007629985000120.tif246131 TIFF0007629985000121.tif234130 TIFF0007629985000122.tif44164 TIFF0007629985000123.tif229149 TIFF0007629985000124.tif229147 TIFF0007629985000125.tif231150 TIFF0007629985000126.tif19147 TIFF0007629985000127.tif225157 TIFF0007629985000128.tif225154 TIFF0007629985000129.tif224154 TIFF0007629985000130.tif224155 TIFF0007629985000131.tif23699 TIFF0007629985000132.tif234148 TIFF0007629985000133.tif23590 TIFF0007629985000134.tif241152 TIFF0007629985000135.tif23852 TIFF0007629985000136.tif236150 TIFF0007629985000137.tif239123 TIFF0007629985000138.tif231146 TIFF0007629985000139.tif110164 TIFF0007629985000140.tif117164 TIFF0007629985000141.tif117164 TIFF0007629985000142.tif141164

[0317] All documents described herein, including priority documents and / or test procedures, are incorporated herein by reference unless inconsistent with this document. As is apparent from the general description and specific embodiments above, embodiments of the present invention have been illustrated and described, but various modifications can be made without departing from the spirit and scope of the present invention. Thus, the present invention is not intended to be limited by the above. Similarly, the term "comprising" is considered to be synonymous with the term "including". Similarly, whenever the transition phrase "comprising" appears before a composition, element, or group of elements, it is understood that the same composition or group of elements may also be considered to include the transition phrase "consisting essentially of," "consisting of," "selected from the group of consisting of," or "is" before the composition, element, or element, and vice versa.

[0318] Certain embodiments and features have been described using a set of upper numerical limits and a set of lower numerical limits. It should be understood that ranges including combinations of any two values ​​are contemplated, for example, combinations of any lower limit with any upper limit, combinations of any two lower limits, and / or combinations of any two upper limits, unless otherwise specified. Particular lower limits, upper limits, and ranges are set forth in one or more claims below. All numerical values ​​are "about" or "approximately" the indicated value, taking into account experimental error and variations that would be expected by one of ordinary skill in the art.

Claims

1. Cyclic olefin monomers and C ２ ~C ２０ An optional comonomer selected from an alpha olefin is reacted with an activator and a copolymer of formula (I): [In the formula: M is Hf or Zr; E and E' are O; A １ QA １’ is a part of a substituted or unsubstituted pyridine ring, where Q is N and A １ and A １’ is independently C or C(R ２２ ) and R ２２ is hydrogen, C １ ~C ２０ Hydrocarbyl, C １ ~C ２０ substituted hydrocarbyl; is part of a substituted or unsubstituted benzene ring or of a benzothiophene or indole heterocycle; is part of a substituted or unsubstituted benzene ring or of a benzothiophene or indole heterocycle; L is a Lewis base; X is an anionic ligand; n is 1, 2 or 3; m is 0, 1, or 2; n+m is 4 or less; R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ , and R ４’ are each independently hydrogen, C １ ~C ４０ Hydrocarbyl, C １ ~C ４０ is a substituted hydrocarbyl, a heteroatom, or a 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, where substitutions on a ring 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 attached to the L group to form a monoanionic bidentate group; Any two X groups may be combined to form a dianionic ligand. A process for polymerization comprising contacting a catalyst system comprising a catalyst compound represented by

2. The catalyst compound has the formula (II): [In the formula: M is Hf or Zr; 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 4 or less; R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ , and R ４’ are each independently hydrogen, C １ ~C ４０ Hydrocarbyl, C １ ~C ４０ is a substituted hydrocarbyl, a heteroatom, or a 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, where substitutions on a ring 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 attached to the L group to form a monoanionic bidentate group; Any two X groups may be combined to form a dianionic ligand; 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, C １ ~C ４０ Hydrocarbyl, C １ ~C ４０ is a substituted hydrocarbyl, a heteroatom or a heteroatom-containing group; 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 linked to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, where substitutions on the rings may be linked to form additional rings. The method of claim 1 , wherein the

3. R １ and R １’ are each independently ４ ~C ４０ a tertiary hydrocarbyl group, or C ４ ~C ４０ 3. The method of claim 1 or 2, wherein the cyclic tertiary hydrocarbyl group is a cyclic tertiary hydrocarbyl group.

4. each X is independently a monovalent radical derived from a compound or structure selected from the group consisting of a substituted or unsubstituted hydrocarbyl radical 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); each L is independently a monovalent radical derived from a compound or structure selected from the group consisting of ethers, thioethers, amines, phosphines, ethyl ethers, tetrahydrofuran, dimethylsulfide, triethylamine, pyridine, alkenes, alkynes, allenes, and carbenes, and combinations thereof (optionally, two or more L may form part of a fused ring or ring system); The method according to any one of claims 1 to 3.

5. R １ and R １’ Both are C ４ ~C ２０ cyclic tertiary alkyl, adamantan-1-yl or substituted adamantan-1-yl; The method of claim 1.

6. X is methyl or chloro and n is 2; The method of claim 1.

7. The catalyst compound has the formula: The method of claim 1 , wherein the compound is one or more compounds represented by

8. The catalyst compound has the formula: The method of claim 1 , wherein the compound is one or more compounds represented by

9. The activator has the formula: [In the formula, A ｄ－ is a non-coordinating anion having a charge d-; d is an integer from 1 to 3; (Z) ｄ ＋ teeth, ] The method according to any one of claims 1 to 8, wherein the compound is represented by

10. The method of any one of claims 1 to 3, further comprising recovering a polymer comprising at least 0.1 mole % of a cyclic olefin as a building block of the polymer.

11. The method of any one of claims 1 to 3, further comprising recovering a polymer comprising at least 1 mol% cyclic olefin as a polymeric building block and at least 20 mol% ethylene or at least 20 mol% propylene as a polymeric building block.

12. The method of claim 1, wherein the cyclic olefin monomer comprises at least one selected from substituted or unsubstituted cyclopentene and substituted or unsubstituted 2-norbornene.

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