Polymer composition containing cyclic compounds obtained using a transition metal bis(phenolate) catalyst complex and method for preparing the same

Abstract

The present invention relates to a process for preparing a cycloolefin-containing polymer composition using a transition metal complex of a dianionic tridentate ligand, said ligand having a central neutral heterocyclic Lewis base and two phenolate donors, wherein the tridentate ligand coordinates with the metal center to form two 8-membered rings. Preferably, the bis(phenol) complex is represented by formula (I), wherein M, L, X, m, n, E, E', Q, R 1 、R 2 、R 3 、R 4 、R 1 ′、R 2 '、R 3 '、R 4 '、A 1 、A 1 '、A 3 —A 2 and A 2’ —A 3’ as defined in the present application, wherein A 1 QA 1’ is part of a heterocyclic Lewis base containing 4 - 40 non-hydrogen atoms, which connects A 2 to A 2’ via a 3-atom bridge, wherein Q is the central atom of the 3-atom bridge.

Description

[0001] Inventors: Jo Ann M. Canich, Nikola S. Lambic, Gursu Culcu, Peijun Jiang, John R. Hagadorn, Sarah J. Mattler

[0002] Cross - Reference to Related Applications

[0003] This application claims the benefit and priority of U.S. Provisional Application No. 63 / 065344, filed on August 13, 2020, the entire content of which is incorporated herein by reference.

[0004] This invention relates to:

[0005] 1) USSN 16 / 788,022, filed on February 11, 2020;

[0006] 2) USSN 16 / 788,088, filed on February 11, 2020;

[0007] 3) USSN 16 / 788,124, filed on February 11, 2020;

[0008] 4) USSN 16 / 787,909, filed on February 11, 2020;

[0009] 5) USSN 16 / 787,837, filed on February 11, 2020;

[0010] 6) PCT Application No. PCT / US2020 / 045819, filed on August 11, 2020;

[0011] 7) PCT Application No. PCT / US2020 / 045820, filed on August 11, 2020; and

[0012] 8) PCT Application No. PCT / US2020 / 045822, filed on August 11, 2020. Field of the Invention

[0013] This invention relates to polymer compositions containing cyclic monomers prepared using novel catalyst compounds comprising Group 4 element bis(phenolate) complexes, to compositions comprising such polymers, and to methods of preparing such copolymers. Background of the Invention

[0015] Currently, attention is focused on improving the structure of polyolefins to obtain new and better combinations of properties, such as melt strength, stiffness, shrinkage, and optical properties. Additionally, high optical transparency, high melt strength, bubble stability, and excellent extrusion characteristics are crucial for blown films, such as for heat-sealable blown films. However, many films made from polyethylene compositions still lack certain properties (such as high tensile and impact strength, puncture resistance, excellent optical properties, and first-class sealing properties). Improved strength properties and excellent stretchability would allow for reduced gauging in blown film applications (such as used as bags).

[0016] The design of catalysts, polymerization reaction engineering, and polymerization process technology have been studied to prepare novel polyolefin materials to meet various industrial needs. The design of catalysts plays a key role in controlling the molecular structure of polyethylene, and thus is crucial for material properties and processability. The polymer market is currently dominated by products prepared using Ziegler-Natta (ZN)-type catalysts and metallocene-type catalysts. The optimization of these polyethylene products almost always involves methods using multiple reactors and / or multiple catalysts. These strategies tend to be complex and expensive. Therefore, there is still a need to discover new catalyst systems that improve the economic viability of catalysts and allow for the preparation of polymers with improved properties.

[0017] Catalysts for olefin polymerization can be based on bis(phenolate) complexes used as catalyst precursors, which are typically activated with aluminoxane or activators containing non-coordinating anions. Examples of bis(phenolate) complexes can be found in the following references:

[0018] KR 2018-022137 (LG Chem.) describes transition metal complexes of bis(methylphenylphenolate)pyridine.

[0019] US 7,030,256 B2 (Symyx Technologies, Inc.) describes bridged diaryl ligands, catalysts, methods for polymerization, and polymers formed therefrom.

[0020] US 6,825,296 (University of Hong Kong) describes transition metal complexes of bis(phenol) ligands, where the ligands coordinate with the metal to form two 6-membered rings.

[0021] US 7,847,099 (California Institute of Technology) describes transition metal complexes of bis(phenol) ligands, where the ligands coordinate with the metal to form two 6-membered rings.

[0022] WO 2016 / 172110 (Univation Technologies) describes complexes of tridentate bis(phenol) ligands having acyclic ether or thioether donors.

[0023] Other relevant literature includes: Baier, M.C. et al., "Post-Metallocenes in the Industrial Production Process of Polyolefins", Angew. Chem. Int. Ed. 2014, 53, 9722 - 9744; and Golisz and Bercaw, "Synthesis of Early Transition Metal Bis(phenoxide) Complexes and Their Use as Olefin Polymerization Catalysts", Macromolecules 2009, 42, 8751 - 8762.

[0024] In addition, it is advantageous to conduct industrial solution polymerization reactions at elevated temperatures. The two main catalyst limiting factors commonly used to prevent such high-temperature polymerization are catalyst efficiency and the molecular weight of the resulting polymer, as both of these factors decrease with increasing temperature. Typical metallocene catalysts suitable for producing polyethylene copolymers have relatively limited molecular weight capabilities, which require low process temperatures to obtain products with the desired low melt flow rate.

[0025] The newly developed single-site catalysts described herein and in the related USSN 16 / 787,909 filed on February 11, 2020, have the ability to prepare high molecular weight polymers at elevated polymerization temperatures. When these catalysts are matched with various types of activators and used in solution processes, polymer compositions with excellent properties can be prepared, such as lower Tm and excellent molecular weight. In addition, the catalysts have high activity, which facilitates their use under industrially relevant process conditions. This new method provides novel polymers with an extended melt flow rate range and can be prepared at increased reactor throughput and higher polymerization temperatures during polymerization preparation. Summary of the Invention

[0027] The present invention relates to polymer compositions containing cycloolefins, such as copolymers formed from cycloolefins with ethylene and / or propylene and / or one or more C4 - C 12 α-olefins, and blends comprising such copolymers, wherein the polymer compositions are prepared by using a transition metal catalyst complex of a bis(phenoxide) ligand in a solution process. Preferably, the bis(phenoxide) ligand is a dianionic tridentate ligand having a central neutral heterocyclic Lewis base and two phenoxide donors, wherein the tridentate ligand coordinates with the metal center to form two 8-membered rings. The polymer and copolymer compositions described herein preferably contain a cycloolefin and a comonomer content of ethylene and / or propylene and optionally C4 or higher α-olefins greater than 0.1 mole %.

[0028] The present invention also relates to polymer compositions, such as copolymers formed from cycloolefins and ethylene and / or propylene and / or one or more C4-C 12 α-olefins, and blends comprising such copolymers, wherein said polymer compositions are prepared using a bis(phenolate) complex in a solution process, preferably a bis(phenolate) complex represented by formula (I):

[0029]

[0030] wherein:

[0031] M is a transition metal of Groups 3 to 6 or a lanthanide element;

[0032] E and E' are each independently O, S or NR 9 , where R 9 is independently hydrogen, a C1-C 40 hydrocarbyl group, a substituted C1-C 40 hydrocarbyl group, or a heteroatom-containing group;

[0033] Q is an atom of Group 14, 15 or 16 that forms a coordinate bond with the metal M;

[0034] A 1 QA 1’ is part of a heterocyclic Lewis base containing 4 - 40 non-hydrogen atoms, which connects A 2 to A 2’ via a 3-atom bridge, where Q is the central atom of the 3-atom bridge, and A 1 and A 1 ' are independently C, N or C(R 22 ), where R 22 is selected from hydrogen, a C1-C 20 hydrocarbyl group, a substituted C1-C 20 hydrocarbyl group;

[0035] is a divalent group containing 2 - 40 non-hydrogen atoms, which connects A 1 to the aryl group bonded to E via a 2-atom bridge;

[0036] is a divalent group containing 2 - 40 non-hydrogen atoms, which connects A 1 ' to the aryl group bonded to E' via a 2-atom bridge;

[0037] L is a neutral Lewis base;

[0038] X is an anionic ligand;

[0039] n is 1, 2 or 3;

[0040] m is 0, 1 or 2;

[0041] n + m is not greater than 4;

[0042] Each R 1 、R 2 、R 3 、R 4 、R 1 ', R 2、 R 3 ' and R 4 ' are independently hydrogen, a C1-C 40 hydrocarbyl group, a substituted C1-C 40 hydrocarbyl group, 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 ′ can be connected together to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles or unsubstituted heterocycles, each of said rings having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings can be connected to form additional rings;

[0043] Any two L groups can be connected together to form a bidentate Lewis base;

[0044] The X group can be connected to the L group to form a monoanionic bidentate group;

[0045] Any two X groups can be connected together to form a dianionic ligand group.

[0046] The present invention also relates to a solution-phase process for polymerizing cycloolefins, the process comprising contacting a catalyst compound as described herein with an activator, a cycloolefin and optionally ethylene and / or propylene and one or more C4-C 10 α-olefin comonomers. The present invention relates to a polymer composition containing cycloolefins prepared by the process described herein.

[0047] Definitions:

[0048] For the purposes of the present invention and the claims, the following definitions shall apply:

[0049] Use the new naming rules of the periodic table as described in Chemical and Engineering News, v.63(5), pg.27(1985). Thus, a "Group 4 metal" is an element selected from Group 4 of the periodic table, such as Hf, Ti, or Zr.

[0050] "Catalyst yield" is a means of measuring the quality of the polymer produced using a known amount of polymerization catalyst. Generally, the unit of "catalyst yield" is kg polymer / kg catalyst, or g polymer / mmol catalyst, etc. If no unit is specified, the unit of "catalyst yield" is g polymer / g catalyst. To calculate the catalyst yield, only the weight of the transition metal component of the catalyst is used (i.e., the activator and / or cocatalyst is ignored). "Catalyst activity" is a means of measuring the quality of the polymer produced per unit time using a known amount of polymerization catalyst in batch and semi-batch polymerization reactions. Generally, the unit of "catalyst activity" is (g polymer) / (mmol catalyst) / hour or (kg polymer) / (mmol catalyst) / hour, etc. If no unit is specified, the unit of "catalyst activity" is (g polymer) / (mmol catalyst) / hour.

[0051] "Conversion" is the percentage of monomer that is converted into the polymer product in a polymerization reaction, with the unit of %, and is calculated based on the polymer yield, the composition of the polymer, and the amount of monomer added to the reactor.

[0052] "Olefin" or "alkene" is a straight-chain, branched, or cyclic hydrocarbon having at least one double bond. For the purposes of this specification and the appended claims, when it is mentioned that a polymer or copolymer contains 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 wt% to 55 wt%, it should be understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and the derived units are present in an amount of 35 wt% to 55 wt% based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer having the same monomer units. A "copolymer" is a polymer having two or more mutually different monomer units. A "terpolymer" is a polymer having three or more mutually different monomer units. Thus, the definition of copolymer used herein encompasses terpolymers, etc. The term "different" used herein means that the monomer units are at least one atom different from each other or are isomerically different. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer containing at least 50 mol% of ethylene-derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer containing at least 50 mol% of propylene-derived units, and so on. A polyethylene composition contains an ethylene polymer or an ethylene copolymer.

[0053] Ethylene shall be regarded as an α-olefin.

[0054] Unless otherwise specified, the term "C n " represents a hydrocarbon having n carbon atoms per molecule, where n is a positive integer.

[0055] The term "hydrocarbon" represents a class of compounds containing hydrogen bonded to carbon and encompasses: (i) saturated hydrocarbon compounds; (ii) unsaturated hydrocarbon compounds; and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated), which include mixtures of various hydrocarbon compounds having different n values. Similarly, "C m -C y " group or compound represents a group or compound containing a total of m to y carbon atoms. Thus, C1-C 50 alkyl represents an alkyl group containing a total of 1-50 carbon atoms.

[0056] The terms "group", "radical" and "substituent" may be used interchangeably.

[0057] The terms "hydrocarbyl group", "hydrocarbon radical" or "hydrocarbon group" may be used interchangeably and are defined to represent a group consisting solely of carbon and hydrogen atoms. Preferred hydrocarbyl groups are C1-C 100 groups, which may be straight-chain, branched or cyclic; and when cyclic, the group is aromatic or non-aromatic. Examples of these groups include, but are not limited to: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc.; aryl groups such as phenyl, benzyl, naphthalen-2-yl, etc.

[0058] Unless otherwise specified (such as for the definition of "substituted hydrocarbyl", etc.), the term "substituted" means that at least one hydrogen atom has been replaced by at least one of the following groups: non-hydrogen groups such as hydrocarbyl groups, heteroatoms or heteroatom-containing groups such as halogens (e.g., Br, Cl, F or I), or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, -(CH2) q -SiR*3, etc., where q is from 1 to 10, and each R* is independently hydrogen, a hydrocarbyl group or a halocarbyl group, and two or more R*s may be joined together to form a substituted or unsubstituted, fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted into the hydrocarbyl ring.

[0059] The term "substituted hydrocarbyl" means a hydrocarbyl group in which at least one hydrogen atom of the hydrocarbyl group has been replaced by at least one heteroatom (such as a halogen, such as Br, Cl, F or I) or a heteroatom-containing group (such as a functional group, such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, -(CH2) q -SiR*3 and the like, where q is from 1 to 10, and each R* is independently hydrogen, a hydrocarbyl group or a halocarbonyl group, and two or more R*s can be joined together to form a substituted or unsubstituted, fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), or in which at least one heteroatom has been inserted into the hydrocarbyl ring.

[0060] The term "aryl" or "aryl group" means an aromatic ring (usually formed by 6 carbon atoms) and their substituted variants, such as phenyl, 2-methyl-phenyl, xylene, 4-bromo-xylene. Similarly, heteroaryl means an aryl group in which one ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom, such as N, O or S. The term "aromatic" as used herein also means a pseudoaromatic heterocycle, which is a heterocyclic substituent having properties and a structure (close to planar) similar to those of an aromatic heterocyclic ligand but not belonging to the definition of aromatic.

[0061] The term "substituted aryl" means an aromatic group in which one or more hydrogen atoms have been replaced by a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom or a heteroatom-containing group.

[0062] "Substituted phenolate" is a phenolate group in which at least one, two, three, four or five hydrogen atoms located at the 2-, 3-, 4-, 5- and / or 6-positions have been replaced by at least one of the following groups: non-hydrogen groups, such as hydrocarbyl groups, heteroatoms or heteroatom-containing groups, such as halogens (such as 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 and the like, where q is from 1 to 10, and each R* is independently hydrogen, a hydrocarbyl group or a halocarbonyl group, and two or more R*s can be joined together to form a substituted or unsubstituted, fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), where the 1-position is a phenolate group (groups Ph-O-, Ph-S- and Ph-N(R^)-, where R^ is hydrogen, C1-C 40 hydrocarbyl, substituted C1-C 40(hydrocarbyl, heteroatom, or heteroatom-containing group). Preferably, the "substituted phenoxide" group in the catalyst compounds described herein is represented by the formula:

[0063]

[0064] wherein R 18 is hydrogen, C1-C 40 hydrocarbyl (e.g., C1-C 40 alkyl) or substituted C1-C 40 hydrocarbyl, heteroatom, or heteroatom-containing group, E 17 is oxygen, sulfur, or NR 17 , and each R 17 , R 19 , R 20 , and R 21 is independently selected from hydrogen, C1-C 40 hydrocarbyl (e.g., C1-C 40 alkyl) or substituted C1-C 40 hydrocarbyl, heteroatom, or heteroatom-containing group, or two or more of the groups R 18 , R 19 , R 20 , and R 21 are joined together to form a C4-C 62 cyclic or polycyclic ring structure, or a combination thereof; and, the wavy line indicates the position where the substituted phenoxide group forms a bond to the remainder of the catalyst compound.

[0065] "Alkyl-substituted phenoxide" is a phenoxide group in which at least one, two, three, four, or five hydrogen atoms located at the 2-, 3-, 4-, 5-, and / or 6-positions have been replaced by at least one of the following groups: alkyl, such as C1-C 40 alkyl or C2-C 20 alkyl or C3-C 12 alkyl, such as methyl, ethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, etc., including their substituted analogs.

[0066] "Aryl-substituted phenoxide" is a phenoxide group in which at least one, two, three, four, or five hydrogen atoms located at the 2-, 3-, 4-, 5-, and / or 6-positions have been replaced by at least one aryl group, such as C1-C 40 aryl or C2-C 20 aryl or C3-C 12Aryl groups, such as phenyl, 4-fluorophenyl, 2-methylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, naphthalen-2-yl, etc., including their substituted analogs.

[0067] The term "ring atom" refers to an atom that is part of a cyclic structure. According to this definition, benzyl has 6 ring atoms and tetrahydrofuran has 5 ring atoms.

[0068] A heterocyclic ring, also known as a heterocycle, is a ring that has a heteroatom in its ring structure, which is different from a "ring substituted with a heteroatom", in which a hydrogen atom on a ring atom is replaced by a heteroatom. For example, tetrahydrofuran is a heterocycle, while 4-N,N-dimethylamino-phenyl is a ring substituted with a heteroatom. A substituted heterocycle refers to such a heterocycle that has one or more hydrogen groups replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a heteroatom-containing group.

[0069] A substituted hydrocarbon ring refers to a ring composed of carbon and hydrogen atoms that has one or more hydrogen groups replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a heteroatom-containing group.

[0070] For the purposes of the present invention, when referring to a catalyst compound (e.g., a substituted bis(phenolate) catalyst compound), the term "substituted" means that a hydrogen atom has been replaced by a hydrocarbon group, a heteroatom, or a heteroatom-containing group (e.g., a halogen (e.g., Br, Cl, F, or I)), or at least one functional group, such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, -(CH2) q -SiR*3, etc., where q is from 1 to 10, and each R* is independently hydrogen, a hydrocarbon group, or a halocarbonyl group, and two or more R* may be joined together to form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted into the hydrocarbon ring.

[0071] A tertiary hydrocarbon group has a carbon atom bonded to three other carbon atoms. When the hydrocarbon group is an alkyl group, the tertiary hydrocarbon group is also called a tertiary alkyl group. Examples of tertiary hydrocarbon 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, etc. The tertiary hydrocarbon group can be represented by formula A:

[0072]

[0073] where R A 、RB and R C is a hydrocarbyl or substituted hydrocarbyl, which may optionally be linked to each other, and the wavy line represents the position where a tertiary hydrocarbyl forms a linkage with other groups.

[0074] The cyclic tertiary hydrocarbyl is defined as a tertiary hydrocarbyl that forms at least one alicyclic (non-aromatic) ring. The cyclic tertiary hydrocarbyl is also referred to as an alicyclic tertiary hydrocarbyl. When the hydrocarbyl is an alkyl group, the cyclic tertiary hydrocarbyl is also referred to as a cyclic tertiary alkyl group or an alicyclic tertiary alkyl group. Examples of the cyclic tertiary hydrocarbyl include 1-adamantyl, 1-methylcyclohexyl, 1-methylcyclopentyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclododecyl, bicyclo[3.3.1]non-1-yl, bicyclo[2.2.1]hept-1-yl, bicyclo[2.3.3]hex-1-yl, bicyclo[1.1.1]pent-1-yl, bicyclo[2.2.2]oct-1-yl, and the like. The cyclic tertiary hydrocarbyl can be represented by Formula B:

[0075]

[0076] wherein R A is a hydrocarbyl or substituted hydrocarbyl, each R D independently is hydrogen, a hydrocarbyl or substituted hydrocarbyl, w is an integer from 1 to about 30, and R A may optionally be connected to one or more R D and / or two or more R D to form additional rings optionally.

[0077] When the cyclic tertiary hydrocarbyl contains more than one alicyclic ring, it may be referred to as a polycyclic tertiary hydrocarbyl; or if the hydrocarbyl is an alkyl group, it may be referred to as a polycyclic tertiary alkyl group.

[0078] The terms "alkyl group" and "alkyl" are used interchangeably herein. In the present invention, "alkyl" is defined as C1-C 100An alkyl group, which may be straight-chain, branched or cyclic. Examples of such alkyl groups can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, including their substituted analogs. A substituted alkyl is one in which at least one hydrogen atom of the alkyl has been replaced by at least one of the following groups: a non-hydrogen group, such as a hydrocarbon group, a heteroatom or a heteroatom-containing group, such as a halogen (e.g., Br, Cl, F or I), or at least one functional group, such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, -(CH2)q-SiR*3, etc., where q is from 1 to 10, and each R* is independently hydrogen, a hydrocarbon group or a halocarbonyl group, and two or more R*s may be joined together to form a substituted or unsubstituted, fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), or in which at least one heteroatom has been inserted into the hydrocarbon ring.

[0079] When isomers of the alkyl, alkenyl, alkoxylate or aryl group exist (e.g., n-butyl, isobutyl, sec-butyl and tert-butyl), if one member of the group (e.g., n-butyl) is mentioned, the remaining isomers in the family (e.g., isobutyl, sec-butyl and tert-butyl) should be explicitly disclosed. Similarly, when no specific isomer of the alkyl, alkenyl, alkoxylate or aryl group is specified (e.g., butyl), this explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl and tert-butyl).

[0080] In this document, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, and Mz is the z-average molecular weight, wt% is the weight percentage, and mol% is the mole percentage. The molecular weight distribution (MWD), also known as the polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all units of molecular weight (e.g., Mw, Mn, Mz) are g / mol (g mol -1 ).

[0081] The following abbreviations may be used in this text: Me is methyl, Et is ethyl, Pr is propyl, cPr is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu is n-butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl, MAO is methylaluminoxane, dme (also known as DME) is 1,2-dimethoxyethane, p-tBu is p-tert-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOA and TNOAL are tris(n-octyl)aluminum, p-Me is p-methyl, Bn is benzyl (i.e., CH2Ph), THF (also known as thf) is tetrahydrofuran, RT is room temperature (23 °C unless otherwise stated), 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.

[0082] 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 pairing before activation, it refers to an unactivated catalyst complex (pre-catalyst) with an activator and optionally a co-activator. When the term is used to describe such a pairing after activation, it refers to the activated complex and the activator or other structural moieties used to balance the charge. The transition metal compound can be neutral as in the pre-catalyst or in a charged form with a counterion as in the activated catalyst system. For the purposes of this invention and the appended claims, when a catalyst system is described as including a component in a neutral stable form, those skilled in the art will understand that the ionic form of the component is the form that can react with monomers to form polymers. A polymerization catalyst system is a catalyst system capable of polymerizing monomers into polymers.

[0083] In this text, a 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 may be used interchangeably.

[0084] An "anionic ligand" is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. The term "anionic donor" may be used interchangeably with "anionic ligand". In this invention, examples of anionic donors include, but are not limited to, methyl, chloride, fluoride, alkoxides, aryloxides, alkyls, alkenyls, thiolates, carboxylates, amidates, methyl, benzyl, hydrido, amidinates, amides, and phenyl. Two anionic donors may be linked to form a dianionic group.

[0085] "Neutral Lewis base" or "neutral donor group" refers to a group that is uncharged (i.e., neutral) and supplies one or more pairs of electrons to a metal ion. Non-limiting examples of neutral Lewis bases include ethers, thioethers, amines, phosphines, ethyl ether, tetrahydrofuran, dimethyl sulfide, triethylamine, pyridine, olefins, alkynes, allenes, and carbenes. Lewis bases can be linked together to form bidentate or tridentate Lewis bases.

[0086] For the purposes of this invention and the appended claims, phenolate donors include Ph-O-, Ph-S-, and Ph-N(R^)- groups, where R^ is hydrogen, C1-C 40 hydrocarbyl, substituted C1-C 40 hydrocarbyl, heteroatom, or heteroatom-containing group, and Ph is an optionally substituted phenyl group.

[0087] Detailed Description

[0088] This invention relates to solution processes using novel catalyst compounds and polymer compositions containing cyclic monomers prepared therefrom, said novel catalysts comprising transition metal complexes of bis(phenolate) ligands, said ligands preferably being dianionic tridentate ligands having a central neutral donor group and two phenolate donors, wherein the tridentate ligand coordinates with the metal center to form two 8-membered rings. In complexes of this type, the central neutral donor is advantageously a heterocyclic group. Particularly advantageously, the heterocyclic group lacks hydrogen at the para position of the heteroatom. In such complexes, it is also advantageous that the phenolate is substituted with one or more cyclic tertiary alkyl substituents. It has been demonstrated that by using phenolates substituted with cyclic tertiary alkyl groups, the ability of these catalysts to prepare high molecular weight polymers can be improved.

[0089] Complexes of substituted bis(phenolate) ligands (e.g., adamantyl-substituted bis(phenolate) ligands) used herein, when combined with an activator, such as a non-coordinating anion or an aluminoxane activator, form active olefin polymerization catalysts. Usable bis(arylphenolate)pyridine complexes comprise tridentate bis(arylphenolate)pyridine ligands that coordinate with Group 4 transition metals to form two 8-membered rings.

[0090] This invention also relates to solution processes for preparing polymer compositions containing cyclic monomers using metal complexes, said processes comprising contacting a metal selected from Group 3-6 or lanthanide metals with a tridentate dianionic ligand containing a neutral Lewis base donor and two anionic donor groups, wherein the neutral Lewis base donor is covalently bonded between the two anionic donor groups, and wherein the metal-ligand complex has a pair of metal-containing 8-membered rings.

[0091] This invention relates to catalyst systems for use in solution processes for preparing polymer compositions containing cyclic monomers, said catalyst systems comprising an activator and one or more catalyst compounds described herein.

[0092] The present invention also relates to a solution process (preferably at elevated temperature) for polymerizing olefins using a catalyst compound as described herein, which process comprises contacting a cyclic monomer and optionally one or more olefin comonomers with a catalyst system comprising an activator and a catalyst compound as described herein.

[0093] The present invention also relates to a catalyst system comprising a transition metal compound and an activator compound as described herein; to the use of such an activator compound for activating the transition metal compound in the catalyst system to polymerize a cyclic monomer and optionally one or more olefin comonomers; and to a process for polymerizing said olefins, which process comprises contacting a cyclic monomer and 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 (e.g., present in an amount of 0 mol% or less than 1 mol% relative to the amount of activator, preferably the catalyst system, the polymerization reaction, and / or the resulting polymer is free of detectable aromatic solvents, such as toluene).

[0094] The polymer composition containing cycloolefins prepared in the present invention preferably contains 0 ppm (or less than 1 ppm, or less than 100 ppm, or less than 500 ppm) of aromatic hydrocarbons, such as toluene. Preferably, the polyethylene composition prepared herein contains 0 ppm (or less than 1 ppm) of toluene.

[0095] The catalyst system described herein preferably contains 0 ppm (or less than 1 ppm) of aromatic hydrocarbons. Preferably, the catalyst system described herein contains 0 ppm (or less than 1 ppm) of toluene.

[0096] Catalyst compound

[0097] The terms "catalyst", "compound", "catalyst compound", and "complex" are used interchangeably to describe a complex of a transition metal or a lanthanide metal which forms an olefin polymerization catalyst when combined with a suitable activator.

[0098] The catalyst complex of the present invention comprises a metal selected from Group 3, 4, 5 or 6 of the Periodic Table or a lanthanide metal and comprises a tridentate dianionic ligand containing a neutral heterocyclic Lewis base donor and two anionic donor groups, wherein the heterocyclic donor is covalently bonded between the two anionic donors. Preferably, the catalyst complex comprises a dianionic tridentate ligand having a central heterocyclic donor group and two phenolate donors, and the tridentate ligand coordinates with the metal center to form two 8-membered rings. Also preferably, the catalyst complex comprises a tridentate dianionic ligand having a central heterocyclic donor linked to two phenolate donors, wherein the central heterocycle is linked to each phenolate donor via a 1,2-arylene bridge (such as 1,2-phenylene).

[0099] The metal is preferably selected from the elements of Group 3, 4, 5 or 6. Metal M is preferably a Group 4 metal. Most preferably, metal M is zirconium or hafnium.

[0100] The heterocyclic Lewis base donor preferably has a nitrogen or oxygen donor atom. Preferred heterocyclic groups include derivatives of pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and substituted variant forms thereof. Preferably, the heterocyclic Lewis base lacks one or more hydrogens at the para position of the donor atom. Particularly preferred heterocyclic Lewis base donors include pyridine, 3-substituted pyridine, and 4-substituted pyridine.

[0101] The anionic donors of the tridentate dianionic ligand can be aryl thiolate, phenolate or N-acylaniline. The preferred anionic donor is phenolate. Preferably, the tridentate dianionic ligand coordinates with the metal center to form a complex lacking a symmetry mirror plane. Preferably, the tridentate dianionic ligand coordinates with the metal center to form a complex having a symmetric two-fold rotation axis; when determining the symmetry of the bis(phenolate) complex, only the metal and the dianionic tridentate ligand are considered (i.e., the remaining ligands are ignored).

[0102] Bis(phenolate) ligands useful in the present invention include dianionic polydentate (such as bidentate, tridentate or tetradentate) ligands having two anionic phenolate donors. Preferably, the bis(phenolate) ligand is a tridentate dianionic ligand that coordinates with metal M to form a pair of 8-membered metal-containing rings. The preferred bis(phenolate) ligand wraps around the metal, thereby forming a complex having a two-fold rotation axis, resulting in C2 symmetry of the complex. The C2 geometry and the 8-membered metal-containing ring are characteristic of these complexes to make them effective catalyst components for preparing polyolefins, especially isotactic poly-α-olefins. If the ligand coordinates with the metal such that the complex has a mirror plane (C s)Symmetry, it is expected that such catalysts can only produce atactic poly(α-olefins); these symmetry-reactivity rules can be found in the review by Bercaw in Macromolecules 2009, v.42, pp. 8751-8762. A pair of 8-membered metal-containing rings of the complexes of the present invention is also a notable feature, which is beneficial to catalyst activity, temperature stability, and isotactic selectivity of monomer chain growth. It is already known that related Group 4 element complexes with smaller 6-membered metal-containing rings (Macromolecules 2009, v.42, pp. 8751-8762) form a mixture of C2 and C s symmetric complexes when used in olefin polymerization, and thus are not very suitable for preparing highly isotactic poly(α-olefins).

[0103] The bis(phenolate) ligands containing oxygen donor groups in the present invention (i.e., in formula (I), E = E' = oxygen) are preferably substituted by alkyl, substituted alkyl, aryl, or other groups. Advantageously, each phenolate group is substituted at the ring position adjacent to the oxygen donor atom. Preferably, the substituent at the position adjacent to the oxygen donor atom is an alkyl group containing 1-20 carbon atoms. Preferably, the substituent at the position adjacent to the oxygen donor atom is a non-aromatic cyclic alkyl group having one or more 5- or 6-membered rings. Preferably, the substituent at the position adjacent to the oxygen donor atom is a cyclic tertiary alkyl group. Highly preferably, the substituent at the position adjacent to the oxygen donor atom is adamantan-1-yl or substituted adamantan-1-yl.

[0104] The neutral heterocyclic Lewis base donor is covalently linked between two anionic donors via a "linking group" for linking the heterocyclic Lewis base to the phenolate group. The "linking group" is represented by (A 3 A 2 ) and (A 2’ A 3’ ) in formula (I). The choice of each linking group can affect catalyst performance, such as the stereoregularity of the resulting poly(α-olefins). Each linking group is generally a C2-C 40 divalent group with a length of two atoms. One or both linking groups can independently be phenylene, substituted phenylene, heteroaryl, vinylene, or an acyclic linking group with a two-carbon length. When one or both linking groups are phenylene, the alkyl substituents on the phenylene can be selected to optimize catalyst performance. Generally, one or both phenylene groups can be unsubstituted, or can be independently substituted by C1-C 20Alkyl substitution, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl or their isomers, such as isopropyl, etc.

[0105] The present invention also relates to a catalyst compound represented by formula (I), and a catalyst system comprising such a compound:

[0106]

[0107] Wherein:

[0108] M is a transition metal of Group 3, 4, 5 or 6 or a lanthanide element (such as Hf, Zr or Ti);

[0109] E and E' are each independently O, S or NR 9 , where R 9 is independently hydrogen, C1-C 40 hydrocarbyl, substituted C1-C 40 hydrocarbyl or a heteroatom-containing group, preferably O, and preferably both E and E' are O;

[0110] Q is an atom of Group 14, 15 or 16, which forms a coordination 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;

[0111] A 1 QA 1’ is part of a heterocyclic Lewis base containing 4-40 non-hydrogen atoms, which connects A 2 to A 2’ via a 3-atom bridge, where Q is the central atom of the 3-atom bridge (A 1 QA 1’ connected to A 1 and A 1’ together with the curve represents the heterocyclic Lewis base), A 1 and A 1 ' are each independently C, N or C(R 22 ), where R 22 is selected from hydrogen, C1-C 20 hydrocarbyl and substituted C1-C 20 hydrocarbyl. Preferably A 1 and A 1 ' are C;

[0112] is a divalent group containing 2-40 non-hydrogen atoms, which connects A 1is connected via a 2-atom bridge to an aryl group bonded to E, such as o-phenylene, substituted o-phenylene, o-arene, indolylene, substituted indolylene, benzothiophene, substituted benzothiophene, pyrrolylene, substituted pyrrolylene, thiophene, substituted thiophene, 1,2-ethylene (-CH2CH2-), substituted 1,2-ethylene, 1,2-vinylidene (-HC=CH-), or substituted 1,2-vinylidene, preferably is a divalent hydrocarbon group;

[0113] is a divalent group containing 2 to 40 non-hydrogen atoms that connects A 1 ' via a 2-atom bridge to an aryl group bonded to E', such as o-phenylene, substituted o-phenylene, o-arene, indolylene, substituted indolylene, benzothiophene, substituted benzothiophene, pyrrolylene, substituted pyrrolylene, thiophene, substituted thiophene, 1,2-ethylene (-CH2CH2-), substituted 1,2-ethylene, 1,2-vinylidene (-HC=CH-), or substituted 1,2-vinylidene, preferably is a divalent hydrocarbon group;

[0114] Each L is independently a Lewis base;

[0115] Each X is independently an anionic ligand;

[0116] n is 1, 2, or 3;

[0117] m is 0, 1, or 2;

[0118] n + m is not greater than 4;

[0119] Each R 1 、R 2 、R 3 、R 4 、R 1 '、R 2 '、R 3 ' and R 4 ' are independently hydrogen, C1-C 40 hydrocarbon group, substituted C1-C 40 hydrocarbon group, heteroatom or heteroatom-containing group (preferably R 1 ' and R 1 are independently cyclic groups, such as cyclic tertiary alkyl groups), 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 ' one or more of which may be joined together to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles or unsubstituted heterocycles, each of said rings having 5, 6, 7 or 8 ring atoms, and wherein substituents on the ring may be joined together to form additional rings;

[0120] Any two L groups may be joined together to form a bidentate Lewis base;

[0121] The X group may be attached to the L group to form a monoanionic bidentate group;

[0122] Any two X groups may be joined together to form a dianionic ligand group.

[0123] The present invention also relates to a catalyst compound represented by formula (II), and a catalyst system comprising such a compound:

[0124]

[0125] wherein:

[0126] M is a transition metal of Group 3, 4, 5 or 6 or a lanthanide element (e.g., Hf, Zr or Ti);

[0127] E and E' are each independently O, S or NR 9 , wherein R 9 is independently hydrogen, C1-C 40 hydrocarbyl, substituted C1-C 40 hydrocarbyl or a heteroatom-containing group, preferably O, and preferably both E and E' are O;

[0128] Each L is independently a Lewis base;

[0129] Each X is independently an anionic ligand;

[0130] n is 1, 2 or 3;

[0131] m is 0, 1 or 2;

[0132] n + m is not greater than 4;

[0133] Each R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ' and R 4 ' are independently hydrogen, C1-C 40 hydrocarbyl, substituted C1-C 40A hydrocarbyl group, 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 ' one or more of which may be joined together to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles or unsubstituted heterocycles, each of said rings having 5, 6, 7 or 8 ring atoms, and wherein substituents on the rings may be joined together to form additional rings;

[0134] Any two L groups may be joined together to form a bidentate Lewis base;

[0135] The X group may be attached to the L group to form a monoanionic bidentate group;

[0136] Any two X groups may be joined together to form a dianionic ligand group;

[0137] Each R 5 、R 6 、R 7 、R 8 、R 5’ 、R 6’ 、R 7’ 、R 8’ 、R 10 、R 11 and R 12 is independently hydrogen, C1-C 40 hydrocarbyl, substituted C1-C 40 hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 5 and R 6 、R 6 and R 7 、R 7 and R 8 、R 5’ and R 6’ 、R 6’ and R 7’ 、R 7’ and R 8’ 、R 10 and R 11 or R 11 and R 12One or more of which may be linked to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each of said rings having 5, 6, 7 or 8 ring atoms, and wherein substituents on the ring may be linked to form additional rings.

[0138] The metal M is preferably selected from elements of Group 3, 4, 5 or 6, more preferably an element of Group 4. The most preferred metal M is zirconium or hafnium.

[0139] The donor atom Q of the neutral heterocyclic Lewis base (in formula (I)) is preferably nitrogen, carbon or oxygen. Preferred Q is nitrogen.

[0140] Non-limiting examples of neutral heterocyclic Lewis base groups include derivatives of pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and their substituted variant forms. Preferred heterocyclic Lewis base groups include derivatives of pyridine, pyrazine, thiazole and imidazole.

[0141] Each A of the heterocyclic Lewis base 1 and A 1’ (in formula I) is independently C, N or C(R 22 ), where R 22 is selected from hydrogen, C1-C 20 hydrocarbon group and substituted C1-C 20 hydrocarbon group. Preferred A 1 and A 1 ' are carbon. When Q is carbon, preferably A 1 and A 1’ are selected from nitrogen and C(R 22 ). When Q is nitrogen, preferably A 1 and A 1’ are carbon. Preferably, Q = nitrogen, and A 1 = A 1’ = carbon. When Q is nitrogen or oxygen, preferably, the heterocyclic Lewis base in formula (I) does not have any hydrogen atoms bonded to the A 1 or A 1’ atoms. This is preferred because it is believed that hydrogen at these positions may undergo unwanted decomposition reactions, which reduce the stability of the catalytically active substance.

[0142] The heterocyclic Lewis base represented by A 1 QA 1’ together with the curve used to connect A 1 and A 1’ (in formula (I)) is preferably selected from the following cases: where each R 23 group is selected from hydrogen, heteroatom, C1-C 20 alkyl group, C1-C 20 alkoxide, C1-C20 Amides and substituted C1-C 20 alkyl groups.

[0143]

[0144] In formula (I) or (II), E and E' are each independently selected from oxygen or NR 9 , where R 9 is independently hydrogen, a C1-C 40 hydrocarbyl group, a substituted C1-C 40 hydrocarbyl group or a heteroatom-containing group. Preferably, E and E' are oxygen. When E and / or E' is NR 9 , preferably, R 9 is selected from C1-C 20 hydrocarbyl groups, alkyl groups or aryl groups. In one embodiment, E and E' are each independently selected from O, S or N(alkyl) or N(aryl), where the alkyl group is preferably a C1-C 20 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, etc., and the aryl group is a C6-C 40 aryl group, such as phenyl, naphthalen-2-yl, benzyl, methylphenyl, etc.

[0145] In one embodiment, and are each independently a divalent hydrocarbyl group, such as a C1-C 12 hydrocarbyl group.

[0146] In the complexes of formula (I) or (II), when E and E' are oxygen, it is advantageous that each phenolate group is substituted at the position adjacent to the oxygen atom (i.e., R 1 and R 1’ in formula (I) or (II)). Thus, when E and E' are oxygen, preferably, each R 1 and R 1 ' is independently a C1-C 40 hydrocarbyl group, a substituted C1-C 40 hydrocarbyl group, a heteroatom or a heteroatom-containing group, more preferably each R 1 and R 1 ' is independently a non-aromatic cyclic alkyl group having one or more 5- or 6-membered rings (such as cyclohexyl, cyclooctyl, adamantyl or 1-methylcyclohexyl, or a substituted adamantyl), most preferably a non-aromatic cyclic tertiary alkyl group (such as 1-methylcyclohexyl, adamantyl or a substituted adamantyl).

[0147] In some embodiments of the formula (I) or (II) of the present invention, each R 1 and R 1'is independently a tertiary hydrocarbon group. In other embodiments of formula (I) or (II) of the present invention, each R 1 and R 1 'is independently a cyclic tertiary hydrocarbon group. In other embodiments of formula (I) or (II) of the present invention, each R 1 and R 1' is independently a polycyclic tertiary hydrocarbon group.

[0148] In some embodiments of formula (I) or (II) of the present invention, each R 1 and R 1' is independently a tertiary hydrocarbon group. In other embodiments of formula (I) or (II) of the present invention, each R 1 and R 1' is independently a cyclic tertiary hydrocarbon group. In other embodiments of formula (I) or (II) of the present invention, each R 1 and R 1' is independently a polycyclic tertiary hydrocarbon group.

[0149] The linking groups (i.e., and in formula (I)) are each preferably part of an ortho-phenylene group, preferably a substituted ortho-phenylene group. Preferably, R 7 and R 7’ in formula (II) are hydrogen or C1-C 20 alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl or their isomers, such as isopropyl, etc. For applications of polymers with high stereoregularity, preferably, R 7 and R 7’ in formula (II) are C1-C 20 alkyl, most preferably R 7 and R 7’ are both C1-C3 alkyl.

[0150] In the embodiments of formula (I) herein, Q is C, N or O, preferably Q is N.

[0151] In the embodiments of formula (I) herein, A 1 and A 1' are independently carbon, nitrogen or C(R 22 ), where R 22 is selected from hydrogen, C1-C 20 hydrocarbon group, substituted C1-C 20 hydrocarbon group. Preferably A 1 and A 1’ are carbon.

[0152] In the embodiments 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 a substituted variant form thereof.

[0153] In the embodiments of formula (I) herein, A 1 QA 1’ is part of a heterocyclic Lewis base containing 2 - 20 non-hydrogen atoms, which connects A 2 to A via a 3 - atom bridge 2’ , where Q is the central atom of the 3 - atom bridge. Preferably, each A 1 and A 1' is a carbon atom, and the A 1 QA 1’ segment forms part of pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan or a substituted variant form of these groups, or a substituted variant form thereof.

[0154] In the embodiments of formula (I) herein, Q is carbon, and each A 1 and A 1' is N or C(R 22 ), where R 22 is selected from hydrogen, C1 - C 20 hydrocarbyl, substituted C1 - C 20 hydrocarbyl, heteroatom or heteroatom - containing group. In this embodiment, the A 1 QA 1’ segment forms part of a cyclic carbene, N - heterocyclic carbene, cyclic aminoalkyl carbene or a substituted variant form of these groups, or a substituted variant form thereof.

[0155] In the embodiments of formula (I) herein, is a divalent group containing 2 - 20 non - hydrogen atoms, which connects A 1 to the aryl group bonded to E via a 2 - atom bridge, where is a straight - chain alkyl group, or forms part of a cyclic group (such as an optionally substituted o - phenylene, or o - aryl), or a substituted variant form thereof.

[0156] is a divalent group containing 2 - 20 non - hydrogen atoms, which connects A 1' to the aryl group bonded to E' via a 2 - atom bridge, where is a straight-chain alkyl group, or forms part of a cyclic group (e.g., an optionally substituted o-phenylene group, or o-aryl group), or a substituted variant thereof.

[0157] In an embodiment of the present invention, in formula (I) or (II), M is a Group 4 metal, such as Hf or Zr.

[0158] In an embodiment of the present invention, in formulas (I) and (II), E and E' are O.

[0159] 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, a C1-C 40 hydrocarbyl group, a substituted C1-C 40 hydrocarbyl group, 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 ' can be joined together to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles or unsubstituted heterocycles, each ring having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the ring can be joined together to form additional rings; preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or their isomers.

[0160] 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 9Independently 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 (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthalen-2-yl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and their isomers.

[0161] In an embodiment of the present invention, in formulas (I) and (II), R 4 and R 4 ′ are independently hydrogen or a C1-C3 hydrocarbon group, such as methyl, ethyl or propyl.

[0162] In an embodiment of the present invention, in formulas (I) and (II), R 9 is hydrogen, a C1-C 40 hydrocarbon group, a substituted C1-C 40 hydrocarbon group or a heteroatom-containing group, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or their isomers. Preferably, R 9 is methyl, ethyl, propyl, butyl, a C1-C6 alkyl group, phenyl, 2-methylphenyl, 2,6-dimethylphenyl or 2,4,6-trimethylphenyl.

[0163] In an embodiment of the present invention, in formulas (I) and (II), each X is independently selected from a hydrocarbon group having 1-20 carbon atoms (such as an alkyl group or an aryl group), a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, an alkyl sulfonate, and their combinations (two or more Xs can form a fused ring or a part of a ring system), preferably each X is independently selected from a halide, an aryl group and a C1-C5 alkyl group, preferably each X is independently a hydride, a dimethylamino group, a diethylamino group, a methyltrimethylsilyl group, a neopentyl group, a phenyl group, a benzyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a fluoro group, an iodo group, a bromo group or a chloro group.

[0164] Alternatively, each X can independently be a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.

[0165] In embodiments of the present invention, in Formulas (I) and (II), each L is independently a Lewis base selected from: ethers, thioethers, amines, nitriles, imines, pyridines, halocarbons, and phosphines, preferably ethers and thioethers, and combinations thereof. Optionally, two or more L's may form part of a fused ring or ring system. Preferably, each L is independently selected from ether and thioether groups. Preferably, each L is an ethyl ether, tetrahydrofuran, dibutyl ether, or dimethyl sulfide group.

[0166] In embodiments of the present invention, in Formulas (I) and (II), R 1 and R 1’ are independently cyclic tertiary alkyl groups.

[0167] In embodiments of the present invention, in Formulas (I) and (II), n is 1, 2, or 3, and is typically 2.

[0168] In embodiments of the present invention, in Formulas (I) and (II), m is 0, 1, or 2, and is typically 0.

[0169] In embodiments of the present invention, in Formulas (I) and (II), R 1 and R 1 ′ are not hydrogen.

[0170] In embodiments of the present invention, in Formulas (I) and (II), M is Hf or Zr; E and E′ are O; each R 1 and R 1’ are independently a C1-C 40 hydrocarbyl group, a substituted C1-C 40 hydrocarbyl group, a heteroatom, or a heteroatom-containing group, each R 2 、R 3 、R 4 、R 2 ′、R 3 ′ and R 4 ′ are independently hydrogen, a C1-C 20 hydrocarbyl group, a substituted C1-C 20 hydrocarbyl group, 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 4One or more of the ′s may be joined to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each ring having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the ring may be joined to form additional rings; each X is independently selected from hydrocarbon groups having 1-20 carbon atoms (such as alkyl or aryl), hydrides, amides, alkoxides, sulfides, phosphides, halides and combinations thereof (two or more X's may form a fused ring or part of a ring system); each L is independently selected from ethers, thioethers and halo carbons (two or more L's may form a fused ring or part of a ring system).

[0171] In an embodiment of the present invention, in formula (II), each R 5 , R 6 , R 7 , R 8 , R 5 ′, R 6 ′, R 7 ′, R 8 ′, R 10 , R 11 and R 12 is independently hydrogen, a C1-C 40 hydrocarbon group, a substituted C1-C 40 hydrocarbon group, a heteroatom or a heteroatom-containing group, or one or more adjacent R groups may be joined to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each ring having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the ring may be joined to form additional rings.

[0172] In an embodiment of the present invention, in formula (II), each R 5 , R 6 , R 7 , R 8 , R 5 ′, R 6 ′, R 7 ′, R 8 ′, R 10 , R 11 and R 12 is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or their isomers.

[0173] In an embodiment of the present invention, in formula (II), each R 5 , R 6 , R 7 , R 8 , R 5 ′, R 6 ′, R 7 ′, R 8 ′, R10 , R 11 and R 12 are 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 (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthalen-2-yl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and their isomers.

[0174] In an embodiment of the present invention, in formula (II), M is Hf or Zr; E and E′ are O; each R 1 and R 1 ′ are independently C1-C 40 hydrocarbyl, substituted C1-C 40 hydrocarbyl, heteroatom or heteroatom-containing group;

[0175] Each R 1 , R 2 , R 3 , R 4 , R 1 ′, R 2 ′, R 3 ′ and R 4 ′ are independently hydrogen, C1-C 20 hydrocarbyl, substituted C1-C 20 hydrocarbyl, heteroatom or 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 ′, one or more of which may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles or unsubstituted heterocycles, each of said rings having 5, 6, 7 or 8 ring atoms, and wherein substituents on the ring may be joined to form additional rings; R 9 is hydrogen, C1-C 20 hydrocarbyl, substituted C1-C 20 hydrocarbyl or heteroatom-containing group, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or their isomers;

[0176] Each X is independently selected from the group consisting of: a hydrocarbyl group having 1 to 20 carbon atoms (such as an alkyl or aryl group), 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 Xs can form part of a fused ring or a ring system); n is 2; m is 0; and each R 5 、R 6 、R 7 、R 8 、R 5 ′、R 6 ′、R 7 ′、R 8 ′、R 10 、R 11 and R 12 are independently hydrogen, a C1-C 20 hydrocarbyl group, a substituted C1-C 20 hydrocarbyl group, a heteroatom or a heteroatom-containing group, or one or more adjacent R groups can be linked to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles or unsubstituted heterocycles, each of said rings having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the ring can be linked to form additional rings, for example each R 5 、R 6 、R 7 、R 8 、R 5 ′、R 6 ′、R 7 '、R 8 '、R 10 、R 11 and R 12 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and their isomers.

[0177] A preferred embodiment of formula (I) is: M is Zr or Hf, Q is nitrogen, A 1 and A 1’ are both carbon, E and E ’ are both oxygen, and R 1 and R 1’ are both C4-C 20 cyclic tertiary alkyl groups.

[0178] A preferred embodiment of formula (I) is: M is Zr or Hf, Q is nitrogen, A 1 and A 1’ are both carbon, E and E' are both oxygen, and R 1 and R 1’ are both adamantan-1-yl or substituted adamantan-1-yl.

[0179] A preferred embodiment of formula (I) is: M is Zr or Hf, Q is nitrogen, A 1 and A 1’ are both carbon, E and E' are both oxygen, X is methyl or chlorine, and n is 2.

[0180] A preferred embodiment of formula (II) is: M is Zr or Hf, E and E' are both oxygen, and R 1 and R 1’ are both C4-C 20 cyclic tertiary alkyl.

[0181] A preferred embodiment of formula (II) is: M is Zr or Hf, E and E' are both oxygen, and R 1 and R 1’ are both adamantan-1-yl or substituted adamantan-1-yl.

[0182] A preferred embodiment of formula (II) is: M is Zr or Hf, E and E' are both oxygen, and each R 1 , R 1’ , R 3 and R 3’ is adamantan-1-yl or substituted adamantan-1-yl.

[0183] A preferred embodiment of formula (II) is: M is Zr or Hf, E and E' are both oxygen, R 1 and R 1’ are both C4-C 20 cyclic tertiary alkyl, and R 7 and R 7’ are both C1-C 20 alkyl.

[0184] Catalyst compounds that are particularly useful in the present invention include one or more of the following: [2',2”'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olato]dimethylzirconium, [2',2”'-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olato]dimethylhafnium, [6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-adamantan-1-yl)-4-methylphenolato]dimethylzirconium, [6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-adamantan-1-yl)-4-methylphenolato]dimethylhafnium, [2',2”'-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-olato)]dimethylzirconium, [2',2”'-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-olato)]dimethylhafnium, [2',2”'-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-olato)]dimethylzirconium, [2',2”'-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-olato)]dimethylhafnium.

[0185] Catalyst compounds that are particularly useful in the present invention include those compounds represented by one or more of the following formulas:

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192] In some embodiments, two or more different catalyst compounds are present in the catalyst systems described herein. In some embodiments, two or more different catalyst compounds are present in the reaction zone for carrying out the methods described in the present invention. Preferably, the same activator is used for the transition metal compound, but two different activators can be used in combination, such as a non-coordinating anion activator and an aluminoxane. If the X group in one or more transition metal compounds is not a hydride, hydrocarbyl or substituted hydrocarbyl, the aluminoxane can be contacted with the transition metal compound before adding the non-coordinating anion activator.

[0193] Two transition metal compounds (precatalysts) can be used in any ratio. The preferred molar ratio (A:B) between the (A) transition metal compound and the (B) transition metal compound is in the range of 1:1000 to 1000:1, or 1:100 to 500:1, or 1:10 to 200:1, or 1:1 to 100:1, or 1:1 to 75:1, or 5:1 to 50:1. The choice of the specific ratio will depend on the actually selected precatalysts, activation methods and the desired final product. In a specific embodiment, when two precatalysts are used and both are activated with the same activator, the available molar percentages based on the molecular weight of the precatalyst are 10 - 99.9% A relative to 0.1 - 90% B, or 25 - 99% A relative to 0.5 - 50% B, or 50 - 99% A relative to 1 - 25% B, or 75 - 99% A relative to 1 - 10% B.

[0194] Method for preparing catalyst compound

[0195] Synthesis of ligand

[0196] The bis(phenol) ligand can be prepared using the general method shown in Route 1. The method (Method 1) of forming the bis(phenol) ligand by coupling Compound A with Compound B can be achieved by known Pd- and Ni-catalyzed couplings, such as Negishi, Suzuki or Kumada couplings. The method (Method 2) of forming the bis(phenol) ligand by coupling Compound C with Compound D can also be achieved by known Pd- and Ni-catalyzed couplings, such as Negishi, Suzuki or Kumada couplings. Compound D can be prepared from Compound E, where Compound E reacts with an organolithium reagent or magnesium metal and then optionally with a main group metal halide (such as ZnCl2) or a boron-based reagent (such as B(O i Pr)3, iPrOB(pin)) reaction. Compound E can be prepared in a non-catalytic reaction, where an aryllithium or aryl Grignard reagent (Compound F) reacts with a dihaloarene (Compound G), such as 1-bromo-2-chlorobenzene. Compound E can also be prepared in a Pd- or Ni-catalyzed reaction, where an arylzinc or arylboron reagent (Compound F) reacts with a dihaloarene (Compound G).

[0197] Route 1

[0198]

[0199] where M’ is an element of Group 1, 2, 12 or 13 or a substituted element, such as Li, MgCl, MgBr, ZnCl, B(OH)2, B(pinacol ester); P is a protecting group, such as methoxymethyl (MOM), tetrahydropyranyl (THP), tert-butyl, allyl, ethoxymethyl, trialkylsilyl, tert-butyldimethylsilyl or benzyl; R is C1-C 40 alkyl, substituted alkyl, aryl, tert-alkyl, cyclic tert-alkyl, adamantyl, or substituted adamantyl; and each X' and X is a halogen, such as Cl, Br, F or I.

[0200] Preferably, the bis(phenol) ligand and the intermediate for preparing the bis(phenol) ligand are prepared and purified without using column chromatography. This can be carried out by various methods, including distillation, precipitation and washing, forming insoluble salts (e.g., by reacting a pyridine derivative with an organic acid) and liquid-liquid extraction. Preferred methods include those described in Practical Method Research and Development–Guide for Organic Chemists, Neal C. Anderson (ISBN: 1493300125X).

[0201] Synthesis of carbene bis(phenol) ligand

[0202] A general synthetic method for preparing a carbene bis(phenol) ligand is shown in Route 2. The substituted phenol can be ortho-brominated and then protected with a known phenol protecting group, such as methoxymethyl ether (MOM), tetrahydropyranyl ether (THP), tert-butyldimethylsilyl (TBDMS), benzyl (Bn), etc. Then the bromide is converted into a borate ester (Compound I) or boric acid, which can be used in a Suzuki coupling reaction with bromoaniline. The biphenyl aniline (Compound J) can be bridged by reacting with dibromoethane or condensing with glyoxal, and then deprotected (Compound K). Reacting with triethyl orthoformate forms an imine salt, and then deprotection gives the carbene.

[0203] Route 2

[0204]

[0205] To a substituted phenol (Compound H) dissolved in dichloromethane was added 1 equivalent of N-bromosuccinimide and 0.1 equivalent of diisopropylamine. After stirring at ambient temperature until the reaction was complete, the reaction was quenched with 10% HCl solution. The organic portion was washed with brine, dried over magnesium sulfate, filtered and concentrated under reduced pressure to afford the bromophenol, which was usually a solid. The substituted bromophenol, methoxymethyl chloride and potassium carbonate were dissolved in dry acetone and stirred at ambient temperature until the reaction was complete. The solution was filtered and the filtrate concentrated to afford the protected phenol (Compound I). Alternatively, the substituted bromophenol and 1 equivalent of dihydropyran were dissolved in dichloromethane and cooled to 0 °C. A catalytic amount of p-toluenesulfonic acid was added and the reaction stirred for 10 minutes, then quenched with trimethylamine. The mixture was washed with water and brine, then dried over magnesium sulfate, filtered and concentrated under reduced pressure to afford the tetrahydropyranyl-protected phenol.

[0206] The aryl bromide (Compound I) was dissolved in THF and cooled to -78 °C. Butyllithium was added slowly, then trimethoxyborate. The reaction was stirred at ambient temperature until the reaction was complete. The solvent was removed and the solid borate washed with pentane. The boronic acid could be prepared by treating the borate with HCl. The borate or boronic acid, 1 equivalent of o-bromoaniline and a catalytic amount of tetrakis(triphenyl)phosphonium palladium were dissolved in toluene. Aqueous sodium carbonate was added and the reaction heated at reflux overnight. On cooling, the layers were separated and the aqueous layer extracted with ethyl acetate. The combined organic portions were washed with brine, dried (MgSO4), filtered and concentrated under reduced pressure. Column chromatography was generally used to purify the coupling product (Compound J).

[0207] The aniline (Compound J) and dibromoethane (0.5 equivalent) were dissolved in acetonitrile and heated at 60 °C overnight. The reaction was filtered and concentrated to afford the ethylidene-bridged diphenylamine. The protected phenol was deprotected by reaction with HCl to afford the bridged diaminobiphenol (Compound K).

[0208] The diamine (Compound K) was dissolved in triethyl orthoformate. Ammonium chloride was added and the reaction heated at reflux overnight. The precipitate formed was recovered by filtration and washing with ether, thereby affording the imine salt. The imine chloride was suspended in THF and treated with lithium or sodium hexamethyldisilazide. At the completion of the reaction, the reaction was filtered and the filtrate concentrated to afford the carbene ligand.

[0209] Preparation of bis(phenolate) complex

[0210] Bis(phenoxide) complexes of transition metals or lanthanide metals are used as catalyst components in the present invention for olefin polymerization. The terms "catalyst" and "catalyst complex" can be used interchangeably. The preparation of bis(phenoxide) complexes of transition metals or lanthanide metals can be accomplished by reacting a bis(phenol) ligand with a metal reactant containing an anionic basic leaving group. Typical anionic basic leaving groups include dialkylamido, 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 such reactions 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)2Cl2 (dimethoxyethane), Hf(NMe2)4, Zr(NMe2)4, and Hf(NEt2)4. Suitable metal reagents also include ZrMe4, HfMe4, and other Group 4 element alkylates that can be formed in situ and used without isolation. The preparation of transition metal bis(phenoxide) complexes is typically carried out in an ether or hydrocarbon solvent or solvent mixture at a temperature generally in the range of -80 °C to 120 °C.

[0211] A second method for preparing bis(phenoxide) complexes of transition metals or lanthanide elements is to react a bis(phenol) ligand with an alkali metal or alkaline earth metal base (such as Na, BuLi, i PrMgBr) to generate a deprotonated ligand, and then react it with a metal halide (such as HfCl4, ZrCl4) to form a bis(phenoxide) complex. Bis(phenoxide) metal complexes containing metal halide, alkoxide, or amido leaving groups can be alkylated by reaction with organolithium, Grignard reagents, and organoaluminum reagents. In the alkylation reaction, an alkyl group is transferred to the bis(phenoxide) metal center, and the leaving group is removed. Reagents commonly used for alkylation reactions include, but are not limited to, MeLi, MeMgBr, AlMe3, Al( i Bu)3, AlOct3, and PhCH2MgCl. Generally, 2 - 20 molar equivalents of the alkylating reagent are added to the bis(phenoxide) complex. The alkylation reaction is generally carried out in an ether or hydrocarbon solvent or solvent mixture at a temperature generally in the range of -80 °C to 120 °C.

[0212] Activator

[0213] The terms "cocatalyst" and "activator" can be used interchangeably herein.

[0214] The catalyst systems described herein generally comprise a catalyst complex, such as the bis(phenolate) complexes of transition metals or lanthanide elements described above, and an activator comprising, for example, an aluminoxane or a non-coordinating anion. These catalyst systems can be formed by combining the catalyst components described herein with an activator in any manner known in the literature. The catalyst system can also be added to a solution polymerization or bulk polymerization (in the monomer), or generated in a solution polymerization or bulk polymerization. The catalyst systems of the present invention can have one or more activators and one, two, or more catalyst components. An activator is defined as any compound that can activate any of the above catalyst compounds by converting a neutral metal compound into a catalytically active metal compound cation. Non-limiting activators include, for example, aluminoxanes, ionizing activators, which can be neutral or ionic, and conventional types of cocatalysts. Preferred activators generally include aluminoxane compounds, modified aluminoxane compounds, and ionizing anion precursor compounds, which abstract a reactive metal ligand to render the metal compound cationic and provide a charge to balance a non-coordinating or weakly coordinating anion, such as a non-coordinating anion.

[0215] Aluminoxane activator

[0216] Aluminoxane activators are used as activators in the catalyst systems described herein. Aluminoxanes are generally oligomeric compounds containing -Al(R 99 )-O- subunits, where R 99 is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, particularly when the ligand that can be abstracted is an alkyl group, halide, alkoxide, or amide. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. Visually clear methylaluminoxane can be preferably used. Turbid or gelled aluminoxanes can be filtered to obtain a clear solution, or clear aluminoxane can be decanted from the turbid liquid. A useful aluminoxane is the modified methylaluminoxane (MMAO) cocatalyst type 3A (which can be obtained from Akzo Chemicals, Inc. under the trade name modified methylaluminoxane type 3A and is protected by U.S. Patent No. 5,041,584). Another useful aluminoxane is the solid polymethylaluminoxane as described in US 9,340,630, US 8,404,880, and US 8,975,209.

[0217] When the activator is an aluminoxane (modified or unmodified), typically the maximum amount of activator is up to 5000-fold molar excess of Al / M (per metal catalytic site) in the catalyst compound. The minimum activator-catalyst compound is a 1:1 molar ratio. Other 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.

[0218] In an alternative embodiment, very little or no aluminoxane is used in the polymerization methods described herein. Preferably, the amount of aluminoxane present is 0 mole %, or the aluminoxane is present in a molar ratio of less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1:1, based on aluminum relative to the transition metal in the catalyst compound.

[0219] Ionizing / noncoordinating anion activator

[0220] The term "non-coordinating anion" (NCA) refers to an anion that does not coordinate with or only weakly coordinates with a cation, thereby remaining sufficiently labile to be displaced by a neutral Lewis base. Additionally, the anion does not convert an anionic substituent or fragment into a cation such that a neutral transition metal compound and a neutral by-product are formed from the anion. The non-coordinating anions useful in the present invention are compatible and capable of stabilizing the transition metal cation in the sense of balancing the ionic charge with a +1 valence, and at the same time remaining sufficiently labile to be displaced during polymerization. The term NCA is also defined to include activators containing a multi-component NCA, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate , which contains 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 active species by abstracting an anionic group. Any metal or metalloid capable of forming a compatible, weakly coordinating complex, or their inclusion in a non-coordinating anion, can be used. 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.

[0221] Ionizing activators are used within the scope of the present invention, which are neutral or ionic. Neutral or ionic activators can also be used alone within the scope of the present invention. Or they can be used in combination with an aluminoxane or a modified aluminoxane activator.

[0222] In an embodiment of the present invention, the activator is represented by formula (III):

[0223] (Z)d+(Ad-)(III)

[0224] wherein Z is (L-H) or a reducible Lewis acid, L is a neutral Lewis base; H is hydrogen; (L-H)+ is a Bronsted acid; A d- is a non-coordinating anion having a d - charge; and d is an integer from 1 to 3 (e.g., 1, 2, or 3), preferably Z is (Ar3C + ), where Ar is an aryl or an aryl substituted with a heteroatom, C1 - C 40 hydrocarbyl or a substituted C1 - C 40 hydrocarbyl. The anionic component Ad− includes those having the formula [Mk+Qn]d−, where k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4); n - k = d; M is an element selected from Group 13 of the Periodic Table, preferably boron or aluminum; and Q is independently a hydride, a bridged or unbridged dialkylamido, a halide, an alkoxide, an aryloxide, a hydrocarbyl, a substituted hydrocarbyl, a halocarbonyl, a substituted halocarbonyl, and a halohydrocarbyl, said Q having at most 40 carbon atoms (optionally provided that the case where Q is a halide occurs no more than once). Preferably, each Q is a fluorinated hydrocarbyl having 1 - 40 (e.g., 1 - 20) carbon atoms, more preferably each Q is a fluorinated aryl, such as a perfluorinated aryl, and most preferably each Q is a pentafluorophenyl or a perfluoronaphthalen-2-yl. A d- Suitable examples of A also include diboron compounds as described in U.S. Patent No. 5,447,895, the entire content of which is incorporated herein by reference.

[0225] When Z is an activating cation (L - H), it can be a Bronsted acid that supplies a proton to a transition metal catalyst precursor, thereby obtaining a transition metal cation, including ammonium, oxonium , , sulfonium, and mixtures thereof, such as ammonium of the following substances: methylamine, aniline, dimethylamine, diethylamine, N - methylaniline, N - methyl - 4 - nonadecyl - N - octadecylaniline, N - methyl - 4 - octadecyl - N - octadecylaniline, diphenylamine, trimethylamine, triethylamine, N,N - dimethylaniline, methyldiphenylamine, pyridine, p - bromo - N,N - dimethylaniline, p - nitro - N,N - dimethylaniline, dioctadecylmethylamine; oxonium derived from triethylphosphine, triphenylphosphine, and diphenylphosphine; oxonium from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and di oxane; sulfonium derived from thioethers such as diethyl sulfide, tetrahydrothiophene; and mixtures thereof.

[0226] In a particularly useful embodiment of the present invention, the activator is soluble in a non - aromatic hydrocarbon solvent, such as an aliphatic solvent.

[0227] In one or more embodiments, a 20 wt% mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear, homogeneous solution at 25 °C, preferably a 30 wt% mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear, homogeneous solution at 25 °C.

[0228] In an embodiment of the present invention, the solubility of the activator described herein in methylcyclohexane at 25 °C (with stirring for 2 hours) is greater than 10 mM (or greater than 20 mM, or greater than 50 mM).

[0229] In an embodiment of the present invention, the solubility of the activator described herein in isohexane at 25 °C (with stirring for 2 hours) is greater than 1 mM (or greater than 10 mM, or greater than 20 mM).

[0230] In an embodiment of the present invention, the solubility of the activator described herein in methylcyclohexane at 25 °C (with stirring for 2 hours) is greater than 10 mM (or greater than 20 mM, or greater than 50 mM), and the solubility of the activator in isohexane at 25 °C (with stirring for 2 hours) is greater than 1 mM (or greater than 10 mM, or greater than 20 mM).

[0231] In a preferred embodiment, the activator is an activator compound that is soluble in non-aromatic hydrocarbons.

[0232] Activator compounds soluble in non-aromatic hydrocarbons for use in the present invention include those represented by formula (V):

[0233]

[0234] Wherein:

[0235] E is nitrogen or phosphorous;

[0236] d is 1, 2, or 3; k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6; n - k = d (preferably d is 1, 2, or 3; k is 3; n is 4, 5, or 6);

[0237] R 1′ 、R 2′ and R 3′ are independently C1-C 50 hydrocarbyl groups, optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups,

[0238] wherein R 1′ 、R 2′ and R 3′ together contain 15 or more carbon atoms;

[0239] Mt is an element selected from Group 13 of the Periodic Table, such as B or Al; and

[0240] each Q is independently a hydride, a bridged or unbridged dialkylamido, a halide, an alkoxide, an aryloxide, a hydrocarbyl, a substituted hydrocarbyl, a halocarbonyl, a substituted halocarbonyl, or a halohydrocarbyl.

[0241] The activator compounds soluble in non-aromatic hydrocarbons for use in the present invention include those represented by formula (VI):

[0242] [R 1′ R 2′ R 3′ EH] + [BR 4′ R 5′ R 6′ R 7′ - (VI)

[0243] wherein: E is nitrogen or phosphorus; R 1′ is methyl; R 2′ and R 3′ are independently C4-C 50 hydrocarbyls, optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups, wherein R 2′ and R 3′ together contain 14 or more carbon atoms; B is boron; and R 4′ 、R 5′ 、R 6′ and R 7′ are independently a hydride, a bridged or unbridged dialkylamido, a halide, an alkoxide, an aryloxide, a hydrocarbyl, a substituted hydrocarbyl, a halocarbonyl, a substituted halocarbonyl, or a halohydrocarbyl.

[0244] The activator compounds soluble in non-aromatic hydrocarbons for use in the present invention include those represented by formula (VII) or formula (VIII):

[0245]

[0246] wherein:

[0247] N is nitrogen;

[0248] R 2′ and R 3′ are independently C6-C 40 hydrocarbyls, optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups, wherein R 2′ and R 3′ (when present) together contain 14 or more carbon atoms;​

[0249] R 8′ , R 9′ and R 10′ Independently C4-C 30 Hydrocarbon or substituted C4-C 30 Hydrocarbon;

[0250] B is boron;

[0251] And R 4′ , R 5′ , R 6′ and R 7′ is independently hydride, bridged or unbridged dialkylamido, halide, alkoxylate, aryloxylate, hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl, or halohydrocarbyl.

[0252] Optionally, in any one of Formulas (V), (VI), (VII) or (VIII) herein, R 4′ , R 5′ , R 6′ and R 7′ It is pentafluorophenyl.

[0253] Optionally, in any one of Formulas (V), (VI), (VII) or (VIII) herein, R 4′ , R 5′ , R 6′ and R 7′ It is pentafluoronaphthalen-2-yl.

[0254] Optionally, in any embodiment of Formula (VIII), R 0′ and R 10′ is a hydrogen atom; R 9′ It is C4-C 30 A hydrocarbon group which is optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups.

[0255] Optionally, in any embodiment of Formula (VIII), R 9′ It is C8-C 22 A hydrocarbon group which is optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups.

[0256] Optionally, in any one embodiment of Formula (VII) or Formula (VIII), R 2′ and R 3′ Independently C 12 -C 22 Hydrocarbon.

[0257] Optionally, R 1′ , R 2′and R 3′ together contain 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 - 100 carbon atoms, such as 25 - 75 carbon atoms).

[0258] Optionally, R 2′ and R 3′ together contain 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 - 100 carbon atoms, such as 25 - 75 carbon atoms).

[0259] Optionally, R 8′ 、R 9′ and R 10′ together contain 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 - 100 carbon atoms, such as 25 - 75 carbon atoms).

[0260] Optionally, when Q is fluorophenyl, R 2′ is not a C1 - C 40 linear alkyl (or R 2′ is not an optionally substituted C1 - C 40 linear alkyl).

[0261] Optionally, each R 4′ 、R 5′ 、R 6′ and R 7′ is aryl (such as phenyl or naphthalen - 2 - yl), wherein at least one of the groups of R 4′ 、R 5′ 、R 6′ and R 7′ is substituted by at least one fluorine atom, preferably each R 4′ 、R 5′ 、R 6′ and R 7′ is perfluorinated aryl (such as perfluorinated phenyl or perfluorinated naphthalen - 2 - yl).

[0262] Optionally, each Q is an aryl group (e.g., phenyl or naphthalene-2-yl), where at least one Q is substituted by at least one fluorine atom, preferably each Q is a perfluorinated aryl group (e.g., perfluorinated phenyl or perfluorinated naphthalene-2-yl).

[0263] Optionally, R 1′ is methyl; R 2′ is C6-C 50 aryl; and R 3′ is independently a C1-C 40 linear alkyl or a C5-C 50 -aryl.

[0264] Optionally, each R 2′ and R 3′ is independently unsubstituted or substituted by a halogen atom, a C1-C 35 alkyl, a C5-C 15 aryl, a C6-C 35 arylalkyl, a C6-C 35 alkylaryl group, where R 2 and R 3 together contain 20 or more carbon atoms.

[0265] Optionally, each Q is independently a hydride, a bridged or unbridged dialkylamido group, a halide, an alkoxide, an aryloxide, a hydrocarbyl group, a substituted hydrocarbyl group, a halocarbonyl group, a substituted halocarbonyl group, or a halohydrocarbyl group, provided that when Q is a fluorophenyl group, R 2′ is not a C1-C 40 linear alkyl, preferably R z′ is not an optionally substituted C1-C 40 linear alkyl (or when Q is a substituted phenyl group, R 2′ is not a C1-C 40 linear alkyl, preferably R 2′ is not an optionally substituted C1-C 40 linear alkyl). 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, where the meta substituents and para substituents are independently an optionally substituted C1-C 40 hydrocarbyl group (e.g., a C6-C 40 aryl or a linear alkyl, C 12 -C 30 aryl or a linear alkyl, or C 10 -C 20(an aryl or straight-chain alkyl), an optionally substituted alkoxy group, or an optionally substituted silyl group. Optionally, each Q is a fluorinated hydrocarbon group having 1-30 carbon atoms, more preferably each Q is a fluorinated aryl group (e.g., phenyl or naphthalene-2-yl), and most preferably each Q is a perfluorinated aryl group (e.g., phenyl or naphthalene-2-yl). [Mt k+ Q n d- Suitable examples of also include diboron compounds as described in U.S. Patent No. 5,447,895, the entire content of which is incorporated herein by reference. Optionally, at least one Q is not a substituted phenyl group. Optionally, all Qs are not substituted phenyl groups. Optionally, at least one Q is not a perfluorinated phenyl group. Optionally, all Qs are not perfluorinated phenyl groups.

[0266] In some embodiments of the present invention, R 1′ is not methyl, R 2′ is not C 18 alkyl, and R 3′ is not C 18 alkyl; or R 1′ is not methyl, R 2′ is not C 18 alkyl, and R 3′ is not C 18 alkyl; and at least one Q is not a substituted phenyl group, optionally all Qs are not substituted phenyl groups.

[0267] Cationic components that can be used in formulas (III) and (V) to (VIII) include those represented by the following formula:

[0268]

[0269] Cationic components that can be used in formulas (III) and (V) to (VIII) include those represented by the following formula:

[0270]

[0271] The anionic components of the activators described herein include those represented by the formula [Mt k+ Q n - ​​Those represented, where k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6 (preferably 1, 2, 3 or 4), (preferably k is 3; n is 4, 5 or 6; preferably when M is B, n is 4); Mt is an element selected from Group 13 of the Periodic Table, preferably boron or aluminum; and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbonyl, substituted halocarbonyl and halohydrocarbyl, said Q having at most 20 carbon atoms, provided that the case where Q is a halide occurs no more than once. Preferably, each Q is a fluorinated hydrocarbyl, optionally having 1 - 20 carbon atoms, more preferably each Q is a fluorinated aryl, and most preferably each Q is a perfluorinated aryl. Preferably at least one Q is not a substituted phenyl, such as perfluorinated phenyl, and preferably all Q are not substituted phenyls, such as perfluorinated phenyls.

[0272] In one embodiment, the borate activator comprises tetrakis(heptafluoronaphthalen-2-yl)borate.

[0273] In one embodiment, the borate activator comprises tetrakis(pentafluorophenyl)borate.

[0274] The anions in the non-coordinating anions for the activator also include those represented by Formula 7:

[0275]

[0276] Wherein:

[0277] M* is a Group 13 atom, preferably B or Al, preferably B;

[0278] Each R 11 is independently a halide, preferably fluorine;

[0279] Each R 12 is independently a halide, a substituted C6-C 20 aromatic hydrocarbyl, or a siloxy group of the formula –O-Si-R a where R a is a C1-C 20 hydrocarbyl or hydrocarbylsilyl, preferably R 12 is fluorine or perfluorinated phenyl;

[0280] Each R 13 is a halide, a substituted C6-C 20 aromatic hydrocarbon group, or a siloxy group of the formula –O-Si-R a where R a is a C1-C 20 hydrocarbyl or hydrocarbylsilyl, preferably R 13 is fluorine or a C6 perfluorinated aromatic hydrocarbon group;

[0281] where R12 and R 13 can form one or more saturated or unsaturated, substituted or unsubstituted rings, preferably R 12 and R 13 form a perfluorinated phenyl ring. Preferably, the anion has a molecular weight greater than 700 g / mol, and preferably at least three substituents on the M* atom each have a molecular volume greater than 180 cubic angstroms of the molecular volume.

[0282] As used herein, "molecular volume" is generally the steric volume of the activator molecule in solution. Substituents with different molecular volumes are compared, such that a substituent with a smaller molecular volume is considered "less bulky" compared to a substituent with a larger molecular volume. Conversely, a substituent with a larger molecular volume can be considered "more bulky" than a substituent with a smaller molecular volume.

[0283] The molecular volume can be calculated as described in "A Simple 'Back-of-the-Envelope' Method for Estimating the Density and Molecular Volume of Liquids and Solids", Journal of Chemical Education, volume 71(11), November 1994, pages 962 - 964. The unit of molecular volume (MV) is cubic angstroms Calculated according to the following formula: MV = 8.3V s , where V s is the scaled volume, V s is the sum of the relative volumes of the constituent atoms and is calculated using the relative volumes shown in Table A below from the molecular formula of the substituent. For fused rings, V s is reduced by 7.5% per fused ring. The total calculated MV of the anion is the sum of the MV of each substituent. For example, the MV of perfluorinated phenyl is and the total calculated MV for tetrakis(perfluorophenyl)borate is four times that, or

[0284] Table A

[0285] Element Relative volume H 1 The first short period, Li to F 2 The second short period, Na to Cl 4 The first long period, K to Br 5 The second long period, Rb to I 7.5 The third long period, Cs to Bi 9

[0286] Examples of useful anions and their scaled volumes and molecular volumes are shown in Table B below. The dashed lines indicate bonding to boron.

[0287] Table B

[0288]

[0289] An activator can be added to the polymerization reaction and is used in the form of an ion pair, such as [M2HTH]+[NCA]-, where the bis(hydrogenated tallow)methylamine (“M2HTH”) cation reacts with the basic leaving group on the transition metal complex, thereby forming a transition metal complex cation and [NCA]-. Alternatively, the transition metal complex can react with a neutral NCA precursor, such as B(C6F5)3, which abstracts an anionic group from the complex to form an activated species. Useful activators include bis(hydrogenated tallow)methylammonium [tetrakis(pentafluorophenyl)borate] (i.e., [M2HTH]B(C6F5)4) and bis(octadecyl)toluylammonium [tetrakis(pentafluorophenyl)borate] (i.e., [DOdTH]B(C6F5)4).

[0290] Activator compounds that are particularly useful in the present invention include one or more of the following compounds:

[0291] N,N-bis(hydrogenated tallow)methylammonium [tetrakis(pentafluorophenyl)borate],

[0292] N-methyl-4-nonadecyl-N-octadecylaniline [tetrakis(pentafluorophenyl)borate] ,

[0293] N-methyl-4-hexadecyl-N-octadecylaniline [tetrakis(pentafluorophenyl)borate] ,

[0294] N-methyl-4-tetradecyl-N-octadecylaniline [tetrakis(pentafluorophenyl)borate] ,

[0295] N-methyl-4-dodecyl-N-octadecylaniline [tetrakis(pentafluorophenyl)borate] ,

[0296] N-methyl-4-decyl-N-octadecylaniline [tetrakis(pentafluorophenyl)borate] ,

[0297] N-methyl-4-octyl-N-octadecylaniline [tetrakis(pentafluorophenyl)borate] ,

[0298] N-methyl-4-hexyl-N-octadecylaniline [tetrakis(pentafluorophenyl)borate] ,

[0299] N-methyl-4-butyl-N-octadecylaniline [tetrakis(pentafluorophenyl)borate] ,

[0300] N-methyl-4-octadecyl-N-decylaniline [tetrakis(pentafluorophenyl)borate] ,

[0301] N-Methyl-4-nonadecyl-N-dodecylaniline tetra(perfluorophenyl)borate ,

[0302] N-Methyl-4-nonadecyl-N-tetradecylaniline tetra(perfluorophenyl)borate ,

[0303] N-Methyl-4-nonadecyl-N-hexadecylaniline tetra(perfluorophenyl)borate ,

[0304] N-Ethyl-4-nonadecyl-N-octadecylaniline tetra(perfluorophenyl)borate ,

[0305] N-Methyl-N,N-dioctadecylammonium tetra(perfluorophenyl)borate,

[0306] N-Methyl-N,N-dicetylammonium tetra(perfluorophenyl)borate

[0307] N-Methyl-N,N-ditetradecylammonium tetra(perfluorophenyl)borate

[0308] N-Methyl-N,N-didodecylammonium tetra(perfluorophenyl)borate

[0309] N-Methyl-N,N-didecylammonium tetra(perfluorophenyl)borate

[0310] N-Methyl-N,N-dioctylammonium tetra(perfluorophenyl)borate

[0311] N-Ethyl-N,N-dioctadecylammonium tetra(perfluorophenyl)borate

[0312] N,N-Di(octadecyl)phenylammonium tetra(perfluorophenyl)borate

[0313] N,N-Di(hexadecyl)phenylammonium tetra(perfluorophenyl)borate

[0314] N,N-Di(tetradecyl)phenylammonium tetra(perfluorophenyl)borate

[0315] N,N-Di(dodecyl)phenylammonium tetra(perfluorophenyl)borate

[0316] N-Octadecyl-N-hexadecylphenylammonium tetra(perfluorophenyl)borate

[0317] N-Octadecyl-N-hexadecylphenylammonium tetra(perfluorophenyl)borate

[0318] N-octadecyl-N-tetradecyl-toluidinium [tetrakis(pentafluorophenyl)borate]

[0319] N-octadecyl-N-dodecyl-toluidinium [tetrakis(pentafluorophenyl)borate]

[0320] N-octadecyl-N-decyl-toluidinium [tetrakis(pentafluorophenyl)borate]

[0321] N-hexadecyl-N-tetradecyl-toluidinium [tetrakis(pentafluorophenyl)borate]

[0322] N-hexadecyl-N-dodecyl-toluidinium [tetrakis(pentafluorophenyl)borate]

[0323] N-hexadecyl-N-decyl-toluidinium [tetrakis(pentafluorophenyl)borate]

[0324] N-tetradecyl-N-dodecyl-toluidinium [tetrakis(pentafluorophenyl)borate]

[0325] N-tetradecyl-N-decyl-toluidinium [tetrakis(pentafluorophenyl)borate]

[0326] N-dodecyl-N-decyl-toluidinium [tetrakis(pentafluorophenyl)borate]

[0327] N-methyl-N-octadecylanilinium [tetrakis(pentafluorophenyl)borate] ,

[0328] N-methyl-N-hexadecylanilinium [tetrakis(pentafluorophenyl)borate] ,

[0329] N-methyl-N-tetradecylanilinium [tetrakis(pentafluorophenyl)borate] ,

[0330] N-methyl-N-dodecylanilinium [tetrakis(pentafluorophenyl)borate] ,

[0331] N-methyl-N-decylanilinium [tetrakis(pentafluorophenyl)borate] , and N-methyl-N-octylanilinium [tetrakis(pentafluorophenyl)borate] 。

[0332] Synthetic methods for other useful activators and activators soluble in non-aromatic hydrocarbons can be found in USSN 16 / 394,166 filed on April 25, 2019, USSN 16 / 394,186 filed on April 25, 2019, and USSN 16 / 394,197 filed on April 25, 2019. These documents are incorporated herein by reference.

[0333] Similarly, particularly useful activators also include dimethylanilinium tetrakis(pentafluorophenyl)borate and dimethylanilinium tetrakis(heptafluoronaphthalen-2-yl)borate. For a more detailed description of available activators, see paragraphs

[00119] to

[00151] on page 72 of WO 2004 / 026921. A list of other particularly useful activators that can be used in the present invention can be found in paragraphs

[00177] to

[00178] on page 72 of WO 2004 / 046214.

[0334] For a description of useful activators, see US 8,658,556 and US 6,211,105.

[0335] Preferred activators for use in the present invention also include N-methyl-4-nonadecyl-N-octadecylanilinium tetrakis(pentafluorophenyl)borate , N-methyl-4-nonadecyl-N-octadecylanilinium 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 , [Me3NH + [B(C6F5)4 - ; 1-(4-(tris(pentafluorophenyl)borato)-2,3,5,6-tetrafluorophenyl)pyrrolidine ; and tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borato)-2,3,5,6-tetrafluoropyridine.

[0336] In a preferred embodiment, the activator comprises a triarylcarbene (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 ).

[0337] In another embodiment, the activator comprises one or more of the following: trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylaniline tetrakis(pentafluorophenyl)borate , dimethyldioctadecylammonium tetrakis(pentafluorophenyl)borate, dimethyldioctadecylammonium tetrakis(perfluoronaphthalen-2-yl)borate, N,N-dimethyl-(2,4,6-trimethylaniline)tetrakis(pentafluorophenyl)borate ), trialkylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dialkylaniline tetrakis(2,3,4,6-tetrafluorophenyl)borate , trialkylammonium tetrakis(perfluoronaphthalen-2-yl)borate, N,N-dialkylaniline tetrakis(perfluoronaphthalen-2-yl)borate , trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylaniline tetrakis(perfluorobiphenyl)borate , trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylaniline tetrakis(3,5-bis(trifluoromethyl)phenyl)borate , N,N-dialkyl-(2,4,6-trimethylaniline)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate ), di(isopropyl)ammonium tetrakis(pentafluorophenyl)borate, (wherein the alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl or tert-butyl).

[0338] Typical activator to catalyst ratios, e.g., for all NCA activators to catalyst ratios, are a molar ratio of about 1:1. Other 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. A particularly useful range is 0.5:1 to 10:1, preferably 1:1 to 5:1.

[0339] Also within the scope of the present invention is that the catalyst compound can be used in combination with a combination of aluminoxane and NCA (see, for example, US 5,153,157, US 5,453,410, EP 0 573 120 B1, WO 1994 / 007928 and WO 1995 / 014044, the entire contents of which are incorporated herein by reference, where the use of aluminoxane and an ionizing activator in combination is discussed).

[0340] Optional scavenger, cocatalyst, chain transfer agent

[0341] Scavengers or co-activators can also be used in addition to the activator compound. A scavenger is a compound that is typically added to scavenge impurities to facilitate polymerization. Some scavengers can also act as activators and can be referred to as co-activators. Non-scavenging co-activators can also be used with the activator to form an active catalyst. In some embodiments, the co-activator can be pre-mixed with the transition metal compound to form an alkylated transition metal compound.

[0342] Co-activators can include aluminoxanes such as methylaluminoxane, modified aluminoxanes such as modified methylaluminoxane, and alkylaluminums such as trimethylaluminum, triisobutylaluminum, triethylaluminum, triisopropylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum or tri-n-dodecylaluminum. When the pre-catalyst is not a dihydrocarbyl or dihydride complex, the co-activator is typically used in combination with a Lewis acid activator and an ionic activator. Sometimes, the co-activator also acts as a scavenger to passivate impurities in the feed or reactor.

[0343] Alkylated aluminum or organoaluminum compounds that can be used as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and dialkylzincs such as diethylzinc.

[0344] A chain transfer agent can be used in the compositions and / or methods described herein. Useful chain transfer agents are typically hydrogen, alkylaluminoxanes, compounds represented by the formula AlR3, ZnR2 (where each R is independently a C1-C8 aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or an isomer thereof) or a combination thereof, such as diethylzinc, trimethylaluminum, triisobutylaluminum, trioctylaluminum or a combination thereof.

[0345] Polymerization method

[0346] The polymerization reaction can be carried out by solution polymerization methods in any manner known to those skilled in the art. In a specific embodiment, the polymerization method can be carried out in a continuous polymerization method. The term "batch" refers to a method in which the entire reaction mixture is removed from the polymerization reaction vessel at the end of the polymerization reaction. In contrast, in a continuous polymerization method, one or more reactants are continuously added to the reactor, and at the same time, a solution containing the polymer product is removed in a co-current or near co-current manner. Solution polymerization refers to a polymerization method in which the resulting polymer is soluble in a liquid polymerization medium, such as an inert solvent or one or more monomers or a blend thereof. Solution polymerization is generally homogeneous. Homogeneous polymerization means that the polymer product is dissolved in the polymerization medium. Such a system is preferably not turbid, see J. Vladimir Oliveira et al., Ind. Eng. Chem. Res., v. 29, 2000, page 4627.

[0347] In a typical solution process, the catalyst components, solvent, monomer, and hydrogen (when used) are added to one or more reactors under pressure. Temperature control in the reactor can generally be achieved by balancing the heat of polymerization and by cooling the contents of the reactor with a reactor jacket or cooling coils, auto-refrigeration, pre-cooling the feed, evaporating the liquid medium (diluent, monomer, or solvent), or a combination of the three. Adiabatic reactors with pre-cooled feeds can also be used. The monomer is dissolved / dispersed in the solvent before being added to the first reactor or dissolved in the reaction mixture. The solvent and monomer are typically purified before entering the reactor to remove potential catalyst poisons. The feed can be heated or cooled before entering the first reactor. Additional monomer and solvent can be added to the second reactor and can be heated or cooled. The catalyst / activator can be added to the first reactor or separately to the two reactors. In solution polymerization, the resulting polymer is molten and remains dissolved in the solvent under reactor conditions, thereby forming a polymer solution (also referred to as the effluent).

[0348] The solution polymerization method of the present invention uses a stirred tank reactor system, which includes one or more stirred polymerization reactors. Generally, the reactor should be operated under conditions that can fully mix the reactants. In a system of multiple reactors, the first polymerization reactor is preferably operated at a lower temperature. The residence time in each reactor will depend on the design and capacity of the reactor. The catalyst / activator can be added only to the first reactor or separately to the two reactors. In an alternative embodiment, a loop reactor and an injection flow reactor can be used in the present invention.

[0349] Then, the polymer solution is withdrawn from the reactor as an effluent stream, and the polymerization reaction is quenched, typically with a coordinating polar compound, to prevent further polymerization. As it leaves the reactor system, the polymer solution passes via a heat exchanger system to a devolatilization system and a polymer distillation process. The depleted phase and volatiles withdrawn downstream of the liquid separation operation can be recycled to a portion of the polymerization feed.

[0350] The polymer can be recovered from the reactor effluent or combined effluents by separating the polymer from the 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-butanol, or the polymer can be recovered by heating and / or by heating with water or steam and vacuum stripping the solvent or other medium. One or more conventional additives such as antioxidants can be introduced into the polymer during the recovery process. Other recovery methods can also be considered, such as using a lower critical solution temperature (LCST) followed by devolatilization.

[0351] Diluents / solvents suitable for carrying out the polymerization reaction include non-coordinating inert liquids. In a specific embodiment, the reaction mixture for the solution polymerization reaction described herein can comprise at least one hydrocarbon solvent. Examples thereof include: straight-chain and branched hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic and cycloaliphatic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof, such as those available commercially (Isopar TM ); halogenated and perhalogenated hydrocarbons such as perfluorinated C4-C 10 alkanes, chlorobenzene and mixtures thereof; and aromatic compounds and alkyl-substituted aromatic compounds such as benzene, toluene, 2,4,6-trimethylbenzene, ethylbenzene, xylene and mixtures thereof. Mixtures of any of the above hydrocarbon solvents can also be used. Suitable solvents also include liquid olefins which can be used as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. In another embodiment, the solvent is not aromatic, preferably the amount of aromatic compounds present in the solvent is less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0 wt%, based on the weight of the solvent.

[0352] Any olefin feed can be polymerized using the polymerization methods and solution polymerization conditions described herein. Suitable olefin feeds include at least one cycloolefin or substituted cycloolefin, and can include any C2-C 40 olefins which can be straight-chain or branched, cyclic or acyclic and end-capped or non-end-capped, optionally containing heteroatom substituents. In a more specific embodiment, the olefin feed can comprise C2-C20 Olefins, especially linear alpha-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-dodecene, which are used in combination with cycloolefins such as, but not limited to, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclononene, cyclodecene and 2-norbornene. Other suitable olefin monomers can include ethylenically unsaturated monomers, dienes having 4-18 carbon atoms, conjugated or non-conjugated dienes, polyenes, and vinyl monomers. Non-limiting olefin monomers can also include norbornadiene, isobutene, isoprene, vinyl-benzocyclobutane, styrene, alkyl-substituted styrene, ethylidene norbornene, and dicyclopentadiene. Any single olefin monomer or any mixture of multiple olefin monomers can be polymerized as described herein.

[0353] In any embodiment, the cycloolefin is selected from substituted or unsubstituted C4-C 20 Cycloolefins, which preferably contain at least one C4-C8 cyclic structure. In any embodiment, the cycloolefin is cyclopentene or C l -C 10 alkyl-substituted cyclopentene, preferably provided that the substitution does not occur at the sp 2 carbon atom.

[0354] In any embodiment, the cycloolefin is a substituted or unsubstituted C6-C 20 Polycyclic olefins, which include bicyclic olefins, which are cycloolefins containing a bridging hydrocarbon group that forms multiple rings throughout the structure. In any embodiment, the cycloolefin is norbornene or C l -C 10 alkyl-substituted norbornene, provided that the substitution position preferably does not occur at the sp 2 carbon atom.

[0355] Preferred cycloolefins include cyclopentene and 2-norbornene.

[0356] Preferred diene monomers for use in the present invention include any hydrocarbon structure having at least two unsaturated bonds, preferably C5-C 30, where at least two unsaturated bonds can be introduced into the polymer to form a crosslinked polymer. Examples of such polyenes include α,ω-dienes (such as butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, and 1,13-tetradecadiene), and certain polycyclic alicyclic fused and bridged cyclo-dienes (such as indene, divinylbenzene, norbornadiene, methyl-indene, dicyclopentadiene, bicyclo-(2.2.1)-hepta-2,5-diene, and alkenyl-, alkylene-, cycloalkenyl- and cycloalkylidene-norbornenes [including, for example, 5-methylene-2-norbornene, 5-ethylene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene and 5-vinyl-2-norbornene]).

[0357] Optionally, no diene is present in the resulting copolymer.

[0358] Useful monomer combinations include ethylene and cycloolefins; propylene and cycloolefins; and ethylene and propylene with cycloolefins.

[0359] The preferred polymerization can be carried out at any temperature and / or pressure suitable for obtaining the desired polymer. Solution polymerization conditions suitable for the polymerization methods described herein include temperatures in the range of about 0 °C to about 300 °C, or about 50 °C to about 250 °C, or about 70 °C to about 200 °C, or about 90 °C to about 180 °C, or about 90 °C to about 140 °C, or about 120 °C to about 140 °C. The pressure can be in the range of about 0.1 MPa to about 15 MPa, or about 0.2 MPa to about 12 MPa, or about 0.5 MPa to about 10 MPa, or about 1 MPa to about 7 MPa. The polymerization run time (residence time) can be up to about 300 minutes, especially in the range of about 5 minutes to about 250 minutes, or about 10 minutes to about 120 minutes.

[0360] Small amounts of hydrogen can be added to one or more feed streams of the reactor to improve control of the melt index and / or molecular weight distribution, such as 1 - 5000 parts per million by weight (ppm) based on the total solution feed to the reactor. In some embodiments, hydrogen can be included in the reactor in a solution polymerization process. Depending on the different embodiments, the concentration of hydrogen in the reaction mixture can be 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 can be present in the reactor 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, no hydrogen is added in this process.

[0361] In a preferred embodiment, the polymerization reaction 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 from atmospheric pressure to 18 MPa (preferably 0.35 - 18 MPa, preferably 0.35 - 10 MPa, preferably 0.45 - 6 MPa, preferably 0.5 - 4 MPa); 3) carried out in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic hydrocarbons and cycloaliphatic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; preferably, the amount of aromatic compounds (such as toluene) present in the solvent is preferably less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0.1 wt%, preferably 0 wt% based on the weight of the solvent); 4) if ethylene is used, the ethylene concentration in the polymerization reactor is 6 moles per liter or less; 5) the polymerization reaction is preferably carried out in a single reaction zone; 6) the yield of the catalyst compound is 50,000 kg of polymer / kg of catalyst or greater (preferably 100,000 kg of polymer / kg of catalyst or greater, such as 150,000 kg of polymer / kg of catalyst or greater, such as 200,000 kg of polymer / kg of catalyst or greater).

[0362] In more specific embodiments, one or more olefin monomers present in the reaction mixtures described herein comprise at least cycloolefins and optionally comprise ethylene and / or propylene, and optionally comprise one or more alpha-olefins such as butene, hexene, and octene. In further more specific embodiments, one or more olefin monomers can comprise cycloolefins and ethylene and / or propylene. In further more specific embodiments, one or more olefin monomers can comprise ethylene and one or more cycloolefins such as cyclopentene and / or norbornene. In further more specific embodiments, one or more olefin monomers can comprise propylene and one or more cycloolefins such as cyclopentene and / or norbornene.

[0363] The molecular weight distribution of polymers made by solution processes can be advantageously controlled by preparing the polymer in multiple reactors operating under different conditions, most often at different temperatures and / or monomer concentrations. These conditions determine the molecular weight and density of the resulting polymer fractions. The relative amounts of the different fractions are controlled by adjusting the process conditions in each reactor. Process conditions commonly used include the type and concentration of catalyst in each reactor, and the reactor residence time. In one embodiment, the polymerization process comprises at least two reactors connected in series and parallel configurations.

[0364] In an embodiment of the present invention, the present invention relates to a polymerization process wherein monomers and optionally comonomers are contacted with a catalyst system comprising an activator and at least one catalyst compound as described above. The catalyst compound and activator can be combined in any order, typically before contact with the monomers. In one embodiment, the catalyst and activator can be added to the polymerization reactor in dry powder or slurry form and there is no need to prepare a homogeneous catalyst solution by dissolving the catalyst into a loading solvent.

[0365] 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 method known in the art can be used. These methods can be operated in batch, semi-batch, or continuous modes. Homogeneous polymerization methods are preferred (a homogeneous polymerization method is preferably a method wherein at least 90 wt% of the product is soluble in the reaction medium). In useful embodiments, the polymerization process is a solution process.

[0366] The "reaction zone", also referred to as the "polymerization zone", is the vessel in which the polymerization reaction occurs, such as a batch reactor. When multiple reactors are used in series or parallel configurations, each reactor is considered a separate polymerization zone. For multi-stage polymerization in batch and continuous reactors, each polymerization stage is considered a separate polymerization zone. In a preferred embodiment, the polymerization occurs in a single reaction zone. In one embodiment, multiple reactors are used in the polymerization process.

[0367] Other additives can also be used in the polymerization as needed, such as one or more scavengers, hydrogen, alkylaluminum, silane, or chain transfer agents (such as alkylaluminoxanes, compounds represented by the formula AlR3 or ZnR2 (where each R is independently a C1-C8 aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, or their isomers), or combinations thereof, such as diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof).

[0368] The method of the present invention can be used to prepare homopolymers of cycloolefins, as well as copolymers of ethylene and cycloolefins, copolymers of propylene and cycloolefins, and can optionally contain additional α-olefins to prepare polymers having a density of, for example, about 0.900 - 0.970 g / cm 3 , especially 0.915 - 0.965 g / cm 3 . As determined by the method of ASTM D - 1238, such polymers can have a melt index in the range of, for example, about 0.1 - 200, especially in the range of about 0.5 - 120 dg / min. The polymers produced can have a narrow or wide molecular weight distribution. For example, the polymers can have an MWD of about 1.5 to 10, especially about 2 to 7. It is believed that the method of the present invention is particularly useful for preparing polymers with a narrow molecular weight distribution.

[0369] The method of the present invention can be used to prepare cycloolefin copolymers of ethylene and / or propylene, as well as copolymers of cycloolefins with ethylene and / or propylene and additional α-olefins, thereby preparing polymers having a density of, for example, about 0.84 - 0.970 g / cm 3 , especially 0.88 - 0.965 g / cm 3 . Such polymers can have a melt index of 0.1 or less as determined by the ASTM D - 1238 method, and in the range of about 0.5 - 120 dg / min.

[0370] Polyolefin product

[0371] The present invention also relates to compositions of substances prepared by the methods described herein. The methods described herein can be used to prepare polymers and copolymers of cycloolefins. The polymers produced can include homopolymers of cyclic monomers, as well as copolymers of cycloolefins with C2 - C 20 olefins. The polymers produced can include copolymers of cycloolefins and ethylene with optional C4 - C 20 olefins; copolymers of cycloolefins and propylene with optional C4 - C 20 olefins; and copolymers of cycloolefins, ethylene, and propylene with optional C4 - C 20 olefins.

[0372] Preferably, no diene is present in the resulting polymer composition.

[0373] In a preferred embodiment, the polymer prepared by the method described herein contains 0.1 mol% or more of cycloolefin monomer, or 0.2 mol% or more of cycloolefin monomer, or 0.5 mol% or more of cycloolefin monomer, or 1.0 mol% or more of cycloolefin monomer, or 2.0 mol% or more of cycloolefin monomer, or 3.0 mol% or more of cycloolefin monomer, or 5 mol% or more of cycloolefin monomer, or 10 mol% or more of cycloolefin monomer, or 15 mol% or more of cycloolefin monomer, or 20 mol% or more of cycloolefin monomer, or 30 mol% or more of cycloolefin monomer, or 40 mol% or more of cycloolefin monomer, or 50 mol% or more of cycloolefin monomer, or 60 mol% or more of cycloolefin monomer, or 70 mol% or more of cycloolefin monomer, or 80 mol% or more of cycloolefin monomer, or 90 mol% or more of cycloolefin monomer, or 100 mol% of cycloolefin.

[0374] The molecular weights (weight-average molecular weight (Mw), number-average molecular weight (Mn), z-average molecular weight (Mz)) and molecular weight distribution (PDI = MWD = Mw / Mn), sometimes also referred to as the polydispersity index (PDI)) of the polymers measured by gel permeation chromatography, as discussed hereinafter, are relative to linear polystyrene standards.

[0375] In a preferred embodiment, the copolymer prepared by the method described herein comprises ethylene and a cycloolefin, wherein the cycloolefin is C5-C 20 cycloolefin, preferably cyclopentene and / or norbornene, the copolymer having an Mn of 3,000 g / mol or greater, or 5,000 g / mol or greater, or 10,000 g / mol or greater, or 50,000 g / mol or greater, or 75,000 g / mol or greater, or 100,000 g / mol or greater, or 200,000 g / mol or greater; and Mw / Mn in the range of 1.0 to 10, or 1.5 to 5.0, or 1.8 to 3.0; and the cycloolefin content is 0.05 - 99 mol%, or 0.1 - 50 mol%, or 0.2 - 40 mol%, or 0.3 - 30 mol%, or 0.5 - 20 mol%. The cycloolefin can be introduced via 1,2-linkage (across the double bond) or 1,3-linkage (from rearrangement) or a combination of the two.

[0376] In a preferred embodiment, the copolymer prepared by the method described herein comprises ethylene, a cycloolefin, and one or more additional C3-C 12 α-olefins, wherein the cycloolefin is C5-C20 Cycloolefins, preferably cyclopentene and / or norbornene, and the copolymer has an Mn of 3,000 g / mol or greater, or 5,000 g / mol or greater, or 10,000 g / mol or greater, or 50,000 g / mol or greater, or 75,000 g / mol or greater, or 100,000 g / mol or greater, or 200,000 g / mol or greater; and the Mw / Mn is in the range of 1.0 to 10, or 1.5 to 5.0, or 1.8 to 3.0, wherein the cycloolefin content is 0.05 - 99 mol%, or 0.1 - 50 mol%, or 0.2 - 40 mol%, or 0.3 - 30 mol%, or 0.5 - 20 mol%. The cycloolefin can be introduced via 1,2-linkage (across the double bond) or 1,3-linkage (from rearrangement) or a combination of the two.

[0377] In some embodiments, the ethylene-cyclopentene copolymer has an Mn of about 2,000 to 2,000,000 g / mol, or about 5,000 to 1,500,000 g / mol, or about 10,000 to 1,000,000 g / mol, or about 50,000 to 800,000, or about 100,000 to 500,000 g / mol.

[0378] In some embodiments, the ethylene-cyclopentene copolymer has an Mw of about 5,000 to 4,000,000 g / mol, or about 10,000 to 3,000,000 g / mol, or about 20,000 to 2,000,000 g / mol, or about 100,000 to 1,500,000 g / mol, or about 200,000 to 1,000,000 g / mol.

[0379] In some embodiments, the ethylene-cyclopentene copolymer has an Mz of about 100,000 to 10,000,000 g / mol, or about 200,000 to 8,000,000 g / mol, or about 300,000 to 6,000,000 g / mol, or about 400,000 to 3,000,000 g / mol, or about 500,000 to 2,000,000 g / mol.

[0380] In some embodiments, the ethylene-cyclopentene copolymer has an Mw / Mn of about 1.0 to 10, or about 1.5 to 5.0, or about 1.8 to 3.0, or about 2.0 to 4.0.

[0381] In some embodiments, the ethylene-cyclopentene copolymer has a cyclopentene content of about 0.05 - 99 mol%, or about 0.1 - 50 mol%, or about 0.2 - 40 mol%, or about 0.3 - 30 mol%, or about 0.5 - 20 mol%. In some embodiments, the ethylene-cyclopentene copolymer has a cyclopentene content of less than 50 mol%, or less than 45 mol%, or less than 40 mol%.

[0382] The cyclopentene monomer can be introduced via 1,2-linkage (across the double bond) or 1,3-linkage (from rearrangement) or a combination of both. In some embodiments, the ethylene-cyclopentene copolymer mainly has 1,2-linkage. Preferably, the 1,2-linkage accounts for 90% or more, or 95% or more, or 98% or more, or 99% or more of the total amount of cyclopentene introduced into the ethylene backbone. In some embodiments, the ethylene-cyclopentene copolymer has 5% or less of 1,3-linkage, or 3% or less, or 2% or less, or 1% or less, or 0.5% or less. In some embodiments, the ternary sequence distribution (ccc, ece, and cce) has a ccc percentage of 12% or more, or 15% or more, or 20% or more, or 30% or more, which indicates clustering of cyclopentene units. In some embodiments, the ternary sequence distribution has an ece percentage of 86% or less, or 84% or less, or 80% or less, or 70% or less, or 60% or less, or 50% or less, which indicates isolated cyclopentene units.

[0383] In some embodiments of the present invention, the ethylene-cyclopentene copolymer has a cyclopentene content of greater than 5 mol%, 90% or more of 1,2-linkage, a ccc sequence distribution of 12% or more, and an ece sequence distribution of 86% or less.

[0384] In some embodiments of the present invention, the ethylene-cyclopentene copolymer has a cyclopentene content of less than 50 mol%, 90% or more of 1,2-linkage, a ccc sequence distribution of 12% or more, and an ece sequence distribution of 86% or less.

[0385] In a preferred embodiment, the ethylene-cyclopentene copolymer has:

[0386] a. Mn greater than 5,000 g / mol, or greater than 10,000 g / mol, or greater than 100,000 g / mol, or greater than 150,000 g / mol;

[0387] b. Mw greater than 10,000 g / mol, or greater than 20,000 g / mol, or greater than 200,000 g / mol, or greater than 300,000 g / mol;

[0388] c. The Mw / Mn is about 1 to 10, or about 1.5 to 5.0, or about 1.8 to 3.0, or about 2.0 - 4.0;

[0389] d. The cyclopentene content is 0.1 mol% or greater, and the upper limit is 50 mol% or less, or 45 mol% or less;

[0390] e. The cyclopentene 1,2-linkage accounts for about 90% or more of the total amount of cyclopentene units introduced into the polymer.

[0391] In some embodiments, the ethylene-norbornene copolymer has an Mn of about 2,000 to 1,500,000 g / mol, or about 5,000 to 1,000,000 g / mol, or about 10,000 to 800,000 g / mol, or about 20,000 to 500,000 g / mol, or about 30,000 to 300,000 g / mol.

[0392] In some embodiments, the ethylene-norbornene copolymer has an Mw of about 5,000 to 3,000,000 g / mol, or about 10,000 to 2,000,000 g / mol, or about 20,000 to 1,000,000 g / mol, or about 50,000 to 800,000 g / mol, or about 100,000 to 500,000 g / mol.

[0393] In some embodiments, the ethylene-norbornene copolymer has an Mz of about 10,000 to 3,000,000 g / mol, or about 20,000 to 2,000,000 g / mol, or about 50,000 to 1,000,000 g / mol, or about 100,000 to 800,000 g / mol, or about 200,000 to 500,000 g / mol.

[0394] In some embodiments, the ethylene-norbornene copolymer has an Mw / Mn of about 1.0 to 10, or about 1.2 to 5.0, or about 1.5 to 4.0, or about 2.0 to 3.0.

[0395] In some embodiments, the ethylene-norbornene copolymer has a norbornene content of about 0.1 - 80 mol%, or about 1 - 70 mol%, or about 2 - 60 mol%, or about 2 - 50 mol%, or about 3 - 50 mol%, or about 3 - 45 mol%, or about 4 - 40 mol%.

[0396] In some embodiments, the ethylene-norbornene copolymer has a norbornene content of 10 mol% or greater, or 20 mol% or greater, or 30 mol% or greater, or 40 mol% or greater, and the upper limit is 90 mol% or less, or 80 mol% or less.

[0397] The norbornene units within the polymer can be isolated, alternating, or block. Preferably, the norbornene units are 10 - 80% isolated, 10 - 80% alternating, and 1 - 50% block, where the total amount of the isolated, alternating, and block units equals 100%. Alternatively, the norbornene units are 20 - 80% isolated, 20 - 80% alternating, and 1 - 45% block.

[0398] In some embodiments of the present invention, the ethylene-norbornene copolymer has a norbornene content of 20 mol% or greater, or 40 mol% or greater, or 45 mol% or greater, or 50 mol% or greater, or 60 mol% or greater, or 70 mol% or greater.

[0399] In some embodiments, the ethylene-norbornene copolymer has a norbornene content of about 10 mol% to 90 mol%, or about 15 mol% to about 80 mol%, or about 20 mol% to about 70 mol%, or about 20 mol% to about 60 mol%.

[0400] In some embodiments, the ethylene-norbornene copolymer has a Tg (°C) of 30°C or higher, or 40°C or higher, or 50°C or higher, or 60°C or higher, and the upper limit is 200°C or lower.

[0401] In a preferred embodiment, the ethylene-norbornene copolymer has:

[0402] a. Mn is greater than 50,000 g / mol, or greater than 100,000 g / mol, or greater than 150,000 g / mol, or greater than 200,000 g / mol;

[0403] b. Mw is 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;

[0404] c. Mw / Mn is about 1.2 to 5.0, or about 1.5 to 4.0, or about 2.0 to 3.0;

[0405] d. The norbornene content is 20 mol% or greater, and the upper limit is 80 mol% or less;

[0406] e. and having 10 - 80% isolated, 10 - 80% alternating, and 1 - 50% block norbornene units, wherein the total amount of the isolated, alternating, and block units equals 100%.

[0407] In a preferred embodiment, the copolymer prepared by the method described herein comprises propylene and a cycloolefin, wherein the cycloolefin is C5 - C 20 cycloolefin, preferably cyclopentene and / or 2 - norbornene, and the copolymer has an Mn of 3,000 g / mol or greater, or 5,000 g / mol or greater, or 10,000 g / mol or greater, or 50,000 g / mol or greater, or 75,000 g / mol or greater, or 100,000 g / mol or greater; and Mw / Mn is from 1.0 to 10, or from 1.5 to 5.0, or from 1.8 to 3.0; and the cycloolefin content is 0.05 - 99 mol%, or 0.1 - 50 mol%, or 0.2 - 40 mol%, or 0.3 - 30 mol%, or 0.5 - 20 mol%. Cyclopentene can be introduced in the form of 1,2 - linkage or 1,3 - linkage or a combination of the two.

[0408] In a preferred embodiment, the copolymer prepared by the method described herein comprises propylene and a cycloolefin, optionally further comprising one or more additional C4 - C 12 α - olefins, wherein the cycloolefin is C5 - C 20 cycloolefin, preferably cyclopentene and / or 2 - norbornene, and the copolymer has an Mn of 3,000 g / mol or greater, or 5,000 g / mol or greater, or 10,000 g / mol or greater, or 50,000 g / mol or greater, or 75,000 g / mol or greater, or 100,000 g / mol or greater, and Mw / Mn is from 1.0 to 10, or from 1.5 to 5.0, or from 1.8 to 3.0, and the cycloolefin content is 0.05 - 99 mol%, or 0.1 - 50 mol%, or 0.2 - 40 mol%, or 0.3 - 30 mol%, or 0.5 - 20 mol%. Cyclopentene can be introduced in the form of 1,2 - linkage or 1,3 - linkage or a combination of the two.

[0409] In some embodiments, the propylene - cyclopentene copolymer has an Mn of about 1,000 to 1,000,000 g / mol, or about 2,000 to 800,000 g / mol, or about 3,000 to 500,000 g / mol, or about 4,000 to 100,000, or about 5,000 to 50,000 g / mol.

[0410] In some embodiments, the propylene-cyclopentene copolymer has an Mw of from about 2,000 to 2,000,000 g / mol, or from about 4,000 to 1,500,000 g / mol, or from about 5,000 to 2,000,000 g / mol, or from about 8,000 to 500,000 g / mol, or from about 10,000 to 200,000 g / mol.

[0411] In some embodiments, the propylene-cyclopentene copolymer has an Mz of from about 5,000 to 4,000,000 g / mol, or from about 10,000 to 2,000,000 g / mol, or from about 20,000 to 1,000,000 g / mol, or from about 25,000 to 500,000 g / mol, or from about 30,000 to 200,000 g / mol.

[0412] In some embodiments, the propylene-cyclopentene copolymer has an Mw / Mn of from about 1.0 to 10, or from about 1.5 to 5.0, or from about 1.8 to 3.0, or from about 2.0 to 4.0.

[0413] In some embodiments, the propylene-cyclopentene copolymer has a cyclopentene content of from about 0.05 - 99 mol%, or from about 0.1 - 50 mol%, or from about 0.2 - 40 mol%, or from about 0.3 - 30 mol%, or from about 0.5 - 20 mol%, or from about 1.0 mol% to about 10 mol%. The cyclopentene monomer can be introduced via 1,2-linkage (across the double bond) or 1,3-linkage (from rearrangement) or a combination of both. In some embodiments, the propylene-cyclopentene copolymer predominantly has 1,2-linkage. Preferably, the 1,2-linkage accounts for 90% or more, or 95% or more, or 98% or more, or 99% or more of the total amount of cyclopentene introduced into the propylene backbone. In some embodiments, the propylene-cyclopentene copolymer has 5% or less of 1,3-linkage, or 3% or less, or 2% or less, or 1% or less, or 0.5% or less.

[0414] In preferred embodiments, the propylene-cyclopentene copolymer has:

[0415] a. an Mn greater than 3,000 g / mol, or greater than 5,000 g / mol, or greater than 10,000 g / mol;

[0416] b. an Mw greater than 6,000 g / mol, or greater than 10,000 g / mol, or greater than 20,000 g / mol;

[0417] c. an Mw / Mn of from about 1 to 10, or from about 1.5 to 5.0, or from about 1.8 to 3.0, or from about 2.0 - 4.0;

[0418] d. The cyclopentene content is 0.1 mol% or greater, and the upper limit is 50 mol% or less, or 45 mol% or less;

[0419] e. And the cyclopentene 1,2-linkage accounts for about 90% or more of the total amount of cyclopentene units introduced into the polymer.

[0420] In some embodiments, the propylene-norbornene copolymer has an Mn of about 1,000 to 1,000,000 g / mol, or about 2,000 to 800,000 g / mol, or about 3,000 to 500,000 g / mol, or about 4,000 to 200,000, or about 5,000 to 100,000 g / mol.

[0421] In some embodiments, the propylene-norbornene copolymer has an Mw of about 2,000 to 2,000,000 g / mol, or about 4,000 to 1,500,000 g / mol, or about 5,000 to 1,000,000 g / mol, or about 8,000 to 500,000 g / mol, or about 10,000 to 300,000 g / mol.

[0422] In some embodiments, the propylene-norbornene copolymer has an Mz of about 4,000 to 3,000,000 g / mol, or about 5,000 to 2,000,000 g / mol, or about 6,000 to 1,500,000 g / mol, or about 10,000 to 800,000 g / mol, or about 10,000 to 500,000 g / mol.

[0423] In some embodiments, the propylene-norbornene copolymer has an Mw / Mn of about 1.0 to 10, or about 1.2 to 5.0, or about 1.5 to 4.0, or about 2.0 to 3.0.

[0424] In some embodiments, the propylene-norbornene copolymer has a norbornene content of about 0.1 - 60 mol%, or about 1 - 50 mol%, or about 2 - 40 mol%, or about 3 - 35 mol%, or about 4 - 30 mol%.

[0425] 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.

[0426] In preferred embodiments, the propylene-norbornene copolymer has:

[0427] a. Mn is greater than 3,000 g / mol, or greater than 5,000 g / mol, or greater than 10,000 g / mol;

[0428] b. Mw is greater than 6,000 g / mol, or greater than 10,000 g / mol, or greater than 20,000 g / mol;

[0429] c. Mw / Mn is about 1.2 to 5.0, or about 1.5 to 4.0, or about 2.0 to 3.0;

[0430] d. The norbornene content is 1 mol% or greater, and the upper limit is 50 mol% or less.

[0431] In some embodiments, the polymer produced is a cyclopentene homopolymer (polycyclopentene) having a Mn of about 100 to 5,000 g / mol, or about 200 to 2,000 g / mol, or about 250 to 1,200 g / mol, or about 300 to 1,000 g / mol.

[0432] In some embodiments, the polymer produced is a cyclopentene homopolymer having a Mw of about 200 to 10,000 g / mol, or about 300 to 5,000 g / mol, or about 350 to 2,000 g / mol, or about 300 to 1,000 g / mol.

[0433] In some embodiments, the polymer produced is a cyclopentene homopolymer having a Mz of about 400 to 20,000 g / mol, or about 500 to 10,000 g / mol, or about 600 to 5,000 g / mol, or about 700 to 1,000 g / mol.

[0434] In some embodiments, the Mn of the polycyclopentene is less than 1,000 g / mol, or less than 800 g / mol, or less than 600 g / mol, or less than 500 g / mol, and the Mn is 200 g / mol or greater, or 250 g / mol or greater, or 300 g / mol or greater.

[0435] In preferred embodiments, as determined by gel permeation chromatography (GPC), the polymer produced has a unimodal or multimodal molecular weight distribution. "Unimodal" means that the GPC chromatogram has a single peak or inflection point. "Multimodal" means that the GPC chromatogram has at least two peaks or inflection points. An inflection point is the point at which the second derivative signal of the curve changes (e.g., from negative to positive, or vice versa).

[0436] Blend

[0437] In another embodiment, the polymer composition produced is combined with one or more additional polymers prior to shaping 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 copolymer, LDPE, LLDPE, HDPE, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, copolymers of acrylic acid, polymethyl methacrylate or any other polymer polymerizable by high pressure free radical methods, polyvinylidene chloride, polybutene-1, isotactic polybutene, ABS resin, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymers, styrenic block copolymers, polyamides, polycarbonates, PET resin, crosslinked polyethylene, copolymer of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1-ester, polyacetal, polyvinylidene fluoride, polyethylene glycol, and / or polyisobutylene.

[0438] In a preferred embodiment, the polymer produced is present in the blend in an amount of 10-99 wt%, based on the total weight of the polymers in the blend, preferably 20-95 wt%, more preferably at least 30-90 wt%, more preferably at least 40-90 wt%, more preferably at least 50-90 wt%, more preferably at least 60-90 wt%, more preferably at least 70-90 wt%.

[0439] The blend can be prepared by mixing the polymer of the present invention with one or more polymers (as described above), where reactors are arranged in series to prepare a reactor blend; or by using more than one catalyst in the same reactor to prepare multiple polymers. These polymers can be mixed together before entering the extruder or can be mixed in the extruder. Alternatively, the blend can be prepared by mixing the polymer of the present invention with one or more polymers (as described above), where multiple reactors are connected in series or in parallel together to prepare a reactor blend.

[0440] The blend can be formed using conventional equipment and methods, such as by dry blending the components in a mixer and then melt blending, or by mixing these components directly together in a mixer, such as a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin screw extruder, which can include using a compounding extruder and a side stream extruder located directly downstream of the polymerization process, which can include blending the resin powder or pellets at the hopper of a film extruder. Additionally, additives can be included in the blend as needed, included in one or more of the components of the blend, and / or included in the product formed from the blend, such as a film. These additives are known in the art and can include, for example: fillers; antioxidants (such as hindered phenols, such as IRGANOX TM 1010 or IRGANOX TM 1076, commercially available from BASF); phosphites (such as IRGAFOS TM 168, available from BASF); anti-slip additives; tackifiers, such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosin; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; talc; and the like.

[0441] Film

[0442] Specifically, any of the above polymers, such as the above polymers or their blends, can be used in a variety of end applications. These applications include, for example, monolayer or multilayer blown, extruded, and / or shrink films. These films can be formed by any number of known extrusion or coextrusion techniques, such as blown film processing techniques, where the composition can be extruded in a molten state through an annular die and then inflated to form a uniaxially or biaxially oriented melt, which is then cooled to form a tubular blown film, which can then be axially slit and unrolled to form a flat film. Thus, these films can be unoriented, uniaxially oriented, or biaxially oriented to the same or different degrees. One or more layers of the film can be oriented in the transverse and / or longitudinal directions to the same or different degrees. Uniaxial orientation can be accomplished using typical cold or hot drawing methods. Biaxial orientation can be accomplished using a tenter frame apparatus or a double bubble process, and can be performed before or after the individual layers are formed 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 to form a film and then oriented. Similarly, oriented polypropylene can be laminated onto oriented polyethylene, or oriented polyethylene can be coated onto polypropylene, and then the combination can optionally be further oriented. Generally, the film is oriented along the machine direction (MD) at a ratio of up to 15, preferably 5 to 7, and along the transverse direction (TD) at a ratio of up to 15, preferably 7 to 9. However, in another embodiment, the film is oriented to the same degree in both the MD and TD directions.

[0443] The films can have different thicknesses, depending on the intended application; however, films having a thickness of 1 - 50 μm are generally suitable. Films for packaging typically have a thickness of 10 - 50 μm. The thickness of the sealant layer is typically 0.2 - 50 μm. The sealant layer can be present on both the inner and outer surfaces of the film, or the sealant layer can be present only on the inner or outer surface.

[0444] In another embodiment, one or more layers can be modified by corona treatment, electron beam irradiation, γ - irradiation, flame treatment, or microwave. In a preferred embodiment, one or both of the surface layers are modified by corona treatment.

[0445] Any of the above polymers and their compositions with optional additives (see, for example, U.S. Patent Application Publication No. 2016 / 0060430, paragraphs

[0082] -

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

[0446] Lubricant and viscosity improver

[0447] The present invention also provides a lubricant composition comprising a blend of an ethylene-cyclic monomer copolymer described herein and a lubricating oil. The concentration of the ethylene-cyclic monomer copolymer in the lubricating oil is 5 wt% or less. The shear stability index (at 30 cycles) of the branched ethylene copolymer in the lubricating oil is from about 10% to about 60%, and the kinematic viscosity at 100 °C is from about 5 cSt to about 20 cSt. The shear stability index (SSI) is measured according to ASTM D6278 using a Kurt Orbahn diesel injection device at 30 cycles. The kinematic viscosity (KV) is measured according to ASTM D445.

[0448] The present invention also relates to:

[0449] 1. A polymerization process comprising contacting a cycloolefin monomer and an optional comonomer selected from C2-C 20 α-olefins with a catalyst system comprising an activator and a catalyst compound represented by formula (I):

[0450]

[0451] Wherein:

[0452] M is a transition metal of Group 3, 4, 5 or 6 or a lanthanide element;

[0453] E and E' are each independently O, S or NR 9 where R 9 is independently hydrogen, a C1-C 40 hydrocarbyl group, a substituted C1-C 40 hydrocarbyl group or a heteroatom-containing group;

[0454] Q is an atom of Group 14, 15 or 16 that forms a coordinate bond with the metal M;

[0455] A 1 QA 1’ is part of a hetero - cyclic Lewis base containing 4 - 40 non - hydrogen atoms, which connects A 2 to A via a 3 - atom bridge 2’ where Q is the central atom of the 3 - atom bridge, and A 1 and A 1 ′ are independently C, N or C(R 22 ), where R 22 is selected from hydrogen, C1 - C 20 hydrocarbyl, substituted C1 - C 20 hydrocarbyl;

[0456] is a divalent group containing 2 - 40 non - hydrogen atoms, which connects A 1 to the aryl group bonded to E via a 2 - atom bridge;

[0457] is a divalent group containing 2 - 40 non - hydrogen atoms, which connects A 1 ' to the aryl group bonded to E' via a 2 - atom bridge;

[0458] L is a Lewis base;

[0459] X is an anionic ligand;

[0460] n is 1, 2 or 3;

[0461] m is 0, 1 or 2;

[0462] n + m is not greater than 4;

[0463] Each R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ' and R 4 ' are independently hydrogen, C1 - C 40 hydrocarbyl, substituted C1 - C 40 hydrocarbyl, heteroatom or heteroatom - containing group, and 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 4One or more of the 's can be linked together to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles or unsubstituted heterocycles, each of said rings having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the ring can be linked together to form additional rings;

[0464] Any two L groups can be linked together to form a bidentate Lewis base;

[0465] The X group can be linked to the L group to form a monoanionic bidentate group;

[0466] Any two X groups can be linked together to form a dianionic ligand group.

[0467] 2. The method according to paragraph 1, wherein the catalyst compound is represented by formula (II):

[0468]

[0469] Wherein:

[0470] M is a transition metal of Group 3, 4, 5 or 6 or a lanthanide element;

[0471] E and E' are each independently O, S or NR 9 , wherein R 9 is independently hydrogen, C1-C 40 hydrocarbyl, substituted C1-C 40 hydrocarbyl or a heteroatom-containing group;

[0472] Each L is independently a Lewis base;

[0473] Each X is independently an anionic ligand;

[0474] n is 1, 2 or 3;

[0475] m is 0, 1 or 2;

[0476] n + m is not greater than 4;

[0477] Each R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ' and R 4 ' are independently hydrogen, C1-C 40 hydrocarbyl, substituted C1-C 40 hydrocarbyl, a heteroatom or a heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R3 and R 4 、R 1 ' and R 2 '、R 2’ and R 3 '、R 3 ' and R 4 ' one or more of and R can be joined to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each of said rings having 5, 6, 7 or 8 ring atoms, and wherein substituents on the ring can be joined to form additional rings; any two L groups can be joined together to form a bidentate Lewis base;

[0478] The X group can be attached to the L group to form a monoanionic bidentate group;

[0479] Any two X groups can be joined together to form a dianionic ligand group;

[0480] Each R 5 、R 6 、R 7 、R 8 、R 5’ 、R 6’ 、R 7’ 、R 8’ 、R 10 、R 11 and R 12 independently is hydrogen, C1-C 40 hydrocarbon group, substituted C1-C 40 hydrocarbon group, heteroatom or heteroatom-containing group, or R 5 and R 6 、R 6 and R 7 、R 7 and R 8 、R 5’ and R 6’ 、R 6’ and R 7’ 、R 7’ and R 8’ 、R 10 and R 11 、or R 11 and R 12 one or more of and R can be joined to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each of said rings having 5, 6, 7 or 8 ring atoms, and wherein substituents on the ring can be joined to form additional rings.

[0481] 3. The method according to paragraph 1 or 2, wherein M is Hf, Zr or Ti.

[0482] 4. The method as described in paragraph 1, 2 or 3, wherein each of E and E' is O.

[0483] 5. The method as described in paragraph 1, 2, 3 or 4, wherein R 1 and R 1’ are independently C4-C 40 tertiary hydrocarbon groups.

[0484] 6. The method as described in paragraph 1, 2, 3 or 4, wherein R 1 and R 1’ are independently C4-C 40 cyclic tertiary hydrocarbon groups.

[0485] 7. The method as described in paragraph 1, 2, 3 or 4, wherein R 1 and R 1’ are independently C4-C 40 polycyclic tertiary hydrocarbon groups.

[0486] 8. The method as described in any one of paragraphs 1-7, wherein each X is independently selected from the group consisting of: substituted or unsubstituted hydrocarbon groups having 1-20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, and combinations thereof (wherein two Xs may form a fused ring or part of a ring system).

[0487] 9. The method as described in any one of paragraphs 1-8, wherein each L is independently selected from the group consisting of: ethers, thioethers, amines, phosphines, ethyl ether, tetrahydrofuran, dimethyl sulfide, triethylamine, pyridine, alkenes, alkynes, allenes, carbenes, and combinations thereof, optionally two or more Ls may form a fused ring or part of a ring system.

[0488] 10. The method as described in paragraph 1, wherein M is Zr or Hf, Q is nitrogen, A 1 and A 1’ are both carbon, E and E' are both oxygen, and R 1 and R 1’ are both C4-C 20 cyclic tertiary alkyl groups.

[0489] 11. The method as described in paragraph 1, wherein M is Zr or Hf, Q is nitrogen, A 1 and A 1’ are both carbon, E and E' are both oxygen, and R 1 and R 1’ are both adamantan-1-yl or substituted adamantan-1-yl.

[0490] 12. The method as described in paragraph 1, wherein M is Zr or Hf, Q is nitrogen, A 1 and A 1’All are carbon, both E and E' are oxygen, X is methyl or chlorine, and n is 2.

[0491] 13. The method according to paragraph 1, wherein Q is nitrogen, A 1 and A 1’ are both carbon, R 1 and R 1’ are both hydrogen, E and E' are both NR 9 , wherein R 9 is selected from C1-C 40 hydrocarbyl, substituted C1-C 40 hydrocarbyl or heteroatom-containing group.

[0492] 14. The method according to paragraph 1, wherein Q is carbon, A 1 and A 1’ are both nitrogen, and E and E' are both oxygen.

[0493] 15. The method according to paragraph 1, wherein Q is carbon, A 1 is nitrogen, A 1’ is C(R 22 ), and E and E' are both oxygen, wherein R 22 is selected from hydrogen, C1-C 20 hydrocarbyl, substituted C1-C 20 hydrocarbyl.

[0494] 16. The method according to paragraph 1, wherein the heterocyclic Lewis base is selected from the groups represented by the following formula:

[0495]

[0496] wherein each R 23 is independently selected from hydrogen, C1-C 20 alkyl and substituted C1-C 20 alkyl.

[0497] 17. The method according to paragraph 2, wherein M is Zr or Hf, E and E' are both oxygen, and R 1 and R 1’ are both C4-C 20 cyclic tertiary alkyl.

[0498] 18. The method according to paragraph 2, wherein M is Zr or Hf, E and E' are both oxygen, and R 1 and R 1’ are both adamantan-1-yl or substituted adamantan-1-yl.

[0499] 19. The method according to paragraph 2, wherein M is Zr or Hf, E and E' are both oxygen, and each R 1 、R 1’ 、R3 and R 3’ is adamantan-1-yl or substituted adamantan-1-yl.

[0500] 20. The method according to paragraph 2, wherein M is Zr or Hf, E and E' are both oxygen, R 1 and R 1’ are both C4-C 20 cyclic tertiary alkyl, and R 7 and R 7 ’ are both C1-C 20 alkyl.

[0501] 21. The method according to paragraph 2, wherein M is Zr or Hf, E and E' are both O, R 1 and R 1’ are both C4-C 20 cyclic tertiary alkyl, and R 7 and R 7 ’ are both C1-C 20 alkyl.

[0502] 22. The method according to paragraph 2, wherein M is Zr or Hf, E and E' are both O, R 1 and R 1’ are both C4-C 20 cyclic tertiary alkyl, and R 7 and R 7 ’ are both C1-C3 alkyl.

[0503] 23. The method according to paragraph 1, wherein the catalyst compound is represented by one or more of the following formulas:

[0504]

[0505]

[0506]

[0507]

[0508]

[0509]

[0510] 24. The method according to paragraph 1, wherein the catalyst compound is one or more of the following compounds:

[0511]

[0512]

[0513] 25. The method according to any one of paragraphs 1-24, wherein the activator comprises an aluminoxane or a non-coordinating anion.

[0514] 26. The method according to any one of paragraphs 1-24, wherein the activator is soluble in a non-aromatic hydrocarbon solvent.

[0515] 27. The method according to any one of paragraphs 1-24, wherein the catalyst system does not contain an aromatic solvent.

[0516] 28. The method according to any one of paragraphs 1-27, wherein the activator is represented by the following formula:

[0517] (Z)d + (A d- )

[0518] wherein Z is (L-H) or a reducible Lewis acid, L is a neutral Lewis base; H is hydrogen; (L-H) + is a Bronsted acid; Ad- is a non-coordinating anion having a charge of d-; and d is an integer from 1 to 3.

[0519] 29. The method according to any one of paragraphs 1-27, wherein the activator is represented by the following formula:

[0520] [R 1′ R 2′ R 3′ EH] d+ [Mt k+ Q n d - (V)

[0521] wherein:

[0522] E is nitrogen or phosphorous;

[0523] d is 1, 2 or 3; k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6; n-k = d;

[0524] R 1′ 、R 2′ and R 3′ are independently C1-C 50 hydrocarbyl groups, which are optionally substituted by one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups,

[0525] wherein R 1′ 、R 2′ and R 3′ together contain 15 or more carbon atoms;

[0526] Mt is an element selected from Group 13 of the Periodic Table; and

[0527] ​Each Q is independently a hydride, a bridged or unbridged dialkylamido, a halide, an alkoxide, an aryloxide, a hydrocarbyl, a substituted hydrocarbyl, a halocarbonyl, a substituted halocarbonyl, or a halohydrocarbyl.

[0528] 30. The method according to any one of paragraphs 1-27, wherein the activator is represented by the following formula:

[0529] (Z)d + (A d- )

[0530] wherein A d- is a non-coordinating anion having a charge of d-; and d is an integer from 1 to 3, and (Z) d + is represented by one or more of the following formulas:

[0531]

[0532]

[0533] 31. The method according to any one of paragraphs 1-27, wherein the activator is one or more of the following compounds:

[0534] N-Methyl-4-nonadecyl-N-octadecylaniline tetra(pentafluorophenyl)borate ,

[0535] N-Methyl-4-nonadecyl-N-octadecylaniline tetra(perfluoronaphthalen-2-yl)borate ,

[0536] Dimethyldioctadecylammonium tetra(pentafluorophenyl)borate,

[0537] Dimethyldioctadecylammonium tetra(perfluoronaphthalen-2-yl)borate,

[0538] N,N-Dimethylaniline tetra(pentafluorophenyl)borate ,

[0539] Triphenylcarbene tetra(pentafluorophenyl)borate ,

[0540] Trimethylammonium tetra(perfluoronaphthalen-2-yl)borate,

[0541] Triethylammonium tetra(perfluoronaphthalen-2-yl)borate,

[0542] Tripropylammonium tetra(perfluoronaphthalen-2-yl)borate,

[0543] Tetra(n-butyl)ammonium tetra(perfluoronaphthalen-2-yl)borate,

[0544] Tri(tert-butyl)ammonium tetra(perfluoronaphthalen-2-yl)borate,

[0545] N,N-Dimethylanilinium tetra(perfluoronaphthalen-2-yl)borate ,

[0546] N,N-Diethylanilinium tetra(perfluoronaphthalen-2-yl)borate ,

[0547] N,N-Dimethyl-(2,4,6-trimethylanilinium) tetra(perfluoronaphthalen-2-yl)borate ),

[0548] Tetra(perfluoronaphthalen-2-yl)borate (tropillium),

[0549] Triphenylcarbenium tetra(perfluoronaphthalen-2-yl)borate ,

[0550] Triphenyltetra(perfluoronaphthalen-2-yl)borate ,

[0551] Triethylsilyl tetra(perfluoronaphthalen-2-yl)borate ,

[0552] Phenyl(diazo)tetra(perfluoronaphthalen-2-yl)borate,

[0553] Trimethylammonium tetra(perfluorobiphenyl)borate,

[0554] Triethylammonium tetra(perfluorobiphenyl)borate

[0555] Tripropylammonium tetra(perfluorobiphenyl)borate

[0556] Tetra(n-butyl)ammonium tetra(perfluorobiphenyl)borate

[0557] Tri(tert-butyl)ammonium tetra(perfluorobiphenyl)borate

[0558] N,N-Dimethylanilinium tetra(perfluorobiphenyl)borate ,

[0559] N,N-Diethylanilinium tetra(perfluorobiphenyl)borate ,

[0560] N,N-Dimethyl-(2,4,6-trimethylanilinium) tetra(perfluorobiphenyl)borate ),

[0561] Tetra(perfluorobiphenyl)borate ,

[0562] Trityl Tetrakis(perfluorobiphenyl)borate ,

[0563] Trityl Tetrakis(perfluorobiphenyl)borate ,

[0564] Triethylsilyl Tetrakis(perfluorobiphenyl)borate ,

[0565] Phenyldiazo Tetrakis(perfluorobiphenyl)borate,

[0566] [4-tert-Butyl-PhNMe2H][(C6F3(C6F5)2)4B],

[0567] Trimethylammonium Tetraphenylborate,

[0568] Triethylammonium Tetraphenylborate,

[0569] Tripropylammonium Tetraphenylborate,

[0570] Tri(n-butyl)ammonium Tetraphenylborate,

[0571] Tri(tert-butyl)ammonium Tetraphenylborate,

[0572] N,N-Dimethylanilinium Tetraphenylborate ,

[0573] N,N-Diethylanilinium Tetraphenylborate ,

[0574] N,N-Dimethyl-(2,4,6-trimethylanilinium ),

[0575] Tetraphenylboric Acid ,

[0576] Trityl Tetraphenylborate ,

[0577] Trityl Tetraphenylborate ,

[0578] Triethylsilyl Tetraphenylborate ,

[0579] Phenyldiazo Tetraphenylborate,

[0580] Trimethylammonium Tetrakis(pentafluorophenyl)borate,

[0581] Triethylammonium Tetrakis(pentafluorophenyl)borate,

[0582] Tripropylammonium Tetrakis(pentafluorophenyl)borate,

[0583] Tri(n-butyl)ammonium Tetrakis(pentafluorophenyl)borate,

[0584] Tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

[0585] N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate ,

[0586] N,N-Diethylanilinium tetrakis(pentafluorophenyl)borate ,

[0587] N,N-Dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate ), tetrakis(pentafluorophenyl)boric acid ,

[0588] Triphenylcarbenium tetrakis(pentafluorophenyl)borate ,

[0589] Triphenyltetrakis(pentafluorophenyl)borate ,

[0590] Triethylsilylium tetrakis(pentafluorophenyl)borate ,

[0591] Phenyl(diazo)tetrakis(pentafluorophenyl)borate,

[0592] Trimethylammonium tetra-(2,3,4,6-tetrafluorophenyl)borate,

[0593] Triethylammonium tetra-(2,3,4,6-tetrafluorophenyl)borate

[0594] Tripropylammonium tetra-(2,3,4,6-tetrafluorophenyl)borate

[0595] Tri(n-butyl)ammonium tetra-(2,3,4,6-tetrafluorophenyl)borate

[0596] Dimethyl(tert-butyl)ammonium tetra-(2,3,4,6-tetrafluorophenyl)borate

[0597] N,N-Dimethylanilinium tetra-(2,3,4,6-tetrafluorophenyl)borate ,

[0598] N,N-Diethylanilinium tetra-(2,3,4,6-tetrafluorophenyl)borate ,

[0599] N,N-Dimethyl-(2,4,6-trimethylanilinium) tetra-(2,3,4,6-tetrafluorophenyl)borate ), tetra-(2,3,4,6-tetrafluorophenyl)boric acid ,

[0600] Triphenylcarbenium tetra-(2,3,4,6-tetrafluorophenyl)borate ,

[0601] Triphenyltetrakis(2,3,4,6 - tetrafluorophenyl)borate ,

[0602] Triethylsilyltetrakis(2,3,4,6 - tetrafluorophenyl)borate ,

[0603] Phenyldiazoniumtetrakis(2,3,4,6 - tetrafluorophenyl)borate,

[0604] Trimethylammoniumtetrakis(3,5 - bis(trifluoromethyl)phenyl)borate,

[0605] Triethylammoniumtetrakis(3,5 - bis(trifluoromethyl)phenyl)borate

[0606] Tripropylammoniumtetrakis(3,5 - bis(trifluoromethyl)phenyl)borate

[0607] Tetrabutylammoniumtetrakis(3,5 - bis(trifluoromethyl)phenyl)borate

[0608] Tert - butylammoniumtetrakis(3,5 - bis(trifluoromethyl)phenyl)borate

[0609] N,N - Dimethylaniliniumtetrakis(3,5 - bis(trifluoromethyl)phenyl)borate ,

[0610] N,N - Diethylaniliniumtetrakis(3,5 - bis(trifluoromethyl)phenyl)borate ,

[0611] N,N - Dimethyl - 2,4,6 - trimethylaniliniumtetrakis(3,5 - bis(trifluoromethyl)phenyl)borate ),

[0612] Tetrakis(3,5 - bis(trifluoromethyl)phenyl)boric acid ,

[0613] Triphenylcarbeniumtetrakis(3,5 - bis(trifluoromethyl)phenyl)borate ,

[0614] Triphenyltetrakis(3,5 - bis(trifluoromethyl)phenyl)borate ,

[0615] Triethylsilyltetrakis(3,5 - bis(trifluoromethyl)phenyl)borate ,

[0616] Phenyldiazoniumtetrakis(3,5 - bis(trifluoromethyl)phenyl)borate,

[0617] Di - (isopropyl)ammoniumtetrakis(pentafluorophenyl)borate

[0618] Dicyclohexylammonium tetrakis(pentafluorophenyl)borate

[0619] Tris(ortho-tolyl) tetrakis(pentafluorophenyl)borate ,

[0620] Tris(2,6-dimethylphenyl) tetrakis(pentafluorophenyl)borate ,

[0621] Triphenylcarbenium tetrakis(pentafluorophenyl)borate ,

[0622] 1-(4-(Tris(pentafluorophenyl)borato)-2,3,5,6-tetrafluorophenyl)pyrrolidine ,

[0623] Tetrakis(pentafluorophenyl)borate salts

[0624] 4-(Tris(pentafluorophenyl)borato)-2,3,5,6-tetrafluoropyridine, and

[0625] Triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate .

[0626] 32. The method according to any one of paragraphs 1-31, wherein the method is a solution method.

[0627] 33. The method according to any one of paragraphs 1-32, wherein the method is carried out at a temperature of about 80 °C to about 300 °C, a pressure of about 0.35 MPa to about 10 MPa and a residence time of at most 300 minutes.

[0628] 34. The method according to any one of paragraphs 1-33, wherein the method is a continuous method.

[0629] 35. The method according to any one of paragraphs 1-34, wherein the polymer comprises at least 0.1 mol% of cycloolefin.

[0630] 36. The method according to any one of paragraphs 1-34, wherein the polymer comprises at least 1 mol% of cycloolefin.

[0631] 37. The method according to any one of paragraphs 1-34, wherein the polymer comprises at least 10 mol% of cycloolefin.

[0632] 38. The method according to any one of paragraphs 1-37, wherein the polymer comprises at least 1 mol% of cycloolefin and at least 20 mol% of ethylene.

[0633] 39. The method according to any one of paragraphs 1-37, wherein the polymer comprises at least 1 mol% of a cycloolefin and at least 20 mol% of propylene.

[0634] 40. A polymer prepared by the method according to any one of paragraphs 1-39, which comprises one or more cycloolefin monomers selected from the group consisting of: substituted or unsubstituted cyclopentene, and substituted or unsubstituted 2-norbornene.

[0635] 41. A polymer prepared by the method according to any one of paragraphs 1-40, which comprises one or more cyclic monomers selected from substituted or unsubstituted cyclopentene.

[0636] 42. A polymer prepared by the method according to any one of paragraphs 1-40, which comprises one or more cyclic monomers selected from substituted or unsubstituted 2-norbornene.

[0637] 43. The method according to any one of paragraphs 1-33, wherein the polymer is a homopolymer of substituted or unsubstituted cyclopentene.

[0638] 44. The method according to paragraph 43, wherein the polymer is a homopolymer of cyclopentene.

[0639] 45. The method according to any one of paragraphs 1-40, wherein the polymer is an ethylene-cyclopentene copolymer having:

[0640] a. Mn is greater than 5,000 g / mol, or greater than 10,000 g / mol, or greater than 100,000 g / mol, or greater than 150,000 g / mol;

[0641] b. Mw is greater than 10,000 g / mol, or greater than 20,000 g / mol, or greater than 200,000 g / mol, or greater than 300,000 g / mol;

[0642] c. Mw / Mn is about 1 to 10, or about 1.5 to 5.0, or about 1.8 to 3.0, or about 2.0 - 4.0;

[0643] d. The cyclopentene content is 0.1 mol% or more, and the upper limit is 50 mol% or less, or 45 mol% or less;

[0644] e. And, the 1,2-linkage of cyclopentene accounts for about 90% or more of the total amount of cyclopentene units introduced into the polymer.

[0645] 46. The method according to any one of paragraphs 1-40, wherein the polymer is an ethylene-norbornene copolymer having:

[0646] a. Mn is greater than 50,000 g / mol, or greater than 100,000 g / mol, or greater than 150,000 g / mol, or greater than 200,000 g / mol;

[0647] b. Mw is 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;

[0648] c. Mw / Mn is about 1.2 to 5.0, or about 1.5 to 4.0, or about 2.0 to 3.0;

[0649] d. The norbornene content is 20 mol% or more, and the upper limit is 80 mol% or less;

[0650] e. And, the norbornene units are 10 - 80% isolated, 10 - 80% alternating, and 1 - 50% block, where the total amount of the isolated, alternating, and block units is equal to 100%.

[0651] 47. The method according to any one of paragraphs 1 - 40, wherein the polymer is a propylene-cyclopentene copolymer having:

[0652] a. Mn is greater than 3,000 g / mol, or greater than 5,000 g / mol, or greater than 10,000 g / mol;

[0653] b. Mw is greater than 6,000 g / mol, or greater than 10,000 g / mol, or greater than 20,000 g / mol;

[0654] c. Mw / Mn is about 1 to 10, or about 1.5 to 5.0, or about 1.8 to 3.0, or about 2.0 - 4.0;

[0655] d. The cyclopentene content is 0.1 mol% or more, and the upper limit is 50 mol% or less, or 45 mol% or less;

[0656] e. And, the 1,2-linkage of cyclopentene accounts for about 90% or more of the total amount of cyclopentene units introduced into the polymer.

[0657] 48. The method according to any one of paragraphs 1 - 40, wherein the polymer is a propylene-norbornene copolymer having:

[0658] a. Mn is greater than 3,000 g / mol, or greater than 5,000 g / mol, or greater than 10,000 g / mol;

[0659] b. Mw is greater than 6,000 g / mol, or greater than 10,000 g / mol, or greater than 20,000 g / mol;

[0660] c. Mw / Mn is about 1.2 to 5.0, or about 1.5 to 4.0, or about 2.0 to 3.0;

[0661] d. The norbornene content is 1 mol% or more, and the upper limit is 50 mol% or less.

[0662] Detection method for large-scale polymerization

[0663] Molecular weight and composition distribution (GPC-IR): The distribution and moments of molecular weight (e.g., Mn, Mw, Mz) and comonomer distribution (C2, C3, C6, etc.) are detected by high-temperature gel permeation chromatography (PolymerChar GPC-IR), which is equipped with a multi-channel band filter based on the infrared detector module IR5, where the broadband channel is used to detect the polymer concentration, and two narrowband channels are used to characterize the composition. Three Agilent PLgel 10μm Mixed-B LS columns are used to provide the separation of the polymer. Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB) and 300 ppm butylated hydroxytoluene (BHT) antioxidant are used as the mobile phase. The TCB mixture is filtered through a 0.1-μm Teflon filter paper and degassed with an on-line degasser before entering the GPC instrument. The nominal flow rate is 1.0 mL / min, and the nominal injection volume is 200 μL. The entire system including transfer lines, columns, and detectors is housed in an oven maintained at 145 °C. A given amount of polymer sample is weighed and sealed in a standard vial containing 10 μL of a flow marker (heptane). After loading the vial into the autosampler, the polymer is automatically dissolved in 8 mL of added TCB solvent in the instrument. The polymer is dissolved at 160 °C, where most PE samples are continuously vibrated for about 1 hour, or PP samples are continuously vibrated for 2 hours. When calculating the concentration, the TCB density used is 1.463 g / ml at room temperature and 1.284 g / ml at 145 °C. The solution concentration of the sample is 0.2 - 2.0 mg / ml, where lower concentrations are used for samples with higher molecular weights.

[0664] The concentration c at each point in the chromatogram is calculated from the baseline-subtracted IR5 broadband signal I using the following formula:

[0665] c = αl

[0666] where α is the mass constant determined using the PE standard NBS1475. The mass recovery is calculated from the ratio of the integrated area of the concentration chromatogram with respect to the elution volume and the injection mass, and the injection mass is equal to the predetermined concentration multiplied by the injection loop volume.

[0667] The molecular weight is detected by combining the universal calibration relationship with column calibration performed with a series of monodisperse polystyrene (PS) standards. The molecular weight is calculated at each elution volume according to the following formula;

[0668]

[0669] where K and α are the coefficients in the Mark-Houwink equation. Symbols with subscript “X” denote the sample being detected, while those with subscript “PS” denote polystyrene. In this method, a PS = 0.67, and K PS = 0.000175, while a X and K X are determined using standard calibration procedures based on the composition of linear ethylene / propylene copolymers and linear ethylene-propylene-diene terpolymers. The composition of the comonomer is detected by the ratio of the IR detector intensity relative to the CH2 and CH3 channels calibrated with a series of PE and PP homopolymer / copolymer standards, the nominal values of which are determined in advance via NMR.

[0670] The LS detector is an 18-angle Wyatt Technology high-temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is detected by analyzing the LS output using the Zimm model for static light scattering (light scattering from polymer solutions; edited by Huglin, M.B.; Academic Press, 1972):

[0671]

[0672] Here, ΔR(θ) is the detected value exceeding the Rayleigh scattering intensity at the scattering angle θ, c is the polymer concentration obtained from IR5 analysis, A2 is the second virial coefficient, P(θ) is the form factor for monodisperse random coils, and K o is the optical constant of the system:

[0673]

[0674] where N Ais the Avogadro constant, and (dn / dc) is the refractive index increment of the system. For TCB, the refractive index n = 1.500 at 145 °C and λ = 665 nm. For the analysis of polyethylene homopolymer, ethylene-hexene copolymer, and ethylene-octene copolymer, dn / dc = 0.1048 ml / mg, and A2 = 0.0015; for the analysis of ethylene-butene copolymer, dn / dc = 0.1048*(1 - 0.00126*w2) ml / mg, and A2 = 0.0015, where w2 is the weight percentage of butene comonomer.

[0675] A high-temperature Agilent (or Viscotek Corporation) viscometer is used to detect the specific viscosity. The viscometer has 4 capillaries and two pressure transducers arranged according to the Wheatstone bridge configuration. One transducer detects the total pressure drop across the detector, while the other transducer is located between the two sides of the bridge and detects the pressure difference. The specific viscosity ηs of the solution flowing through the viscometer is calculated from the output values of these solutions. The intrinsic viscosity [η] at each point in the chromatogram is calculated from the formula [η] = η S / c, where c is the concentration and is measured from the output value of the IR5 broadband channel. The viscosity MW at each point is calculated according to the following formula:

[0676]

[0677] where α ps is 0.67, and K PS is 0.000175.

[0678] The branching index (g'vis) is calculated as follows using the output values of the GPC-IR5-LS-VIS method. The average intrinsic viscosity [η] of the sample is calculated according to the following formula: avg :

[0679]

[0680] where the summation is over the entire chromatographic thin layer, i.e., between the integration limits.

[0681] The branching index g'vis is defined as:

[0682]

[0683] where Mv is the viscosity-average molecular weight, which is based on the molecular weight determined via LS analysis, and K and α are for a reference linear polymer, where for linear ethylene polymers in the present invention, 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; 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 percentage of the butene comonomer; for ethylene–hexene copolymers, α is 0.695 and K is 0.000579*(1 - 0.0075*w2b), where w2b is the bulk weight percentage of the hexene comonomer; and for ethylene–octene copolymers, α is 0.695 and K is 0.000579*(1 - 0.0077*w2b), where w2b is the bulk weight percentage of the octene comonomer. Unless otherwise stated, the unit of concentration is g / cm 3 , the unit of molecular weight is grams per mole, and the unit of the intrinsic viscosity (and thus K in the Mark–Houwink equation) is dL / g. The w2b value is calculated as described above.

[0684] Details of the experiments and analyses not mentioned above, including how to calibrate the detector and how to calculate the dependence of the composition on the Mark-Houwink parameters and the second virial coefficient, can be found in T. Sun, P. Brant, R. R. Chance, and W. W. Graessley (Macromolecules, 2001, v. 34(19), pp. 6812-6820).

[0685] According to ASTM D3418-03, the peak melting temperature Tm (also known as the melting point), peak crystallization temperature Tc (also known as the crystallization temperature), glass transition temperature (Tg), heat of fusion (ΔHf or Hf), and percent crystallinity were determined using the following DSC protocol. Differential scanning calorimetry (DSC) data were obtained using a TA Instruments model DSC2500 instrument. Samples weighing approximately 5 - 10 mg were weighed and sealed in aluminum hermetic sample pans. The DSC data were recorded as follows: The sample was first ramped up 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, then held isothermally for 2 minutes, and then heated to 200 °C at a rate of 10 °C / min. The thermal history of the first and second cycles was recorded. The area under the endothermic peak was measured and used to determine the heat of fusion and percent crystallinity. The percent crystallinity was calculated using the following formula: [Area under the melting peak (J / g) / B (J / g)] * 100, where B is the heat of fusion of the 100% crystalline homopolymer of the major monomer component. The Polymer Handbook (4th Edition, published by John Wiley and Sons, New York 1999) provides these B values; however, the value 189 J / g (B) was used as the heat of fusion of 100% crystalline polypropylene and the value 290 J / g was used as the heat of fusion of 100% crystalline polyethylene. Unless otherwise noted, the melting and crystallization temperatures reported herein were obtained during the second heating / cooling cycle.

[0686] For polymers showing 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. The percent crystallinity was calculated using the sum of the heats of fusion of all endothermic peaks. Some of the resulting polymer blends showed minor melting / cooling peaks that overlapped with the main peak, and these were considered together as a single melting / cooling peak. The highest value of these peaks was considered the peak melting temperature / crystallization point. For amorphous polymers, which have a low degree of crystallinity, the melting temperature was typically measured and reported during the first heating cycle. Prior to DSC measurements, the samples were aged (usually held at ambient temperature for 2 days) or annealed to achieve the maximum level of crystallinity.

[0687] The melt index (I2) was measured according to ASTM D1238 at a temperature of 190 °C using a 2.16 kg load. The melt index (I 21 ) was measured according to ASTM D1238 at a temperature of 190 °C using a 21.6 kg load.

[0688] The density was measured on compression-molded samples according to ASTM D1505 using a density gradient column as described in ASTM D1505, where the samples had been slowly cooled to room temperature (i.e., over a period of 10 minutes or longer) and allowed to age for a sufficient time for the density to be constant within + / - 0.001 g / cm 3 inside.

[0689] Experiment

[0690] The catalysts for the polymerization reaction were synthesized according to the procedures described in US 2020-0255553, USSN 62 / 972953, USSN 62 / 972936, US 2020-0255555, US2020-0254431 and US 2020-0255556.

[0691] Cat-Hf (Complex 5), Cat-Zr (Complex 6) and Complex 66 were prepared as described below:

[0692] Raw material

[0693] Used as received 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Aldrich), 2,6-dibromopyridine (Aldrich), 2-bromoiodobenzene (Acros), 2.5 M in hexane nBuLi (Chemetal 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 (AkzoNobel), silica gel 60 (40 - 63 µm; Merck), CDCl3 (Deutero GmbH). Benzene-d6 (Deutero GmbH) and dichloromethane-d2 (Deutero GmbH) were dried with MS 4A before use. THF used in organometallic synthesis was freshly distilled from sodium-benzophenone ketyl. Toluene and hexane used in organometallic synthesis were dried with MS 4A. 2-(Adamantan-1-yl)-4-(tert-butyl)phenol was prepared from 4-tert-butylphenol (Merck) and adamantan-1-ol (Aldrich) as described in Organic Letters, 2015, 17(9), 2242 - 2245.

[0694] 2-(Adamantan-1-yl)-6-bromo-4-(tert-butyl)phenol:

[0695]

[0696] At room temperature, a solution of 10.4 mL (203 mmol) of bromine in 200 mL of chloroform was added dropwise to a solution of 57.6 g (203 mmol) of 2-(adamantan-1-yl)-4-(tert-butyl)phenol in 400 mL of chloroform over 30 minutes. The resulting mixture was diluted with 400 mL of water. The resulting mixture was extracted with dichloromethane (3 x 100 mL), and the combined organic extracts were washed with 5% NaHCO3, dried over Na2SO4, and then evaporated to dryness. 71.6 g (97%) of a white solid was obtained. 1 1H NMR (CDCl3, 400 MHz): δ 7.32 (d, J = 2.3 Hz, 1H), 7.19 (d, J = 2.3 Hz, 1H), 5.65 (s, 1H), 2.18 - 2.03 (m, 9H), 1.78 (m, 6H), 1.29 (s, 9H). 1313C 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.

[0697] 1-(3-Bromo-5-(tert-butyl)-2-(methoxymethoxy)phenyl)adamantane:

[0698]

[0699] At room temperature, 8.28 g (207 mmol, 60 wt% in mineral oil) of sodium hydride was added portionwise to a solution of 71.6 g (197 mmol) of 2-(adamantan-1-yl)-6-bromo-4-(tert-butyl)phenol in 1000 mL of THF. 16.5 mL (217 mmol) of methoxymethyl chloride was added dropwise to the resulting suspension over 10 minutes at room temperature. The resulting mixture was stirred overnight and then poured into 1000 mL of water. The resulting mixture was extracted with dichloromethane (3 x 300 mL), the combined organic extracts were washed with 5% NaHCO3, dried over Na2SO4, and then evaporated to dryness. 80.3 g (~quant.) of a white solid was obtained. 1 1H NMR (CDCl3, 400 MHz): δ 7.39 (d, J = 2.4 Hz, 1H), 7.27 (d, J = 2.4 Hz, 1H), 5.23 (s, 2H), 3.71 (s, 3H), 2.20 - 2.04 (m, 9H), 1.82 - 1.74 (m, 6H), 1.29 (s, 9H). 13 13C NMR (CDCl3, 100 MHz): δ 150.88, 147.47, 144.42, 128.46, 123.72, 117.46, 99.53, 57.74, 41.31, 38.05, 36.85, 34.58, 31.30, 29.08.

[0700] (2-(3-Adamantan-1-yl)-5-(tert-butyl)-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane:

[0701]

[0702] At -80 °C, 23.2 mL (57.9 mmol, 2.5 M) of nBuLi was added for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 14.5 mL (71.7 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The resulting suspension was stirred at room temperature for 1 hour, then poured into 300 mL of water. The resulting mixture was extracted with dichloromethane (3 x 300 mL), the combined organic extracts were dried over Na2SO4, and then evaporated to dryness. 25.0 g (~quant.) of a colorless viscous oil was obtained. 1 H NMR (CDCl3, 400MHz): δ7.54(d,J=2.5Hz,1H),7.43(d,J=2.6Hz,1H),5.18(s,2H),3.60(s ,3H),2.24-2.13(m,6H),2.09(br.s.,3H),1.85-1.75(m,6H),1.37(s,12H),1.33(s,9H). 13 C NMR (CDCl3, 100MHz): δ159.64,144.48,140.55,130.58,127.47,100.81,83.48,57.63,41.24,37.29,37.05,34.40,31.50,29.16,24.79.

[0703] 1-(2'-bromo-5-(tert-butyl)-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane:

[0704]

[0705] Then, 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 was added to 200 mL of distilled water. To the solution in oxane was added 15.6 g (55.0 mmol) of 2-bromoiodobenzene, 19.0 g (137 mmol) of potassium carbonate and 100 mL of water. The resulting mixture was purged with argon for 10 minutes, and then 3.20 g (2.75 mmol) of Pd(PPh3)4 was added. The resulting mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 100 mL of water. The resulting mixture was extracted with dichloromethane (3 x 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 um, eluent: hexane-dichloromethane = 10: 1, by volume). 23.5 g (88%) of a white solid was obtained. 1HNMR(CDCl3, 400 MHz): δ 7.68 (dd, J = 1.0, 8.0 Hz, 1H), 7.42 (dd, J = 1.7, 7.6 Hz, 1H), 7.37 - 7.32 (m, 2H), 7.20 (dt, J = 1.8, 7.7 Hz, 1H), 7.08 (d, J = 2.5 Hz, 1H), 4.53 (d, J = 4.6 Hz, 1H), 4.40 (d, J = 4.6 Hz, 1H), 3.20 (s, 3H), 2.23 - 2.14 (m, 6H), 2.10 (br.s., 3H), 1.86 - 1.70 (m, 6H), 1.33 (s, 9H). 13 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.

[0706] 2-(3'-(Adamantan-1-yl)-5'-(tert-butyl)-2'-(methoxymethoxy)-[1,1′-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

[0707]

[0708] At -80 °C, 25.6 mL (63.9 mmol, 2.5 M) of BuLi in hexane was added dropwise to 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 anhydrous THF over 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 16.5 mL (80.7 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The resulting suspension was stirred at room temperature for 1 hour, then poured into 300 mL of water. The resulting mixture was extracted with dichloromethane (3 x 300 mL), the combined organic extracts were dried over Na2SO4, and then evaporated to dryness. 32.9 g (~quant.) of a colorless glassy solid was obtained. n 1 ​1H NMR (CDCl3, 400 MHz): δ 7.75 (d, J = 7.3 Hz, 1H), 7.44 - 7.36 (m, 1H), 7.36 - 7.30 (m, 2H), 7.30 - 7.26 (m, 1H), 6.96 (d, J = 2.4 Hz, 1H), 4.53 (d, J = 4.7 Hz, 1H), 4.37 (d, J = 4.7 Hz, 1H), 3.22 (s, 3H), 2.26 - 2.14 (m, 6H), 2.09 (br.s., 3H), 1.85 - 1.71 (m, 6H), 1.30 (s, 9H), 1.15 (s, 6H), 1.10 (s, 6H). 13 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.

[0709] (2′,2”′-(Pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1′-biphenyl]-2-ol)):

[0710]

[0711] Then, to 32.9 g (62.0 mmol) of 2-(3′-(adamantan-1-yl)-5′-(tert-butyl)-2′-(methoxymethoxy)-[1,1′-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane in 140 mL of di- To a solution in alkane was added 7.35 g (31.0 mmol) of 2,6-dibromopyridine, 50.5 g (155 mmol) of cesium carbonate and 70 mL of water. The resulting mixture was purged with argon for 10 minutes, and then 3.50 g (3.10 mmol) of Pd(PPh3)4 was added. The mixture was stirred at 100 °C for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The resulting mixture was extracted with dichloromethane (3 x 50 mL), the combined organic extracts were dried over Na2SO4, and then evaporated to dryness. Subsequently, 300 mL of THF, 300 mL of methanol and 21 mL of 12N HCl were added to the resulting oil. 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 x 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, the resulting precipitate was filtered off, washed with 2 x 20 mL of n-pentane, and dried under vacuum. 21.5 g (87%) of a mixture of two isomers was obtained as a white powder. 1 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 13C NMR (CDCl3, 100 MHz, the shifts of the minor isomer are marked 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*.

[0712] (2',2”'-(Pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olato))dimethylhafnium (Cat-Hf; Complex 5):

[0713]

[0714] At 0 °C, 14.6 mL (42.2 mmol, 2.9 M) of MeMgBr in diethyl ether was added in one portion via syringe to 3.22 g (10.05 mmol) of hafnium tetrachloride (<0.05% Zr) in 250 mL of anhydrous toluene. The resulting suspension was stirred for 1 minute 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 minute. The reaction mixture was stirred at room temperature for 36 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. Subsequently, the filtrate was evaporated to dryness. The residue was triturated with 50 mL of n-hexane, the resulting precipitate was filtered off (G3), washed with 20 mL of n-hexane (2 x 20 mL), and then dried in vacuo. 6.66 g (61%, ~1:1 solvate with n-hexane) of a light brown solid was obtained. For C 59 H 69 HfNO2×1.0(C6H 14 ) Calculated for: C, 71.70; H, 7.68; N, 1.29. Found: C 71.95; H, 7.83; N 1.18. 1 1H NMR (C6D6, 400 MHz): δ 7.58 (d, J = 2.6 Hz, 2H), 7.22 - 7.17 (m, 2H), 7.14 - 7.08 (m, 4H), 7.07 (d, J = 2.5 Hz, 2H), 7.00 - 6.96 (m, 2H), 6.48 - 6.33 (m, 3H), 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, 18H), -0.12 (s, 6H). 1313C 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.

[0715] (2',2”'-(Pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olato))dimethylzirconium (Cat-Zr; Complex 6):

[0716]

[0717] At 0 °C, 18.2 mL (52.7 mmol, 2.9 M) of MeMgBr in diethyl ether was added in one portion via syringe to a suspension of 2.92 g (12.56 mmol) of zirconium tetrachloride in 300 mL of anhydrous toluene. 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)) was added in one portion immediately to the resulting suspension. 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. Subsequently, the filtrate was evaporated to dryness. The residue was triturated with 50 mL of n-hexane, the resulting precipitate was filtered off (G3), washed with n-hexane (2 x 20 mL), and then dried in vacuo. 8.95 g (74%, ~1:0.5 solvate with n-hexane) of a pale yellow solid was obtained. For C 59 H 69 ZrNO2×0.5(C6H 14 ) Calculated for: C, 77.69; H, 7.99; N, 1.46. Found: C 77.90; H, 8.15; N 1.36. 11H NMR (C6D6, 400 MHz): δ 7.56 (d, J = 2.6 Hz, 2H), 7.20 - 7.17 (m, 2H), 7.14 - 7.07 (m, 4H), 7.07 (d, J = 2.5 Hz, 2H), 6.98 - 6.94 (m, 2H), 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, 18H), 0.09 (s, 6H). 13 13C 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.

[0718] (3-(Adamantan-1-yl)-2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)lithium

[0719]

[0720] Hexane (100 mL) was added to 1-(2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)adamantane (12.15 g, 31.59 mmol), forming a clear pale yellow solution. BuLi (12.69 mL, 31.59 mmol) was added dropwise to form a yellow solution. DME (3.284 mL, 31.59 mmol) was added rapidly. After stirring overnight, the white solid was collected on a frit and washed with hexane (3 x 10 mL). The solid was dried under reduced pressure. 1H NMR analysis showed the presence of 0.88 equivalent of DME. Used without further purification. Yield: 8.36 g, 56.3%.

[0721] 1-(2'-Bromo-2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-3-yl)adamantane

[0722]

[0723] Toluene (120 mL) was added to (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 toluene solution (25 mL) of 1-bromo-2-chlorobenzene (3.747 g, 19.57 mmol) was added dropwise over 3.5 h. After stirring overnight, the turbid mixture was transferred to a separatory funnel and extracted with water (5 x 50 mL), then with brine (2 x 10 mL). The organic phase was dried over MgSO4, filtered and evaporated to give a pale yellow oil. 1H NMR showed the presence of 0.5 equivalent of toluene in the crude product. Used without further purification. Yield: 9.92 g, 95.2%.

[0724] 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:

[0725]

[0726] 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 cooling bath and heated to near ambient temperature over 25 min. Then, the mixture was cooled to -40 °C and a cold hexane solution (2 mL) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.964 g, 26.68 mmol) was added in one portion. The mixture was slowly heated to ambient temperature and then stirred at ambient temperature. After 1 h, the turbid mixture was poured into a separatory funnel and extracted with water (6 x 100 mL) until the aqueous layer was neutral. The organic phase was extracted with brine (2 x 20 mL). The organic phase was dried over MgSO4, filtered and dried under reduced pressure for several days to give the product as an amorphous solid. Used without further purification. Yield: 9.197 g, 92.6%.

[0727] 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):

[0728]

[0729] In a 500 mL round-bottom flask, 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 mmol), Na2CO3 (4.154 g, 39.19 mmol), dioxane (180 mL) and water (90 mL) were charged. The mixture was purged with nitrogen for 50 minutes, and then solid Pd(PPh3)4 (0.906 g, 0.784 mmol) was added. The mixture was purged for an additional 40 minutes, then stirred rapidly and heated in an oil bath maintained at 100 °C. After 20 hours, the volatiles were evaporated to give a yellow foamy solid. The solid was triturated and stirred with water (200 mL) for several minutes. The solid was then collected on a frit and washed with water (3 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 diethyl ether (200 mL) and loaded into a separatory funnel. The organic phase was extracted with dilute NaHCO3 (100 mL), with water (4 x 150 mL), and then with brine (20 mL). The organic phase was 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: 4.92 g, 72.0%. Same as above

[0730] (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-olato))zirconium dichloride (Complex 66-dichloride):

[0731]

[0732] Benzene (4 mL) was added to ZrCl2(NMe2)2(dme) (0.0374 g, 0.110 mmol) to form a slightly turbid solution. Then 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 added, and the mixture was stirred at 35 °C. After 30 minutes, a sample was taken for 1H NMR analysis, which showed the formation of the intended dichloride very clearly. Then, the solution was heated to 80 °C for 25 minutes. 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 reduced pressure and at 80 °C for about 5 minutes. Yield: 0.0948 g, 80.7%.

[0733] (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-olato))zirconium dimethyl (Complex 66):

[0734]

[0735] Toluene (6 mL) was added to Complex 33-dichloride (0.0948 g, 0.0887 mmol) to form a clear colorless solution. The mixture was cooled to -15 °C, and MeMgBr (0.0995 mL, 0.326 mmol) was added. The mixture was heated to ambient temperature in about 15 minutes. After 1 hour, the solution was evaporated to give a residue, and a very small amount of isohexane (1 mL) was added. The mixture was stirred and evaporated. A very small amount of isohexane (1 mL) was added to dissolve the residue, and then the volatiles were evaporated again. Then the residue was dried under reduced pressure. Then, the residue was extracted with isohexane (10 mL), filtered through Celite 503, evaporated to give a residue and dried under reduced pressure. The Schlenk flask was scraped to give Complex 33 as a light brown solid. Yield: 0.0819 g, 90.0%.

[0736] The following complexes were used in small-scale and large-scale polymerization trials. The complex numbers shown correspond to the Cat-ID numbers.

[0737]

[0738]

[0739] The following coordination compounds were used in the following small-scale polymerization tests. C-# denotes the catalyst ID (Cat-ID).

[0740]

[0741] Small-scale polymerization examples:

[0742] The solvents, polymerization-grade toluene and / or isohexane were supplied by ExxonMobil Chemical Company and purified by passing through the following series of columns: two 500 cm 3 cylinders of Oxyclear (from Labclear, Oakland, California); followed by two 500 cm columns packed with dry 3 molecular sieves (8 - 12 mesh; Aldrich Chemical Company); and two 500 cm columns packed with dry 3 molecular sieves (8 - 12 mesh; Aldrich Chemical Company).

[0743] 2-Norbornene (NB, Aldrich Chemical Company) was diluted with toluene, purged with nitrogen, and then passed down a column of Brockman 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 and passed down a column of neutral alumina and stored on molecular sieves. Tri-(n-octyl)aluminum (TNOA or TnOAl) was purchased from Aldrich Chemical Company or Akzo Nobel and used as received.

[0744] Polymerization-grade ethylene was passed through the following series of columns for further purification: a 500 cm 3 cylinder of Oxyclear (from Labclear, Oakland, California), followed by a 500 cm column packed with dry 3 molecular sieves (8 - 12 mesh; Aldrich Chemical Company), and a 500 cm column packed with dry 3 molecular sieves (8 - 12 mesh; Aldrich Chemical Company).

[0745] Pass the polymer-grade propylene through the following series of columns for further purification: 2,250 cm 3 cylindrical column of Oxyclear (from Labclear); followed by a 2,250 cm column filled with 3 molecular sieve (8 - 12 mesh; Aldrich Chemical Company), followed by two 500 cm columns in series filled with dry 3 molecular sieve (8 - 12 mesh; Aldrich Chemical Company), a 500 cm 3 column filled with Selexsorb CD (BASF), and finally a 500 cm 3 column filled with Selexsorb COS (BASF).

[0746] N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate is purchased from Boulder Scientific or W.R. Grace. N,N-dimethylanilinium tetrakis(perfluoronaphthalen-2-yl)borate is purchased from W.R. Grace. Add all the complexes and activators as dilute solutions in toluene to the reactor. Select the concentrations of the solutions of the activator, scavenger, and complex added to the reactor such that 40 - 200 μL of the solution is added to the reactor to ensure accurate feeding.

[0747] Description and preparation of the reactor. The polymerization reaction is carried out in an autoclave in an inert atmosphere (N2) dry box, which is equipped with an external heater for controlling temperature, a glass insert (for tests containing C2, the internal volume of the reactor = 23.5 mL; for tests containing C3, the internal volume of the reactor = 22.5 mL), a diaphragm inlet, and regulated supplies of nitrogen, ethylene, and propylene, and is equipped with a disposable polyether ether ketone mechanical stirrer (800 RPM). The preparation of the autoclave is to purge it with dry nitrogen at 110 °C or 115 °C for 5 hours, and then purge it at 25 °C for 5 hours.

[0748] Polymerization of ethylene (PE), copolymerization of ethylene / cycloolefin (E-cP or E-NB), and homopolymerization of cycloolefin (p-cP).

[0749] Prepare the reactor as described above, then purge with ethylene or, in the case of a reactor not using ethylene, purge with nitrogen. Add the isohexane (solvent, unless otherwise stated) and the cyclic comonomer via syringe at room temperature and atmospheric pressure. Then bring the reactor to the process temperature (usually 100 °C) and charge ethylene (if used) while stirring at 800 RPM. Then, add the scavenger solution (e.g., TNOA in isohexane or toluene) via syringe to the reactor under process conditions. Add the non-coordinating activator (e.g., N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate ) solution (in toluene) via syringe to the reactor under process conditions, and then add the precatalyst (i.e., the complex or catalyst, labeled CatID) solution (in toluene) via syringe to the reactor under process conditions. If ethylene is used, admit ethylene to the autoclave during polymerization (using a computer-controlled solenoid valve) while maintaining the reactor gauge pressure (+ / -2 psi). Monitor the reactor temperature so that it generally remains within + / -1 °C. The polymerization is stopped by adding approximately 50 psi of compressed dry air mixture to the autoclave for approximately 30 seconds. The polymerization is quenched after a predetermined cumulative amount of ethylene has been added (when used) or after reaching the maximum minute value of the polymerization time. The reactor is cooled and emptied. After removing the solvent in vacuo, the polymer is isolated. The yields reported include the total weight of the polymer and the residual catalyst. The unit of catalyst activity is g polymer / mmol transition metal compound / hour of reaction time (g / mmol / hr). "C#" represents a comparative example. Microliters (μl or μL) are represented as uL or ul in the following table.

[0750] Polymerization of propylene (PP) and copolymerization of propylene / cycloolefin (P-cP or P-NB).

[0751] Prepare the reactor as described above, then heat to 40 °C and purge with propylene at atmospheric pressure. Add the isohexane (solvent, unless otherwise stated), the cyclic comonomer, and liquid propylene via syringe. Then heat the reactor to the process temperature (usually 100 °C) and stir at 800 RPM simultaneously. Then, add the scavenger solution (e.g., TNOA in isohexane or toluene) via syringe to the reactor under process conditions. Add the non-coordinating activator (e.g., N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate or N,N-dimethylanilinium tetrakis(perfluoronaphthalen-2-yl)borate ) solution (in toluene) is added to the reactor via a syringe under process conditions, and then a solution of the precatalyst (i.e., the complex or catalyst, labeled as Cat ID) (in toluene) is added to the reactor via a syringe under process conditions. The reactor temperature is monitored and is typically maintained within + / - 1 °C. Unless otherwise stated, the polymerization is stopped by adding a mixture of approximately 50 psi compressed dry air (or, when mentioned, CO2) to the autoclave for approximately 30 seconds. The polymerization is quenched based on a predetermined pressure loss of approximately 8 psi (unless otherwise stated) or a maximum polymerization time of 30 minutes (unless otherwise stated). The reactor is cooled and emptied. After removing the solvent in vacuo, the polymer is separated. The reported yield includes the total weight of the polymer and the residual catalyst. The unit of catalyst activity is typically g polymer / mmol transition metal compound / hour of reaction time (g / mmol / hr).

[0752] The quench time (s, seconds) is the actual time of polymerization and is determined by the indicated maximum uptake (quench value) or maximum quench time. The quench value (psi) is the ethylene uptake set value for polymerization using ethylene or the total pressure loss in the case of polymerization without using ethylene. The maximum reaction (rxn) time is the value set for the longest time that the polymerization can run if not quenched via the uptake value.

[0753] Characterization of small-scale polymers

[0754] For analytical detection, the polymer is dissolved in 1,2,4-trichlorobenzene (TCB, 99+% purity, from Sigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%, from Aldrich) in a vibrating oven at 165 °C for approximately 3 hours to prepare a polymer sample solution. The typical concentration of the polymer in the solution is 0.1 to 0.9 mg / mL, and the BHT concentration is 1.25 mg BHT / mL TCB. For detection, the sample is cooled to 135 °C.

[0755] High temperature size exclusion chromatography was performed using an automated "Rapid GPC" system as described in U.S. Patents 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388, each of which is incorporated herein by reference. The molecular weight of the polymer (weight average molecular weight (Mw), number average molecular weight (Mn), z-average molecular weight (Mz)) and molecular weight distribution (PDI = MWD = Mw / Mn, sometimes also referred to as the polydispersity index (PDI)) were determined by gel permeation chromatography using Symyx Technology GPC, which is equipped with an evaporative light scattering detector (ELSD) and calibrated using polystyrene standards (Polymer Laboratories: polystyrene calibration kit S-M-10: Mp (peak Mw) between 5,000 and 3,390,000). Alternatively, these samples were determined by gel permeation chromatography using Symyx Technology GPC, which is equipped with a dual wavelength infrared detector and calibrated using polystyrene standards (Polymer Laboratories: polystyrene calibration kit S-M-10: Mp (peak Mw) between 580 and 3,039,000). Samples (250 μL of a polymer solution in TCB were injected into the system) were run at an eluent flow rate of 2.0 ml / min (sample temperature of 135 °C, oven / column temperature of 165 °C) using three Polymer Laboratories: PLgel 10 μm Mixed-B 300 x 7.5 mm columns in series. No column spreading correction was used. Data analysis was performed using software available from Symyx Technologies or Automation Studio software available from Freeslate. The resulting molecular weights were relative to linear polystyrene standards. Molecular weight data were reported in the table below under the headings Mn, Mw, Mz, and PDI as defined above.

[0756] Differential scanning calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point of the polymer. Samples were pre-annealed at 220 °C for 15 minutes (first melt), then cooled to room temperature overnight. Then, the samples were heated to 220 °C at a rate of 100 °C / min (second melt), and then cooled at a rate of 50 °C / min. Multiple melting points were collected during heating. The reported value is the peak melting temperature, referred to as the second melt in the present invention. The results are listed in the table below under the heading T m as follows.

[0757] of ethylene-cyclopentene copolymer 1 1H NMR detection: Unless otherwise specified, the ethylene-cyclopentene (E-Cp) sample for 1 1H NMR spectroscopy was dissolved in 1,1,2,2-tetrachloroethane-d2 (tc-d2) at a concentration of 30 mg / mL at 140 °C, and the sample was recorded at 120 °C using a Bruker NMR spectrometer, where 1 the frequency of 1H NMR was 600 MHz or greater, a 10 mm cryoprobe was used, a 30° pulse, at least 512 scans and a 5 s delay were applied. The chemical shift of E-Cp was referenced to the solvent tc-d2 at 5.98 ppm.

[0758]

[0759]

[0760] E = ethylene, Cp = cyclopentene, 1000C = 1000 backbone carbons. This calculation is for the 1,2 addition of the major Cp.

[0761] of polycyclopentene 1 1H NMR detection: Unless otherwise specified, the polycyclopentene (polyCp) sample for 1 1H NMR spectroscopy was dissolved in 1,1,2,2-tetrachloroethane-d2 (tc-d2) at a concentration of 30 mg / mL at 140 °C, and the sample was recorded at 120 °C using a Bruker NMR spectrometer, where 1 the frequency of 1H NMR was 500 MHz or greater, a 30° pulse, at least 512 scans and a 5 s delay were applied. The chemical shift of polyCp was referenced to the solvent tc-d2 at 5.98 ppm.

[0762]

[0763] of ethylene-norbornene (E-NB) polymer 1 1H NMR detection: Unless otherwise specified, the ethylene-norbornene copolymer (E-NB) sample for 1 1H NMR spectroscopy was dissolved in 1,1,2,2-tetrachloroethane-d2 at a concentration of 30 mg / mL at 140 °C, and the sample was recorded at 120 °C using a Bruker NMR spectrometer, where 1 the frequency of 1H NMR was 600 MHz or greater, a 10 mm cryoprobe was used, a 30° pulse, 512 scans and a 15 s delay were applied.

[0764]

[0765] of the copolymer 13 13C NMR detection: Unless otherwise specified, the copolymer samples (E-Cp, PP-Cp, E-NB, and PP-NB) used for 13 13C NMR spectroscopic detection were dissolved in 1,1,2,2-tetrachloroethane-d2 (tc-d2) at a concentration of 33 - 67 mg / mL at 140 °C, and the samples were recorded at 120 °C using a Bruker NMR spectrometer, where 13 the frequency of 13C NMR was 150 MHz or greater, a 10 mm cryoprobe was used for gated decoupling experiments, with a 90° pulse, at least 512 transients, and a 10 s delay. For ethylene-based polymers, the chemical shift was referenced to the main PE peak at 29.98 ppm; for propylene-based polymers, the chemical shift was referenced to the main isotactic CH3 peak at 21.83 ppm.

[0766] Ethylene-cyclopentene copolymer (E-Cp): For ethylene-cyclopentene copolymer, the arrangement and basic calculations regarding the 1,3-cis and 1,3-trans addition of cyclopentene and the 1,2 addition of cyclopentene can be found in M. Napoli et al., "Copolymerization of Ethylene with Cyclopentene or 2-Butene Using a Half-Sandwich Titanocene Catalyst", Journal of Polymer Science A: Polymer Chemistry, v. 46, pp. 4725 - 4733, (2008).

[0767] The sequence arrangement and nomenclature of the 1,2 addition of cyclopentene-ethylene copolymer can be found in A. Jerschow et al., "Nuclear Magnetic Resonance Evidence for Novel Microstructures in Ethylene-Cyclopentene Copolymers", Macromolecules, v. 28, pp. 7095 - 7099, (1995). c = Cp, e = ethylene

[0768]

[0769] 1,2 addition sequence distribution, where the triad distribution is represented by ccc, ece, and cce.

[0770]

[0771] Propylene-cyclopentene copolymer (P-Cp): The arrangement and nomenclature of propylene-cyclopentene (P-Cp) are based on N. Naga, Y. Imanishi, "Structure of Cyclopentene Units in Propylene Copolymers Obtained Using Stereoselective Zirconocene Catalysts", Polymer, v. 43, pp. 2133 - 2139, (2002). These arrangements are only for 1,2 addition.

[0772]

[0773]

[0774] Ethylene-norbornene copolymer (E-NB): The composition (mole %) and the arrangement and quantification of the composition distribution (isolated, alternating, and block) of E-NB (ethylene-norbornene) are based on Bergstrom et al., "Effect of Polymerization Conditions on the Microstructure of Norbornene-Ethylene Copolymers Prepared with Metallocene Catalysts and MAO", Journal of Applied Polymer Science, v. 63, pp. 1071-1076, (1997).

[0775]

[0776]

[0777] Propylene-norbornene copolymer (P-NB): The arrangement and numbering of P-NB (propylene-norbornene) are based on I. Tritto et al., "Propylene-Norbornene Copolymers: Synthesis and Analysis of Polymer Structure by 13 13C NMR Spectroscopy and Ab Initio Chemical Shift Calculations", Macromolecules, v. 36, pp. 882-890 (2003). The calculation of the composition (mole %) is shown below.

[0778]

[0779]

[0780]

[0781]

[0782]

[0783]

[0784]

[0785] Table 2 - Part 2: 13C NMR characterization of ethylene-cyclopentene copolymer products selected from Table 1 - Part 1 Cp and c represent cyclopentene, and E and e represent ethylene units. 13 13C NMR characterization Cp and c represent cyclopentene, and E and e represent ethylene units.

[0786]

[0787] Table 2 - Part 3. 1H NMR end-group unsaturation and calculated polymer Mn of polycyclopentene polymerization products selected from Table 1 - Part 1 1 1H NMR end-group unsaturation and calculated polymer Mn

[0788]

[0789] Table 3 - Part 1. Copolymerization of Ethylene - Norbornene

[0790] Standard polymerization conditions include 1.1 equivalents of N,N - dimethylanilinium tetrakis(pentafluorophenyl)borate activator, 0.50 μmol of TNOA scavenger, 100 °C polymerization temperature, 209 μL of pure norbornene, 20 psi ethylene (C2) intake or a maximum reaction time of 30 minutes. The reported 2 - norbornene values are the amounts of pure norbornene; norbornene was added to the reactor as a 42 wt% solution in toluene. The toluene amounts listed in the table below include the toluene from the norbornene solution as well as the toluene used as a diluent for the catalyst and activator.

[0791]

[0792]

[0793]

[0794] Table 3 – Part 2. Ethylene - Norbornene Copolymerization—Polymer Characterization by 13 13C NMR to detect the norbornene incorporated into the polymer, where NB is norbornene.

[0795]

[0796]

[0797]

[0798]

[0799]

[0800]

[0801]

[0802] Table 6. Propylene - Norbornene Copolymerization

[0803] Standard polymerization conditions include 0.080 μmol of catalyst complex, 1.1 equivalents of N,N - dimethylanilinium tetrakis(pentafluorophenyl)borate Activator, 0.50 μmol of TNOA scavenger, 209 μL of pure norbornene (NB), 378 μL of toluene, a polymerization temperature of 100 °C, a pressure loss (quenching value) of 8 psi or a maximum reaction time of 30 minutes. The reported 2-norbornene values are the amounts of pure norbornene; norbornene was added to the reactor as a 42 wt% solution in toluene. The toluene amounts listed in the table below include the toluene from the norbornene solution as well as the toluene used as a diluent for the catalyst and activator.

[0804]

[0805]

[0806]

[0807] Large-scale polymerization

[0808] Polymerization was carried out in a continuous stirred tank reactor system. A 1 L autoclave reactor was equipped with a stirrer, a pressure controller, and a water-cooling / steam-heating device with a temperature controller. The reactor was operated at a pressure above the bubble point pressure of the reactant mixture under liquid filling conditions, keeping the reactants in the liquid phase. Isohexane was fed into the reactor via 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%. This solution was added to the reactor using a metering pump. Ethylene flowed as a gas through a Brooks flow controller under its own pressure. The monomers (e.g., ethylene and norbornene) were combined into a single stream and then mixed with the isohexane stream. Then, the mixture was added to the reactor via a single pipeline. The scavenger solution was also added to the combined solvent and monomer stream just before it entered the reaction to further reduce any catalyst poisons. Similarly, the catalyst solution was added to the reactor via a separate pipeline using an ISCO injection pump. Isohexane (used as a solvent), the norbornene solution, and ethylene were purified using beds of alumina and molecular sieves. The toluene used to prepare the catalyst solution was purified using the same technique. Unless otherwise stated, all reactions were carried out at a pressure of approximately 2.4 MPa / g.

[0809] A solution of tri-n-octylaluminum (TNOA) in isohexane (25 wt% in hexane, Sigma Aldrich) was used as the scavenger solution. The catalyst solution was prepared by combining the precatalyst (Complex 6 or Comparative Complex C-7) with N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (A1) Prepared by combining in 900 mL of toluene in a molar ratio of about 1:1, or by combining with (Hydrogenated tallow alkyl) methylammonium tetrakis(pentafluorophenyl)borate (A2, 10 wt% in methylcyclohexane) in a molar ratio of about 1:1 in 900 mL of toluene. Both of these activators are available from Boulder Scientific Company.

[0810] The polymer produced in the reactor is discharged via a backpressure control valve that reduces the pressure to atmospheric pressure. This causes the unreacted monomers in the solution to rapidly enter the vapor phase, which is discharged from the top of the gas-liquid separator. The liquid phase mainly contains the polymer and the solvent, and this liquid phase is collected to recover the polymer. The collected sample is first precipitated with isopropanol and stabilized with IRGANOX 1076 (from BASF), and then dried in a vacuum oven at a temperature of about 90 °C for about 12 hours. The sample dried in the vacuum oven is weighed to obtain the yield. The Tg is determined using DSC as described above, and the norbornene content is determined using proton NMR. The detailed polymerization conditions for Examples G1 to G20 are listed in Tables 8 to 10 below.

[0811] Table 8

[0812] Example # G1 G2 G3 G4 Polymerization temperature (°C) 120 120 120 120 Pressure (psig) 350 350 350 350 H2 (cc / min) Ethylene feed rate (g / min) 4.52 3.39 2.26 0.57 Norbornene feed rate (g / min) 20.0 20.0 20.0 20.0 Catalyst / activator 6 / A1 6 / A1 6 / A1 6 / A1 Catalyst feed rate (mol / min) 1.82E-07 1.82E-07 1.82E-07 1.82E-06 TNOA feed rate (mol / min) 3.70E-06 3.70E-06 3.70E-06 3.70E-06 Isohexane feed rate (g / min) 22.7 22.7 22.7 22.7 Collection time (min) 20 20 20 25 Polymer obtained (g) 96.8 166.1 78 67.8 Conversion rate (%) 19.7％ 35.5％ 17.5％ 13.2％ Catalyst yield (kg polymer / kg catalyst) 29,035 49,822 23,396 1,627 Ethylene content (wt%) 45.2％ 40.3％ 34.4％ 22.8％ NB content (wt%) 54.8％ 59.7％ 65.6％ 77.2％ Tg (°C) 31.7 52.4 58.9 110.1

[0813] Table 9

[0814] Example # G5 G6 G7 G8 G9 Polymerization temperature (°C) 120 120 120 120 120 Pressure (psig) 320 320 320 320 320 H2 (cc / min) 10 10 10 10 10 Ethylene feed rate (g / min) 4.52 3.39 2.26 2.26 2.26 Norbornene feed rate (g / min) 14.5 14.5 14.5 14.5 14.5 Catalyst / activator 6 / A2 6 / A2 6 / A2 6 / A2 6 / A2 Catalyst feed rate (mol / min) 5.83E-07 5.83E-07 5.83E-07 5.83E-07 9.71E-07 TNOA feed rate (mol / min) 5.47E-06 5.47E-06 5.47E-06 5.47E-06 5.47E-06 Isohexane feed rate (g / min) 22 22 22 22 22 Collection time (min) 40 22 40 40 40 Polymer obtained (g) 185 127.4 163.1 163.1 176.9 Conversion rate (%) 25.1％ 33.2％ 24.8％ 24.8％ 26.9％ Catalyst yield (kg polymer / kg catalyst) 8,672 10,858 7,646 7,646 4,976 Ethylene content (wt%) 38.4％ 43.0％ NB content (wt%) 61.6％ 57.0％ Tg (°C) 54.2 63.2 67.7 61.8 69.5

[0815] Table 9 (continued)

[0816] Table 10 Comparative Examples

[0817]

[0818] All documents mentioned herein are incorporated herein by reference in accordance with the disclosure herein, including any priority documents and / or test protocols. From the foregoing general description and specific embodiments, the invention has been described and illustrated, but various changes may be made without departing from the spirit and scope of the invention. Accordingly, the invention is not limited thereto. Similarly, the term "comprising" is considered synonymous with the term "including". Similarly, when a modifying term "comprising" is present before a composition, element, or group of elements, it should be understood that the same composition or group of elements having the modifying terms "consisting essentially of", "consisting of", "selected from the group consisting of", or "is", or vice versa, is also contemplated.

[0819] A set of numerical upper limits and a set of numerical lower limits have been used to describe specific embodiments and features. It should be understood that, unless otherwise stated, these ranges include any combination of any two values, such as considering any combination of any one lower limit and any one upper limit, any combination of any two lower limits, and / or any combination of any two upper limits. Specific lower limits, upper limits, and ranges appear in one or more of the appended claims. All numerical values are values modified by "about" or "approximately" and take into account experimental error and variations expected by those skilled in the art.

Claims

1. A polymerization process, which comprises contacting a cycloolefin monomer and ethylene and / or propylene and / or one or more C4-C 12 α-olefins with a catalyst system comprising an activator and a catalyst compound represented by formula (I): Wherein: M is a Group 4 transition metal; E and E' are each independently O; Q is an atom of Group 14, 15 or 16, which forms a coordinate bond with the metal M; A 1 QA 1’ is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, which attaches A 2 to A via a 3-atom bridge 2’ , where Q is the central atom of the 3-atom bridge, A 1 and A 1 ′ are independently C, N or C(R 22 ), where R 22 is selected from hydrogen, C1-C 20 hydrocarbyl, substituted C1-C 20 hydrocarbyl; is a divalent group containing 2 to 40 non-hydrogen atoms, which connects A 1 to the aryl group bonded to E via a 2-atom bridge; is a divalent group containing 2 to 40 non-hydrogen atoms, which connects A 1′ to the aryl group linked to E' via a 2-atom bridge; L is a Lewis base; X is an anionic ligand; n is 1, 2 or 3; m is 0, 1 or 2; n + m is not greater than 4; Each R 1 and R 1′ independently is C1-C 40 hydrocarbyl, substituted C1-C 40 hydrocarbyl, a heteroatom or a heteroatom-containing group; Each R 2 、R 3 、R 4 、R 2 、R 3′ and R 4′ is independently hydrogen, a C1-C 40 hydrocarbyl group, a substituted C1-C 40 hydrocarbyl group, a heteroatom or a heteroatom-containing group, And, 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 R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, and R can be linked to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each of said rings having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings can be linked to form additional rings; Any two L groups can be connected together to form a bidentate Lewis base; The X group can be connected to the L group to form a monoanionic bidentate group; Any two X groups can be connected together to form a dianionic ligand group.

2. The method according to claim 1, wherein the catalyst compound is represented by formula (II): Wherein: M is a Group 4 transition metal; E and E' are each independently 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 not greater than 4; Each R 1 and R 1′ is independently a C1-C 40 hydrocarbyl, substituted C1-C 40 hydrocarbyl, a heteroatom or a heteroatom-containing group; Each R 2 、R 3 、R 4 、R 2′ 、R 3′ and R 4′ is independently hydrogen, a C1-C 40 hydrocarbyl group, a substituted C1-C 40 hydrocarbyl group, 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′ one or more of which may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles or unsubstituted heterocycles, each of said rings having 5, 6, 7 or 8 ring atoms, and wherein substituents on the rings may be joined to form additional rings; any two L groups may be joined together to form a bidentate Lewis base; The X group can be connected to the L group to form a monoanionic bidentate group; Any two X groups can be connected together to form a dianionic ligand group; Each R 5 、R 6 、R 7 、R 8 、R 5’ 、R 6’ 、R 7’ 、R 8’ 、R 10 、R 11 and R 12 are independently hydrogen, a C1-C 40 hydrocarbyl group, a substituted C1-C 40 hydrocarbyl group, a heteroatom or a heteroatom-containing group, or one or more of 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 can be joined together to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles or unsubstituted heterocycles, each of said rings having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings can be joined together to form additional rings.

3. The method according to claim 1 or 2, wherein M is Hf, Zr or Ti; R 1 and R 1’ are independently C4-C 40 tertiary hydrocarbon group or C4-C 40 cyclic tertiary hydrocarbon group.

4. The method according to claim 1 or 2, wherein each X is independently selected from the group consisting of: substituted or unsubstituted hydrocarbyl groups having 1 - 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, and combinations thereof; and wherein each L is independently selected from the group consisting of: ethers, thioethers, amines, phosphines, olefins, alkynes, carbenes, and combinations thereof; optionally two or more Ls can form part of a fused ring or ring system.

5. The method according to claim 1, wherein M is Zr or Hf, Q is nitrogen, A 1 and A 1’ are both carbon, E and E ’ are both oxygen, and R 1 and R 1’ are both C4-C 20 cyclic tertiary alkyl, adamantan-1-yl or substituted adamantan-1-yl.

6. The method according to claim 1, wherein M is Zr or Hf, Q is nitrogen, A 1 and A 1’ are both carbon, E and E ’ are both oxygen, X is methyl or chlorine, and n is 2.

7. The method according to claim 1, wherein Q is carbon, A 1 and A 1’ are both nitrogen, and E and E ’ are both oxygen; or where Q is carbon, A 1 is nitrogen, A 1’ is C(R 22 ), and E and E ’ are both oxygen, where R 22 is selected from hydrogen, C1-C 20 hydrocarbyl, substituted C1-C 20 hydrocarbyl.

8. The method according to claim 1, wherein the heterocyclic Lewis base is selected from the groups represented by the following formula: where each R 23 is independently selected from hydrogen, C1-C 20 alkyl and substituted C1-C 20 alkyl.

9. The method according to claim 1, wherein the catalyst compound is represented by one or more of the following formulas:

10. The method according to claim 1, wherein the catalyst compound is one or more compounds of the following formula: 。 11. The method according to claim 1 or 2, wherein the activator is represented by the following formula: (Z) d +(A d -) where A d - is a non-coordinating anion having a charge of d-; d is an integer from 1 to 3, and (Z) d + is represented by one or more of the following formulas:

12. The method according to claim 1 or 2, the method further comprising recovering a polymer, wherein the polymer comprises at least 0.1 mol% of a cycloolefin.

13. The method according to claim 1 or 2, the method further comprising recovering a polymer, wherein the polymer comprises at least 1 mol% of a cycloolefin, and comprises at least 20 mol% of ethylene or at least 20 mol% of propylene.

14. A polymer prepared by the method according to claim 1 or 2, which comprises one or more cycloolefin monomers selected from substituted or unsubstituted cyclopentene and substituted or unsubstituted 2 - norbornene.

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