Catalysts for copolymerization

Abstract

The present disclosure relates to catalyst compounds, catalyst systems containing such compounds, and uses thereof. In some embodiments, a process for producing ethylene copolymers is provided, comprising reacting ethylene and C3-C6 ethylene copolymers in a reactor at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30°C to 230°C. 22 Alpha-olefins, C4-C 40 Conjugated dienes, C5-C 20 Cyclic olefins, C6-C 60 A process comprising the step of polymerizing a comonomer selected from the group consisting of a metal hydrocarbenyl transfer agent, and combinations thereof, to form an ethylene copolymer by introducing ethylene, a chain transfer agent, and any comonomer into a reactor along with a catalyst system, the catalyst system comprising a compound represented by formula (I):

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 483,869, filed February 8, 2023, the disclosure of which is incorporated herein by reference. The present disclosure relates to catalyst compounds, catalyst systems containing such compounds, and uses thereof. [Background technology]

[0002] Copolymers of olefins and conjugated dienes have demonstrated beneficial properties in the tire industry, such as aging resistance, puncture resistance, repairability, rolling resistance, and abrasion resistance. Copolymers formed from ethylene and butadiene monomers have been shown to improve such properties when incorporated into one or more of the tire's components. However, copolymerization of ethylene and butadiene has been challenging due to the different reaction mechanisms and relative reactivities between these two monomers, making it difficult to develop highly efficient methods for producing high molecular weight ethylene-butadiene random copolymers. To overcome these problems, current efforts are focused on developing methods for implementing catalyst systems that are tolerant to both monomers and capable of copolymerizing both monomers within the same process window. Exemplary catalyst systems based on halide complexes of transition metals, such as titanium, provide for the copolymerization of ethylene and conjugated dienes. Japanese Patent Specifications JP-10237131A, JP-09316118A, and JP-11171930A disclose copolymers of ethylene and butadiene, into which butadiene can be inserted in the form of cis-cyclopentyl and trans-cyclopentyl linkages. These copolymers are obtained using catalyst systems containing dimethylsilyl(pentamethylcyclopentadienyl)(t-butylamido)titanium dichloride and methylalumoxane.

[0003] Given the tire industry's growing interest in copolymers of olefins and conjugated dienes over the last decade, the development of highly active catalysts for industrial-scale production of these elastomers is necessary. Currently, the lack of active, cost-competitive catalysts is a major obstacle to the widespread commercialization of the corresponding novel copolymers. There is a need for catalyst systems that can polymerize monoolefins and conjugated dienes with high activity (e.g., within the same process window) and provide commercially scalable polymerizations (e.g., high activity under mild conditions).

[0004] References cited in the Information Disclosure Statement (37 C.FR 1.97(h)) may include the following: U.S. Patent Nos. 11,214,634; 11,203,654; 11,248,070; 11,254,763; 5,191,052; 8,962,744; 9,139,680; 10,030,092; 9,181,376; 9 ,670,302; 9,056,936; 8,969,496; 10,457,765; 10,844,149; 10,822,475; 8,039,565; 11,155,656; 11,136,422; 11,254,804; 11,286,369; 7,547,654; 10,752,712; U.S. Patent Publication No. 2 017 / 0073450;2022 / 0135717;PCT Publications WO2021 / 155168;WO2021 / 155158;WO2017 / 097831;WO2022 / 112699;WO2022 / 106769;WO2021 / 053294;WO2021 / 023924;WO2020 / 128249;WO2022 / 112700;WO2022 / 112692 ;WO2022 / 112690;WO2022 / 112691;WO2020 / 070443;Foreign patents:JP5656686;JP5675434;JP2013155360;JP2013147567;JP5612511;JP2013159626;EP3988583;FR3108610;CN113307901;Academic journal article:Macromolecules, 2021, 54, 20, pp. 9445-9451. Summary of the Invention

[0005] The present disclosure relates to catalyst compounds, catalyst systems containing such compounds, and uses thereof. In some embodiments, the process for producing an ethylene copolymer comprises ethylene and C3-C 22 Alpha-olefins, C4-C 40 Conjugated dienes, C5-C 20 Cyclic olefins, C6-C 60The method includes polymerizing an optional comonomer selected from the group consisting of a metal hydrocarbenyl transfer agent, and combinations thereof in a reactor at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. by introducing ethylene, a chain transfer agent, and the optional comonomer together with a catalyst system to form an ethylene copolymer. The catalyst system is represented by formula (I): [ka] [In the formula, M is a Group 3 transition metal or a lanthanide metal; E and E' are each independently oxygen, sulfur, or NR A and R A are independently hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 is a hydrocarbyl or heteroatom-containing group, Q is a Group 14 atom, a Group 15 atom, or a Group 16 atom; A 1 QA 1’ is a part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, and is connected to A via a three-atom bridge with Q as the central atom of the three-atom bridge. 2 A 2’ It is connected to A 1 and A 1 Each of ' is independently carbon, nitrogen, or C(R B ) and R B is hydrogen, C1-C 20 Hydrocarbyl and substituted C1-C 20 is selected from hydrocarbyl, [ka] is a divalent group containing 2 to 40 non-hydrogen atoms, and is connected via a two-atom bridge to A 1 is linked to the E-linked aryl group shown in formula (I), and A 3 and A 2combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings can be joined to form additional rings; [ka] is a divalent group containing 2 to 40 non-hydrogen atoms, and is connected via a two-atom bridge to A 1 ' is linked to the E'-linked aryl group shown in formula (I), and A 3’ and A 2’ combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings can be joined to form additional rings; each L is independently a Lewis base; X is an anionic ligand; any two or more L groups may be linked together to form a multidentate Lewis base; The X group may be attached to the L group to form a monoanionic bidentate group; n is 1, m is 0, 1, or 2; n+m does not exceed 3, R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4 Each of ' is independently hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 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 R4 one or more of ' may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substituents on a ring may be joined to form additional rings. The compound includes a compound represented by the formula:

[0006] In some embodiments, the present disclosure provides a catalyst system comprising an activator and a catalyst compound of the present disclosure. In some embodiments, a tire includes a composition. The composition includes from about 10 parts by weight per hundred rubber (phr) to about 150 phr of filler. The composition includes a copolymer having ethylene units, conjugated diene units, from about 0.1 mol % to about 10 mol % of 1,2-cyclopentane units, and functionalized vinyl transfer agent units. DETAILED DESCRIPTION OF THE INVENTION

[0007] The present disclosure provides a bis(phenolate)-type catalyst system based on a Group 3 element or a rare earth element that can be used to produce copolymers of ethylene and conjugated dienes at high conversion rates under mild conditions. The catalyst system disclosed herein is an attractive option for implementation into industrial-scale processes for the high-throughput production of copolymer materials, such as copolymers derived from ethylene and butadiene monomers, with tunable physical properties, polymer backbone structures, and different functional groups. Additionally, polar side group moieties can be incorporated into the polymer chain during copolymerization. Such functionalized polymers may be desirable for the tire industry due to enhanced interactions between the copolymer and fillers present with the copolymer during use as tire materials. Because polar side group moieties can be incorporated along the backbone of the disclosed copolymers (rather than simply as end-group functional groups), the amount of polar side group moieties can be increased (compared to copolymers having merely end-group functional groups), thereby enabling the amount of filler incorporated into compositions used as tire materials to be reduced.

[0008] definition The new numbering system for the periodic table groups is used as described in Chemical and Engineering News, v. 63(5), pg. 27 (1985). Thus, a "Group 3 metal" is an element in Group 3 of the periodic table, e.g., Sc, Y, or Nd.

[0009] "Olefins," alternatively referred to as "alkenes," are linear, branched, or cyclic compounds of carbon and hydrogen having at least one double bond. For purposes of this specification and the accompanying claims, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is described as having an "ethylene" content of 35% to 55% by weight, it is understood that the repeating species units in the copolymer are derived from ethylene in the polymerization reactants, and that the derived units are present in an amount of 35% to 55% by weight, based on the weight of the copolymer. A "polymer" has two or more of the same or different repeating species units. A "homopolymer" is a polymer having the same repeating species unit. A "copolymer" is a polymer having two or more different repeating species units. A "terpolymer" is a polymer having three different repeating species units. Thus, the definition of copolymer, as used herein, includes terpolymers, etc. "Different," when used to refer to repeating species units, indicates that the repeating species units differ from one another by at least one atom or that the repeating species units are different isomers. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer containing at least 50 mole percent ethylene-derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer containing at least 50 mole percent propylene-derived units, and so forth.

[0010] Ethylene should be considered an alpha-olefin. Unless otherwise stated, "C n The term "" means a hydrocarbon having n carbon atoms per molecule, where n is a positive integer. The term "hydrocarbon" refers to a class of compounds containing carbon-bonded hydrogen and includes (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds having different n values. Similarly, "Cm -C y " group or compound refers to a group or compound containing a total number of carbon atoms in the range of m to y. Thus, C1-C 50 The alkyl group refers to an alkyl group containing a total of 1 to 50 carbon atoms. The terms "group," "radical," and "substituent" can be used interchangeably.

[0011] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" may be used interchangeably and are defined to mean a group consisting solely of hydrogen and carbon atoms. Hydrocarbyl is a C1-C 100 The radical may be linear, branched, or cyclic, and if cyclic, may be aromatic or non-aromatic. Examples of such radicals include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, and aryl groups such as phenyl, benzyl, naphthalenyl, and the like. Unless otherwise indicated (e.g., except for the definitions for "substituted hydrocarbyl," "substituted aromatic," etc.), the term "substituted" means that at least one hydrogen atom has been replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, such as a halide (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 (in the formula, each R *are independently hydrocarbyl or halocarbyl radicals, 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 at least one heteroatom is inserted within the hydrocarbyl ring.

[0012] The term "substituted hydrocarbyl" refers to a hydrocarbyl radical in which at least one hydrogen atom of the hydrocarbyl radical has been replaced with at least one heteroatom (e.g., a halide, such as Br, Cl, F, or I) or heteroatom-containing group (e.g., a functional group, such as -NR * 2, -OR * , -SeR * , -TeR * , -PR * 2, -AsR * 2, -SbR * 2, -SR * , -BR * 2, -SiR * 3. -GeR * 3. -SnR * 3. -PbR * 3 (in the formula, each R * are independently hydrocarbyl or halocarbyl radicals, 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 system), or at least one heteroatom is inserted within the hydrocarbyl ring.

[0013] The term "aryl" or "aryl group" refers to roughly substituted variations of aromatic rings, e.g., phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Similarly, "heteroaryl" refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) is replaced with a heteroatom, e.g., N, O, or S. As used herein, the term "aromatic" also refers to pseudo-heteroaromatic rings, which are heterocyclic substituents that have similar properties and structure (nearly planar) to aromatic heterocyclic ligands, but which are not aromatic by definition. Similarly, the term aromatic refers to substituted aromatics.

[0014] The term "substituted aromatic" means an aromatic group in which one or more hydrogen radicals have been replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group. A "substituted phenolate" is a phenolate in which at least one, two, three, four, or five hydrogen atoms are replaced at the 2-, 3-, 4-, 5-, and / or 6-positions with at least one non-hydrogen group, e.g., a hydrocarbyl 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, e.g., -NR * 2, -OR * , -SeR * , -TeR * , -PR * 2, -AsR * 2, -SbR * 2, -SR * , -BR * 2, -SiR * 3. -GeR * 3. -SnR * 3. -PbR * 3 (in the formula, each R * are independently hydrogen, hydrocarbyl, or halocarbyl radicals, and two or more R * may be bonded together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), and the 1-position is a phenolate group (Ph-O-, Ph-S-, and Ph-N(R ^) group, where R is hydrogen, C1-C4 hydrocarbyl, C1-C4 substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group. For example, the "substituted phenolate" group of the catalyst compounds described herein can be represented by the formula: [ka] [In the formula, R 18 is hydrogen, C1-C 40 Hydrocarbyl (e.g., C-C 40 alkyl) or C1-C 40 is a substituted hydrocarbyl, heteroatom or heteroatom-containing group, 17 is oxygen, sulfur, or NR 17 and R 17 , R 19 , R 20 , and R 21 each independently represents hydrogen, C-C 40 Hydrocarbyl (e.g., C-C 40 alkyl) or C1-C 40 substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R 18 , R 19 , R 20 , and R 21 Two or more of these are bonded together to form C4-C 62 forming a cyclic or polycyclic ring structure, or combination thereof, and the wavy line indicates the position where the substituted phenolate group forms a bond to the remainder of the catalyst compound. It is expressed as R 18 , R 19 , R 20 , and / or R 21 At least one of them is not hydrogen.

[0015] "Alkyl-substituted phenolate" refers to an alkyl group in which at least one, two, three, four, or five hydrogen atoms are attached to at least one alkyl group, e.g., C-C 40 , instead of C2-C 20 , instead of C3-C 12and phenolate groups substituted with alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantanyl, and the like, including substituted analogs thereof. An "aryl substituted phenolate" is an aryl group having at least one, two, three, four, or five hydrogen atoms at the 2-, 3-, 4-, 5-, and / or 6-positions, substituted with at least one aryl group, e.g., C-C 40 , instead of C2-C 20 , instead of C3-C 12 and phenolate groups substituted with aryl groups such as phenyl, 4-fluorophenyl, 2-methylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, mesityl, 2-ethylphenyl, naphthalenyl, and the like, including substituted analogs thereof.

[0016] The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has 6 ring atoms and a tetrahydrofuran has 5 ring atoms. Heterocycles, also called heterocyclic rings, are rings that have heteroatoms in the ring structure, in contrast to "heteroatom-substituted rings" in which hydrogen atoms on ring atoms are replaced with heteroatoms. For example, tetrahydrofuran is a heterocycle, and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Substituted heterocycles refer to heterocycles in which one or more hydrogen groups are replaced with hydrocarbyls, substituted hydrocarbyls, heteroatoms, or heteroatom-containing groups. A substituted hydrocarbyl ring means a ring composed of carbon and hydrogen atoms in which one or more hydrogen groups has been replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0017] For purposes of this disclosure, the term "substituted," in connection with a catalyst compound (e.g., a substituted bis(phenolate) catalyst compound), refers to a group in which a hydrogen group is replaced with a hydrocarbyl 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 etc. (wherein, each R * are independently hydrogen, hydrocarbyl, or halocarbyl radicals, 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 at least one heteroatom is inserted within the hydrocarbyl ring.

[0018] A tertiary hydrocarbyl group has a carbon atom bonded to three other carbon atoms. When the hydrocarbyl group is an alkyl group, the tertiary hydrocarbyl group is also called a tertiary alkyl group. Examples of tertiary hydrocarbyl groups include tert-butyl, 2-methylbutan-2-yl, 2-methylhexan-2-yl, 2-phenylpropan-2-yl, 2-cyclohexylpropan-2-yl, 1-methylcyclohexyl, 1-adamantanyl, bicyclo[2.2.1]heptan-1-yl, and the like. A tertiary hydrocarbyl group has the formula: [ka] [In the formula, R A , R B and R Care independently hydrocarbyl or substituted hydrocarbyl groups which may be bonded to each other, and the wavy line indicates the position where the tertiary hydrocarbyl group forms a bond to another group. This can be shown as: The tertiary hydrocarbyl group can be a cyclic tertiary hydrocarbyl group. A cyclic tertiary hydrocarbyl group is defined as a tertiary hydrocarbyl group that forms at least one alicyclic (non-aromatic) ring. A cyclic tertiary hydrocarbyl group is also called an alicyclic tertiary hydrocarbyl group. When the hydrocarbyl group is an alkyl group, the cyclic tertiary hydrocarbyl group is also called a cyclic tertiary alkyl group or an alicyclic tertiary alkyl group. Examples of cyclic tertiary hydrocarbyl groups include 1-adamantanyl, 1-methylcyclohexyl, 1-methylcyclopentyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclododecyl, bicyclo[3.3.1]nonan-1-yl, bicyclo[2.2.1]heptan-1-yl, bicyclo[2.3.3]hexan-1-yl, bicyclo[1.1.1]pentan-1-yl, bicyclo[2.2.2]octan-1-yl, and the like. The cyclic tertiary hydrocarbyl group can be represented by formula B: [ka]

[0019] [In the formula, R A is a hydrocarbyl group or a substituted hydrocarbyl group, and each R D are independently hydrogen or a hydrocarbyl group or a substituted hydrocarbyl group; w is an integer from 1 to about 30; R A and one or more R D and / or two or more R D may be linked to each other to form an additional ring. It can be shown by: If the cyclic tertiary hydrocarbyl group contains more than one alicyclic ring, the cyclic tertiary hydrocarbyl group may be referred to as a polycyclic tertiary hydrocarbyl group, or if the hydrocarbyl group is an alkyl group, the cyclic tertiary hydrocarbyl group may be referred to as a polycyclic tertiary alkyl group.

[0020] The terms "alkyl radical" and "alkyl" are used interchangeably throughout this disclosure. For purposes of this disclosure, an "alkyl radical" refers to a C-C alkyl group that may be straight-chained, branched, or cyclic. 100

[0023] The term "alkyl" refers to a group of alkyl radicals. Examples of such radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, including substituted analogs thereof. A substituted alkyl radical is one in which at least one hydrogen atom of the alkyl radical has been replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom or heteroatom-containing group, such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group, such as -NR * 2, -OR * , -SeR * , -TeR * , -PR * 2, -AsR * 2, -SbR * 2, -SR * , -BR * 2, -SiR * 3. -GeR * 3. -SnR * 3. -PbR * 3 etc. (wherein, each R * are independently hydrogen, hydrocarbyl, or halocarbyl radicals, 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 at least one heteroatom is inserted within the hydrocarbyl ring.

[0021] Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl), when the alkyl, alkenyl, alkoxide, or aryl group is mentioned without specifying a particular isomer (e.g., butyl), this expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl).

[0022] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, Mz is z-average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mole (g mol -1 ) The following abbreviations may be used herein: Me is methyl, MAO is methylalumoxane, Bn is benzyl (i.e., CHPh), THF (also called thf) is tetrahydrofuran, RT is room temperature (and 23° C. unless otherwise noted), tol is toluene, Cp is cyclopentadienyl, NMR is nuclear magnetic resonance, and TMA is trimethylaluminum.

[0023] A "catalyst system" is a combination of at least one catalyst compound, an activator, an optional activator, and an optional support material. When "catalyst system" is used to describe such a pair prior to activation, it refers to the unactivated catalyst complex (pre-catalyst), the activator, and optionally a co-activator, combined together. When used to describe such a pair after activation, it refers to the activated complex and the activator or other charge-balancing moiety. The catalyst compound may be neutral, as in the case of a pre-catalyst, or may be a charged species with a counterion, as in the case of an activated catalyst system. For purposes of this disclosure and the claims thereto, when a catalyst system is described as including the neutral stable form of a component, it is well understood by those skilled in the art that the ionic form of the component is the form that reacts with a monomer to produce a polymer. A polymerization catalyst system is a catalyst system capable of polymerizing a monomer into a polymer. Furthermore, the catalyst compounds and activators represented by the formulas herein (including support-bound activators) encompass both the neutral and ionic forms of the catalyst compounds and activators. In the description herein, the catalyst may be described as a catalyst, a catalyst precursor, a pre-catalyst compound, a catalyst compound, a metal compound, a transition metal or lanthanide metal, or a transition metal compound or lanthanide metal compound, and these terms are used interchangeably.

[0024] An "anionic ligand" is a negatively charged ligand that donates one or more counterelectrons to a metal ion. The term "anionic donor" is used interchangeably with "anionic ligand." Examples of anionic donors include, but are not limited to, methyl, chloride, fluoride, alkoxide, aryloxide, alkyl, alkenyl, thiolate, carboxylate, amide, benzyl, hydride, amidinate, amidate, and phenyl. Two anionic donors can combine to form a dianionic group. A "neutral Lewis base" or "neutral donor group" is an uncharged (neutral) group that donates one or more pairs of electrons to a metal ion. Non-limiting examples of neutral Lewis bases include ethers, thioethers, amines, phosphines, diethyl ether, tetrahydrofuran, dimethyl sulfide, triethylamine, pyridine, alkenes, alkynes, allenes, and carbenes. Lewis bases can combine together to form bidentate or tridentate Lewis bases.

[0025] For purposes of this disclosure and the claims thereto, phenolate donors include Ph-O-, Ph-S-, and Ph-N(R ** )-group (wherein, R ** is hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 Ph may contain substituted hydrocarbyl, heteroatom or heteroatom-containing group, and Ph may be optionally substituted phenyl. Lanthanide metals (La-Lu) include La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

[0026] catalyst The catalyst of the present disclosure can be a "post-metallocene" catalyst having oxygen and / or nitrogen atoms. For example, the catalyst of the present disclosure can be a metal complex having a metal selected from Group 3 or lanthanide metals and a tridentate dianionic ligand containing two anionic donor groups and a neutral Lewis base donor, where the neutral Lewis base donor is covalently bonded between the two anionic donors, and the metal-ligand complex is characterized by a pair of eight-membered metallocyclic rings. The catalyst complexes of the present disclosure include a metal selected from Group 3 or Lanthanide metals of the Periodic Table of the Elements and a tridentate dianionic ligand containing two anionic donor groups and a neutral heterocyclic Lewis base donor, where the heterocyclic donor is covalently bonded between the two anionic donors. In some embodiments, the dianionic tridentate ligand features a central heterocyclic donor group and two phenolate donors, which coordinate to the metal center to form two eight-membered rings.

[0027] In some embodiments, the heterocyclic Lewis base donor of the catalyst compound is characterized by a nitrogen or oxygen donor atom. For example, heterocyclic groups include derivatives of pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and substituted variations thereof. In some embodiments, the heterocyclic Lewis base does not have a hydrogen atom alpha to the donor atom. In some embodiments, the heterocyclic Lewis base donor includes pyridine, trisubstituted pyridine, and tetrasubstituted pyridine. The anionic donor of the tridentate dianionic ligand can be an arylthiolate, phenolate, or anilide. In some embodiments, the anionic donor is a phenolate. The tridentate dianionic ligand coordinates to a metal center to form a complex that may lack a plane of mirror symmetry. In some embodiments, the tridentate dianionic ligand coordinates to a metal center to form a complex with a two-fold axis of rotational symmetry. When determining the symmetry of a bis(phenolate) complex, only the metal and the dianionic tridentate ligand are considered (i.e., the remaining ligands are ignored).

[0028] The catalyst compound of the present disclosure can be a bis(arylphenolate)pyridine complex. The bis(arylphenolate)pyridine complex can have a tridentate bis(arylphenolate)pyridine ligand that coordinates to a Group 3 transition metal or a lanthanide metal to form two eight-membered rings. In some embodiments, the bis(arylphenolate)pyridine complex includes a dianionic tridentate transition metal or lanthanide metal complex featuring a central neutral donor group and two phenolate donors that coordinate to the metal center to form two eight-membered rings; for example, the postmetallocene catalyst can be an 8-8 catalyst. In this type of complex, it is advantageous for the central neutral donor to be a heterocyclic group. It is advantageous for the heterocyclic group to not have a hydrogen atom alpha to the heteroatom. In some embodiments, the bis(phenolate) ligand can be a tridentate dianionic ligand that coordinates to the metal M in such a way that a pair of eight-membered metallocyclic rings is formed. The bis(phenolate) ligand wraps around the metal, forming a complex with a two-fold axis, thereby providing symmetry to complex C2. The C2 geometry and the eight-membered metallocyclic ring are characteristics that make these complexes useful as catalytic components for the production of polyolefins.

[0029] Bis(phenolate), anilide, and / or arylthiolate ligands containing donor groups (e.g., oxygen, nitrogen, or sulfur, respectively) can be substituted with alkyl, substituted alkyl, aryl, or other groups. It can be advantageous for each phenolate group to be substituted at the ring position adjacent to the donor atom on the ring structure. For example, the substituent at the position adjacent to the donor atom can be an alkyl group containing 1 to 20 carbon atoms. In this type of complex, it can also be advantageous for the phenolate to be substituted with one or more alkyl substituents (e.g., ortho and / or para to the phenolate oxygen). In some embodiments, the substituent at the position adjacent to the donor atom can be a non-aromatic cyclic alkyl group having one or more five- or six-membered rings. In this type of complex, it can also be advantageous for the phenolate to be substituted with one or more cyclic tertiary alkyl substituents. The use of tertiary cyclic alkyl-substituted phenolates can improve the ability of these catalysts to produce high molecular weight polymers. In some embodiments, the substituent at the position next to the oxygen donor atom is adamantan-1-yl or substituted adamantan-1-yl.

[0030] The neutral heterocyclic Lewis base donor is covalently bonded between two anionic donors (e.g., between two phenolate groups) via a "linker group" that connects the heterocyclic Lewis base to the anionic donor. For example, the "linker group" can be (A 3 A 2 ) and (A 2’ A 3’) and are described in more detail below. The selection of each linker group can affect catalytic performance. Each linker group is a two-atom long C2-C 40 One or both linker groups may independently be phenylene, substituted phenylene, heteroaryl, vinylene, or an acyclic two-carbon long linker group. In some embodiments, one or both phenylenes may be unsubstituted or independently C-C 20 It may be substituted with alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or an isomer thereof, for example, isopropyl. In some embodiments, the catalyst compound has the formula (I): [ka]

[0031] [In the formula, M is a Group 3 transition metal or a lanthanide metal (e.g., Sc, Y, La, Lu, or Nd); E and E' are each independently O, S, or NR A and R A are independently hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 a hydrocarbyl, or heteroatom-containing group, such as O, e.g., E and E' are both O; Q is a Group 14, 15, or 16 atom, for example, Q is C, O, S, or N, for example, Q is C, N, or O, for example, Q is N; A 1 QA 1’ is a part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, and is connected to A via a three-atom bridge with Q as the central atom of the three-atom bridge. 2 A 2’ It is connected to (A 1 QA 1’ is A1 and A 1’ (together with the curve showing the bond, represents a heterocyclic Lewis base) A 1 and A 1 Each of ' is independently C, N, or C(R B ) and R B is hydrogen, C1-C 20 Hydrocarbyl and substituted C1-C 20 hydrocarbyl (e.g., A 1 and A 1 ' is C), [ka] is connected to A via a two-atom bridge. 1 is a divalent group containing 2 to 40 non-hydrogen atoms linking A to an E-linked aryl group; 3 and A 2 taken together form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings can be joined to form additional rings, e.g., A 3 and A 2 combine to form ortho-phenylene, substituted ortho-phenylene, ortho-arene, substituted ortho-arene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene; [ka] is connected via a two-atom bridge to A 1 A is a divalent group containing 2 to 40 non-hydrogen atoms linked to an aryl group to which E' is attached, 3’ and A 2’ may combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may be joined to form additional rings, for example, A 3’ and A 2’combine to form, for example, ortho-phenylene, substituted ortho-phenylene, ortho-arene, substituted ortho-arene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene; each L is independently a Lewis base; X is an anionic ligand; any two or more L groups may be linked together to form a multidentate (e.g., bidentate) Lewis base; The X group may be attached to the L group to form a monoanionic bidentate group; n is 1, m is 0, 1, or 2; n+m does not exceed 3, R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4 Each of ' is independently hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom or heteroatom-containing group (e.g., R 1 ' and R 1 are independently a hydrocarbyl group, e.g., a tertiary alkyl group, or a cyclic hydrocarbyl group, e.g., a cyclic tertiary alkyl group), or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1 ' and R 2 ', R 2’ and R 3 ', R 3 ' and R 4 one or more of ' may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substituents on a ring may be joined to form additional rings. It is expressed as:

[0032] The metal M is selected from the group 3 elements or the lanthanide elements, for example, the metal M is Sc, Y, La, Lu, or Nd. The donor atom Q (in formula (I)) of the neutral heterocyclic Lewis base can be nitrogen, sulfur, or oxygen. In some embodiments, Q is nitrogen. Non-limiting examples of neutral heterocyclic Lewis base groups include pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and substituted variations thereof. In some embodiments, the heterocyclic Lewis base group can include pyridine, pyrazine, thiazole, or imidazole and substituted variations thereof.

[0033] In some embodiments, A 1 and A 1’ each independently represents C, N, or C(R 22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl and substituted C1-C 20 In some embodiments, A is selected from the group consisting of aryl, ... 1 and A 1 Each of Q' is a carbon. If Q is a carbon, then A 1 and A 1’ each independently represents a nitrogen and a C(R 22 ) can be selected from. When Q is nitrogen, A 1 and A 1’ Each of A can be carbon. In some embodiments, Q=nitrogen and A 1 =A 1’ When Q is nitrogen or oxygen, the heterocyclic Lewis base of formula (I) has a structure in which both hydrogen atoms are A 1 or A 1’ It may be, and in some cases is preferred, that the hydrogens at these positions are not bonded to the atoms, as it is believed that they may undergo undesirable decomposition reactions that reduce the stability of certain catalytic activities.

[0034] In at least one embodiment of formula (I), Q is carbon and A 1 and A 1 Each of ' is N or C(R 22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 In such embodiments, A is selected from the group consisting of a hydrocarbyl, a heteroatom, and a heteroatom-containing group. 1 QA 1’ The fragment forms part of a cyclic carbene, an N-heterocyclic carbene, a cyclic aminoalkylcarbene, or a substituted variant thereof.

[0035] A 1 and A 1’ Combined with the connecting curve, A 1 QA 1’ The heterocyclic Lewis base (formula (I)) represented by the formula: 23 The group can be hydrogen, heteroatoms, C1-C 20 Alkyl, C1-C 20 Alkoxides, C1-C 20 Amides and substituted C1-C 20 alkyl. [ka]

[0036] In some embodiments, A 1 and A 1’ Combined with the connecting curve, A 1 QA 1’ The heterocyclic Lewis base represented by formula (I) is a six-membered ring containing zero or one ring heteroatom, or a five-membered ring containing zero, one, two or three ring heteroatoms. 1 and A 1’ Combined with the connecting curve, A 1 QA 1’ The heterocyclic Lewis base represented by the formula (I) is not a six-membered ring containing two or more ring heteroatoms. In some embodiments of Formula (I), A 1 QA 1’is a part of a heterocyclic Lewis base containing 2 to 20 non-hydrogen atoms, and is connected to A via a three-atom bridge with Q as the central atom of the three-atom bridge. 2 A 2’ In some embodiments, each A 1 and A 1 ' is a carbon atom, and A 1 QA 1’ The fragment may form part of a pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or a substituted version of that group, or a substituted version thereof.

[0037] In some embodiments of Formula (I), M is Sc, Y, La, Lu, or Nd; Q is nitrogen; and A 1 and A 1’ are both carbon, and E and E ’ are both oxygen, and R 1 and R 1’ are both independently C4-C 20 is a hydrocarbyl group, preferably C4-C 20 Tertiary alkyl groups and cyclic tertiary alkyl groups. In some embodiments of Formula (I), M is Sc, Y, La, Lu, or Nd; Q is nitrogen; and A 1 and A 1’ are both carbon, and E and E ’ are both oxygen, and R 1 and R 1’ are both independently adamantan-1-yl or substituted adamantan-1-yl. In some embodiments of Formula (I), M is Sc, Y, La, Lu, or Nd; Q is nitrogen; and A 1 and A 1’ are both carbon, and E and E ’ are both oxygen, and R 1 and R 1’ are both independently acyclic tertiary alkyl, for example, tert-butyl, or tert-pentyl.

[0038] In some embodiments, the catalyst compound has the formula (II): [ka] [In the formula, M is a Group 3 metal or a lanthanide metal (e.g., Sc, Y, La, Lu, or Nd); E and E' are each independently O, S, or NR A and R A are independently hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, or heteroatom-containing groups, such as E and E ’ are both O, each L is independently a Lewis base; X is an anionic ligand; any two or more L groups may be linked together to form a multidentate (e.g., bidentate) Lewis base; The X group may be attached to the L group to form a monoanionic bidentate group; n is 1, m is 0, 1, or 2; n+m does not exceed 3, R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4 Each of ' is independently hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 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 4one or more of ' may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may be joined to form additional rings; R 5 , R 6 , R 7 , R 8 , R 5’ , R 6’ , R 7’ , R 8’ , R 10 , R 11 , and R 12 each independently represents hydrogen, C-C 40 Hydrocarbyl, substituted C1-C 40 hydrocarbyl, 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 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substituents on a ring may be joined to form additional rings. It is expressed as:

[0039] In formula (II), E and E′ are each independently oxygen or NR A Selected from R A are independently hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 In some embodiments, E and E' are oxygen. E and / or E' are NRA In the case of R A is C1-C 20 In one embodiment, E and E' are each independently selected from O, S, N(alkyl), or N(aryl), where alkyl is C-C 20 Alkyl can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, etc., and aryl can be C-C 40 Aryl groups include, for example, phenyl, naphthalenyl, benzyl, methylphenyl, and the like.

[0040] In some embodiments, the catalyst compound has Formula (III), Formula (IV), or Formula (V): [ka]

[0041] [In the formula, M in formula (III), formula (IV) or formula (V) represents Sc, Y or La-Lu lanthanide metal; Q' in formula (III), formula (IV) or formula (V) is a Group 15 heteroatom, preferably N or P, most preferably N; X in formula (III), formula (IV) or formula (V) is an anionic ligand; each L in formula (III), formula (IV), or formula (V) is independently a Lewis base; two or more L groups of any of formula (III), formula (IV) or formula (V) may be linked together to form a multidentate (e.g. bidentate) Lewis base; The X group of formula (III), formula (IV) or formula (V) may be attached to the L group to form a monoanionic bidentate group; In formula (III), formula (IV), or formula (V), n is 1; In formula (III), formula (IV), or formula (V), m is 0, 1, or 2; n+m in formula (III), formula (IV) or formula (V) does not exceed 3; R of formula (III), formula (IV) or formula (V) 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4 Each of ' is independently hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 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 ' may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may be joined to form additional rings; R of formula (III), formula (IV) or formula (V) 5 , R 6 , R 7 , R 8 , R 5’ , R 6’ , R 7’ , R 8’ , R 10 , R 11 , and R 12 each independently represents hydrogen, C-C 40 Hydrocarbyl, substituted C1-C 40 hydrocarbyl, 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 R8’ , R 10 and R 11 , or R 11 and R 12 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substituents on a ring may be joined to form additional rings; Each G in formula (III), formula (IV) or formula (V) is a Group 15 or Group 16 heteroatom or heteroatom group, e.g., S, O, NR', PR', where R' is a hydrogen atom and a C1-C 40 selected from hydrocarbyl or substituted hydrocarbyl groups. It is expressed as:

[0042] In some embodiments of the catalyst compound of Formula (I-II), when E and E′ are oxygen, each phenolate group is located at the position adjacent to the oxygen atom (i.e., R 1 and R 1’ ) can be substituted. Thus, when E and E' are oxygen, R 1 and R 1 Each of the ' is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 is a hydrocarbyl, heteroatom or heteroatom-containing group, such as R 1 and R 1 Each of ' is independently a non-aromatic cyclic alkyl group having one or more 5- or 6-membered rings (e.g., cyclohexyl, cyclooctyl, adamantanyl, or 1-methylcyclohexyl, or substituted adamantanyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantanyl, or substituted adamantanyl).

[0043] In some embodiments of the catalyst compound of formula (III-V), each phenolate group is located at the position next to the oxygen atom (i.e., R 1 and R 1’ ) can be substituted. Therefore, R 1 and R1 Each of the ' is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 is a hydrocarbyl, heteroatom or heteroatom-containing group, such as R 1 and R 1 Each of ' is independently a non-aromatic cyclic alkyl group having one or more 5- or 6-membered rings (e.g., cyclohexyl, cyclooctyl, adamantanyl, or 1-methylcyclohexyl, or substituted adamantanyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantanyl, or substituted adamantanyl). In some embodiments of the catalyst compound of formula (IV), R 1 and R 1 Each of R ' is independently a tertiary hydrocarbyl group. In another embodiment of formula (IV), R 1 and R 1 Each of R ' is independently a (substituted or unsubstituted) cyclic tertiary hydrocarbyl group. In another embodiment of the catalyst compound of formula (IV), R 1 and R 1 Each of the ' is independently a (substituted or unsubstituted) polycyclic tertiary hydrocarbyl group.

[0044] In some embodiments of the catalyst compound of Formula (I-II), when E and E′ are oxygen, each phenolate group is positioned para to the oxygen atom (i.e., R 3 and R 3’ ) can be substituted. Thus, when E and E' are oxygen, R 3 and R 3 Each of the ' is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 is a hydrocarbyl, heteroatom or heteroatom-containing group, such as R 3 and R 3 Each of the ' is independently C1-C 20 alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or an isomer thereof. Alternatively, R3 and R 3 Each of ' is independently a non-aromatic cyclic alkyl group having one or more 5- or 6-membered rings (e.g., cyclohexyl, cyclooctyl, adamantanyl, or 1-methylcyclohexyl, or substituted adamantanyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantanyl, or substituted adamantanyl).

[0045] In some embodiments of the catalyst compound of Formula (III-V), each phenolate group is positioned para to the oxygen atom (i.e., R 3 and R 3 ) can be substituted in R 3 and R 3 Each of the ' is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 is a hydrocarbyl, heteroatom or heteroatom-containing group, such as R 3 and R 3 Each of the ' is independently C1-C 20 alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or an isomer thereof. Alternatively, R 3 and R 3 Each of ' is independently a non-aromatic cyclic alkyl group having one or more 5- or 6-membered rings (e.g., cyclohexyl, cyclooctyl, adamantanyl, or 1-methylcyclohexyl, or substituted adamantanyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantanyl, or substituted adamantanyl).

[0046] In some embodiments of the catalyst compound of formula (IV), R 3 and R 3 Each of ' is independently a (substituted or unsubstituted) C-C 20alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or an isomer thereof. In some embodiments of the catalyst compound of formula (IV), R 3 and R 3 Each of R ' is independently a (substituted or unsubstituted) acyclic tertiary hydrocarbyl group. In another embodiment of formula (IV), R 3 and R 3 Each of ' is independently tert-butyl. In some embodiments, R of formula (II-V) 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', R 4 ', R 5 , R 6 , R 7 , R 8 , R 5’ , R 6’ , R 7’ , R 8’ , R 10 , R 11 , or R 12 one or more of are independently hydrogen or C-C 20 Alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or isomers thereof, such as isopropyl. In some embodiments of Formula (IV), M is a Group 3 metal, for example, Sc, Y, La, Lu, or Nd.

[0047] In some embodiments of formulas (I) and (II), each of E and E' is O. In some embodiments of Formula (IV), R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R3 ', and R 4 Each of ' is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, adamantanyl, and isomers thereof.

[0048] In embodiments of Formula (IV), X is selected from a hydrocarbyl radical having 1 to 20 carbon atoms (e.g., alkyl or aryl), a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, or an alkylsulfonate; for example, X is selected from a halide, an aryl, and a C1-C5 alkyl group; for example, X is a hydride, dimethylamide, diethylamide, bis(dimethylsilyl)amide, bis(trimethylsilyl)amide, methylenetrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl, fluoro, iodo, bromo, or chloro group. In some embodiments, X is selected from bis(dimethylsilyl)amide, bis(trimethylsilyl)amide, and methylenetrimethylsilyl.

[0049] Alternatively, X may be a halide, hydride, alkyl group, or alkenyl group. In some embodiments of Formula (IV), each L is independently a Lewis base selected from an ether, a thio-ether, an amine, a nitrile, an imine, a pyridine, a halocarbon, and a phosphine, e.g., an ether, a thioether, or a combination thereof, and optionally two or more L may form part of a fused ring or ring system, e.g., each L is independently selected from an ether or a thioether group, e.g., each L is an ethyl ether, tetrahydrofuran, dibutyl ether, or dimethyl sulfide group.

[0050] In some embodiments of Formula (IV), R 1 and R 1’ Each of is independently a cyclic tertiary alkyl group. In some embodiments of Formula (IV), m is 0, 1 or 2, for example, 0. In some embodiments of Formula (IV), R 1 and R 1 ' is not hydrogen. In some embodiments of Formula (IV), R 3 and R 3 ' is not hydrogen. In some embodiments of Formulas (I) and (II), M is Sc, Y, La, Lu, or Nd; each of E and E′ is O; and R 1 and R 1’ Each of C1-C 40 Hydrocarbyl, substituted C1-C 40 is a hydrocarbyl, heteroatom, or heteroatom-containing group, and R 2 , R 3 , R 4 , R 2 ', R 3 ', and R 4 Each of ' is independently hydrogen, C1-C 20 Hydrocarbyl or substituted C1-C 20 It is a hydrocarbyl.

[0051] In some embodiments of Formula (III-V), M is Sc, Y, La, Lu, or Nd, and R 1 and R 1’Each of C1-C 40 Hydrocarbyl, substituted C1-C 40 is a hydrocarbyl, heteroatom, or heteroatom-containing group, and R 2 , R 3 , R 4 , R 2 ', R 3 ', and R 4 Each of ' is independently hydrogen, C1-C 20 Hydrocarbyl or substituted C1-C 20 It is a hydrocarbyl. In some embodiments of formula (II-V), 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 an isomer thereof. In some embodiments of formula (II-V), R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ' 、 R 10 , R 11 and R 12are independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, or an isomer thereof.

[0052] In some embodiments of Formula (II), M is Sc, Y, La, Lu, or Nd; each of E and E′ is O; and R 1 and R 1 Each of the ' is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 is a hydrocarbyl, heteroatom, or heteroatom-containing group, and R 3 and R 3 Each of the ' is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 is a hydrocarbyl, heteroatom, or heteroatom-containing group, and R 1 , R 2 , R 4 , R 1 ', R 2 ', and R 4 Each of ' is 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 4one or more of ' may combine to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substituents on a ring may combine to form additional rings; X is selected from the group consisting of substituted or unsubstituted hydrocarbyl radicals (e.g., alkyl or aryl) having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, and ethers; n is 1, m is 1, and R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ' 、 R 10 , R 11 and R 12 each independently represents hydrogen, C-C 20 Hydrocarbyl, substituted C1-C 20 R may be a hydrocarbyl, heteroatom, or heteroatom-containing group, or one or more adjacent R groups may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substituents on a ring may be joined to form additional rings, e.g., R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ' 、 R 10 , R 11 and R 12is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

[0053] In some embodiments of formula (IV-V), Q' is N. In some embodiments of Formula (III-V), M is Sc, Y, La, Lu, or Nd, and R 1 and R 1 Each of the ' is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 is a hydrocarbyl, heteroatom, or heteroatom-containing group, and R 3 and R 3 Each of the ' is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 is a hydrocarbyl, heteroatom, or heteroatom-containing group, and R 1 , R 2 , R 4 , R 1 ', R 2 ', and R 4 Each of ' is 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 R4 one or more of ' may combine to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may combine to form additional rings; X is selected from the group consisting of substituted or unsubstituted hydrocarbyl radicals (e.g., alkyl or aryl) having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, and ethers; n is 1, m is 1, and R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ' 、 R 10 , R 11 and R 12 each independently represents hydrogen, C-C 20 Hydrocarbyl, substituted C1-C 20 R may be a hydrocarbyl, heteroatom, or heteroatom-containing group, or one or more adjacent R groups may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substituents on a ring may be joined to form additional rings, e.g., R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ' 、 R 10 , R 11 and R 12is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

[0054] In some embodiments of Formula (II), M is Sc, Y, La, Lu, or Nd, and E and E ’ are both oxygen, and R 1 and R 1’ are both independently C4-C 20 is a cyclic tertiary alkyl, and R 3 and R 3’ are both independently C1-C 10 It is alkyl. In some embodiments of Formula (III-V), M is Sc, Y, La, Lu, or Nd, and R 1 and R 1’ are both independently C4-C 20 is a cyclic tertiary alkyl, and R 3 and R 3’ are both independently C1-C 10 It is alkyl. In some embodiments of Formula (II), M is Sc, Y, La, Lu, or Nd, and E and E ’ are both oxygen, and R 1 and R 1’ are both adamantan-1-yl or substituted adamantan-1-yl, and R 3 and R 3’ are both C1-C 10 It is alkyl.

[0055] In some embodiments of Formula (III-V), M is Sc, Y, La, Lu, or Nd, and R 1 and R 1’ are both adamantan-1-yl or substituted adamantan-1-yl, and R 3 and R 3’ are both C1-C 10 It is alkyl. In some embodiments of Formula (II), M is Sc, Y, La, Lu, or Nd, and E and E ’ are both oxygen, and R 1 , R 1’ each is independently adamantan-1-yl or substituted adamantan-1-yl, and R 3 and R 3’ are both independently methyl or tert-butyl. In some embodiments of Formula (III-V), M is Sc, Y, La, Lu, or Nd, and R 1 , R 1’ is independently adamantan-1-yl or substituted adamantan-1-yl, and R 3 and R 3’ are both independently methyl or tert-butyl.

[0056] In some embodiments of formula (IV-V), G is S, O, NR', PR', where R' is selected from hydrogen and a hydrocarbyl or substituted hydrocarbyl group. In some embodiments of formula (IV-V), G is S or O, more preferably S. In some embodiments of formula (IV-V), G is NR′, PR′, and R′ is a hydrogen atom and a C1-C 20 It is selected from hydrocarbyl and substituted hydrocarbyl. In some embodiments of Formula (IV-V), G is NR', PR', and R' is selected from hydrogen or methyl.

[0057] In some embodiments of Formula (III), M is Sc, Y, La, Lu, or Nd, and R 1 , R 1’each of R is adamantan-1-yl or substituted adamantan-1-yl; 3 and R 3’ are both tert-butyl or methyl, and R 2 , R 2’ , R 4 , R 4’ , R 5 , R 5’ , R 6 , R 6’ , R 7 , R 7’ , R 8 , R 8’ , R 10 , R 11 and R 12 is hydrogen. In some embodiments of Formula (III), M is Sc, Y, La, Lu, or Nd, and R 1 , R 1’ is tert-butyl, and R 3 and R 3’ are both tert-butyl or methyl, and R 2 , R 2’ , R 4 , R 4’ , R 5 , R 5’ , R 6 , R 6’ , R 7 , R 7’ .R 8 , R 8’ , R 10 , R 11 and R 12 is hydrogen.

[0058] In some embodiments of Formula (V), M is Sc, Y, La, Lu, or Nd; G is S; and R 1 , R 1’ are both tert-butyl, and R 3 and R 3’ are both methyl, and R 2 , R 2’ , R 4 , R 4’ , R 5 , R 5’ , R 6 , R 6’ , R7 , R 7’ .R 8 , R 8’ , R 10 , R 11 and R 12 is hydrogen. In some embodiments of Formula (V), M is Sc, Y, La, Lu, or Nd; G is S; and R 1 , R 1’ are both adamantan-1-yl or substituted adamantan-1-yl, and R 3 and R 3’ are both methyl or tert-butyl, and R 2 , R 2’ , R 4 , R 4’ , R 5 , R 5’ , R 6 , R 6’ , R 7 , R 7’ .R 8 , R 8’ , R 10 , R 11 and R 12 is hydrogen.

[0059] activator The terms "cocatalyst" and "activator" are used interchangeably herein. The catalyst systems described herein can include the catalyst compounds described above and an activator, such as an alumoxane or a non-coordinating anion, and can be formed by combining the catalyst compounds described herein with an activator in any manner known in the literature, including combining them with a support such as silica. The catalyst systems can also be added to or produced in solution or bulk polymerizations (in monomer). The catalyst systems of the present disclosure can have one or more activators and one, two, or more catalyst components. An activator is defined as any compound capable of activating any one of the catalyst compounds described above by converting a neutral metal compound to a catalytically active metal compound cation. Non-limiting activators include, for example, alumoxanes, aluminum alkyls, and ionizing activators, which can be neutral or ionic, and conventional types of cocatalysts. Suitable activators can include alumoxane compounds, modified alumoxane compounds, and ionizable anion precursor compounds that abstract reactive σ-bonded metal ligands to render the metal compounds cationic and provide charge-balancing non-coordinating or weakly coordinating anions, e.g., non-coordinating anions. In at least one embodiment, the catalyst system comprises an activator, and a catalyst compound of formula (IV), or a combination thereof.

[0060] Alumoxane Activator Alumoxane activators are utilized as activators in the catalyst systems described herein. Alumoxanes are generally —Al(R a’’’ )-O-subunit (wherein R a’’’is an alkyl group). Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, for example, when the extractable ligand is an alkyl, halide, alkoxide, or amide. Mixtures of different alumoxanes and modified alumoxanes can also be used. It may be appropriate to use a visually clear methylalumoxane. Cloudy or gel-like alumoxane can be filtered to produce a clear solution, or clear alumoxane can be decanted from the cloudy solution. A useful alumoxane is modified methylalumoxane (MMAO) cocatalyst type 3A (as described in U.S. Pat. No. 5,041,584, incorporated herein by reference, and commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane Type 3A). Another useful alumoxane is solid polymethylaluminoxane, which is described in US Pat. No. 9,340,630, US Pat. No. 8,404,880, and US Pat. No. 8,975,209, which are incorporated herein by reference.

[0061] When the activator is an alumoxane (modified or unmodified), in at least one embodiment, up to a 5,000-fold molar excess of Al / M of activator relative to the catalyst compound (per metal catalyst moiety) can be used. The minimum molar ratio of activator to catalyst compound can be 1:1. Alternative ranges can include from about 1:1 to about 500:1, alternatively from about 1:1 to about 200:1, alternatively from about 1:1 to about 100:1, or alternatively from about 1:1 to about 50:1. In alternative embodiments, little or no alumoxane is used in the polymerization processes described herein, for example, alumoxane can be present at zero mole percent, or alternatively, alumoxane can be present at a molar ratio of aluminum to catalyst compound metal of less than 500:1, such as less than 300:1, such as less than 100:1, or such as less than 1:1.

[0062] Ionizing / Non-Coordinating Anion Activators The term "noncoordinating anion" (NCA) refers to an anion that does not coordinate to a cation, or coordinates only weakly to a cation, and is therefore sufficiently labile to be displaced by a Lewis base. A "compatible" noncoordinating anion is one that does not decompose to neutrality upon decomposition of the initially formed complex. Furthermore, the anion does not transfer anionic substituents or fragments to the cation, resulting in the formation of a neutral metal compound and neutral by-products from the anion. Noncoordinating anions useful according to the present disclosure are compatible, in the sense that they balance their ionic charge at +1, thereby stabilizing the metal cation and yet retaining sufficient lability to allow displacement during polymerization. Suitable ionization activators can include NCAs, such as compatible NCAs.

[0063] It is within the scope of this disclosure to use neutral or ionic ionizing activators. It is also within the scope of this disclosure to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators. For a description of some suitable activators, see U.S. Patent Nos. 8,658,556 and 6,211,105, which are incorporated herein by reference. Additional suitable activators are described in U.S. Patent Publication No. 2021 / 0179650, which is incorporated herein by reference.

[0064] In some embodiments, the activator can be one or more of N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, dioctadecylmethylammonium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbenium tetra(perfluorophenyl)borate.

[0065] In at least one embodiment, the activator is selected from one or more of triarylcarbeniums (e.g., triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, or triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate). A suitable activator to catalyst ratio, e.g., the ratio of all NCA activators to catalyst, can be about a 1:1 molar ratio. Alternative ranges include about 0.1:1 to about 100:1, alternatively about 0.5:1 to about 200:1, alternatively about 1:1 to about 500:1, and alternatively about 1:1 to about 1000:1. A suitable range can be about 0.5:1 to about 10:1, e.g., about 1:1 to about 5:1.

[0066] It is also within the scope of the present disclosure that the catalyst compound can be combined with a combination of an alumoxane and an NCA (see, e.g., U.S. Pat. No. 5,153,157; ​​U.S. Pat. No. 5,453,410; U.S. Pat. No. 5,817,725; WO 1994 / 007928; and WO 1995 / 014044, which are incorporated herein by reference, and which discuss the use of an alumoxane in combination with an ionizing activator). Chain transfer agents can be used in the polymerization process of the present disclosure. Useful chain transfer agents can be hydrogen, alkylalumoxanes, compounds represented by the formula AlR3, ZnR2 (each R is independently a C1-C8 aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyloctyl, or an isomer thereof), or combinations thereof, such as diethylzinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof. For some catalysts, particularly for the Sc-based catalysts of formulas (I)-(V), chain transfer agents can be used to control the molecular weight of the polymer produced. Preferred chain transfer agents for polymer molecular weight control include tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-isobutylaluminum, and diisobutylaluminum hydride. Chain transfer agents for polymer molecular weight control can include tri-n-octylaluminum and tri-isobutylaluminum. In some embodiments, the chain transfer agent is used in a molar ratio of chain transfer agent to catalyst of from 1:1 to 1,000:1, alternatively from 1:1 to 1:500, alternatively from 1:1 to 1:100, alternatively from 1:1 to 1:50, or alternatively from 1:1 to 1:25. Additionally, the catalyst system of the present disclosure may comprise a compound of the formula: Al(R') 3-v (R'') v wherein each R' is independently C1-C 30 or each R″ may independently be a C-C hydrocarbyl group with a terminal vinyl group. 20and v can be a hydrocarbenyl group, and v can be 0.1 to 3. The compound may contain a metal hydrocarbenyl chain transfer agent represented by the formula:

[0067] Carrier material In embodiments herein, the catalyst system may include an inert support material. The support material can be a porous support material, such as talc, and inorganic oxides. Other support materials include zeolites, clays, organoclays, or other organic or inorganic support materials, or mixtures thereof. The support material can be an inorganic oxide. The inorganic oxide can be in finely divided form. Inorganic oxide materials suitable for use in the catalyst system herein can include Group 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica or alumina can be magnesia, titania, and zirconia. However, other suitable support materials can also be used, such as finely divided functionalized polyolefins, such as finely divided polyethylene. Examples of suitable supports include magnesia, titania, zirconia, montmorillonite, phyllosilicates, zeolites, talc, and clay. Combinations of these support materials can also be used, such as silica-chromium, silica-alumina, and silica-titania. In at least one embodiment, the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica clay, silicon oxide / clay, or mixtures thereof.

[0068] The support material, e.g., inorganic oxide, has a surface area of ​​about 10 m 2 / g~about 700m 2 / g, pore volume approximately 0.1 cm 3 / g ~ approx. 4.0cm 3 The surface area of ​​the support material can be about 50 m / g and have an average particle size of about 5 μm to about 500 μm. 2 / g~about 500m 2 / g, and the pore volume is approximately 0.5 cm3 / g ~ approx. 3.5cm 3 / g, and the average particle size can be about 10 μm to about 200 μm. For example, the surface area of ​​the support material can be about 100 m 2 / g~about 400m 2 / g, with a pore volume of about 0.8 cm 3 / g~approx.3.0cm 3 / g, and the average particle size can be from about 5 μm to about 100 μm. The average pore size of the support materials useful in the present disclosure can be from about 10 Å to about 1000 Å, e.g., from about 50 Å to about 500 Å, e.g., from about 75 Å to about 350 Å. In at least one embodiment, the support material is a high surface area amorphous silica (surface area = 300 m 2 / gm; pore volume = 1.65 cm 3 / gm). For example, a suitable silica can be commercially available from Davison Chemical Division of W.R. Grace and Company under the tradename DAVISON™ 952 or DAVISON™ 955. In other embodiments, DAVISON™ 948 is used. Alternatively, the silica can be, for example, calcined (e.g., at 875° C.) ES-70™ silica (PQ Corporation, Malvern, Pennsylvania).

[0069] The support material should be dry, i.e., free or substantially free of absorbed water. Drying of the support material can be accomplished by heating or calcining at about 100°C to about 1000°C, e.g., at least about 600°C. When the support material is silica, it is heated to at least 200°C, e.g., about 200°C to about 850°C, e.g., at about 600°C, for about 1 minute to about 100 hours, about 12 hours to about 72 hours, or about 24 hours to about 60 hours. The calcined support material should have at least some reactive hydroxyl (OH) groups to produce the supported catalyst system of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

[0070] A support material having reactive surface groups, e.g., hydroxyl groups, is slurried in a non-polar diluent, and the resulting slurry is contacted with a solution of catalyst compound and activator. In at least one embodiment, the support material slurry is first contacted with the activator for a period of about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. The catalyst compound solution is then contacted with the isolated support / activator. In at least one embodiment, the supported catalyst system is generated in situ. In an alternative embodiment, the support material slurry is first contacted with the catalyst compound for a period of about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. The supported catalyst compound slurry is then contacted with the activator solution.

[0071] The mixture of catalyst, activator, and support is heated to about 0° C. to about 70° C., for example, about 23° C. to about 60° C., for example, at room temperature. The contact time can be about 0.5 hours to about 24 hours, for example, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. Suitable non-polar diluents are those materials in which all of the reactants used herein, e.g., activator and catalyst compound, are at least partially soluble and which are liquid at the polymerization temperature. Non-polar diluents can be alkanes, e.g., isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials can also be utilized, including cycloalkanes, e.g., cyclohexane, aromatics, e.g., benzene, toluene, and ethylbenzene. In at least one embodiment, the support material is supported methylalumoxane (SMAO), which is an MAO activator treated with silica (eg, ES-70-875 silica).

[0072] Polymerization Process The present disclosure relates to a polymerization process in which a monomer (e.g., ethylene; propylene), and optionally a comonomer, is contacted with a catalyst system comprising an activator and at least one catalyst compound, as described above. The catalyst compound and activator can be combined in any suitable order. The catalyst compound and activator can be combined prior to contact with the monomer. Alternatively, the catalyst compound and activator can be introduced separately into a polymerization reactor and subsequently reacted to form an active catalyst.

[0073] As a monomer, substituted or unsubstituted C2-C 40 Alpha olefins, e.g., C2-C 20 Alpha olefins, e.g., C2-C 12 Alpha olefins may include, for example, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof. In at least one embodiment, the monomers are ethylene and one or more C3-C 40 Olefins, e.g., C4-C 20 Olefins, e.g., C6-C 12 Contains any comonomer containing olefins. C3-C 40 The olefin monomers may be linear, branched, or cyclic. 40 The cyclic olefin may be strained or unstrained, monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups. In another embodiment, the monomers are ethylene and one or more C3-C 40 Olefins, e.g., C4-C 20 Olefins, e.g., C6-C 12 Includes optional comonomers including olefins. C4-C 40 The olefin monomers may be linear, branched, or cyclic. 40 Cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups.

[0074] As comonomers, substituted or unsubstituted C4-C 30 Conjugated dienes, e.g., C4-C 20 Conjugated dienes, such as C4-C6 conjugated dienes, can include 1,3-butadiene, 2-methyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1,3-nonadiene, 1,3-decadiene, and cyclopentadiene. In at least one embodiment, the monomers are ethylene and one or more C4-C6 30 Conjugated dienes, e.g., C4-C 20 Optional comonomers include conjugated dienes, e.g., C4-C6 conjugated dienes. 30 The conjugated diene may be linear, branched, or cyclic. 30 Cyclic conjugated dienes may be strained or unstrained, monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups.

[0075] Example C2~C 40 Olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, ethylidene norbornene, vinylnorbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and the like. Isomers such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives such as norbornene, norbornadiene, and dicyclopentadiene. Exemplary C4-C 30Conjugated diene comonomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1,3-nonadiene, 1,3-decadiene, cyclopentadiene, and methylcyclopentadiene.

[0076] The polymerization process of the present disclosure can be carried out in any suitable manner. Any suitable suspension, homogeneous, bulk, solution, slurry, or gas-phase polymerization process can be used. Such processes can be operated in batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry processes can be used. Bulk homogeneous processes can be used. Alternatively, no solvent or diluent is present in or added to the reaction medium (except for small amounts used as a support for the catalyst system or other additives, or the amount contained in the monomer, e.g., propane in propylene). In another embodiment, the process is a slurry process. As used herein, the term "slurry polymerization process" refers to a polymerization process in which a supported catalyst is utilized and the monomer is polymerized onto the supported catalyst particles. At least 95% by weight of the polymer product derived from the supported catalyst is in granular form as solid particles (not dissolved in the diluent). The polymerization of the present disclosure can include copolymerization of butadiene and ethylene. Generally, copolymerization of ethylene and butadiene on an industrial scale is considered to be a difficult process due to the believed differences in polymerization reaction mechanisms and relative reactivities of the monomers. The polymerization process described herein has been found to reduce the manufacturing and processing problems associated with such polymers, and the process has been shown to produce high molecular weight polymers with higher catalytic activity.

[0077] In some embodiments, the polymerization process is carried out via contacting a monomer composition comprising ethylene and one or more conjugated dienes with a catalyst system having one or more catalyst compounds and activators, as described above. The catalyst compounds and activators may be combined in any order, and are typically combined before contact with the monomers.

[0078] Exemplary conjugated diene monomers include any hydrocarbon structure, e.g., C4-C6, having at least two unsaturated bonds adjacent to each other. 30 Examples of conjugated dienes include isoprene, 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1,3-nonadiene, 1,3-decadiene, cyclopentadiene, dicyclopentadiene, or higher ring containing diolefins with or without substituents at various ring positions.

[0079] The polymerization process can be carried out in any suitable manner known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas-phase polymerization process can be used. Such processes can be operated in batch, semi-batch, or continuous mode. Homogeneous and slurry polymerization processes can be utilized. (A homogeneous polymerization process is defined as a process in which at least 90% by weight of the product is soluble in the reaction medium.) The homogeneous process can be a bulk homogeneous process. (A bulk process is defined as a process in which the monomer concentration of all feeds to the reactor is 70% by volume or greater.) Alternatively, no solvent or diluent is present or added to the reaction medium (except for small amounts used as supports for the catalyst system or other additives or amounts normally contained in the monomer). In another embodiment, the process is a slurry process. As used herein, the term "slurry polymerization process" refers to a polymerization process in which a supported catalyst is utilized and the monomer is polymerized onto the supported catalyst particles. At least 95% by weight of the polymer product derived from the supported catalyst is in granular form as solid particles (not dissolved in the diluent).

[0080] Suitable diluents / solvents for the polymerization include non-coordinating, inert liquids. Examples include linear and branched hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as those commercially available (Isopar®); perhalogenated hydrocarbons such as perfluorinated C 4-10 Examples of suitable solvents include alkanes, chlorobenzene, and aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins that can serve 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 some embodiments, the aliphatic hydrocarbon solvent is one that is used as a solvent, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, and preferably, aromatics are present in the solvent at less than 1% by weight, for example, less than 0.5% by weight, for example, less than 0% by weight, based on the weight of the solvent.

[0081] In at least one embodiment, the feed concentration of monomer and comonomer to the polymerization in the feed stream to the reactor is such that the diluent is 60% by volume or less, e.g., 40% by volume or less, e.g., 20% by volume or less, based on the total amount of the feed stream. In at least one embodiment, the polymerization is operated in a bulk process. The polymerization can be operated at any temperature and / or pressure suitable to obtain the desired polymer. Suitable temperatures and / or pressures include temperatures from about 0°C to about 300°C, e.g., from about 20°C to about 200°C, e.g., from about 35°C to about 160°C, e.g., from about 80°C to about 160°C, e.g., from about 85°C to about 140°C. The polymerization can be operated at a pressure from about 0.1 MPa to about 25 MPa, e.g., from about 0.45 MPa to about 6 MPa, or from about 0.5 MPa to about 4 MPa. In suitable polymerizations, the reaction run time can be up to about 1,500 minutes, e.g., about 1,200 minutes, e.g., about 300 minutes, e.g., about 5 minutes to about 250 minutes, e.g., about 10 minutes to about 120 minutes, e.g., about 20 minutes to about 90 minutes, e.g., about 30 minutes to about 60 minutes. In a continuous process, the run time can be the average residence time of the reactor. In at least one embodiment, the reaction run time is up to about 180 minutes. In a continuous process, the run time can be the average residence time of the reactor.

[0082] In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of from about 0.001 psig to about 50 psig (0.007 kPa to 345 kPa), e.g., from about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), e.g., from about 0.1 psig to about 10 psig (0.7 kPa to 70 kPa). In at least one embodiment, the hydrogen content is from about 0.0001 ppm to about 2,000 ppm, e.g., from about 0.0001 ppm to about 1,500 ppm, e.g., from about 0.0001 ppm to about 1,000 ppm, e.g., from about 0.0001 ppm to about 500 ppm. Alternatively, hydrogen can be present at zero ppm.

[0083] In at least one embodiment, the alumoxane can be present at zero mole percent; alternatively, the alumoxane can be present at a molar ratio of aluminum to transition metal or lanthanide metal of less than 500:1, e.g., less than 300:1, e.g., less than 100:1, e.g., less than 1:1.

[0084] In at least one embodiment, the polymerization is carried out 1) at a temperature of about 0°C to about 300°C (e.g., about 25°C to about 250°C, e.g., about 50°C to about 160°C, e.g., about 80°C to about 140°C); 2) at atmospheric pressure up to about 10 MPa (e.g., about 0.35 MPa to about 10 MPa, e.g., about 0.45 MPa to about 6 MPa, e.g., about 0.5 MPa to about 4 MPa); 3) in an aliphatic hydrocarbon diluent (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, e.g., cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; for example, aromatics are present in the diluent at less than 1 wt. %, e.g., less than 0.5 wt. %, for example, 0 wt. %, based on the weight of the diluent); 4) the catalyst system used in the polymerization comprises less than 0.5 mol. %, e.g., about 0 mol. %, of alumoxane, or alternatively, the alumoxane is present at a molar ratio of aluminum to transition metal or lanthanide metal of less than 500:1, e.g., less than 300:1, e.g., less than 100:1, for example, less than 1:1; 5) the polymerization occurs within one reaction zone; 6) optionally, a scavenger (e.g., a trialkylaluminum compound) is absent (e.g., present at zero mol. %, alternatively, the scavenger is present at a molar ratio of aluminum to transition metal or lanthanide metal of less than 500:1, e.g., less than 300:1, e.g., less than 100:1, for example, less than 1:1). 6) hydrogen is present in a molar ratio to the lanthanide metal of less than 100:1, e.g., less than 50:1, e.g., less than 15:1, e.g., less than 10:1; and 7) optionally, hydrogen is present in the polymerization reactor at a partial pressure of from about 0.001 psig to about 50 psig (0.007 kPa to 345 kPa) (e.g., from about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), e.g., from about 0.1 psig to about 10 psig (0.7 kPa to 70 kPa)). In at least one embodiment, the catalyst system used in the polymerization comprises no more than one catalyst compound. The "reaction zone" is also called the "polymerization zone," which is the vessel in which the polymerization takes place, e.g., a stirred-tank reactor or a loop reactor. When multiple reactors are used in a continuous polymerization process, each reactor is considered a separate polymerization zone. For multi-stage polymerization in a batch polymerization process, each polymerization stage is considered a separate polymerization zone.In at least one embodiment, polymerization occurs in one reaction zone. Room temperature is 23° C. unless otherwise specified.

[0085] If desired, other additives may also be used in the polymerization, such as one or more scavengers, hydrogen, aluminum alkyls, or chain transfer agents, such as alkylalumoxanes, compounds of the formula AlR or ZnR, where each R is independently a C-C aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyloctyl, or an isomer thereof, or combinations thereof, such as diethylzinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof.

[0086] In some embodiments, the polymerization process is a solution-phase polymerization process. Solution polymerization is a polymerization process in which a polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer, or a blend thereof. Solution polymerization is typically a homogeneous polymerization. Homogeneous polymerization is a polymerization in which the polymer product is dissolved in the polymerization medium. Such systems are not turbid, as described in Oliveira, JV et al. (2000) Ind. Eng. Chem. Res. v. 29, pg. 4627. Solution polymerization may involve polymerization in a continuous reactor in which polymer is formed, and the starting monomer and catalyst feeds are agitated to reduce or avoid concentration gradients, where the monomer acts as a diluent or solvent, or where a hydrocarbon is used as a diluent or solvent. Suitable processes can operate at temperatures of about 0°C to about 250°C, e.g., about 50°C to about 170°C, e.g., about 80°C to about 150°C, and / or at pressures of about 0.1 MPa or greater, e.g., 0.5 MPa or greater. The upper pressure limit is not particularly limited, but can be about 200 MPa or less, e.g., 120 MPa or less, e.g., 30 MPa or less. Temperature control in the reactor can be achieved by balancing the heat of polymerization reaction with reactor cooling via a reactor jacket or cooling coils to cool the reactor contents, self-refrigeration, a pre-chilled feed, evaporation of the liquid medium (diluent, monomer, or solvent), or a combination of all three. Adiabatic reactors with pre-chilled feeds can also be used. The purity, type, and amount of solvent can be optimized to maximize catalyst productivity for a particular type of polymerization. The solvent can also be introduced as a catalyst support. The solvent can be introduced in the gas or liquid phase, depending on the pressure and temperature. Advantageously, the solvent is maintained in the liquid phase and can be introduced as a liquid. The solvent can be introduced in the feed to the polymerization reactor.

[0087] The processes described herein can be solution polymerization processes that can be carried out in a batch mode (e.g., batch; semi-batch) or continuous process. Suitable reactors can include tank, loop, and tube designs. In at least one embodiment, the process is carried out in a continuous mode and uses dual loop reactors in a series configuration. In at least one embodiment, the process is carried out in a continuous mode and uses dual continuous stirred tank reactors (CSTRs) in a series configuration. Additionally, the process can be carried out in a continuous mode and uses a tubular reactor. In another embodiment, the process is carried out in a continuous mode and uses a one-loop reactor and a single CSTR in a series configuration. The process can also be carried out in a batch mode and uses a single stirred tank reactor.

[0088] Catalytic activity and polymer properties Unless otherwise indicated, catalyst activity is a measure of the activity of a catalyst and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP / molcat) or as the mass of product polymer (P) produced per gram of catalyst (cat) used (gP / gcat). The amount (mole or mass) of catalyst refers to the amount (moles or mass) of metal element in the catalyst. Catalytic activity can also be expressed over a period of time, T, and is reported as the mass of product polymer (P) produced per mole or millimole of catalyst (cat) used, with units of gPmmolcat. -1 time -1 The activity of a catalyst utilized in the copolymerization of ethylene and a conjugated diene depends on the structure of the catalyst, the activator used, the metal element incorporated within the catalyst, the catalyst concentration in the reaction medium, and / or the composition of the monomer system being copolymerized. In some embodiments, the catalyst activator is N,N-dimethylanilinium tetrakis(perfluorophenyl)borate ("DIMAH-D4") or MAO. In some embodiments, the co-activator is diisobutylaluminum hydride (DIBAL). In some embodiments, the catalyst activity is about 0.01 kg ポリマー / mol cat~approx. 1000kg ポリマー / mol cat , for example, about 10 kg ポリマー / mol cat ~approx. 490kg ポリマー / mol cat , for example, about 25 kg ポリマー / mol cat to about 480kg ポリマー / mol cat、 For example, about 100 kg ポリマー / mol cat ~approx. 470kg ポリマー / mol cat In some embodiments, the catalytic activity is about 0.01 kg ポリマー / mol cat ~about 15kg ポリマー / mol cat In some embodiments, the catalytic activity is about 25 kg ポリマー / mol LN ~about 50kg ポリマー / mol cat In some embodiments, the catalytic activity is about 100 kg ポリマー / mol cat ~About 300kg ポリマー / mol cat , for example, about 200 kg ポリマー / mol cat ~about 285kg ポリマー / mol cat In some embodiments, the catalytic activity is about 400 kg ポリマー / mol cat ~approx. 500kg ポリマー / mol cat , for example, about 450 kg ポリマー / mol cat ~approx. 465kg ポリマー / mol cat Most notably, the catalyst systems disclosed herein have increased catalytic activity (e.g., >405 kg) over previously reported catalytic activities for ethylene-butadiene copolymerization. ポリマー / mol cat )(Macromolecules 2021, v.54, pg. 9445).

[0089] In some embodiments, the polyolefin product produced is formed via copolymerization of ethylene and a conjugated diene. Generally, copolymerization of ethylene and a conjugated diene on an industrial scale is considered a difficult process due to the different polymerization mechanisms and relative reactivities of the monomers. The polymerization process described herein has been found to reduce the manufacturing and processing problems associated with such polymers, and the process has been shown to produce high molecular weight polymers with higher catalytic activity.

[0090] In some embodiments, the copolymer formed in the copolymerization between ethylene and butadiene is [ka] It is expressed as: A notable aspect of the copolymer includes butadiene units in the main chain having two adjacent carbon atoms of a cyclopentane ring. Some butadiene is incorporated in the trans 1,4 configuration, forming a linear main chain with one unsaturated bond. Some butadiene may also be incorporated into the copolymer in the cis 1,4 configuration, again forming a linear main chain with one unsaturated bond, but with both hydrogens associated with the double-bonded carbon on the same side of the double bond. Finally, some butadiene may be incorporated in the 1,2 configuration, usually with little to no contribution, leaving pendant vinyl groups as unsaturated branches on a saturated carbon chain. Thus, copolymers can be formed with sufficient residual unsaturation in the main chain or side chains for ultimate use in specific applications, such as crosslinking or chemical modification.

[0091] The ethylene copolymers of the present disclosure have improved properties resulting from more efficient use of diene comonomers, particularly for controlling the crystallinity of the polymer. That is, the efficient use of diene comonomers involves improved isolation of the comonomer molecules along the polyethylene chain, something not previously achieved for such ethylene copolymers. Thus, not only are the polymers of the present disclosure particularly well suited for previous uses utilizing such polymers, but they also exhibit superior overall physical properties, representing a significant improvement over previously available materials. The improved properties of the polymers result from the isolated distribution of the diene comonomer and other comonomers along the sequence of the polymer molecule. In some embodiments, the ethylene copolymers of the present disclosure have a Mw of from about 10,000 g / mol to about 1,100,000 g / mol, e.g., from about 100,000 g / mol to about 600,000 g / mol, e.g., from about 100,000 g / mol to about 350,000 g / mol, e.g., from about 150,000 g / mol to about 300,000 g / mol, e.g., from about 200,000 g / mol to about 300,000 g / mol, alternatively from about 300,000 g / mol to about 400,000 g / mol, alternatively from about 400,000 g / mol to about 500,000 g / mol.

[0092] In some embodiments, the ethylene copolymers of the present disclosure have an Mn of from about 1,000 g / mol to about 1,000,000 g / mol, e.g., from about 2,500 g / mol to about 50,000 g / mol, e.g., from about 5,000 g / mol to about 25,000 g / mol, e.g., from about 7,500 g / mol to about 15,000 g / mol, e.g., from about 9,000 g / mol to about 13,000 g / mol. In some embodiments, the ethylene copolymers of the present disclosure have from about 0.01 mol % to about 10 mol % cyclopentane along the polymer backbone, e.g., from about 0.1 mol % to about 7 mol %, e.g., from about 0.2 mol % to about 5 mol %, e.g., from about 0.3 mol % to about 3.5 mol %, e.g., from about 0.35 mol % to about 0.4 mol % cyclopentane. In some embodiments, the ethylene copolymers of the present disclosure have from about 0.1 mol % to about 5 mol % butadiene in a 1,2 configuration along the backbone of the polymer, e.g., from about 0.5 mol % to about 4 mol %, e.g., from about 1 mol % to about 3 mol % butadiene.

[0093] In some embodiments, the ethylene copolymers of the present disclosure have from about 0.01 mol % to about 10 mol % butadiene in the 1,4-trans configuration along the backbone of the polymer, e.g., from about 0.5 mol % to about 8 mol %, e.g., from about 1 mol % to about 6 mol %, e.g., from about 2 mol % to about 5 mol %, e.g., from about 3 mol % to about 4 mol % butadiene. In some embodiments, the ethylene copolymers of the present disclosure have from about 0.5 mol % to about 40 mol % butadiene in the 1,4-cis configuration along the backbone of the polymer, e.g., from about 1 mol % to about 35 mol %, e.g., from about 5 mol % to about 35 mol %, e.g., from about 10 mol % to about 30 mol %, e.g., from about 20 mol % to about 25 mol % butadiene. In some embodiments, the ethylene copolymers of the present disclosure have a Mw / Mn (PDI) value of from about 2 to about 65, such as from about 5 to about 55, such as from about 10 to about 40, such as from about 15 to about 35, or alternatively from about 20 to about 30.

[0094] In some embodiments, the molar ratio of activator to polymerization catalyst is about 1:1 to about 80:1, e.g., about 40:1 to about 60:1. It has been noted that increasing the activator content relative to the catalyst compound results in increased catalytic activity. Furthermore, increasing the activator content relative to the catalyst results in lower Mw of the polymer product, thereby enabling precise control of Mw in the polymerization process. This is consistent with a coordinate chain transfer mechanism of polymerization. In some embodiments, the ethylene copolymer has a glass transition temperature (Tg) of about -105°C to about -100°C, such as about -101°C to about -104°C, for example, about -102°C to about -103°C. In some embodiments, the ethylene copolymer has a thermal melting temperature (Tm) of from about 90° C. to about 140° C., e.g., from about 100° C. to about 125° C., e.g., from about 115° C. to about 125° C. In some embodiments, the ethylene copolymer simultaneously has two thermal melting temperatures.

[0095] Polymer Functionalization In some cases, it may be desirable to incorporate polar groups along the backbone of the polymer so that subsequent reactions can occur after polymerization. In some embodiments, the polymerizations described herein further include utilizing a third monomer that is a metal hydrocarbenyl transfer agent (any Group 12 or Group 13 metal agent containing at least one transferable group with an allyl chain end group), such as an aluminum vinyl transfer agent, also known as AVTA, which is any aluminum agent containing at least one transferable group with an allyl chain end group. Suitable catalyst systems of the present disclosure have high rates of olefin propagation and chain transfer to AVTA or other chain transfer agents, e.g., aluminum alkyls, when present, relative to little or no chain termination via beta hydride elimination, beta methyl elimination, or chain transfer to monomer.

[0096] In some embodiments, the concentration of aluminum vinyl monomer in the polymerization process of the present disclosure can be from about 0.01 mol % to about 10.0 mol %, for example, from about 0.1 wt % to about 5 wt %.

[0097] In at least one embodiment of the present disclosure, the aluminum vinyl transfer agent has the formula (A): Al(R') v (R”) 3-v wherein R' is a hydrocarbyl group containing 1 to 30 carbon atoms, R" is a hydrocarbenyl group containing 4 to 20 carbon atoms having an allyl chain end group, and v is 0.1 to 3, alternatively 1 to 3, alternatively 1.1 to less than 3, alternatively v is 0.5 to 2.9, 1.1 to 2.9, alternatively 1.5 to 2.7, alternatively 1.5 to 2.5, alternatively 1.8 to 2.2. Represented by the formula Al(R') 3-v (R”) v Suitable compounds of formula (B): [Al(R') 4-w (R”) w ] - Anionic formulations of the formula: wherein w is 0.1 to 4, R' is a hydrocarbyl group containing 1 to 30 carbon atoms, and R" is a hydrocarbenyl group containing 4 to 20 carbon atoms with an allyl chain end group may be envisioned.

[0098] In at least one embodiment of any of the formulas for the aluminum vinyl transfer agents described herein, each R' is independently selected from the group consisting of C1 to C 30 Hydrocarbyl groups (e.g., C1-C 20 alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or isomers thereof), and R″ is selected from the group consisting of: -(CH2) n CH=CH2 [In the formula, n is an integer of 2 to 18, for example, 6 to 18, for example, 6 to 12, for example, 6] It is expressed as:

[0099] Aluminum vinyl transfer agents include tri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum, tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum, tri(dec-9-en-1-yl)aluminum, tri(dodec-11-en-1-yl)aluminum, dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum, dimethyl(dec-9-en-1-yl)aluminum, diethyl(dec-9-en-1-yl)aluminum, and dibutyl(dec-9-en-1-yl)aluminum. The compound may include one or more of aluminum, diisobutyl(dec-9-en-1-yl)aluminum, and diisobutyl(dodec-11-en-1-yl)aluminum, methyl-di(oct-7-en-1-yl)aluminum, ethyl-di(oct-7-en-1-yl)aluminum, butyl-di(oct-7-en-1-yl)aluminum, isobutyl-di(oct-7-en-1-yl)aluminum, isobutyl-di(non-8-en-1-yl)aluminum, methyl-di(dec-9-en-1-yl)aluminum, ethyl-di(dec-9-en-1-yl)aluminum, butyl-di(dec-9-en-1-yl)aluminum, isobutyl-di(dec-9-en-1-yl)aluminum, and isobutyl-di(dodec-11-en-1-yl)aluminum.

[0100] In at least one embodiment of the present disclosure, particularly useful AVTAs include, but are not limited to, tri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum, tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum, tri(dec-9-en-1-yl)aluminum, dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum, diisobutyl(dodec-11-en-1-yl)aluminum, etc. Mixtures of one or more AVTAs may also be used. In some embodiments of the present disclosure, isobutyl-di(oct-7-en-1-yl)-aluminum, isobutyl-di(dec-9-en-1-yl)-aluminum, isobutyl-di(non-8-en-1-yl)-aluminum, isobutyl-di(hept-6-en-1-yl)-aluminum are suitable.

[0101] Aluminum vinyl transfer agents can include the reaction product of an organoaluminum compound between an aluminum reagent (AlR3) and an alkyl diene. Suitable alkyl dienes include those having two of the above-described "alpha olefins" at the two ends of the carbon chain. The alkyl diene can be linear or branched alkyl chain and substituted or unsubstituted. Exemplary alkyl dienes include, but are not limited to, 1,3-butadiene, 1,4-pentadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, 1,14-pentadecadiene, 1,15-hexadecadiene, 1,16-heptadecadiene, 1,17-octadecadiene, 1,18-nonadecadiene, 1,19-eicosadiene, 1,20-heneicosadiene, etc. Exemplary aluminum reagents include triisobutylaluminum, diisobutylaluminum hydride, isobutylaluminum dihydride, and aluminum hydride (AlH). Useful compounds can be prepared by combining an aluminum reagent (e.g., an alkylaluminum) having at least one secondary alkyl moiety (e.g., triisobutylaluminum) and / or at least one hydride, such as a dialkylaluminum hydride, a monoalkylaluminum dihydride, or an aluminum trihydride (aluminum hydride, AlH), with an alkyldiene and heating to a temperature that causes the release of an alkylene by-product. The use of a solvent is not required. However, nonpolar solvents, such as hexane, pentane, toluene, benzene, xylene, and the like, or combinations thereof, can be utilized. In at least one embodiment of the present disclosure, AVTA does not contain coordinating polar solvents, such as tetrahydrofuran and diethyl ether. After the reaction is complete, the solvent, if present, can be removed, and the product can be used directly without further purification.

[0102] In at least one embodiment, R" of Formula (A) is butenyl, pentenyl, heptenyl, octenyl, or decenyl, for example, R" is octenyl or decenyl. R' of Formula (A) can be methyl, ethyl, propyl, isobutyl, or butyl, for example, R' is isobutyl. In at least one embodiment of the present disclosure, v in formula (A) is about 2, or v is 2. In at least one embodiment, v in Formula (A) is about 1, or v is 1, for example, from about 1 to about 2. In some embodiments, v in Formula (A) can be an integer or a non-integer, for example, v is from 1.1 to 2.9, for example, from about 1.5 to about 2.7, for example, from about 1.6 to about 2.4, for example, from about 1.7 to about 2.4, for example, from about 1.8 to about 2.2, for example, from about 1.9 to about 2.1, and all ranges therebetween.

[0103] In at least one embodiment of the present disclosure, R' is isobutyl, each R" is octenyl or decenyl, and v is 1.1 to 2.9, e.g., about 1.5 to about 2.7, e.g., about 1.6 to about 2.4, e.g., about 1.7 to about 2.4, e.g., about 1.8 to about 2.2, e.g., about 1.9 to about 2.1.

[0104] The amount of v is determined by the formula: (3-v)+v=3, and Al(R') v (R”) 3-v where R" is a hydrocarbenyl group containing 4 to 20 carbon atoms with an allylic chain end group, R' is a hydrocarbyl group containing 1 to 30 carbon atoms, and v is 0.1 to 3 (e.g., 1.1 to 3). This formulation allows for the observed average ( 1As measured by H NMR, the mixture may include any of Al(R')3, Al(R')2(R"), Al(R')(R")2, and Al(R")3. In yet another embodiment, the aluminum vinyl-transfer agent has less than 50 wt. % dimers present, e.g., less than 40 wt. %, such as less than 30 wt. %, for example, less than 20 wt. %, such as less than 15 wt. %, for example, less than 10 wt. %, for example, less than 5 wt. %, such as less than 2 wt. %, for example, less than 1 wt. %, for example, 0 wt. % dimers present, based on the weight of AVTA. Alternatively, the dimers may be present in an amount of 0.1 to It is present in 50% by weight, alternatively 1-20% by weight, alternatively 2-10% by weight. The dimer is the dimer product of the alkyl diene used to prepare AVTA. Dimers can form under certain reaction conditions by insertion of a diene molecule into the Al-R bond of AVTA, followed by β-hydride elimination. For example, if the alkyl diene used is 1,7-octadiene, the dimer is 7-methylenepentadeca-1,14-diene. Similarly, if the alkyl diene is 1,9-decadiene, the dimer is 9-methylenenonadeca-1,18-diene.

[0105] For the polymerizations of the present disclosure, the molar ratio of AVTA to catalyst complex can be greater than 5, alternatively greater than 10, alternatively greater than 15, alternatively greater than 20, alternatively greater than 25, alternatively greater than 30. In at least one embodiment of the present disclosure, the metal hydrocarbenyl chain transfer agent has the formula: Al(R') 3-v (R'') v wherein each R' is independently C1-C 30 is a hydrocarbyl group, and each R″ is independently a C-C 20 and v is 0.1 to 3, e.g., each R″ is independently a C4-C aryl group having an allyl chain end group. 20 is a hydrocarbenyl group, and v is 0.1 to 3, for example, v=2.

[0106] This technology allows for the production of in-chain functionalized ethylene / butadiene copolymers. Furthermore, the process disclosed herein allows for the in-chain functionalization of ethylene / butadiene copolymers in a single reactor. The Al-carbon bond can react with various electrophiles (and other reagents), such as oxygen, halogens, carbon dioxide, etc., to form functionalized vinyl transfer agent units. For example, the Al-carbon bond can react with carbon dioxide to form carbon dioxide-functionalized vinyl transfer agent units. In some embodiments, polymers having functionalized vinyl transfer agent units of the present disclosure have a Tm of from about 90°C to about 130°C, for example, from about 103°C to about 122°C.

[0107] 13 C NMR Samples can be dissolved in deuterated 1,1,2,2-tetrachloroethane (tce-d2) at a concentration of 34 mg / mL at 140° C. Spectra can be recorded at 120° C. using a Bruker NMR spectrometer at least 600 MHz equipped with a 10 mm cryoprobe. A 90° pulse, a 10 second delay, 512 transients, and gated decoupling are used. 13 C NMR spectra can be measured. Polymer resonance peaks can be referenced to the main polyethylene peak at 29.98 ppm. Spectral assignments can be based on the following references: Llauro et al., Macromolecules, v. 34(18), (2001), pp. 6304-6311; Makhiyanov, Polymer Sci., (2012), pp. 60-90; and Longo et al., Macromolecules, v. 36, (2003), pp. 9067-6074. [ka]

[0108] The following signals were used to calculate the composition: [Table 1]

[0109] 1 H NMR Samples can be dissolved in deuterated 1,1,2,2-tetrachloroethane (tce-d2) at a concentration of at least 30 mg / mL at 140°C. Spectra can be recorded at 120°C using a Bruker NMR spectrometer at least 600 MHz equipped with a 10 mm cryoprobe. A 30° pulse, 5 second delay, and 512 transients were recorded. 1 H NMR can be used to measure peaks, which can be referenced to the residual solvent peak at 5.98 ppm.

[0110] [Table 2]

[0111] GPC-4D: Unless otherwise indicated, the molecular weight distribution and molecular weight moments (Mw, Mn, Mz, Mw / Mn, etc.) and comonomer content are approximately 2700 cm -1 ~About 3000cm -1The chromatographic properties of the polymers were determined using high-temperature gel permeation chromatography (Polymer Char GPC-IR) equipped with a multichannel band-filter-based infrared detector ensemble IR5, an 18-angle light scattering detector, and a viscometer. Polymer separation was achieved using three Agilent PLgel 10 μm Mixed-BLS columns. Reagent-grade 1,2,4-trichlorobenzene (TCB) (Sigma-Aldrich) containing approximately 300 ppm of the antioxidant 2,6-di-tert-butyl-4-methoxyphenol (BHT) was used as the mobile phase at a nominal flow rate of approximately 1.0 mL / min and a nominal injection volume of approximately 200 μL. The entire system, including the transfer line, column, and detector, was contained in an oven maintained at approximately 145 °C. A given amount of sample was weighed and sealed in a standard vial with approximately 10 μL of flow marker (heptane) added to the sample. After loading the vials into the autosampler, the oligomers or polymers can be automatically dissolved in the instrument using approximately 8 mL of TCB solvent added with continuous shaking at approximately 160 °C. The concentration of the sample solution can be approximately 0.2 to approximately 2.0 mg / mL, with lower concentrations being used for higher molecular weight samples. The concentration, c, at each point in the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal, I, using the equation: c = αI, where α is the mass constant determined using polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area over the elution volume of the concentration chromatograph to the injected mass, which is equal to the predetermined concentration multiplied by the injection loop volume. The conventional molecular weight (IR MW) is determined by combining a universal calibration with a column calibration performed using a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 mg / mol. The MW at each elution volume is calculated using the following equation:

number

[0112] The comonomer composition is determined by the intensity ratio of the IR5 detector corresponding to the CH2 and CH3 channels, which is calibrated using a series of PE and PP homo / copolymer standards with nominal values ​​determined by NMR or FTIR. Specifically, this gives the number of methyls per 1000 total carbons (CH3 / 1000TC) as a function of molecular weight. The short chain branch (SCB) content per 1000TC (SCB / 1000TC) is then calculated as a function of molecular weight by applying a chain end correction to the CH3 / 1000TC function, assuming each chain is linear and terminated with a methyl group. The weight percent comonomer is then obtained from the following formula (where f is 0.3, 0.4, 0.6, 0.8, etc. for C3, C4, C6, C8, etc. comonomers, respectively): w2=f*SCB / 1000TC

[0113] The bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtained by considering the total signal in the CH3 and CH2 channels during the integration interval of the concentration chromatogram. First, the following ratio is obtained:

number

[0114] The LS detector is an 18-angle Wyatt Technology High Temperature DAWN HELEOS II. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, MB, Ed.; Academic Press, 1972.):

number

number

[0115] tire In some embodiments, the copolymers of the present disclosure can be used as components of tires. The tire (also referred to herein as a "tire product") can be any suitable tire, for example, a rubber tire having an outer (visible) rubber sidewall layer, the outer sidewall layer comprising the copolymer of the present disclosure. The tire can be constructed, shaped, molded to include the outer sidewall (rubber sidewall layer), and cured by a variety of methods readily apparent to those skilled in the art. Blends of highly saturated specialty elastomers blended with highly unsaturated polymers may be desirable to improve the performance window of the blend (e.g., oxygen and ozone resistance, thermal stability, tackiness, etc.). With respect to tire treads, the tire tread compound, in particular, determines the tire's properties, such as wear, traction, and rolling resistance. Achieving excellent traction, low rolling resistance while providing good treadwear is a technical challenge. This challenge hinges on the trade-off between wet traction and rolling resistance / treadwear. Using the methods of the present disclosure, the need for fillers to be incorporated into the final tire product is reduced or eliminated, and therefore the reduction or absence of fillers in the tire product results in improved wear resistance of the tire product (tire tread), such as the reduction or elimination of crack initiation and growth.

[0116] The term "filler," as used herein, refers to any material used to enhance or modify the physical properties of the composition (as a tire product), to impart certain processing characteristics, or to reduce the cost of the tire. Examples of inorganic fillers include calcium carbonate, clay, mica, silica, silicates, talc, titanium dioxide, alumina, zinc oxide, starch, wood flour, or combinations thereof. Fillers can be of any size and range, for example, in the tire industry, they can be from 0.0001 μm to 100 μm.

[0117] As used herein, the term "silica" is intended to refer to silica of any type or particle size, or another silicic acid derivative, or silicic acid, further processed by solution, pyrogenic, or other processes, including untreated silica, precipitated silica, crystalline silica, colloidal silica, aluminum or calcium silicate, fumed silica, and the like. The precipitated silica can be conventional silica, semi-highly disperse silica, or highly disperse silica. The filler may be commercially available from Rhodia Company under the trade name ZEOSIL® Z1165 or ZEOSIL® 1165MP.

[0118] The functionalized copolymers of the present disclosure can provide improved interactions between the copolymer and additives, allowing for the use of smaller amounts of additives compared to conventional tire compositions. In some embodiments, the composition (as a tire product) contains less than 150 parts by weight of filler (e.g., silica) per 100 parts by weight of rubber (phr), e.g., from about 10 to about 150 phr. In another embodiment, the composition (as a tire product) contains from about 30 to about 130 phr of filler. In a further embodiment, the composition contains from about 50 to about 90 phr of filler. [Example]

[0119] Catalyst synthesis [ka] Ln(Me3SiCH2)3(THF)2 (Ln = Sc, Y, Lu) was synthesized from (trimethylsilyl)methyllithium (0.7 M in hexane; Acros Organics) and anhydrous LnCl3 (Aldrich) as described in Chemical Communications 2016, v.52(31), pp. 5425-5427. Ln(N(SiMe2H)2)3(THF) n(Ln = Sc, Y, La, Nd) were prepared as described in the literature (Organometallics 2013, v.32, pp. 1528-1530 and J. Org. Chem. 2007, v.72(23), pp. 8648-8655). The ligand precursor, 2',2'''-(pyridine-2,6-diyl)bis(3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-ol), was synthesized as described in WO2020 / 167824. The ligand precursor, 6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-(tert-butyl)-4-methylphenol), was synthesized as described in WO2020 / 167819. The ligand precursor, 2',2'''-(pyridin-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol), was synthesized as described in US Pat. No. 11,254,763. All other reagents were commercially available, and all solvents were dried and degassed before use using typical methods reported previously. Catalysts and metal complexes, also referred to as precatalysts, were prepared under an inert atmosphere.

[0120] Example 1 Synthesis of complex Y-1 [ka]

[0121] To a suspension of 204 mg (0.368 mmol) of 2',2'''-(pyridin-2,6-diyl)bis(3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-ol) in 10 ml of hexane in a 20 ml scintillation vial, 182 mg of Y(MeSiCH)(THF) (0.368 mmol) was added in one portion at -30 °C. The resulting mixture was stirred at room temperature for 6 hours, and the vial was placed in a refrigerator (-30 °C). After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After 12 hours, the formed precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to dryness to give 145 mg (49%) of product as a beige powder. Elemental analysis: C 47 H 58 Calculated values ​​for YNO3Si: C, 70.39; H, 7.29; N, 1.75. Found values: C 70.65; H 7.68; N 1.51. 1 H NMR (400 MHz, benzene-d6): δ 7.53 (dd, J = 7.5, 1.3 Hz, 1H), 7.18 - 7.38 (m, 6H), 6.94 - 7.06 (m, 4H), 6.88 (dd, J = 7.8, 1.1 Hz, 1H), 6.66 (d, J = 2.3 Hz, 1H), 6.52 (t, J = 7.8 Hz, 1H), 6.32 (dd, J = 7.8, 1.1 Hz, 1H), 3.69 - 3.75 (m, 2H), 3.57 - 3.63 (m, 2H), 2.28 (s, 3H), 2.20 (s, 3H), 1.67 (s, 9H), 1.56 (s, 9H), 1.11 - 1.14 (m, 4H), 0.27 (s, 9H), -0.41 (dd ,J = 11.4, 3.9 Hz, 1H), -2.05 (dd, J = 11.4, 4.0 Hz, 1H).

[0122] Example 2 Synthesis of complex Sc-1 [ka]

[0123] To a suspension of 150 mg (0.270 mmol) of 2',2'''-(pyridin-2,6-diyl)bis(3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-ol) in 10 ml of hexane in a 20 ml scintillation vial, 121 mg of Sc(MeSiCH)(THF) (0.270 mmol) was added in one portion at -30 °C. The resulting solution was stirred at room temperature for 6 hours, and the vial was placed in a refrigerator (-30 °C). After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After 12 hours, the formed precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to dryness to give 125 mg (66%) of the product as an off-white solid. Elemental analysis: C 47 H 58 Calculated values ​​for ScNO3Si: C, 74.47; H, 7.71; N, 1.85. Found values: C 74.80; H 7.58; N 1.74. 1H NMR (400 MHz, ベンゼン-d6): δ 7.49 (d, J = 7.3 Hz, 1H), 7.35 (dt, J = 7.2, 2.1 Hz, 1H), 7.22 - 7.30 (m, 4H), 7.20 (d, J = 7.6 Hz, 1H), 7.08 (dt, J = 7.5, 1.4 Hz, 1H), 7.00 (dt, J = 7.5, 1.4 Hz, 1H), 6.97 (d, J = 2.1 Hz, 1H), 6.86 (dd, J = 7.4, 1.2 Hz, 1H), 6.72 (dd, J = 7.6, 1.1 Hz, 1H), 6.67 (d, J = 1.9 Hz, 1H), 6.52 (t, J = 7.8 Hz, 1H), 6.26 (d, J = 7.8 Hz, 1H), 3.88 - 3.94 (m, 2H), 3.75 - 3.81 (m, 2H), 2.25 (s, 3H), 2.18 (s, 3H), 1.64 (s, 9H), 1.57 (s, 9H), 1.15 - 1.22 (m, 4H), 0.26 (d, J = 11.6 Hz, 1H), 0.23 (s, 9H), -1.90 (d, J = 11.6 Hz, 1H). 13 C NMR (400 MHz, ベンゼン-d6): δ 158.8, 158.7, 145.0, 143.3, 138.7, 138.6, 138.0, 137.4, 136.1, 135.6, 133.4, 132.2, 131.5, 131.2, 130.7, 130.65, 130.6, 129.7, 127.7, 127.1, 124.5, 124.4, 123.8, 123.0, 73.1, 35.8, 35.7, 31.9, 30.7, 25.4, 21.4, 21.3, 4.4.

[0124] (Example 3) Synthesis of wrong body Lu-1

change

[0125] To a suspension of 86 mg (0.155 mmol) of 2',2'''-(pyridin-2,6-diyl)bis(3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-ol) in 10 ml of hexane in a 20 ml scintillation vial, 90 mg of Lu(MeSiCH)(THF) (0.155 mmol) was added in one portion at -30 °C. The resulting solution was stirred at room temperature for 6 hours, and the vial was placed in a refrigerator (-30 °C). After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After 12 hours, the formed precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to dryness to yield 113 mg (82%) of the product as an off-white solid. Elemental analysis: C 47 H 58 Calculated values ​​for LuNO3Si: C, 63.57; H, 6.58; N, 1.58. Found values: C 63.85; H 6.82; N 1.37. 1 H NMR (400 MHz, benzene-d6): δ 7.50 (d, J = 7.5 Hz, 1H), 7.36 (dt, J = 7.4, 1.6 Hz, 1H), 7.26 - 7.30 (m, 2H), 7.20 - 7.26 (m, 3H), 7.00 - 7.09 (m, 3H), 6.95 (dd, J = 7.3, 1.5 Hz, 1H), 6.72 (dd, J = 7.8, 1.0 Hz, 1H), 6.64 (d, J = 1.8 Hz, 1H), 6.51 (t, J = 7.8 Hz, 1H), 6.30 (dd, J = 7.8, 1.0 Hz, 1H), 3.73 - 3.79 (m, 2H), 3.63 - 3.67 (m, 2H), 2.28 (s, 3H), 2.19 (s, 3H), 1.68 (s, 9H), 1.53 (s, 9H), 1.11 - 1.16 (m, 4H), 0.26 (s, 9H), -0.65 (d, J = 11.7 Hz, 1H), -2.24 (d, J = 11.7 Hz, 1H). 13C NMR (400 MHz, benzene-d6): δ 162.3, 160.3, 158.93, 158.86, 144.9, 143.8, 138.9, 138.8, 137.8, 136.7, 136.5, 136.1, 133.0, 131.5, 131.4, 131.3, 131.0, 130.95, 130.1, 129.8, 127.7, 127.1, 124.7, 123.8, 123.0, 122.98, 72.5, 35.8, 35.6, 31.7, 31.6, 30.9, 30.5, 25.4, 21.5, 21.3, 5.0.

[0126] Example 4 Synthesis of complex Y-2 [ka]

[0127] To a suspension of 135 mg (0.202 mmol) of 6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-(tert-butyl)-4-methylphenol) in 10 ml of hexane and 0.5 ml of toluene in a 20 ml scintillation vial, 100 mg of Y(MeSiCH)(THF) (0.202 mmol) was added in one portion at room temperature. The resulting solution was stirred at room temperature for 12 hours, and the vial was placed in a refrigerator (-30 °C). After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After 12 hours, the formed precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to dryness to yield 124 mg (67%) of the product as an off-white solid. Elemental analysis: C 51 H 58 Calculated values ​​for YNS2O3Si: C, 67.01; H, 6.40; N, 1.53. Found values: C 66.85; H 6.65; N 1.31. 1H NMR (400 MHz, ベンゼン-d6): δ 7.61 (d, J = 7.9 Hz, 1H), 7.55 (d, J = 7.9 Hz, 1H), 7.51 (d, J = 7.9 Hz, 1H), 7.36 (d, J = 2.0 Hz, 1H), 7.28 (dt, J = 7.5, 1.1 Hz, 1H), 7.17 - 7.21 (m, 2H), 6.93 - 7.10 (m, 5H), 6.77 (t, J = 7.8 Hz, 1H), 6.28 (dd, J = 7.7, 1.1 Hz, 1H), 6.21 (d, J = 7.7 Hz, 1H), 3.80 - 3.93 (m, 4H), 2.26 (s, 3H), 2.22 (s, 3H), 1.48 (s, 9H), 1.09 - 1.15 (m, 4H), 1.05 (s, 9H), 0.19 (s, 9H), -0.59 (dd, J = 11.3, 3.9 Hz, 1H), -2.18 (dd, J = 11.3, 4.0 Hz, 1H). 13 C NMR (400 MHz, ベンゼン-d6): δ 162.9, 160.1, 156.9, 153.8, 152.0, 145.8, 142.6, 141.7, 140.2, 139.6, 139.4, 136.9, 130.6, 130.3, 130.1, 130.0, 129.6, 126.2, 125.8, 125.6, 125.5, 124.9, 124.6, 124.3, 123.6, 123.5, 123.2, 123.1, 122.8, 122.7, 122.2, 72.0, 35.8, 35.3, 30.4, 30.2, 29.9, 29.5, 25.2, 21.34, 21.31, 4.6.

[0128] (Example 5) Synthesis of wrong body Sc-2

change

[0129] To a suspension of 170 mg (0.255 mmol) of 6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-(tert-butyl)-4-methylphenol) in 10 mL of hexane and 0.5 mL of toluene in a 20 mL scintillation vial, 115 mg of Sc(MeSiCH)(THF) (0.255 mmol) was added in one portion at room temperature. The resulting solution was stirred at room temperature for 12 hours, and the vial was placed in a refrigerator (-30°C). After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to dryness to yield 127 mg (57%) of the product as an off-white solid. Elemental analysis: C 51 H 58 Calculated values ​​for ScNS2O3Si: C, 70.39; H, 6.72; N, 1.61. Found values: C 70.68; H 6.98; N 1.50. 1 H NMR (400 MHz, benzene-d6): δ 7.73 (d, J = 8.0 Hz, 1H), 7.55 (d, J = 8.0 Hz, 1H), 7.51 (d, J = 8.0 Hz, 1H), 7.40 (d, J = 1.7 Hz, 1H), 7.31 (dt, J = 7.2, 1.0 Hz, 1H), 7.15 - 7.21 (m, 2H), 7.00 - 7.14 (m, 5H), 6.91 (dt, J = 8.0, 1.0 Hz, 1H), 6.79 (t, J = 7.8 Hz, 1H), 6.22 (dd, J = 7.7, 1.1Hz, 1H), 6.11 (d, J = 7.8 Hz, 1H), 4.10 - 4.17 (m, 2H), 3.97 - 4.05 (m, 2H), 2.25 (s, 3H), 2.21 (s, 3H), 1.50 (s, 9H), 1.15 - 1.24 (m, 4H), 0.98 (s, 9H), 0.17 (d, J = 11.3 Hz, 1H), 0.12 (s, 9H), -1.59 (d, J = 11.3 Hz, 1H). 13C NMR (400 MHz, benzene-d6): δ 162.6, 159.5, 156.9, 154.3, 151.0, 145.0, 142.9, 141.5, 140.0, 139.7, 139.6, 139.1, 136.8, 132.6, 130.6, 130.2, 129.7, 129.6, 126.0, 125.97, 125.6, 125.4, 125.3, 124.9, 124.2, 124.1, 123.6, 123.5, 123.2, 122.8, 122.3, 72.7, 35.9, 35.3, 30.1, 29.5, 25.2, 21.8, 21.3, 4.1.

[0130] Example 6 Synthesis of complex Lu-2 [ka]

[0131] To a suspension of 110 mg (0.165 mmol) of 6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-(tert-butyl)-4-methylphenol) in 10 ml of hexane and 0.5 ml of toluene in a 20 ml scintillation vial, 96 mg of Lu(MeSiCH)(THF) (0.165 mmol) was added in one portion at room temperature. The resulting solution was stirred at room temperature for 12 hours, and the vial was placed in a refrigerator (-30 °C). After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After 12 hours, the formed precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to dryness to give 107 mg (65%) of the product as an off-white solid. Elemental analysis: C 51 H 58 Calculated values ​​for LuNS2O3Si: C, 61.24; H, 5.85; N, 1.40. Found values: C 61.46; H 6.07; N 1.26. 1H NMR (400 MHz, ベンゼン-d6): δ 7.65 (d, J = 8.0 Hz, 1H), 7.54 (d, J = 8.0 Hz, 1H), 7.51 (d, J = 8.0 Hz, 1H), 7.38-7.41 (m, 1H), 7.30 (dt, J = 7.2, 1.0 Hz, 1H), 7.16 - 7.22 (m, 2H), 6.90 - 7.10 (m, 5H), 6.77 (t, J = 7.8 Hz, 1H), 6.26 (dd, J = 7.7, 1.0 Hz, 1H), 6.16 (d, J = 7.9 Hz, 1H), 3.93 - 4.01 (m, 2H), 3.84 - 3.93 (m, 2H), 2.27 (s, 3H), 2.23 (s, 3H), 1.47 (s, 9H), 1.11 - 1.16 (m, 4H), 1.03 (s, 9H), 0.17 (s, 9H), -0.80 (d, J = 11.5 Hz, 1H), -2.26 (d, J = 11.5 Hz, 1H). 13 C NMR (400 MHz, ベンゼン-d6): δ 163.6, 161.0, 157.1, 153.9, 151.2, 145.8, 142.8, 141.6, 140.3, 140.0, 139.5, 139.4, 137.4, 131.1, 130.15, 130.12, 129.9, 129.7, 126.2, 126.0, 125.7, 125.67, 125.5, 124.9, 124.6, 124.4, 123.5, 123.4, 123.1, 122.8, 122.7, 122.3, 72.3, 35.8, 35.3, 33.4, 30.4, 30.1, 29.5, 29.4, 25.2, 4.7.

[0132] (Example 7) Synthesis of wrong body Sc-3

change

[0133] To a suspension of 526 mg (0.660 mmol) of 2',2'''-(pyridin-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) in 40 ml of hexane and 6.5 ml of toluene in a 20 ml scintillation vial, 294 mg of Sc(MeSiCH)(THF) (0.660 mmol) was added in one portion at room temperature. The resulting solution was stirred at room temperature for 12 hours, and the vial was placed in a refrigerator (-30°C). After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE) and the mother liquor was returned to the refrigerator. After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE) and the mother liquor was evaporated to give 103 mg (15%) of the product as an off-white solid. Elemental analysis: C 65 H 82 Calculated values ​​for ScNO3Si: C, 78.20; H, 8.28; N, 1.40. Found values: C 78.42; H 8.61; N 1.26. 1H NMR (400 MHz, ベンゼン-d6): δ 7.67 (d, J = 7.2 Hz, 1H), 7.66 (d, J = 2.8 Hz, 1H), 7.53 (d, J = 2.7 Hz, 1H), 7.39 - 7.47 (m, 3H), 7.34 (d, J = 7.1 Hz, 1H), 7.30 (d, J = 2.7 Hz, 1H), 7.19 - 7.22 (m, 2H), 7.04 - 7.08 (m, 1H), 6.86 - 6.90 (m, 2H), 6.65 (t, J = 7.8 Hz, 1H), 6.36 (dd, J = 7.7, 1.0 Hz, 1H), 3.98 - 4.06 (m, 2H), 3.68 - 3.74 (m, 2H), 2.66 - 2.73 (m, 3H), 2.43 - 2.63 (m, 6H), 2.30 - 2.39 (m, 6H), 2.27 (br.s, 3H), 2.14 - 2.22 (m, 3H), 1.90 - 2.12 (m, 9H), 1.46 (s, 9H), 1.34 (s, 9H), 1.20 - 1.28 (m, 4H), 0.31 (s, 9H), 0.14 (d, J = 11.4 Hz, 1H), -1.88 (d, J = 11.5 Hz, 1H). 13 C NMR (400 MHz, ベンゼン-d6): δ 161.8, 159.3, 158.3, 158.1, 145.9, 144.5, 138.6, 138.5, 137.7, 137.2, 136.7, 136.0, 135.8, 133.2, 131.7, 131.3, 130.9, 130.8, 130.2, 129.9, 129.7, 127.1, 126.7, 126.0, 125.2, 124.9, 124.0, 123.8, 122.0, 73.1, 42.8, 41.3, 38.7, 38.3, 38.1, 37.8, 34.7, 34.5, 32.5, 32.3, 30.23, 30.18, 25.4, 4.5.

[0134] (Example 8) Synthesis of wrong body Y-3 [ka]

[0135] To a suspension of 101 mg (0.127 mmol) of 2',2'''-(pyridin-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) in 20 mL of n-hexane and 1.5 mL of toluene in a 20 mL scintillation vial, 63 mg of Y(MeSiCH)(THF) (0.127 mmol) was added in one portion at room temperature. The resulting solution was stirred at room temperature for 12 hours, and the vial was placed in a refrigerator (-30 °C). After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to yield 110 mg (83%) of the product as an off-white solid. Elemental analysis:C 65 H 82 Calculated values ​​for YNO3Si: C, 74.90; H, 7.93; N, 1.34. Found values: C 75.27; H 8.12; N 1.19. 1H NMR (400 MHz, ベンゼン-d6): δ 7.62 (d, J = 7.6, 1.0 Hz, 1H), 7.52 (d, J = 2.7 Hz, 1H), 7.41 (d, J = 2.7 Hz, 1H), 7.37 (dt, J = 7.5, 1.5 Hz, 1H), 7.25 - 7.34 (m, 5H), 7.23 (d, J = 2.7 Hz, 1H), 6.97 - 7.13 (m, 6H), 6.80 - 6.82 (m, 2H), 6.58 (t, J = 7.8 Hz, 1H), 6.32 (dd, J = 7.8, 1.0 Hz, 1H), 3.65 - 3.72 (m, 2H), 3.42 - 3.50 (m, 2H), 2.60 - 2.67 (m, 3H), 2.49 - 2.56 (m, 3H), 2.34 - 2.41 (m, 3H), 2.16 - 2.28 (m, 9H), 2.04 - 2.11 (m, 3H), 1.85 - 1.93 (m, 9H), 1.38 (s, 9H), 1.26 (s, 9H), 1.04 - 1.11 (m, 4H), 0.26 (s, 9H), -0.63 (dd, J = 11.3, 3.8 Hz, 1H), -2.03 (dd, J = 11.3, 3.9 Hz, 1H).

[0136] (Example 9) Synthesis of wrong body Lu-3

change

[0137] To a suspension of 162 mg (0.203 mmol) of 2',2'''-(pyridin-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) in 20 mL of hexane and 1.5 mL of toluene in a 20 mL scintillation vial, 118 mg of Lu(MeSiCH)(THF) (0.203 mmol) was added in one portion at room temperature. The resulting solution was stirred at room temperature for 12 h, and the vial was placed in a refrigerator (-30 °C). After 12 h, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After 12 h, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to dryness to give 200 mg (87%) of the product as an off-white solid. Elemental analysis:C 65 H 82 Calculated values ​​for LuNO3Si: C, 69.19; H, 7.32; N, 1.24. Found values: C 69.43; H 7.44; N 1.28. 1H NMR (400 MHz, ベンゼン-d6): δ 7.67 (d, J = 7.7 Hz, 1H), 7.64 (d, J = 2.7 Hz, 1H), 7.52 (d, J = 2.7 Hz, 1H), 7.34 - 7.48 (m, 4H), 7.19 - 7.21 (m, 2H), 7.11 (d, J = 7.3, 2.1 Hz, 1H), 6.92 (dd, J = 7.8, 1.0 Hz, 1H), 6.87 (d, J = 2.7 Hz, 1H), 6.66 (t, J = 7.8 Hz, 1H), 6.41 (dd, J = 7.7, 1.0 Hz, 1H), 3.79 - 3.91 (m, 2H), 3.54 - 3.64 (m, 2H), 2.69 - 2.77 (m, 3H), 2.52 - 2.66 (m, 3H), 2.24 - 2.48 (m, 12H), 2.13 - 2.20 (m, 3H), 1.90 - 2.06 (m, 9H), 1.48 (s, 9H), 1.35 (s, 9H), 1.14 - 1.21 (m, 4H), 0.34 (s, 9H), -0.78 (d, J = 11.5 Hz, 1H), -2.13 (d, J = 11.5 Hz, 1H). 13 C NMR (400 MHz, ベンゼン-d6): δ 162.8, 160.8, 158.5, 158.45, 145.4, 144.9, 138.83, 138.79, 137.1, 137.0, 136.9, 136.6, 136.2, 132.7, 131.2, 131.15, 131.0, 130.9, 130.5, 130.1, 129.7, 127.2, 126.1, 124.8, 124.7, 124.2, 123.7, 122.1, 72.3, 42.6, 42.2, 41.2, 38.6, 38.5, 38.3, 38.2, 38.1, 37.9, 34.7, 34.5, 32.8, 32.6, 32.4, 30.4, 30.3, 30.2, 30.1, 25.5, 5.0.

[0138] (Example 10) Synthesis of wrong body Sc-3-N [ka]

[0139] In a 20 mL scintillation vial, [Sc{N(SiMeH)}]·THF (207 mg, 0.4 mmol) was dissolved in 2 mL of THF. Then, with stirring at ambient temperature, solid 2',2'''-(pyridin-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) (312 mg, 0.39 mmol) was slowly added. After the addition, the reaction mixture was diluted by adding 3 mL of THF. The resulting mixture was stirred at 60 °C for 2 h, and then volatiles were removed under a stream of nitrogen. n-Pentane (5 mL) was added to the pale yellow oily residue and evaporated to aid in the removal of residual THF. This step was repeated twice to yield a pale yellow powder. This powder was dissolved in n-pentane (5 mL) and filtered. The filtrate was concentrated to approximately 1 / 5 of its original volume and cooled to −35° C. The white crystals were decanted off and dried in vacuo to give 129 mg (33%) of the desired product. 1 The broadness of the resonance signals in the 1 H NMR spectrum prevents their accurate integration. 1 H NMR (400 MHz, benzene-d6): δ 7.47 (d, J = 2.7 Hz, 2H), 7.43 (d, J = 2.8 Hz, 2H), 7.30-7.11 (m, 6H), 7.01-6.95 (m, 2H), 6.55-6.49 (m, 3H), 4.34 (m, 2H, Si-H), 3.62 (s, 4H, THF), 2.45-2.42 (m, 6H), 2.26-2.21 (m, 12H), 1.97-1.85 (m, 14H), 1.36-1.35 (m, 4H), 1.30 (s, 18 H, C(CH3)3), 0.20 (d, J = 10.8 Hz, 12H, SiMe2).

[0140] Example 11 Synthesis of complex Y-3-N [ka]

[0141] In a 20 mL scintillation vial, [Y{N(SiMe2H)2}3]·1.5THF (235 mg, 0.39 mmol) was dissolved in 2 mL of THF. Then, with stirring at ambient temperature, solid 2',2'''-(pyridin-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) (305 mg, 0.38 mmol) was slowly added. After the addition, the reaction mixture was diluted by adding 3 mL of THF. The resulting mixture was stirred at 60 °C for 2 h, and then the volatiles were removed under a stream of nitrogen. n-Pentane (5 mL) was added to the pale yellow oily residue and evaporated to aid in the removal of the remaining THF. This step was repeated twice to give a pale yellow powder. This powder was dissolved in toluene (1 mL). The resulting solution was layered with n-pentane and stored at −35° C. The precipitated white solid product was collected by filtration and washed twice with cold n-pentane (0.5 mL each). It was then dried under vacuum with gentle heating (<40° C.) to give 273 mg of white solid product (64%). 1 H NMR (400 MHz, benzene-d6): δ 7.48-7.33 (m, 5H), 7.25-7.00 (m, 6H), 6.85-6.75 (m, 2H), 6.54 (t, 7.5 Hz, 1H) 6.28 (m, 1H), 4.45 ( s, 2H, SiH), 3.74-3.45 (m, 4H), 2.61-2.44 (m, 6H), 2.26-2.11 (m, 11H), 1.98 (m, 6H), 1.88-1.85 (m, 7H), 1.37-1.15 (m, 22H), 0.26 (dd, J = 18.7 and 2.1 Hz, 12 H, SiMe2).

[0142] Example 12 Synthesis of the complex La-3-N [ka]

[0143] In a 20 mL scintillation vial, [La{N(SiMeH)}]·1.5THF (243 mg, 0.35 mmol) was dissolved in 2 mL of THF. Then, with stirring at ambient temperature, solid 2',2'''-(pyridin-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) (273 mg, 0.34 mmol) was slowly added. After the addition, the reaction mixture was diluted by adding 3 mL of THF. The resulting mixture was stirred at 60 °C for 2 h, then volatiles were removed under a stream of nitrogen and heated at 60 °C. n-Pentane (5 mL) was added to the pale yellow oily residue and evaporated to aid in the removal of residual THF and HN(SiMeH). This step was repeated five times to yield a pale yellow powder. The powder was washed twice with n-pentane (7 ml each time). The resulting product was dissolved in toluene (3 ml), and the resulting solution was then passed through a glass microfiber filter and a plug of Celite. The filtrate was concentrated to approximately 0.5 mL and layered with n-pentane at −35° C., resulting in the precipitation of yellow crystals. These were collected by decantation and dried under vacuum for 4 hours to give 297 mg of product (70%). 1 H NMR (400 MHz, benzene-d6): δ 7.43-7.40 (m, 4H), 7.29-7.11 (m, 6H), 7.06-6.98 (m, 2H), 6.61-6.54 (m, 3H), 4.48 (septet, 2.9 Hz, 2H, SiH), 3.46 (s, 4H, THF), 2.46-2.16 (m, 18H), 2.02-1.99 (m, 6H), 1.90-1.87 (m, 6H), 1.32 (s, 18H, tBu), 1.16-1.13 (m, 4H), 0.26 (dd, J = 22.4 and 3.0 Hz, 12H, SiMe2).

[0144] Example 13 Synthesis of the complex Nd-3-N [ka]

[0145] In a 20 mL scintillation vial, [Nd{N(SiMeH)}]·2THF (300 mg, 0.44 mmol) was dissolved in 2 mL of THF. Then, with stirring at ambient temperature, solid 2',2'''-(pyridin-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) (342 mg, 0.43 mmol) was slowly added. After the addition, the reaction mixture was diluted by adding 3 mL of THF. The resulting mixture was stirred at 60 °C for 2 h, and then the volatiles were removed by heating at 60 °C under a stream of nitrogen. The resulting bright green oily residue was dissolved in toluene (2 mL) and layered with n-pentane. Blue crystals of the product solvated with the solvent molecule, (Nd-3-N)·pentane, precipitated from the resulting mixture at −35°C for 16 h. The crystals were collected and dried under vacuum to yield 119 mg of a greenish solid (25%). The molecular structure of (Nd-3-N)·pentane was confirmed in the crystalline state by single-crystal X-ray diffraction.

[0146] Polymerization Example Example 14 Small scale polymerization: The catalyst was activated by adding iBuAlH (DIBAL) and DEATPFPB (DIMAH-D4) or MAO (13 wt% Al in toluene) to the reactor in an inert atmosphere in a N2-ventilated glovebox. The catalyst-containing solution was then stirred for approximately 10 minutes. A solution of butadiene in toluene (10–20 wt%) or isoprene was added to the catalyst solution (approximately 2500 butadiene equivalents / catalyst). The reactor was heated to 100°C, stirred at 225 rpm, and then pressurized with approximately 250 psi ethylene (Sigma, 99.5%). The ethylene was purified by passing it through a column containing activated adsorbent (AZ-300). If the pressure dropped below 240 psi during the first hour, the reactor was repressurized. After 14 hours, the reactor was cooled and then depressurized. For isolation of the polymer product, the contents of each reactor were precipitated and washed with acetone and methanol. The solids were then filtered and washed with copious amounts of acetone and methanol. The polymer samples were then dried in a 50°C vacuum oven for 18 hours.

[0147] Example 15 Polymerization using a Parr reactor: In a glovebox, catalyst Sc-3 (prepared in Example 7, 20 mg, 0.02 mmol, 1 equiv.) was added to an oven-dried glass liner, followed by DIMAH-D4 (24 mg, 0.03 mmol, 1.5 equiv.). Separately, DIBAL (57 μL, 0.32 mmol, 15 equiv.) was dissolved in 20 mL of toluene and then added to the glass liner. The glass liner was placed in a Parr reactor, sealed, and then removed from the glovebox. The reactor was heated to 40°C, and then 80 mL of a toluene solution containing DIBAL (100 μL, 0.56 mmol, 28 equiv.) and 5.41 g of butadiene (100 mmol, 5000 equiv., purified by passage through activated basic alumina) was forced into the reactor using ethylene (100 psi). After reaching 100°C, the ethylene pressure was increased to 250 psi. After the specified time, the reactor was cooled and the unreacted monomer was removed by ventilation. The polymer was precipitated by adding methanol containing BHT (25 mg) and then washed successively with 100 mL each of acetone and methanol under vigorous stirring. The washed polymer was dried in a vacuum oven at 55 °C for 18 h.

[0148] [Table 3]

[0149] Polymerization reactions with more uniform mass and heat transfer were carried out on a 10 g scale in a Parr reactor with mechanical stirring. Notably, catalyst activity was nearly three times higher when purified (dry) ethylene feed was used (Runs 1 and 2, Table 4). The highest amount of polymer (462 kg) was obtained. ポリマー / mol sc The optimum residence time for producing ethylene and butadiene was found to be around 2 hours (Run 3). Interestingly, this activity is the highest catalyst activity reported in the scientific literature for the copolymerization of ethylene and butadiene (405 kg ポリマー / mol sc), (7) Therefore, the application of bis(phenolate) catalyst systems to copolymerization is advantageous over metallocene-based catalysts due to their high productivity.

[0150] Example 16 Intrachain functionalization In a glovebox, catalyst Sc-3 (prepared in Example 7, 20 mg, 0.02 mmol, 1 equiv.), DIMAH-D4 (24 mg, 0.03 mmol, 1.5 equiv.), and DIBAL (57 μL, 0.32 mmol, 15 equiv.) were added to an oven-dried glass liner containing 20 mL of toluene. The glass liner was placed in a Parr reactor, sealed, and then removed from the glovebox. Separately, 32 mL of a 19.8 wt. % solution of butadiene (5.49 g, 0.10 mol) in toluene was added to a liquid-filled system along with 7-octenyldiisobutylaluminum (1,8-AVTA, 25.2 mg, 252 mg, or 1.26 g for 0.1 mol%, 1.0 mol%, or 5 mol%, respectively), DIBAL (100 μL), and 48 mL of toluene. The Parr reactor was then heated to 40°C, and the solution in the liquid-fill system was introduced into the reactor using 100 psi ethylene. The reaction was stirred for 5 minutes, and then the reactor was heated to 100°C and stirred at this temperature for 17 hours. Unreacted ethylene and butadiene were then removed by venting, and the system was pressurized with CO2 (200 psi). After stirring at 100°C for 1.5 hours, the reactor was cooled to ambient temperature, and residual CO2 was removed by venting. The polymer was precipitated by adding methanol containing 2,6-di-tert-butyl-4-methoxyphenol (BHT, 25 mg) and then washed successively with 100 mL portions of acetone and methanol under vigorous stirring. The washed polymer was dried in a vacuum oven at 55°C for 18 hours.

[0151] [Table 4]

[0152] Successful incorporation of polar groups into the polymer chain was achieved by adding 1,8-AVTA (7-octenyldiisobutylaluminum) during copolymerization with a bis(phenolate) catalyst system and subsequent reaction of the organoaluminum center with CO2. To our knowledge, this is the first example of in-chain functionalization for an ethylene / butadiene copolymer carried out in a single reactor. Significantly higher catalyst Sc-3 activity was observed in the reaction mixture containing 0.1 mol% AVTA (543 kg). ポリマー / mol sc , Table 5, Run 1), produced ethylene-rich copolymers. Increasing AVTA concentration resulted in lower activity (Runs 2 and 3).

[0153] Example 17 Catalyst Screening: Screening of nine Group 3 or lanthanide catalysts (Scheme 2) bearing alkyl or amide groups attached to the metal center, activated with two common substrates, DIMAH-D4 / DIBAL or MAO, was accomplished on a small scale (approximately 1 g of BD), allowing for the rapid identification of the most promising catalyst candidates for further evaluation. Catalysts featuring the 2-tBu-4-Me-phenolate fragment (43 kg) were used. ポリマー / mol Ln Relatively low activity was observed for ethylene and butadiene (up to 1.2 mol%) (Table 1, runs 1-6). Catalysts Y-1, Sc-2, and Y-2 copolymerized ethylene and butadiene only when activated with MAO, yielding ethylene-rich products with low butadiene incorporation (<1.2 mol%). On the other hand, the scandium-based system Sc-3, which has a more sterically crowded ligand framework, copolymerized ethylene and butadiene at 285 and 252 kg / mcg when activated with DIMAH-D4 / DIBAL and MAO, respectively. ポリマー / mol LnWe demonstrated activity of Sc-3 (Runs 7 and 8). Furthermore, catalyst Sc-3 tolerates conjugated dienes, resulting in the incorporation of 50 mol% butadiene into the polymer product. In contrast, much lower activity and lower incorporation of BD were observed for the borate-activated Y-analogue (Y-3) (Run 9). Activation of Y-3 with MAO resulted in the formation of gel as the major product. Bisphenolate catalysts with amide ancillary ligands do not exhibit high activity, except for the Sc-complex Sc-3-N (Runs 11–18). However, the activity of Sc-3-N (Runs 11 and 12) remains lower than that of its alkyl analogue, Sc-3 (Runs 7 and 8), despite the polymerization mechanism being essentially identical.

[0154] [Table 5]

[0155] Example 18 Effect of activator content: The role of various equivalents of DIBAL on the catalytic activity, product composition, and molecular weight of copolymerization induced by the scandium bis(phenolate) catalyst Sc-3 was investigated in detail. The catalytic activity was evaluated by varying the DIBAL concentration from 20 to 60 equivalents (66.8 to 263.5 kg / L). ポリマー / mol sc ), the reaction rate improved significantly, followed by 80 equivalents of DIBAL (204.1 kg ポリマー / mols c , Table 4). Higher concentrations of DIBAL resulted in a lower M w Thus, in the polymerization process, w This observation is consistent with a coordination chain transfer mechanism of copolymerization. The products show a broad molecular weight distribution ranging from 10.8 to 52.34. The T observed in DSC of the resulting polymers was m The melting peak at 112–128°C suggests the presence of a PE-rich block.

[0156] [Table 6]

[0157] Interestingly, catalyst Sc-3 can be used for ethylene homopolymerization when activated only with DIBAL (Runs 1 and 2, Table 5). The presence of a borate activator significantly reduces activity for ethylene polymerization. In contrast to the homopolymerization and C2 / C4 copolymerization with ethylene, catalyst Sc-3 does not show any significant activity for butadiene homopolymerization in the presence of different activators (Runs 7-12).

[0158] [Table 7]

[0159] High-throughput polymerization examples of alkene homopolymerization and copolymerization Pre-catalyst solutions were made using toluene (ExxonMobil Chemical, anhydrous, stored under N2) (98%). Pre-catalyst solutions were typically 0.5 mmol / L. The solvent, polymerization-grade toluene and / or isohexane, was supplied by ExxonMobil Chemical Co. and purified by passage through the following series of columns: two 500-cc Oxyclear cylinders in series, manufactured by Labclear (Oakland, Calif.), followed by two 500-cc columns in series packed with dry 3 Å mol sieves (8–12 mesh; Aldrich Chemical Company), and two 500-cc columns in series packed with dry 5 Å mol sieves (8–12 mesh; Aldrich Chemical Company).

[0160] Preparation of dry-heat methylaluminoxane (DHMAO) In a drybox, 500 ml of methylaluminoxane (Albemarle, 30 wt. % in toluene) was added to a 1-liter flask equipped with a Kontes closure and a sidearm. The flask was then removed and connected to a Schlenk line. The toluene and volatile trimethylaluminum were removed in vacuo and collected in a liquid nitrogen-cooled trap. After approximately 4 hours, only solid remained. At this point, the flask was heated to 70°C under vacuum for 8 hours to remove residual solvent and additional trimethylaluminum. The flask was then placed under nitrogen and allowed to cool to room temperature before being transferred to the drybox and the aggregated solid mixed. The flask was returned to the Schlenk line and reheated under vacuum to 70°C for an additional 6 hours. The flask was then placed under nitrogen and allowed to cool to room temperature before being returned to the drybox and 142.3 g of a white solid was recovered. 1-Octene (C8; 98%, Aldrich Chemical Company) was dried by stirring over NaK overnight, followed by filtration through basic alumina (Aldrich Chemical Company, Brockman Basic 1).

[0161] Polymerization grade ethylene (C2) was used and further purified by passage through the following series of columns: a 500 cc Oxyclear cylinder manufactured by Labclear (Oakland, Calif.), followed by a 500 cc column packed with dry 3 Å mol sieves (8-12 mesh; Aldrich Chemical Company), and a 500 cc column packed with dry 5 Å mol sieves (8-12 mesh; Aldrich Chemical Company). Various scavengers were used, including tri-n-octylaluminum (TNOAL, Neat, AkzoNobel), tri-isobutylaluminum (TIBAL, Neat, Aldrich), and dried and heated MAO (DHMAO, prepared as described above). Scavenger solutions were typically used as 5.0 mmol / L solutions in toluene. Scavenger agents can also be referred to as activators and / or chain transfer agents.

[0162] Reactor description and preparation: Polymerizations were carried out in an inert atmosphere (N2) drybox using an autoclave equipped with an external heater for temperature control, a glass insert (internal reactor volume = 23.5 mL for C2 and C2 / C8), a septum inlet, regulated feeds for nitrogen, ethylene, and propylene, and a disposable PEEK mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110 or 115 °C for 5 h, then at 25 °C for 5 h.

[0163] Ethylene polymer (PE) or ethylene / 1-octene copolymer (EO): The reactor was prepared as described above and then purged with ethylene. Toluene (5.0 mL for PE experiments and 4.9 mL for EO experiments) and 1-octene (100 μL, if used) were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to process temperature (80°C, 100°C, or 110°C) and stirred at 800 RPM while ethylene was dosed under process pressure (75 psig = 618.5 kPa). The scavenger solution, followed by the catalyst solution, was injected into the reactor via syringe under process conditions. Ethylene was allowed to enter the autoclave (via the use of computer-controlled solenoid valves) during polymerization to maintain reactor gauge pressure (±2 psig). Reactor temperature was monitored and typically maintained within ±1°C. Polymerization was terminated by adding approximately 50 psi of compressed dry gas mixture or 100% CO2 gas to the autoclave for approximately 30 seconds. Polymerizations were quenched after adding a predetermined cumulative amount of ethylene (maximum quench value 20 psid) or after a maximum polymerization time of 30 minutes. The reactor was then cooled and vented. The solvent was removed under vacuum, and the polymer was isolated. The reported yield includes the total weight of polymer and the remaining catalyst. The catalyst activity is reported in grams of polymer obtained per mmol of transition metal or lanthanide metal compound per hour of reaction time (g / mmol·h). The polymerization experiments are summarized in Table 6.

[0164] Polymer characterization For analytical testing, polymer sample solutions were prepared by dissolving the polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity, Sigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%, Aldrich) at 165°C in a shaker oven for approximately 3 hours. Typical concentrations of polymer in solution were between 0.1 and 0.9 mg / mL, and the BHT concentration was 1.25 mg BHT / mL of TCB. Samples were cooled to 135°C for testing.

[0165] High temperature size exclusion chromatography was performed using an automated "Rapid GPC" system as described in U.S. Pat. Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388, each of which is incorporated herein by reference. Polymer molecular weights (weight average molecular weight (Mw) and number average molecular weight (Mn)) and molecular weight distributions (MWD = Mw / Mn), sometimes referred to as polydispersity index (PDI), were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector (ELSD) and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10; Mp (peak Mw) between 5000 and 3,390,000). Alternatively, samples were measured by gel permeation chromatography using a Symyx Technology GPC equipped with a dual-wavelength infrared detector and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10; Mp (peak Mw) between 580 and 3,039,000). Samples (250 μL of polymer solution in TCB injected into the system) were run using three Polymer Laboratories PLgel 10 μm Mixed-B 300 × 7.5 mm columns in series at an eluent flow rate of 2.0 mL / min (135°C sample temperature, 165°C oven / column). No column spreading correction was employed. Numerical analysis was performed using Epoch® software available from Symyx Technologies or Automation Studio software available from Freeslate. Molecular weights obtained are relative to linear polystyrene standards.In Table 6, molecular weight data are reported under the headings Mn, Mw and PDI as defined above.

[0166] Differential scanning calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting points of the polymers. The samples were pre-annealed at 220°C for 15 minutes and then allowed to cool to room temperature overnight. The samples were then heated to 220°C at a rate of 100°C / min and then cooled at a rate of 50°C / min. Melting points were collected during the heating period. The results are reported in Table 6 under the heading Tm (°C). Samples were prepared for infrared analysis by depositing the stabilized polymer solution onto a silanized wafer (Part Number S10860, Symyx). This method deposits approximately 0.12 mg to 0.24 mg of polymer onto the wafer cell. Samples were then analyzed on a Brucker Equinox 55 FTIR spectrometer equipped with a Pikes MappIR specular sample accessory. Spectra were measured at 5000 cm. -1 ~500cm -1 In the spectral range of 2cm -1 32 scans were collected at 1000 x g resolution. For ethylene-1-octene copolymer, approximately 1375 cm -1 The mass % of octene in the copolymer was determined via measurement of the methyl deformation band at 1000 Hz. The peak height of this band is approximately 4321 cm. -1 The normalized peak height is calculated by the coupling and overtone bands at 1 Correlation with individual standard curves obtained from H NMR data predicts the octene content in wt. % within a concentration range of approximately 2-35 wt. % relative to octene. 2 A correlation of 0.98 or better is achieved. These values ​​are reported in Table 6 under the heading C8 wt %.

[0167] The polymerization results are collected in Table 6 below. "Ex#" represents the example number. "Cat" identifies the catalyst / complex used in the experiment. The corresponding number identifying the precatalyst (also called precatalyst, complex, or compound) can be found in the Synthetic Experiments section. "Cat (μmol)" is the amount of catalyst added to the reactor. "Scav" identifies the scavenger used. "Scav (μmol)" is the amount of scavenger / activator used, and "Scav / Cat (mol)" is the molar ratio of scavenger / activator to catalyst used. "C8 (μl)" is the amount of 1-octene used. T (°C) is the polymerization temperature, typically maintained within + / - 1°C. "Yield" is the polymer yield, not corrected for catalyst residues. "Quench Time" is the duration of the actual polymerization run, in seconds. "Quench Value (psid)" for ethylene-based polymerization runs is the maximum set amount of ethylene uptake (conversion) for the experiment. If the polymerization quench time was less than the set maximum time, it meant that the polymerization was run until the maximum set value of ethylene uptake was reached.

[0168] [Table 8-1] [Table 8-2] [Table 8-3] [Table 8-4] [Table 8-5] [Table 8-6] As can be seen in Table 8, increasing the ratio of scavenger to catalyst causes a decrease in polymer molecular weight. Typically, the molecular weight distribution also decreases as the molar ratio of scavenger to catalyst increases, especially at higher polymerization temperatures. Overall, the disclosed rare earth-based bis(phenolate)-type catalyst system can be used to produce ethylene and butadiene copolymers at high conversion rates under mild conditions. The catalyst system disclosed herein is an attractive option for implementation into industrial-scale processes for the high-throughput production of copolymer materials derived from, for example, ethylene and butadiene monomers, with tunable physical properties, polymer backbone structures, and different functional group moieties. In addition, polar side group moieties can be incorporated into the polymer chain during copolymerization. Such functionalized polymers may be desirable for the tire industry due to enhanced interactions between the copolymer and fillers present with the copolymer during use as tire materials.

[0169] Unless otherwise specified, the phrases "consists essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether specifically described herein or not, provided that such steps, elements, or materials do not additionally affect the basic and novel characteristics of the disclosure, and further, these phrases do not exclude impurities and errors normally associated with the elements and materials used.

[0170] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, a range from any lower limit can be combined with any upper limit to describe a range not explicitly stated, and similarly, a range from any lower limit can be combined with any other lower limit to describe a range not explicitly stated, and similarly, a range from any upper limit can be combined with any other upper limit to describe a range not explicitly stated. Furthermore, a range includes all points or individual values ​​between its endpoints, even if they are not explicitly stated. Thus, any point or individual value can serve as a lower or upper limit, and in combination with any other point or individual value, or any other lower or upper limit, to describe a range not explicitly stated.

[0171] All documents set forth herein, including any prevailing documents and / or testing procedures, are incorporated herein by reference to the extent that they do not contradict the text of this specification. While aspects of the present disclosure have been illustrated and described, as is apparent from the foregoing general description and specific embodiments, various changes may be made without departing from the spirit and scope of the present disclosure. Accordingly, the present disclosure is not intended to be limited thereto. Similarly, for purposes of U.S. law, the term "comprising" is considered to have the same meaning as the term "including." Similarly, when a composition, element, or group of elements is preceded by the transitional phrase "comprising," it is understood that the same composition or group of elements with the transitional phrase "consisting essentially of," "consisting of," "selected from the group consisting of," or "is" preceding the composition, element, or list of elements is also contemplated, and vice versa. While the present disclosure has been described with respect to certain embodiments and examples, those skilled in the art, having the benefit of this disclosure, will recognize that other embodiments may be devised which do not depart from the scope and spirit of the present disclosure.

Claims

1. 1. A process for producing an ethylene copolymer, comprising: Ethylene and C 3 -C 22 Alpha-olefins, C 4 -C 40 Conjugated dienes, C 5 -C 20 Cyclic olefins, C 6 -C 60 polymerizing an optional comonomer selected from the group consisting of ethylene, a chain transfer agent, and a metal hydrocarbenyl transfer agent, and combinations thereof, to form an ethylene copolymer by introducing ethylene, a chain transfer agent, and the optional comonomer together with a catalyst system, wherein the catalyst system is a catalyst represented by formula (I): 【Chemistry 1】 [In the formula, M is a Group 3 transition metal or a lanthanide metal; E and E' are each independently oxygen, sulfur, or NR A and R A are independently hydrogen, C 1 -C 40 Hydrocarbyl, substituted C 1 -C 40 is a hydrocarbyl or heteroatom-containing group, Q is a Group 14 atom, a Group 15 atom, or a Group 16 atom; A 1 QA 1’ is a part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, and is connected to A via a three-atom bridge with Q as the central atom of the three-atom bridge. 2 A 2’ It is connected to A 1 and A 1 Each of ' is independently carbon, nitrogen, or C(R B ) and R B is hydrogen, C 1 -C 20 Hydrocarbyl, substituted C 1 -C 20 hydrocarbyl, or heteroatom-containing hydrocarbyl; 【Chemistry 2】 is a divalent group containing 2 to 40 non-hydrogen atoms, and is connected via a two-atom bridge to A 1 is linked to the E-linked aryl group shown in formula (I), and A 3 and A 2 combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings can be joined to form additional rings; 【Transformation 3】 is a divalent group containing 2 to 40 non-hydrogen atoms, and is connected via a two-atom bridge to A 1 is linked to the E'-linked aryl group shown in formula (I), and A 3’ and A 2’ combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings can be joined to form additional rings; each L is independently a Lewis base; X is an anionic ligand; any two or more L groups may be linked together to form a multidentate Lewis base; The X group may be joined to the L group to form a monoanionic bidentate group; n is 1, m is 0, 1, or 2; n+m does not exceed 3, R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4 Each of ' is independently hydrogen, C 1 -C 40 Hydrocarbyl, substituted C 1 -C 40 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 ' may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substituents on a ring may be joined to form additional rings. and obtaining an ethylene copolymer; A method comprising:

2. 2. The method of claim 1, wherein M is selected from the group consisting of Sc, Y, La, Lu, and Nd.

3. 3. The method of claim 1, wherein each of E and E' is oxygen.

4. The method of any one of claims 1 to 3, wherein Q is nitrogen.

5. A 1 and A 1 5. The method of claim 1, wherein each of is carbon.

6. A 3 and A 2 are combined to form an optionally substituted first ortho-phenylene; A 3’ and A 2’ The method of any one of claims 1 to 5, wherein combine to form a second optionally substituted ortho-phenylene.

7. A 3 and A 2 combine to form a first group selected from the group consisting of indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, and substituted thiophene; A 3’ and A 2’ combine to form a second group selected from the group consisting of indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, and substituted thiophene; The method according to any one of claims 1 to 5.

8. A 3 and A 2 combine to form an optionally substituted first benzothiophene, A 3’ and A 2’ combine to form an optionally substituted second benzothiophene; The method of claim 7.

9. The compound is represented by formula (III), formula (IV), or formula (V): 【Chemistry 4】 [In the formula, M, L, X, m, n, R 1 , R 2 , R 3 , R 4 , R 1’ , R 2’ , R 3’ , and R 4’ is defined as in claim 1, Q' is a Group 15 heteroatom; R of formula (III), formula (IV), or formula (V) 5 , R 6 , R 7 , R 8 , R 5’ , R 6’ , R 7’ , R 8’ , R 10 , R 11 , and R 12 each independently represents hydrogen, C 1 -C 40 Hydrocarbyl, substituted C 1 -C 40 hydrocarbyl, 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 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substituents on a ring may be joined to form additional rings; Each G in formula (III), formula (IV), or formula (V) is a Group 15 or Group 16 heteroatom or a heteroatom group selected from S, O, NR′, and PR′, and R′ is a hydrogen atom or C 1 -C 40 selected from hydrocarbyl or substituted hydrocarbyl groups. The method of claim 1 , wherein

10. R of formula (I), formula (II), formula (III), formula (IV), or formula (V) 1 ' and R 1 The method of any one of claims 1 to 9, wherein each of is independently a cyclic tertiary alkyl group or a substituted cyclic tertiary alkyl group.

11. R of formula (I), formula (II), formula (III), formula (IV), or formula (V) 1 ' and R 1 11. The method of claim 10, wherein each of is independently selected from the group consisting of adamantan-1-yl or substituted adamantan-1-yl.

12. R of formula (I), formula (II), formula (III), formula (IV), or formula (V) 1 ' and R 1 The method of any one of claims 1 to 9, wherein each of is independently an acyclic tertiary alkyl group or a substituted acyclic tertiary alkyl group.

13. R of formula (I), formula (II), formula (III), formula (IV), or formula (V) 1 ' and R 1 13. The method of claim 12, wherein each of is tert-butyl, tert-pentyl, substituted tert-butyl, or substituted tert-pentyl.

14. R of formula (I), formula (II), formula (III), formula (IV), or formula (V) 3 and R 3 Each of the ' is independently a substitution C 1 -C 20 Alkyl or unsubstituted C 1 -C 20 The method according to any one of claims 1 to 13, wherein the alkyl is alkyl.

15. R of formula (I), formula (II), formula (III), formula (IV), or formula (V) 3 and R 3 15. The method of claim 14, wherein each of is independently methyl or tert-butyl.

16. R of formula (I), formula (II), formula (III), formula (IV), or formula (V) 2 , R 4 , R 2 ', R 4 ', R 5 , R 6 , R 7 , R 8 , R 5’ , R 6’ , R 7’ , R 8’ , R 10 , R 11 , and R 12 The method of any one of claims 1 to 15, wherein each of is hydrogen.

17. The method of any one of claims 1 to 16, wherein X in formula (I), formula (II), formula (III), formula (IV), or formula (V) is independently dimethylamide, diethylamide, bis(dimethylsilyl)amide, bis(trimethylsilyl)amide, or methylenetrimethylsilyl.

18. The method of any one of claims 1 to 17, wherein each L in formula (I), formula (II), formula (III), formula (IV), or formula (V) is tetrahydrofuran.

19. C 4 -C 40 C includes introducing a conjugated diene together with a catalyst system; 4 -C 40 The conjugated diene is selected from the group consisting of isoprene, 1,3-butadiene, and combinations thereof, and the ethylene copolymer is C 4 -C 40 The method of any one of claims 1 to 18, comprising conjugated diene units.

20. The catalyst system weighs approximately 400 kg. ポリマー / mol cat ~ Approximately 1000 kg ポリマー / mol cat The method according to any one of claims 1 to 19, having a catalytic activity of

21. The method of any one of claims 1 to 20, wherein the ethylene copolymer has from about 0.1 mol % to about 10 mol % of 1,2-cyclopentane units.

22. C 6 -C 60 introducing a metal hydrocarbenyl transfer agent with the catalyst system, wherein the ethylene copolymer is C 6 -C 60 22. The method of any one of claims 1 to 21, further comprising a metal hydrocarbenyl transfer agent unit.

23. C 6 -C 60 23. The method of claim 22, wherein the metal hydrocarbenyl transfer agent is selected from the group consisting of tri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum, tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum, tri(dec-9-en-1-yl)aluminum, dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum, diisobutyl(dodec-11-en-1-yl)aluminum, and combinations thereof.

24. 24. The process of any one of claims 1 to 23, carried out in a reactor at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30°C to 230°C.

25. about 10 parts by weight per 100 parts by weight of rubber (phr) to about 150 phr of filler; ethylene units, conjugated diene units, about 0.1 mol % to about 10 mol % of 1,2-cyclopentane units, and Functionalized vinyl transfer agent units a copolymer comprising A composition comprising , including tire materials.

26. 26. The tire material of claim 25, wherein the conjugated diene of the conjugated diene units is 1,3-butadiene.

27. 27. The tire material of claim 25 or 26, wherein the functionalized vinyl transfer agent unit is a carbon dioxide functionalized vinyl transfer agent unit.

28. A tire material according to any one of claims 25 to 27, wherein the filler is silica.

29. C 3 -C 22 The process of any one of claims 1 to 18, comprising the step of introducing the alpha-olefin together with the catalyst system.

30. C 5 -C 20 30. The process of any one of claims 1 to 18 and 29, comprising introducing a cyclic olefin with the catalyst system.

31. A process according to any one of claims 1 to 30, wherein the molecular weight of the polymer produced depends on the amount of chain transfer agent used.

32. The method of any one of claims 1 to 31, wherein the chain transfer agent is an alumoxane, a zinc alkyl, or an aluminum alkyl.

33. 33. The method of claim 32, wherein the chain transfer agent is selected from the group consisting of tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-isobutylaluminum, diethylzinc, methylalumoxane, diisobutylaluminum hydride, and combinations thereof.

34. The process of any one of claims 1 to 33, wherein the molar ratio of chain transfer agent to catalyst is from 1:1 to 1,000:

1.

35. 35. The process of claim 34, wherein the molar ratio of chain transfer agent to catalyst is from 1:1 to 100:

1.

36. Formula (I): 【Transformation 5】 [In the formula, M is a lanthanide metal; E and E' are each independently oxygen, sulfur, or NR A and R A are independently hydrogen, C 1 -C 40 Hydrocarbyl, substituted C 1 -C 40 is a hydrocarbyl or heteroatom-containing group, Q is a Group 14 atom, a Group 15 atom, or a Group 16 atom; A 1 QA 1’ is a part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, and is connected to A via a three-atom bridge with Q as the central atom of the three-atom bridge. 2 A 2’ It is connected to A 1 and A 1 Each of ' is independently carbon, nitrogen, or C(R B ) and R B is hydrogen, C 1 -C 20 Hydrocarbyl, substituted C 1 -C 20 hydrocarbyl, or heteroatom-containing hydrocarbyl; 【Transformation 6】 is a divalent group containing 2 to 40 non-hydrogen atoms, and is connected via a two-atom bridge to A 1 is linked to the E-linked aryl group shown in formula (I), and A 3 and A 2 combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings can be joined to form additional rings; 【Transformation 7】 is a divalent group containing 2 to 40 non-hydrogen atoms, and is connected via a two-atom bridge to A 1 A' is linked to the E'-linked aryl group shown in formula (I), 3’ and A 2’ combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings can be joined to form additional rings; each L is independently a Lewis base; X is an anionic ligand; any two or more L groups may be linked together to form a multidentate Lewis base; The X group may be joined to the L group to form a monoanionic bidentate group; n is 1, m is 0, 1, or 2; n+m does not exceed 3, R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4 Each of ' is independently hydrogen, C 1 -C 40 Hydrocarbyl, substituted C 1 -C 40 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 ' may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substituents on a ring may be joined to form additional rings. A compound represented by the formula:

37. 37. The compound of claim 36, wherein M is selected from the group consisting of La, Lu, and Nd.

38. 38. The compound of claim 36 or 37, wherein the A2'-A3' and A2-A3 linkers are independently substituted or unsubstituted heterocycles.

39. A catalyst system comprising an activator and a compound according to any one of claims 36 to 38.

40. 40. The catalyst system of claim 39 further comprising a support material.

41. The support material is Al 2 O 3 , ZrO 2 , SiO 2 , SiO 2 / Al 2 O 3 , SiO 2 / TiO 2 41. The catalyst system of claim 40, wherein the catalyst is selected from the group consisting of silica clays, silicon oxide / clays, and mixtures thereof.

42. 40. The catalyst system of claim 39, wherein the activator comprises a non-coordinating anion activator.

43. 40. The catalyst system of claim 39, wherein the activator comprises an alkylalumoxane.

44. 44. A process for producing a polymer, comprising polymerizing an alpha-olefin and an optional comonomer in a reactor at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30°C to 230°C by introducing the alpha-olefin and the optional comonomer together with the catalyst system of any one of claims 39 to 43 to form a polymer.

45. 44. A process for producing an ethylene copolymer, comprising the step of polymerizing ethylene and at least one conjugated diene in a reactor at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30°C to 230°C by introducing the ethylene and the conjugated diene together with the catalyst system of any one of claims 39 to 43 to form an ethylene copolymer.

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