Polyolefin catalysts and processes therefor

Abstract

The present disclosure relates to catalyst compounds, catalyst systems containing such compounds and uses thereof. In some embodiments, the catalysts contain Group 3, 4, 5 or 6 transition metals or lanthanide metals and are characterized by one seven-membered and one five-membered metal ring.

Description

[0001] Inventor: Georgy P. Goryunov, Pavel S. Kulyabin, Kristina M. Li, Oleg V.Samsonov, Mikhail I. Sharikov, Dmitry V. Uborsky, Alexander Z. Voskoboynikov, John R. Hagadorn, and Jo Ann M. Canich

[0002] Cross-reference to related applications

[0003] This application claims the benefit and priority of U.S. Provisional Application No. 63 / 561,632, filed March 5, 2024, the disclosure of which is incorporated herein by reference. Technical Field

[0004] This disclosure relates to catalyst compounds, catalyst systems comprising such compounds, and their uses. Background Technology

[0005] Polyolefin materials are widely used in industrial and commercial applications. These materials are ubiquitous in society in a variety of forms, from plastic containers and foodstuffs to various components for automobiles and engineering equipment. The widespread use and application of polyolefin materials highlights the economic incentives for the mass production of these polymers through industrially scalable processes.

[0006] In the field of polyolefin materials, the most commonly associated polymer is polyethylene (PE). Different methods of PE synthesis can be specifically designed to guide materials to exhibit different macromolecular characteristics and physical properties, as exemplified by the production of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE). Furthermore, various polymerization methods can be extended to other olefin monomer systems to produce polymers with diverse chemical compositions, molecular weights, polydispersity, stereoregularity, crystallinity, physical properties, and thermal properties.

[0007] In some cases, it is desirable to controllably adjust and / or regulate various chemical, macromolecular, and physical properties of polyolefin materials to meet specific objectives. Therefore, considerable interest and research have been directed towards developing novel catalyst systems for polyolefin synthesis. Such catalyst systems typically contain at least a catalyst complex and an activator compound. When implemented in polyolefin synthesis, the composition of the catalyst system should be carefully considered, as it can influence various properties of the resulting polyolefin. Furthermore, when developing new olefin polymerization catalyst systems, aspects of the catalyst composition (e.g., catalyst activity, chemical resistance, thermal stability, chemical stability, and shelf life) should be considered.

[0008] Typically, in the synthesis of polyolefins, olefin monomers are contacted with a catalyst system via one or more gas-phase, solution-phase, and bulk-phase polymerization methods. However, it is important to consider that the polymerization should be industrially feasible, producing large quantities of polyolefins with high productivity (e.g., catalyst activity). Additionally, it is desirable to produce polyolefins with higher molecular weights to meet the physical property requirements associated with the intended application.

[0009] While there are reports of catalyst systems capable of producing high molecular weight polyolefins, the resulting polymer materials typically have high molecular weights and broad molecular weight distributions, and therefore may often be difficult to process due to the hardness provided by the small amount of extremely high molecular weight polymer components in the produced polyolefin product. Furthermore, such catalyst systems typically exhibit low catalytic activity (e.g., polymer yield per time period).

[0010] Therefore, there is a need to develop new catalyst compounds and systems that possess high catalytic activity and the ability to form high molecular weight polyolefins without adversely affecting material properties and processability.

[0011] References cited in the information disclosure statement (37 CFR 1.97(h)): Baier, MC et al. Angew.Chem.Int.Ed. 2014, 53 , 9722-9744; US2020 / 0095349; Kulyabin, PS et al., Chemistry-A European Journal 2019 25 (44), 10478-10489; Hagadorn, JR et al., Polymer Preprints (American Chemical Society, Division of Polymer Chemistry) , 2011, 52 (1); US Patent Nos. 5,041,584; 9,340,630; 8,404,880; 8,975,209; 5,447,895; 8,658,556. Summary of the Invention

[0012] This disclosure relates to catalyst compounds, catalyst systems containing such compounds, and their uses.

[0013] In some implementations, the compound is represented by the following formula:

[0014]

[0015] in:

[0016] M is a transition metal or lanthanide metal belonging to Groups 3, 4, 5, or 6;

[0017] A 2Selected from unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, and substituted heteroaryl groups;

[0018] J is a heterocyclic Lewis base;

[0019] E 1 Selected from unsubstituted hydrocarbon groups, substituted hydrocarbon groups, and unsubstituted silyl hydrocarbon groups or substituted silyl hydrocarbon groups;

[0020] E 2 Selected from unsubstituted hydrocarbon groups, substituted hydrocarbon groups, and unsubstituted silyl hydrocarbon groups or substituted silyl hydrocarbon groups;

[0021] J and E 2 Optional fusion to form one or more unsubstituted hydrocarbon rings, substituted hydrocarbon rings, unsubstituted heterocycles, or substituted heterocycles;

[0022] Each L is an independent Lewis base;

[0023] Each X is an anionic ligand independently;

[0024] n is 1, 2, or 3;

[0025] m is 0, 1, or 2;

[0026] n+m is 4 or less;

[0027] R 1 Selected from unsubstituted C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups and unsubstituted or substituted C1-C 40 Groups containing heteroatoms;

[0028] Any two L groups can bond together to form a bidentate Lewis base;

[0029] The X group can combine with the L group to form a monoanionic bidentate group; and

[0030] Any two X groups can join together to form a bianionic ligand group.

[0031] In some embodiments, the catalyst system comprises an activator and the catalyst compound of this disclosure.

[0032] In some implementations, the polymerization method includes mixing one or more C2-C... 20 An α-olefin monomer and a catalyst system are introduced into a reactor, the catalyst system comprising an activator and a catalyst compound disclosed herein. Detailed Implementation

[0033] This disclosure relates to catalyst compounds, catalyst systems containing such compounds, and their uses.

[0034] The catalyst compounds disclosed herein, and the catalyst systems containing such compounds, provide high catalyst activity, and the polyolefins formed using such catalyst compounds and systems can have high molecular weight values.

[0035] The catalyst compounds disclosed herein are phenolate-heterocyclic-amino (amido) ligands coordinated to Group 4 transition metals. The complexes contain a tripentate ligand characterized by a central neutral heterocyclic donor group, an anionic phenolate donor, and an anionic amino donor. The tripentate ligand coordinates with the metal center to form five-membered and seven-membered rings. These complexes have been found to be usable as catalyst compounds for olefin polymerization. For example, the catalyst compounds disclosed herein can provide high molecular weight polymers with high catalytic activity suitable for commercial production.

[0036] In some embodiments, this disclosure provides a catalyst system comprising an activator and the catalyst of this disclosure.

[0037] In some embodiments, this disclosure provides a polymerization method comprising a) introducing one or more olefin monomers with a catalyst system, said catalyst system comprising: i) an activator and ii) a catalyst compound of this disclosure.

[0038] In some embodiments, this disclosure provides polyolefins formed by the catalyst system and / or methods of this disclosure.

[0039] In some embodiments, this disclosure provides a method for producing ethylene-α-olefin copolymers, comprising reacting ethylene and (optionally) at least one C3-C in, for example, at least one continuous stirred tank reactor or loop reactor. 20 α-olefins are contacted with a catalyst system to polymerize ethylene and (optionally) at least one C3-C 20 α-olefins.

[0040] In some embodiments, this disclosure provides a method for producing propylene α-olefin copolymers, comprising, for example, reacting propylene with at least one ethylene and / or at least one C4-C in at least one continuous stirred tank reactor or loop reactor. 20 α-olefins are contacted with a catalyst system to polymerize propylene and (optionally) at least one ethylene and / or (optionally) C4-C 20 α-olefins.

[0041] definition

[0042] Use such as Chemical and Engineering News The new numbering scheme for the periodic table groups is described in Volume 63(5), page 27 (1985). Therefore, “Group 3 metals” are elements from Group 4 of the periodic table, such as Sc, Y, or Nd.

[0043] The room temperature is approximately 23°C, unless otherwise stated.

[0044] "Olefin," optionally referred to as "olefin," is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For the purposes of this specification and the appended claims, when a polymer or copolymer is referred to as containing an olefin, the olefin present in such a polymer or copolymer is a polymeric form of an olefin. For example, when a copolymer is claimed to have 35% to 55% by weight of "ethylene," it should be understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and the derived units are present in 35% to 55% by weight, based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A homopolymer is a polymer having identical monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. A "terpolymer" is a polymer having three monomer units that are different from each other. Thus, the definition of copolymer as used herein includes terpolymers, etc. The term "different" used to refer to monomer units means that the monomer units are different from each other at at least one atom or are isomerically different. "Ethylene polymer" or "ethylene copolymer" is a polymer or copolymer containing at least 50 mol% of ethylene-derived units, "propylene polymer" or "propylene copolymer" is a polymer or copolymer containing at least 50 mol% of propylene-derived units, and so on.

[0045] Ethylene should be considered an α-olefin.

[0046] Unless otherwise stated, the term "C" is used in conjunction with other terms. n "This means a hydrocarbon (one or more) with n carbon atoms (one or more) per molecule, where n is a positive integer."

[0047] The term "hydrocarbon" refers to a class of compounds containing hydrogen bound to carbon, and includes (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds with different n values. Similarly, "C m -C y "A group or compound refers to a group or compound containing a total number of carbon atoms ranging from m to y. Therefore, C1-C..." 50 Alkyl groups are alkyl groups that contain a total number of carbon atoms ranging from 1 to 50.

[0048] The terms “group”, “radical”, and “substituent” are used interchangeably.

[0049] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl group" are used interchangeably and are defined as a group consisting only of hydrogen and carbon atoms. Hydrocarbyl groups can be C1-C2. 100 A functional group, which may be linear, branched, or cyclic, or a combination thereof, and when cyclic, is aromatic or non-aromatic. This includes combinations of linear, branched, and / or cyclic groups. Examples of such groups include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc.; alkenyl groups such as vinyl, propenyl, etc.; aryl groups such as phenyl, tolyl, benzyl, naphthyl, etc.; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, norbornyl, adamantyl, substituted adamantyl, such as 3-methyladamantyl or 3,5-dimethyladamantyl, fluorenyl, substituted fluorenyl, such as 9-methylfluorenyl. When two adjacent or hydroxyl groups are joined together, they can form a hydrocarbon ring.

[0050] Unless otherwise specified (e.g., the definition of "substituted hydrocarbon group", "substituted aromatic compound", etc.), the term "substituted" means that at least one hydrogen atom has been replaced by at least one non-hydrogen group, such as a hydrocarbon 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, where each R Independently a hydrocarbon group or a halohydrocarbon group, and two or more R groups They can join together to form substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic structures, or at least one heteroatom may have been inserted into the hydrocarbon ring. When two adjacent or co-substituted hydrocarbon groups or one substituted hydrocarbon group and one hydrocarbon group join together, they can form a substituted hydrocarbon ring. Substituted hydrocarbon rings can, by definition, include heterocycles and substituted heterocycles.

[0051] The term "substituted hydrocarbon group" means a hydrocarbon group in which at least one hydrogen atom of the hydrocarbon group is replaced by at least one heteroatom (e.g., a halogen, such as Br, Cl, F, or I) or a 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, where each R Independently a hydrocarbon group or a halohydrocarbon group, and two or more R groups They can be joined together to form substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic structures, or at least one heteroatom may have been inserted into the hydrocarbon ring. Alternatively, the substituted hydrocarbon group may have at least one heteroatom or heteroatom group inserted between two adjacent carbon atoms of the hydrocarbon group. For example, -NR can be inserted... -、-O-、-Se-、-Te-、-PR -、-AsR -、-SbR -、-S、-BR -、-SiR 2-、-GeR 2-、-SnR 2-、-PbR 2- is inserted between two carbon atoms. R As defined above.

[0052] When used to define substituents, "heteroatom-containing group" refers to a group in which the heteroatom is directly bonded to the substrate. For example, when a heteroatom-containing group is bonded to an aromatic ring, the heteroatom is directly bonded to the aromatic ring. The terms heteroatom-containing group and functional group are used interchangeably.

[0053] An unsubstituted hydrocarbon group contains only carbon and hydrogen atoms. The terms hydrocarbon group and unsubstituted hydrocarbon group are used interchangeably.

[0054] A silyl hydrocarbon group (also called a silyl hydrocarbon group) is a group in which the silyl functional group is directly bonded to one or more atoms. Examples of bonding with one atom include SiH3 and SiH2R. SiHR 2. SiR 3. SiH2(OR) ), SiH(OR) 2. Si(OR) 3. SiH2(NR) 2) SiH(NR) 2)2、Si(NR 2) 3, where R Independently a hydrocarbon group, and two or more R groups They can bond together to form substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic structures. Examples of bonding with two atoms include SiH2 and SiHR. SiR 2. SiR (OR ), SiH(OR) ), Si(OR) 2. SiH(NR) 2) SiR (NR 2) Si(NR) 2)2, where R As stated above.

[0055] The term “aryl” or “aryl group” means an aromatic ring (including its variants), such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Similarly, “heteroaryl” means an aryl group in which a ring carbon atom (or two or three ring carbon atoms) is replaced by a heteroatom such as N, O, or S, and includes its variants such as pyridyl, 4-methylpyridyl, furanyl, benzofuranyl, thiophene, benzo[b]thiophene, etc. As used herein, the term “aromatic compound” also refers to a pseudo-aromatic heterocycle, which is a heterocyclic substituent having properties and structure (approximately planar) similar to aromatic heterocyclic ligands, but is not an aromatic heterocyclic ligand by definition; similarly, the term aryl also includes substituted aryl groups, and the term heteroaryl includes substituted heteroaryl groups.

[0056] The term "substituted aryl" refers to an aryl group in which one or more hydrogen groups are replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a heteroatom-containing group. The term "substituted heteroaryl" refers to a heteroaryl group in which one or more hydrogen groups are replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a heteroatom-containing group. Heteroaryl groups are also called heterocyclic groups.

[0057] The term "heteroatom" refers to any element in Groups 13-17, excluding carbon. Heteroatoms can include B, Si, Ge, Sn, N, P, As, O, S, Se, Te, F, Cl, Br, and I. The term "heteroatom-containing group" can include the above elements bonded with hydrogen, such as BH, BH2, SiH2, OH, NH, NH2, etc., or a heteroatom-containing group in which one or more hydrogen atoms are replaced by a hydrocarbon group or a substituted hydrocarbon group, such as BR', BR'2, SiR'2, OR', NR', NR'2, etc., where R' represents a hydrocarbon group or a substituted hydrocarbon group.

[0058] The term "heterocyclic Lewis base" refers to a Lewis base that is also heterocyclic. Examples of heterocyclic Lewis bases may include pyridine, imidazole, thiazole, and furan.

[0059] The terms "alkyl group" and "alkyl" are used interchangeably throughout this disclosure. For the purposes of this disclosure, "alkyl group" is defined as C1-C64. 100 Alkyl groups can be linear, branched, or cyclic, or combinations thereof. Examples of such groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, methylcyclohexyl, etc. A substituted alkyl group is one in which at least one hydrogen atom of the alkyl group is replaced by at least a non-hydrogen group, such as 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. Substituted groups, wherein each R Independently a hydrogen, hydrocarbon, or haloalkyl group, and two or more R groups. They can be joined together to form substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic structures, or at least one heteroatom of which has been inserted into the hydrocarbon ring.

[0060] When isomers of a specified alkyl, alkenyl, alkoxy, or aryl group (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl) are present, references to the alkyl, alkenyl, alkoxy, or aryl group without specifying a particular isomer (e.g., butyl) explicitly disclose all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0061] A "phenolate" is a salt in which one, two, three, four, or five hydrogen atoms optionally at positions 2, 3, 4, 5, and / or 6 are surrounded by at least one non-hydrogen group such as a hydrocarbon group, a heteroatom, or a heteroatom-containing group such as a halogen (e.g., Br, Cl, F, or I) or at least one functional group such as -NR. 2. -OR -SeR -TeR -PR 2. -AsR 2. -SbR 2. -SR -BR 2, -SiR 3. -GeR 3. -SnR 3. -PbR 3. Alternating phenolic salt groups, wherein each R Independently a hydrogen, hydrocarbon, or haloalkyl group, and two or more R groups. These can be joined together to form substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic structures, wherein the 1-position is a phenolic salt group (Ph-O-, Ph-S-). For example, the "substituted phenolic salt" group in the catalyst compounds described herein is represented by the following formula:

[0062]

[0063] Where R 18 Hydrogen, C1-C 40 Hydrocarbon groups (e.g., C1-C) 40 Alkyl) or C1-C 40 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups, E 17 It is oxygen, sulfur, and R 19 R 20 and R 21 Each is independently selected from hydrogen, C1-C 40 Hydrocarbon groups (e.g., C1-C) 40 Alkyl) or C1-C 40 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups, or R 18 R 19 R 20 and R 21Two or more of them join together to form C4-C 62 Cyclic or polycyclic structures, or combinations thereof, and wavy lines indicate the positions where substituted phenolic groups form bonds with the rest of the catalyst compound.

[0064] "Amino" is optionally represented by one, two, three, four, or five hydrogen atoms at positions 2, 3, 4, 5, and / or 6, which are surrounded by at least one non-hydrogen group such as a hydrocarbon group, a heteroatom, or a heteroatom-containing group such as a halogen (e.g., Br, Cl, F, or I) or at least one functional group such as -NR. 2. -OR -SeR -TeR -PR 2. -AsR 2. -SbR 2. -SR -BR 2, -SiR 3. -GeR 3. -SnR 3. -PbR 3. Alternating aniline groups, wherein each R Independently a hydrogen, hydrocarbon, or haloalkyl group, and two or more R groups. They can be joined together to form substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic structures, wherein the 1-position is an aniline group (Ph-N(R)). ^ )- group, wherein R ^ Hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 (Hydrocarbon group, heteroatom or heteroatom-containing group). For example, the "substituted amino" group in the catalyst compounds described herein is represented by the following formula:

[0065]

[0066] Where R 18 Hydrogen, C1-C 40 Hydrocarbon groups (e.g., C1-C) 40 Alkyl) or C1-C 40 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups, E 17 It is nitrogen, and R 19 R 20 R 21 and R 22 Each is independently selected from hydrogen, C1-C 40 Hydrocarbon groups (e.g., C1-C) 40 Alkyl) or C1-C 40Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups, or R 18 R 19 R 20 R 21 and R 22 Two or more of them join together to form C4-C 62 Cyclic or polycyclic structures, or combinations thereof, and wavy lines indicate the positions where substituted amino groups form bonds with the rest of the catalyst compound.

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

[0068] A heterocyclic ring, also known as a heterocycle, is a ring structure containing a heteroatom in its ring structure, as opposed to a "heteroatom-substituted ring," in which a hydrogen atom on the ring is replaced by a heteroatom. For example, tetrahydrofuran is a heterocycle, and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. A substituted heterocycle is a heterocycle in which one or more hydrogen groups are replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a heteroatom-containing group.

[0069] As used herein, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, and Mz is the z-average molecular weight; wt% is the weight percentage, and mole% is the mole percentage. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol (g·mol⁻¹). -1 ).

[0070] The following abbreviations may be used in this document: Me is methyl, MAO is methylaluminoxane, THF is tetrahydrofuran, RT is room temperature (and 23°C unless otherwise stated), tol is toluene, Cp is cyclopentadienyl, NMR is nuclear magnetic resonance, and TMA is trimethylaluminum.

[0071] A “catalyst system” is a combination of at least one catalyst compound, an activator, an optional co-activator, and an optional support material. When used to describe such a pairing prior to activation, “catalyst system” means an unactivated catalyst complex (pre-catalyst) together with an activator and an optional co-activator. When used to describe such a pairing after activation, it means an activated complex and an activator or other charge-balanced structural component. The catalyst compound can be neutral, as in a pre-catalyst, or charged with counterions, as in an activated catalyst system. For the purposes of this disclosure and its claims, when a catalyst system is described as comprising a neutral, stable form of a component, it is fully understood by those skilled in the art that the ionic form of the component is the form in which it reacts with the monomer to produce a polymer. A polymerization catalyst system is a catalyst system that can polymerize monomers into polymers. Furthermore, catalyst compounds and activators (including support-bonded activators) represented by the formulas herein include both neutral and ionic forms of the catalyst compound and the activator.

[0072] In this specification, a catalyst may be described as a catalyst, a precatalyst, a precatalyst compound, a catalyst compound, or a transition metal compound, and these terms are used interchangeably.

[0073] An "anionic ligand" is a negatively charged ligand that donates one or more electron pairs to a metal ion. The terms "anionic donor" and "anionic ligand" are used interchangeably. Examples of anionic donors include, but are not limited to, methyl, chloro, fluoro, alkoxy, aryloxy, alkyl, alkenyl, thiol, carboxyl, amino, benzyl, hydrogen, amido, amidate, and phenyl. Two anionic donors can combine to form a dianionic group.

[0074] A “neutral Lewis base” or “neutral donor group” is an uncharged (neutral) group that donates one or more electron pairs to a metal ion. Non-limiting examples of neutral Lewis bases include ethers, thioethers, amines, phosphine, diethyl ether, tetrahydrofuran, dimethyl sulfide, triethylamine, pyridine, alkenes, alkynes, alene, and carbene. Lewis bases can bond together to form bidentate or tripentate Lewis bases.

[0075] For the purposes of this disclosure and its claims, phenoxy donors may include Ph-O-, Ph-S-, and Ph-N-. )- group, in which Hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 The substituted hydrocarbon group, heteroatom or heteroatom-containing group, and Ph is an optionally substituted phenyl group.

[0076] The lanthanide metals (La-Lu) include La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

[0077] Catalyst compounds

[0078] In some implementations, the catalyst can be represented by formula (I):

[0079] (I)

[0080] in:

[0081] M is a transition metal or lanthanide metal belonging to Groups 3, 4, 5, or 6;

[0082] A 2 Selected from aryl, substituted aryl, heteroaryl and substituted heteroaryl groups;

[0083] J is a heterocyclic Lewis base;

[0084] E 1 Selected from hydrocarbon groups, substituted hydrocarbon groups, and unsubstituted or substituted silyl hydrocarbon groups;

[0085] E 2 Selected from hydrocarbon groups, substituted hydrocarbon groups, and unsubstituted or substituted silyl hydrocarbon groups, wherein J and E 2 Optionally joined to form one or more hydrocarbon rings, substituted hydrocarbon rings, heterocycles, or substituted heterocycles;

[0086] Each L is an independent Lewis base;

[0087] Each X is an anionic ligand independently;

[0088] n is 1, 2, or 3;

[0089] m is 0, 1, or 2;

[0090] n+m is not greater than 4;

[0091] R 1 Selected from unsubstituted C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups and unsubstituted or substituted C1-C 40 Groups containing heteroatoms;

[0092] Any two L groups can bond together to form a bidentate Lewis base;

[0093] The X group can combine with the L group to form a monoanionic bidentate group; and

[0094] Any two X groups can join together to form a bianionic ligand group.

[0095] In at least one embodiment, the catalyst compound represented by formula (I) is characterized by a seven-membered and a five-membered metal ring. The seven-membered metal ring contains an atom from metal M, an oxygen atom (e.g., a group such as part of a phenolic salt), an aryl group, a substituted aryl group, a heteroaryl group, or a substituted heteroaryl group A. 2 Two atoms, hydrocarbon group, substituted hydrocarbon group or silyl hydrocarbon group E 2 One atom from the metal M and two atoms from the bridging Lewis base group J. The pentagonal metal ring contains an atom from the metal M, nitrogen, a hydrocarbon group, a substituted hydrocarbon group, or a silyl hydrocarbon group E. 1 The atoms and two atoms from the bridging Lewis base group J.

[0096] In some implementations, metal M is a Group 4 metal, such as zirconium or hafnium.

[0097] In at least one embodiment, the catalyst compound represented by formula (I) is characterized by a seven-membered and a five-membered metal ring. The seven-membered metal ring contains atoms from metal M, phenolic oxygen, and an aryl group A. 2 Two atoms, a hydrocarbon group, or a substituted hydrocarbon group E 2 One atom from the metal M and two atoms from the bridging Lewis base J. The pentagonal metal ring contains an atom from the metal M, nitrogen (from the amino group), and an atom from a hydrocarbon group or a substituted hydrocarbon group E. 1 The atoms and two atoms from the bridging Lewis base group J.

[0098] In at least one embodiment, each L of the catalyst represented by formula (I) may be independently selected from ethers, amines, phosphine, thioethers, esters, Et2O, MeO t Bu, Et3N, PhNMe2, MePh2N, tetrahydrofuran, and dimethyl sulfide. In at least one embodiment, m of the catalyst represented by formula (I) is 0. In at least one embodiment, each X of the catalyst represented by formula (I) may be independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydroxyl, chlorine, fluorine, bromine, iodine, trifluoromethanesulfonate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino, for example, chlorine, for example, methyl. In at least one embodiment, n of the catalyst represented by formula (I) is 2.

[0099] In some embodiments, X is selected from methyl or benzyl, n is 2, and m is zero.

[0100] In some implementation schemes, E 1 Optional from C(R) 15 (R) 16 ) and Si(R 15 (R)16 R 15 and R 16 Each can be independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms and C1-C 40 Groups containing heteroatoms, or R 15 and R 16 They can be joined to form one or more C3-C atoms, each having 5, 6, 7 or 8 ring atoms. 20 A hydrocarbon ring, a substituted hydrocarbon ring, a heterocycle, or a substituted heterocycle, wherein the substituents on the ring can join to form additional rings.

[0101] In some implementation schemes, E 2 Optional from C(R) 25 (R) 26 ), Si(R) 25 (R) 26 ) and C = C(R 25 (R) 26 R 25 and R 26 Each can be independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms and C1-C 40 Groups containing heteroatoms, or R 25 and R 26 They can be joined to form one or more C3-C atoms, each having 5, 6, 7 or 8 ring atoms. 20 A hydrocarbon ring, a substituted hydrocarbon ring, a heterocycle, or a substituted heterocycle, wherein the substituents on the ring can join to form additional rings.

[0102] In some implementation schemes, E 1 and E 2 Independently selected from -CH2, -CMe2, -CEt2, -CHMe, -CHEt, -CPh2, -CHPh, -SiMe2, -SiEt2, -SiPh2 and -SiMePh, for example -CH2.

[0103] In some implementation schemes, E 1 Selected from CH2, CMe2, CEt2, CHMe, CHEt, CPh2, CHPh, SiMe2, SiEt2, SiPh2, SiMePh, and E 2Selected from CH2, CMe2, CEt2, CHMe, CHEt, CPh2, CHPh, SiMe2, SiEt2, SiPh2, SiMePh, C=CH2, C=CMe2, C=CEt2, C=CPh2, C=CHMe, C=CHEt and C=CHPh.

[0104] In some implementation schemes, E 1 CH2 and E 2 Selected from CH2 and C=CMe2.

[0105] In at least one implementation, R 1 Selected from substituted or unsubstituted C6-C 40 Aryl groups, such as phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, isopropylphenyl, diisopropylphenyl, triisopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, tri-tert-butylphenyl, methylisopropylphenyl, methyl-tert-butylphenyl, ethyl-isopropylphenyl, ethyl-tert-butylphenyl, methylnaphthyl, ethylnaphthyl, isopropylnaphthyl, and tert-butylnaphthyl. Alternatively, R 1 It is selected from all isomers of methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

[0106] In some implementation schemes, R 1 It is selected from 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl and 2,6-diisopropyl-4-methylphenyl.

[0107] In at least one embodiment, A of formula (I) 2 It can be expressed by the following formula:

[0108]

[0109] Where R 11 R 12 R 13 and R 14 Each is independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, and substituted or unsubstituted C1-C 40 A group containing heteroatoms. In at least one embodiment, R 11 R 12 R 13 and R 14 Each is independently selected from hydrogen and C1-C 10 Alkyl group. In at least one embodiment, R 11 R 12 R13 and R 14 Each is independently selected from all isomers of hydrogen, methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. In some embodiments, R 11 C5-C 30 cycloalkyl or C5-C 30 The substituted cycloalkyl group is used, for example, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, fluorenyl, 9-methylfluorenyl, adamantyl, or a substituted adamantyl group. In some embodiments, R... 11 It can be C1-C 10 Alkyl groups, such as tert-butyl, tert-pentyl, and tert-octyl (2,4,4-trimethylpentyl-2-yl), or R 11 It can be a heteroatom-containing group, such as trimethylsilyl, carbazole-9-yl, or a substituted carbazole-9-yl. Alternatively, R 11 It can be aryl, such as for R 1 As defined. In some implementations, R 13 For C1-C 20 Hydrocarbon groups, such as methyl, tert-butyl, n-octyl, etc.

[0110] In some implementation schemes, R 11 It is selected from tert-butyl, adamantyl, substituted adamantyl, carbazole-9-yl, substituted carbazole-9-yl, fluorene-9-yl, substituted fluorene-9-yl, phenyl and substituted phenyl.

[0111] In some implementation schemes, R 11 It is selected from tert-butyl, adamantyl, 3-methyladamantane-1-yl, 3,5-dimethyladamantane-1-yl, carbazole-9-yl, 2,7-di-tert-butylcarbazole-9-yl, fluorene-9-yl, 9-methylfluorene-9-yl, phenyl, 3,5-di-tert-butylphenyl, 3,5-diisopropylphenyl, and 3,5-dimethylphenyl.

[0112] In some implementation schemes, R 13 Selected from methyl or tert-butyl.

[0113] In some implementations, J in equation (I) can be represented by the following equation:

[0114] (IA) or (IB) or (IC)

[0115] Where E 3 Selected from O, S and N(R) 10 ), and R 2 R 3 R 4 R5 and R 10 Each is independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms and C1-C 40 Groups containing heteroatoms, or R 2 and R 3 Or R 3 and R 4 One or more pairs of rings may join to form one or more hydrocarbon rings, substituted hydrocarbon rings, heterocycles, or substituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may join to form additional rings. In at least one embodiment, R 2 R 3 and R 4 Each is independently selected from hydrogen and C1-C 10 Alkyl group. In at least one embodiment, R 2 R 3 and R 4 Each is independently selected from all isomers of hydrogen, methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl. In at least one embodiment, E 3 It can be selected from group 16 atoms (e.g., sulfur (e.g., J = thiazole); oxygen (e.g., J = oxazole)) or N (R 10 ), where R 10 It is hydrogen or C1-C 10 Hydrocarbon group, C1-C 10 Substitution of hydrocarbon groups, heteroatoms, or C1-C 10 (A group containing heteroatoms). In at least one embodiment, J of formula (I) has the structure described above (IA).

[0116] In some implementations, J and E of formula (I) 2 Joined to form a ring as represented by the following formula:

[0117] (1D) or (1E)

[0118] Where E 3 Selected from O, S and N(R) 10 ), where R 2 R 3 R 6 R 7 R 8 and R 10 Each is independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, and substituted or unsubstituted C1-C 40Groups containing heteroatoms, or R 6 and R 7 Or R 7 and R 8 Or R 2 and R 3 Or R 3 and R 6 One or more pairs of rings may join to form one or more hydrocarbon rings, substituted hydrocarbon rings, heterocycles, or substituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may join to form additional rings. In at least one embodiment, R 2 R 3 R 6 R 7 R 8 and R 10 Each is independently selected from hydrogen and C1-C 10 Alkyl group. In at least one embodiment, R 2 R 3 R 6 R 7 R 8 and R 10 Each is independently selected from all isomers of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.

[0119] In some implementations, the catalyst may be represented by formula (II):

[0120] (II)

[0121] in:

[0122] M is a transition metal from Group 3, 4, 5 or 6, or a lanthanide metal;

[0123] A 2 Selected from aryl, substituted aryl, heteroaryl and substituted heteroaryl groups;

[0124] E 1 Selected from hydrocarbon groups, substituted hydrocarbon groups, and unsubstituted or substituted silyl hydrocarbon groups;

[0125] E 2 Selected from hydrocarbon groups, substituted hydrocarbon groups, and unsubstituted or substituted silyl hydrocarbon groups, wherein E 2 Optional fusion with a Lewis base to form one or more hydrocarbon rings, substituted hydrocarbon rings, heterocycles, or substituted heterocycles;

[0126] Each L is an independent Lewis base;

[0127] Each X is an anionic ligand independently;

[0128] n is 1, 2, or 3;

[0129] m is 0, 1, or 2;

[0130] n+m is not greater than 4;

[0131] R 1 Selected from unsubstituted C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups and substituted or unsubstituted C1-C 40 Groups containing heteroatoms;

[0132] Each R 2 R 3 and R 4 Independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups and substituted or unsubstituted C1-C 40 Groups containing heteroatoms;

[0133] Any two L groups can bond together to form a bidentate Lewis base;

[0134] The X group can combine with the L group to form a monoanionic bidentate group; and

[0135] Any two X groups can join together to form a bianionic ligand group.

[0136] In at least one embodiment, the catalyst compound represented by formula (II) is characterized by a seven-membered metal ring and a five-membered metal ring. The seven-membered metal ring contains an atom from metal M, a phenolic oxygen, an aryl group, or a substituted aryl group A. 2 Two atoms, a hydrocarbon group, or a substituted hydrocarbon group E 2 One atom from the metal M and two atoms from the bridging Lewis base. The pentagonal metal ring contains an atom from the metal M, nitrogen, and an E group derived from or substituted with a hydrocarbon group. 1 The atoms and the two atoms bridging the Lewis base.

[0137] In some implementations, metal M is a Group 4 metal, such as zirconium or hafnium.

[0138] In at least one embodiment, each L of the catalyst represented by formula (II) can be independently selected from ethers, amines, phosphine, thioethers, esters, Et2O, MeO tBu, Et3N, PhNMe2, MePh2N, tetrahydrofuran, and dimethyl sulfide. In at least one embodiment, m of the catalyst represented by formula (II) is 0. In at least one embodiment, each X of the catalyst represented by formula (II) may be independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydroxyl, chlorine, fluorine, bromine, iodine, trifluoromethanesulfonate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino, such as chlorine, such as methyl. In at least one embodiment, n of the catalyst represented by formula (II) is 2.

[0139] In some embodiments, X is selected from methyl or benzyl, n is 2, and m is zero.

[0140] In some implementation schemes, E 1 Optional from C(R) 15 (R) 16 ) and Si(R 15 (R) 16 R 15 and R 16 Each can be independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, and substituted or unsubstituted C1-C 40 Groups containing heteroatoms, or R 15 and R 16 They can be joined to form one or more C3-C atoms, each having 5, 6, 7, or 8 ring atoms. 20 An alkyl group, a hydrocarbon ring, a substituted hydrocarbon ring, a heterocycle, or a substituted heterocycle, wherein the substituents on the ring can join to form an additional ring.

[0141] In some implementation schemes, E 2 Optional from C(R) 25 (R) 26 ), Si(R) 25 (R) 26 ) and C = C(R 25 (R) 26 R 25 and R 26 Each can be independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms and C1-C 40 Groups containing heteroatoms, or R 25 and R 26 They can be joined to form one or more C3-C atoms, each having 5, 6, 7, or 8 ring atoms. 20An alkyl group, a hydrocarbon ring, a substituted hydrocarbon ring, a heterocycle, or a substituted heterocycle, wherein the substituents on the ring can join to form an additional ring.

[0142] In some implementation schemes, E 1 and E 2 Independently selected from -CH2, -CMe2, -CEt2, -CHMe, -CHEt, -CPh2, -CHPh, -SiMe2, -SiEt2, -SiPh2 and -SiMePh, for example -CH2.

[0143] In some implementation schemes, E 1 Selected from CH2, CMe2, CEt2, CHMe, CHEt, CPh2, CHPh, SiMe2, SiEt2, SiPh2, SiMePh, and E 2 Selected from CH2, CMe2, CEt2, CHMe, CHEt, CPh2, CHPh, SiMe2, SiEt2, SiPh2, SiMePh, C=CH2, C=CMe2, C=CEt2, C=CPh2, C=CHMe, C=CHEt and C=CHPh.

[0144] In some implementation schemes, E 1 It is CH2 and E 2 Selected from CH2 and C=CMe2.

[0145] In at least one implementation, R 1 Selected from substituted or unsubstituted C6-C 40 Aryl groups, such as phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, isopropylphenyl, diisopropylphenyl, triisopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, tri-tert-butylphenyl, methylisopropylphenyl, methyl-tert-butylphenyl, ethyl-isopropylphenyl, ethyl-tert-butylphenyl, methylnaphthyl, ethylnaphthyl, isopropylnaphthyl, and tert-butylnaphthyl. Alternatively, R 1 It is selected from all isomers of methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

[0146] In some implementation schemes, R 1 It is selected from 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl and 2,6-diisopropyl-4-methylphenyl.

[0147] In some implementation schemes, R 2 R 3 and R 4 Each is independently selected from hydrogen, C1-C40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms and C1-C 40 Groups containing heteroatoms, or R 2 and R 3 Or R 3 and R 4 One or more pairs of rings may join to form one or more hydrocarbon rings, substituted hydrocarbon rings, heterocycles, or substituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may join to form additional rings. In at least one embodiment, R 2 R 3 and R 4 Each is independently selected from hydrogen and C1-C 10 Alkyl group. In at least one embodiment, R 2 R 3 and R 4 Each is independently selected from all isomers of hydrogen, methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

[0148] In at least one embodiment, A of formula (II) 2 It can be expressed by the following formula:

[0149]

[0150] Where R 11 R 12 R 13 and R 14 Each is independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, and substituted or unsubstituted C1-C 40 A group containing heteroatoms. In at least one embodiment, R 11 R 12 R 13 and R 14 Each is independently selected from hydrogen and C1-C 10 Alkyl group. In at least one embodiment, R 11 R 12 R 13 and R 14 Each is independently selected from all isomers of hydrogen, methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. In some embodiments, R 11 C5-C 30 cycloalkyl or C5-C 30Substituted cycloalkyl groups, such as cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, fluorenyl, 9-methylfluorenyl, adamantyl, or substituted adamantyl. In some embodiments, R 11 It can be C1-C 10 Alkyl groups, such as tert-butyl, tert-pentyl, and tert-octyl (2,4,4-trimethylpentyl-2-yl), or R 11 It can be a heteroatom-containing group, such as trimethylsilyl, carbazole-9-yl, or a substituted carbazole-9-yl. Alternatively, R 11 It can be aryl or substituted aryl, for example, for R 1 Defined. In some implementations, R 13 It is C1-C 20 Hydrocarbon groups, such as methyl, tert-butyl, n-octyl, etc.

[0151] In some implementation schemes, R 11 It is selected from tert-butyl, adamantyl, substituted adamantyl, carbazole-9-yl, substituted carbazole-9-yl, fluorene-9-yl, substituted fluorene-9-yl, phenyl and substituted phenyl.

[0152] In some implementation schemes, R 11 It is selected from tert-butyl, adamantyl, 3-methyladamantane-1-yl, 3,5-dimethyladamantane-1-yl, carbazole-9-yl, 2,7-di-tert-butylcarbazole-9-yl, fluorene-9-yl, 9-methylfluorene-9-yl, phenyl, 3,5-di-tert-butylphenyl, 3,5-diisopropylphenyl and 3,5-dimethylphenyl.

[0153] In some implementation schemes, R 13 Selected from methyl or tert-butyl.

[0154] In some implementations, the catalyst may be represented by formula (III):

[0155] (III)

[0156] in:

[0157] M is a transition metal or lanthanide metal belonging to Groups 3, 4, 5, or 6;

[0158] E 1 Selected from hydrocarbon groups, substituted hydrocarbon groups, and silyl hydrocarbon groups;

[0159] E 2 Selected from hydrocarbon groups, substituted hydrocarbon groups, and silyl hydrocarbon groups, wherein E 2 Optionally fused with a Lewis base to form one or more hydrocarbon rings, substituted hydrocarbon rings, heterocycles, or substituted heterocycles;

[0160] Each L is an independent Lewis base;

[0161] Each X is an anionic ligand independently;

[0162] n is 1, 2, or 3;

[0163] m is 0, 1, or 2;

[0164] n+m is not greater than 4;

[0165] R 1 Selected from C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups and substituted or unsubstituted C1-C 40 Groups containing heteroatoms;

[0166] Each R 2 R 3 R 4 R 11 R 12 R 13 and R 14 Independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups and substituted or unsubstituted C1-C 40 Groups containing heteroatoms;

[0167] Any two L groups can bond together to form a bidentate Lewis base;

[0168] The X group can combine with the L group to form a monoanionic bidentate group; and

[0169] Any two X groups can join together to form a bianionic ligand group.

[0170] In at least one embodiment, the catalyst compound represented by formula (III) is characterized by a seven-membered and a five-membered metal ring. The seven-membered metal ring comprises an atom from metal M, a phenolic oxygen atom, two atoms of an aryl group, and a hydrocarbon group or a substituted hydrocarbon group E. 2 One atom from the metal M and two atoms from the bridging Lewis base. The pentagonal metal ring contains an atom from the metal M, nitrogen, and an atom from a hydrocarbon group or a substituted hydrocarbon group E. 1 The atoms and two atoms from the bridging Lewis base.

[0171] In some implementations, metal M is a Group 4 metal, such as zirconium or hafnium.

[0172] In at least one embodiment, each L of the catalyst represented by formula (III) can be independently selected from ethers, amines, phosphine, thioethers, esters, Et2O, MeO tBu, Et3N, PhNMe2, MePh2N, tetrahydrofuran, and dimethyl sulfide. In at least one embodiment, the catalyst represented by formula (III) has m = 0. In at least one embodiment, each X of the catalyst represented by formula (III) may be independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydroxyl, chlorine, fluorine, bromine, iodine, trifluoromethanesulfonate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino, such as chlorine, such as methyl. In at least one embodiment, the catalyst represented by formula (III) has n = 2.

[0173] In some embodiments, X is selected from methyl or benzyl, n is 2, and m is zero.

[0174] In some implementation schemes, E 1 Can be selected from C(R) 15 (R) 16 ) and Si(R 15 (R) 16 R 15 and R 16 Each can be independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, and substituted or unsubstituted C1-C 40 Groups containing heteroatoms, or R 15 and R 16 They can be joined to form one or more C3-C atoms, each having 5, 6, 7, or 8 ring atoms. 20 An alkyl group, a hydrocarbon ring, a substituted hydrocarbon ring, a heterocycle, or a substituted heterocycle, wherein the substituents on the ring can join to form an additional ring.

[0175] In some implementation schemes, E 2 Can be selected from C(R) 25 (R) 26 ), Si(R) 25 (R) 26 ) and C = C(R 25 (R) 26 R 25 and R 26 Each can be independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, and substituted or unsubstituted C1-C 40 Groups containing heteroatoms, or R 25 and R 26 They can be joined to form one or more C3-C atoms, each having 5, 6, 7, or 8 ring atoms. 20An alkyl group, a hydrocarbon ring, a substituted hydrocarbon ring, a heterocycle, or a substituted heterocycle, wherein the substituents on the ring can join to form an additional ring.

[0176] In some implementation schemes, E 1 and E 2 Independently selected from -CH2, -CMe2, -CEt2, -CHMe, -CHEt, -CPh2, -CHPh, -SiMe2, -SiEt2, -SiPh2 and -SiMePh, for example -CH2.

[0177] In some implementation schemes, E 1 Selected from CH2, CMe2, CEt2, CHMe, CHEt, CPh2, CHPh, SiMe2, SiEt2, SiPh2, and SiMePh, and E 2 Selected from CH2, CMe2, CEt2, CHMe, CHEt, CPh2, CHPh, SiMe2, SiEt2, SiPh2, SiMePh, C=CH2, C=CMe2, C=CEt2, C=CPh2, C=CHMe, C=CHEt and C=CHPh.

[0178] In some implementation schemes, E 1 It is CH2 and E 2 Selected from CH2 and C=CMe2.

[0179] In at least one implementation, R 1 Selected from substituted or unsubstituted C6-C 40 Aryl groups, such as phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, isopropylphenyl, diisopropylphenyl, triisopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, tri-tert-butylphenyl, methylisopropylphenyl, methyl-tert-butylphenyl, ethyl-isopropylphenyl, ethyl-tert-butylphenyl, methylnaphthyl, ethylnaphthyl, isopropylnaphthyl, and tert-butylnaphthyl. Alternatively, R 1 It is selected from all isomers of methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

[0180] In some implementation schemes, R 1 It is selected from 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl and 2,6-diisopropyl-4-methylphenyl.

[0181] In some implementation schemes, R 2 R 3 and R 4 Each is independently selected from hydrogen, C1-C40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, and substituted or unsubstituted C1-C 40 Groups containing heteroatoms, or R 2 and R 3 Or R 3 and R 4 One or more pairs of rings can join to form one or more hydrocarbon rings, substituted hydrocarbon rings, heterocycles, or substituted heterocycles having 5, 6, 7, or 8 ring atoms, wherein substituents on the rings can join to form additional rings. In at least one embodiment, R 2 R 3 and R 4 Each is independently selected from hydrogen and C1-C 10 Alkyl group. In at least one embodiment, R 2 R 3 and R 4 Each is independently selected from all isomers of hydrogen, methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

[0182] In some implementation schemes, R 11 R 12 R 13 and R 14 Each is independently selected from hydrogen, substituted or unsubstituted C1-C. 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms and C1-C 40 A group containing heteroatoms. In at least one embodiment, R 11 R 12 R 13 and R 14 Each is independently selected from hydrogen and C1-C 10 Alkyl group. In at least one embodiment, R 11 R 12 R 13 and R 14 Each is independently selected from all isomers of hydrogen, methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. In some embodiments, R 11 It is C5-C 30 cycloalkyl or C5-C 30 Substituted cycloalkyl groups, such as cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, fluorenyl, 9-methylfluorenyl, adamantyl, or substituted adamantyl. In some embodiments, R 11 It can be C1-C 10 Alkyl groups, such as tert-butyl, tert-pentyl, and tert-octyl (2,4,4-trimethylpentyl-2-yl), or R 11It can be a heteroatom-containing group, such as trimethylsilyl, carbazole-9-yl, or a substituted carbazole-9-yl. Alternatively, R 11 It can be aryl or substituted aryl, such as for R 1 As defined. In some implementations, R 13 It is C1-C 20 Hydrocarbon groups, such as methyl, tert-butyl, n-octyl, etc.

[0183] In some implementation schemes, R 11 It is selected from tert-butyl, adamantyl, substituted adamantyl, carbazole-9-yl, substituted carbazole-9-yl, fluorene-9-yl, substituted fluorene-9-yl, phenyl and substituted phenyl.

[0184] In some implementation schemes, R 11 It is selected from tert-butyl, adamantyl, 3-methyladamantane-1-yl, 3,5-dimethyladamantane-1-yl, carbazole-9-yl, 2,7-di-tert-butylcarbazole-9-yl, fluorene-9-yl, 9-methylfluorene-9-yl, phenyl, 3,5-di-tert-butylphenyl, 3,5-diisopropylphenyl and 3,5-dimethylphenyl.

[0185] In some implementation schemes, R 13 Selected from methyl or tert-butyl.

[0186] In some implementations, the catalyst can be represented by formula (IV):

[0187] (IV)

[0188] in:

[0189] M is a transition metal or lanthanide metal belonging to Groups 3, 4, 5, or 6;

[0190] A 2 Selected from aryl, substituted aryl, heteroaryl and substituted heteroaryl;

[0191] E 1 Selected from hydrocarbon groups, substituted hydrocarbon groups, and substituted or unsubstituted silyl hydrocarbon groups;

[0192] Each L is independently a Lewis base;

[0193] Each X is an anionic ligand independently;

[0194] n is 1, 2, or 3;

[0195] m is 0, 1, or 2;

[0196] n+m is not greater than 4;

[0197] R 1 Selected from C1-C40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups and substituted or unsubstituted C1-C 40 Groups containing heteroatoms;

[0198] R 2 R 3 R 6 R 7 and R 8 Each is independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, substituted or unsubstituted C1-C 40 Groups containing heteroatoms;

[0199] Any two L groups can bond together to form a bidentate Lewis base;

[0200] The X group can combine with the L group to form a monoanionic bidentate group; and

[0201] Any two X groups can join together to form a bianionic ligand group.

[0202] In at least one embodiment, the catalyst compound represented by formula (IV) is characterized by a seven-membered and a five-membered metal ring. The seven-membered metal ring contains an atom from metal M, a phenolic oxygen, an aryl group, or a substituted aryl group A. 2 The five-membered metal ring contains two atoms from metal M, nitrogen, and three atoms from a bridging Lewis base fused with a hydrocarbon group or a substituted hydrocarbon group E. 1 The atom and two atoms from the bridging Lewis base.

[0203] In some implementations, metal M is a Group 4 metal, such as zirconium or hafnium.

[0204] In at least one embodiment, each L of the catalyst represented by formula (IV) can be independently selected from ethers, amines, phosphine, thioethers, esters, Et2O, MeO t Bu, Et3N, PhNMe2, MePh2N, tetrahydrofuran, and dimethyl sulfide. In at least one embodiment, m of the catalyst represented by formula (IV) is 0. In at least one embodiment, each X of the catalyst represented by formula (IV) may be independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydroxyl, chlorine, fluorine, bromine, iodine, trifluoromethanesulfonate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino, such as chlorine, such as methyl. In at least one embodiment, n of the catalyst represented by formula (IV) is 2.

[0205] In some embodiments, X is selected from methyl or benzyl, n is 2, and m is zero.

[0206] In some implementation schemes, E 1 Can be selected from C(R) 15 (R) 16 ) and Si(R 15 (R) 16 R 15 and R 16 Each can be independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, and substituted or unsubstituted C1-C 40 Groups containing heteroatoms, or R 15 and R 16 They can be joined to form one or more C3-C atoms, each having 5, 6, 7, or 8 ring atoms. 20 An alkyl group, a hydrocarbon ring, a substituted hydrocarbon ring, a heterocycle, or a substituted heterocycle, wherein the substituents on the ring can join to form an additional ring.

[0207] E 1 The components are selected from CH2, CMe2, CEt2, CHMe, CHEt, CPh2, CHPh, SiMe2, SiEt2, SiPh2, and SiMePh, with CH2 being the most preferred.

[0208] In at least one implementation, R 1 Selected from substituted or unsubstituted C6-C 40 Aryl groups, such as phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, isopropylphenyl, diisopropylphenyl, triisopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, tri-tert-butylphenyl, methylisopropylphenyl, methyl-tert-butylphenyl, ethyl-isopropylphenyl, ethyl-tert-butylphenyl, methylnaphthyl, ethylnaphthyl, isopropylnaphthyl, and tert-butylnaphthyl. Alternatively, R 1 It is selected from all isomers of methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

[0209] In some implementation schemes, R 1 It is selected from 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl and 2,6-diisopropyl-4-methylphenyl.

[0210] In some implementation schemes, R 2 R 3 R 6 R 7 and R8 Each is independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, and substituted or unsubstituted heteroatom-containing groups, or R 6 and R 7 Or R 7 and R 8 Or R 2 and R 3 Or R 3 and R 6 One or more pairs of rings may join to form one or more hydrocarbon rings, substituted hydrocarbon rings, heterocycles, or substituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may join to form additional rings. In at least one embodiment, R 2 R 3 R 6 R 7 and R 8 Each is independently selected from hydrogen and C1-C 10 Alkyl group. In at least one embodiment, R 2 R 3 R 6 R 7 and R 8 Each is independently selected from all isomers of hydrogen, methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

[0211] In some implementations, A of formula (IV) 2 It can be expressed by the following formula:

[0212]

[0213] Where R 11 R 12 R 13 and R 14 Each is independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, and substituted or unsubstituted C1-C 40 A group containing heteroatoms. In at least one embodiment, R 11 R 12 R 13 and R 14 Each is independently selected from hydrogen and C1-C 10 Alkyl group. In at least one embodiment, R 11 R 12 R 13 and R 14Each is independently selected from all isomers of hydrogen, methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. In some embodiments, R 11 It is C5-C 30 cycloalkyl or C5-C 30 Substituted cycloalkyl groups, such as cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, fluorenyl, 9-methylfluorenyl, adamantyl, or substituted adamantyl. In some embodiments, R 11 It can be C1-C 10 Alkyl groups, such as tert-butyl, tert-pentyl, and tert-octyl (2,4,4-trimethylpentyl-2-yl), or R 11 It can be a heteroatom-containing group, such as trimethylsilyl, carbazole-9-yl, or a substituted carbazole-9-yl. Alternatively, R 11 It can be aryl or substituted aryl, for example, as in R 1 As defined. In some implementations, R 13 It is C1-C 20 Hydrocarbon groups, such as methyl, tert-butyl, n-octyl, etc.

[0214] In some implementation schemes, R 11 It is selected from tert-butyl, adamantyl, substituted adamantyl, carbazole-9-yl, substituted carbazole-9-yl, phenyl or substituted phenyl.

[0215] In some implementation schemes, R 11 It is selected from tert-butyl, adamantyl, 3-methyladamantane-1-yl, 3,5-dimethyladamantane-1-yl, carbazole-9-yl, 2,7-di-tert-butylcarbazole-9-yl, fluorene-9-yl, 9-methylfluorene-9-yl, phenyl, 3,5-di-tert-butylphenyl, 3,5-diisopropylphenyl, 3,5-dimethylphenyl.

[0216] In some implementation schemes, R 13 Selected from methyl or tert-butyl.

[0217] In some implementations, the catalyst can be represented by formula (V):

[0218] (V)

[0219] in:

[0220] M is a transition metal or lanthanide metal belonging to Groups 3, 4, 5, or 6;

[0221] E 1 Selected from hydrocarbon groups, substituted hydrocarbon groups, and substituted or unsubstituted silyl hydrocarbon groups;

[0222] Each L is an independent Lewis base;

[0223] Each X is an anionic ligand independently;

[0224] n is 1, 2, or 3;

[0225] m is 0, 1, or 2;

[0226] n+m is not greater than 4;

[0227] R 1 Selected from C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups and substituted or unsubstituted C1-C 40 Groups containing heteroatoms;

[0228] R 2 R 3 R 6 R 7 R 8 R 11 R 12 R 13 and R 14 Each is independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups and substituted or unsubstituted C1-C 40 Groups containing heteroatoms;

[0229] Any two L groups can bond together to form a bidentate Lewis base;

[0230] The X group can combine with the L group to form a monoanionic bidentate group; and

[0231] Any two X groups can be joined together to form a bianionic ligand group.

[0232] In at least one embodiment, the catalyst compound represented by formula (V) is characterized by a seven-membered and a five-membered metal ring. The seven-membered metal ring comprises an atom from metal M, a phenolic oxygen atom, two atoms from an aryl group, and three atoms from a bridging Lewis base fused with a hydrocarbon group or a substituted hydrocarbon group. The five-membered metal ring comprises an atom from metal M, nitrogen, and a hydrocarbon group E from a hydrocarbon group or a substituted hydrocarbon group. 1 The atoms and two atoms from the bridging Lewis base.

[0233] In some implementations, metal M is a Group 4 metal, such as zirconium or hafnium.

[0234] In at least one embodiment, each L of the catalyst represented by formula (V) may be independently selected from ethers, amines, phosphine, thioethers, esters, Et2O, MeO tBu, Et3N, PhNMe2, MePh2N, tetrahydrofuran, and dimethyl sulfide. In at least one embodiment, the catalyst represented by formula (V) has m = 0. In at least one embodiment, each X of the catalyst represented by formula (V) may be independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydroxyl, chlorine, fluorine, bromine, iodine, trifluoromethanesulfonate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino, for example, chlorine, for example, methyl. In at least one embodiment, the catalyst represented by formula (V) has n = 2.

[0235] In some embodiments, X is selected from methyl or benzyl, n is 2, and m is zero.

[0236] In some implementation schemes, E 1 Optional from C(R) 15 (R) 16 ) and Si(R 15 (R) 16 R 15 and R 16 Each can be independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, and substituted or unsubstituted C1-C 40 Groups containing heteroatoms, or R 15 and R 16 They can be joined to form one or more C3-C atoms, each having 5, 6, 7 or 8 ring atoms. 20 An alkyl group, a hydrocarbon ring, a substituted hydrocarbon ring, a heterocycle, or a substituted heterocycle, wherein the substituents on the ring can join to form an additional ring.

[0237] E 1 The components are selected from CH2, CMe2, CEt2, CHMe, CHEt, CPh2, CHPh, SiMe2, SiEt2, SiPh2, and SiMePh, with CH2 being the most preferred.

[0238] In at least one implementation, R 1 Selected from substituted or unsubstituted C6-C 40 Aryl groups, such as phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, isopropylphenyl, diisopropylphenyl, triisopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, tri-tert-butylphenyl, methylisopropylphenyl, methyl-tert-butylphenyl, ethyl-isopropylphenyl, ethyl-tert-butylphenyl, methylnaphthyl, ethylnaphthyl, isopropylnaphthyl, and tert-butylnaphthyl. Alternatively, R 1It is selected from all isomers of methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

[0239] In some implementation schemes, R 1 It is selected from 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl and 2,6-diisopropyl-4-methylphenyl.

[0240] In some implementation schemes, R 2 R 3 R 6 R 7 and R 8 Each is independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups and substituted or unsubstituted heteroatom-containing groups, or R 6 and R 7 Or R 7 and R 8 Or R 2 and R 3 Or R 3 and R 6 One or more pairs of rings may join to form one or more hydrocarbon rings, substituted hydrocarbon rings, heterocycles, or substituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may join to form additional rings. In at least one embodiment, R 2 R 3 R 6 R 7 and R 8 Each is independently selected from hydrogen and C1-C 10 Alkyl group. In at least one embodiment, R 2 R 3 R 6 R 7 and R 8 Each is independently selected from all isomers of hydrogen, methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

[0241] In some implementation schemes, R 11 R 12 R 13 and R 14 Each is independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, and substituted or unsubstituted heteroatom-containing groups. In at least one embodiment, R 11 R 12 R 13 and R 14Each is independently selected from hydrogen and C1-C 10 Alkyl group. In at least one embodiment, R 11 R 12 R 13 and R 14 Each is independently selected from all isomers of hydrogen, methyl, ethyl and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. In some embodiments, R 11 For C1-C 20 A hydrocarbon group or a substituted hydrocarbon group, such as 9-methylfluorenyl. In some embodiments, R 11 C5-C 30 cycloalkyl or C5-C 30 Substituted cycloalkyl groups, such as cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, fluorenyl, 9-methylfluorenyl, adamantyl, or substituted adamantyl. In some embodiments, R 11 It can be C1-C 10 Alkyl groups, such as tert-butyl, tert-pentyl, and tert-octyl (2,4,4-trimethylpentyl-2-yl), or R 11 It can be a heteroatom-containing group, such as trimethylsilyl, carbazole-9-yl, or a substituted carbazole-9-yl. Alternatively, R 11 It can be aryl or substituted aryl, such as for R. 1 As defined. In some implementations, R 13 For C1-C 20 Hydrocarbon groups, such as methyl, tert-butyl, n-octyl, etc.

[0242] In some implementation schemes, R 11 It is selected from tert-butyl, adamantyl, substituted adamantyl, carbazole-9-yl, substituted carbazole-9-yl, fluorene-9-yl, substituted fluorene-9-yl, phenyl or substituted phenyl.

[0243] In some implementation schemes, R 11 It is selected from tert-butyl, adamantyl, 3-methyladamantane-1-yl, 3,5-dimethyladamantane-1-yl, carbazole-9-yl, 2,7-di-tert-butylcarbazole-9-yl, fluorene-9-yl, 9-methylfluorene-9-yl, phenyl, 3,5-di-tert-butylphenyl, 3,5-diisopropylphenyl or 3,5-dimethylphenyl.

[0244] In some implementation schemes, R 13 Selected from methyl or tert-butyl.

[0245] In one or more embodiments, the catalyst is selected from the group consisting of:

[0246]

[0247] catalyst system

[0248] In this article, the terms "co-catalyst" and "activator" are used interchangeably.

[0249] The catalyst system described herein may comprise the catalyst complexes and activators described above, such as aluminoxanes or noncoordinate anions, and may be formed by combining the catalyst components described herein with the activator in any manner known in the art (including optionally combining the catalyst and activator with a support (e.g., silica)). The catalyst system may also be added to or generated in solution polymerization or bulk polymerization (in monomers). The catalyst system disclosed herein may have one or more activators and one, two, or more catalyst compounds. An activator is defined as any compound that can activate any of the catalyst compounds described above by converting a neutral metal compound into a catalytically active metal compound cation. Non-limiting activators may include, for example, aluminoxanes, alkylaluminum, ionized activators (which may be neutral or ionic), and conventional types of co-catalysts. Suitable activators may include aluminoxane compounds, modified aluminoxane compounds, and ionized anion precursor compounds that abstract reactive, α-bound metal ligands, such that the metal compound becomes a cationized and charge-balanced noncoordinate or weakly coordinated anion, such as a noncoordinate anion.

[0250] In at least one embodiment, the catalyst system comprises one or more catalyst compounds and activator compounds represented by formulas (I), (II), (III), (IV), and (V) above. The activator compounds may include, but are not limited to, aluminoxane catalysts and ionized / non-coordinated anionic activators.

[0251] Aluminoxane activator

[0252] Aluminoxane activators are used as activators in the catalyst systems described herein. Aluminoxanes are typically oligomers containing -Al(Ra”)-O- subunits, where Ra”’’ is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, particularly when the abstractable ligand is alkyl, halogen, alkoxy, or amino (amide). Mixtures of different aluminoxanes and modified aluminoxanes can also be used. Visually clear methylaluminoxanes are preferred. Turbid or gelled aluminoxanes can be filtered to produce a clear solution, or clear aluminoxane can be decanted from a turbid solution. A useful aluminoxane is modified methylaluminoxane (MMAO) cocatalyst type 3A (commercially available under the trade name Modified Methylalumoxane type 3A from Akzo). Chemicals, Inc. (which is included in U.S. Patent No. 5,041,584, which is incorporated herein by reference). Other available aluminoxanes are solid polymethylaluminoxanes as described in U.S. Patent Nos. 9,340,630, 8,404,880, and 8,975,209, which are incorporated herein by reference.

[0253] When the activator is an aluminoxane (modified or unmodified), at least one embodiment selects a maximum amount of activator of up to 5,000 molar excess Al / M of catalyst compound (per metal catalytic site). The minimum activator-to-catalyst compound ratio can be 1:1 molar ratio. Possible ranges include about 1:1 to about 500:1, for example about 1:1 to about 200:1, for example about 1:1 to about 100:1, for example about 1:1 to about 50:1.

[0254] In alternative embodiments, a small amount or no aluminoxane is used in the polymerization method described herein. For example, the aluminoxane may be present at zero molar %, or alternatively, the aluminoxane may be present at a molar ratio of aluminum to the transition metal of the catalyst compound of less than about 500:1, for example less than about 300:1, for example less than about 100:1, for example less than about 1:1.

[0255] Ionized / noncoordinated anion activators

[0256] The term "noncoordinate anion" (NCA) means an anion that does not coordinate with a cation or only weakly coordinates to a cation, thus retaining sufficient activity to be replaced by a Lewis base. "Compatible" noncoordinate anions are those that do not degrade to neutral when the initially formed complex decomposes. Furthermore, the anion does not transfer anionic substituents or fragments to the cation, resulting in the formation of neutral transition metal compounds and neutral byproducts from the anion. Noncoordinate anions useful according to this disclosure are those that are compatible, stabilize transition metal cations (in the sense of balancing the ionic charge of the transition metal cation to +1), and still retain sufficient activity to allow substitution during polymerization. Ionizing activators available herein typically include NCAs, particularly compatible NCAs.

[0257] In some embodiments, the activator is an ionized activator, neutral or ionic. In some embodiments of this disclosure, the neutral or ionic activator may be used alone or in combination with an aluminoxane or modified aluminoxane activator.

[0258] In some embodiments, the catalyst system of this disclosure may comprise at least one noncoordinate anionic (NCA) activator. In at least one embodiment, a boron-containing NCA activator may be used, wherein the boron-containing NCA activator is represented by the following formula:

[0259] (Z) d + (A d- )

[0260] Where: Z is (LH) or a reducible Lewis acid; L is a Lewis base; H is hydrogen; (LH) is a Brønsted acid; A d- It is a boron-containing noncoordinate anion with charge d-; d is 1, 2 or 3.

[0261] Cation component Z d + It may include Brønsted acids, such as protonated or protonated Lewis bases, or reducible Lewis acids that can protonate bulky ligand transition metal catalyst precursors or abstract structural moieties such as alkyl or aryl from bulky ligand transition metal catalyst precursors, thereby producing cationic transition metal substances.

[0262] Activated cation Z d + It can also be a structural component of materials such as silver, tropylium, carbenium, ferrocenium, and mixtures such as carbenium and ferrocenium. d + It can be a triphenylcarbene. Reducible Lewis acids can be triarylcarbenes (where the aryl group can be substituted or unsubstituted, for example, those represented by the following formula: (Ar3C)+ ), where Ar is an aryl group or a heteroatom, C1-C 40 Hydrocarbon group or substituted C1-C 40 Hydrocarbon-substituted aryl groups, such as reducible Lewis acids “Z”, may include those represented by the formula: (Ph3C), where Ph is a substituted or unsubstituted phenyl group, for example, a phenyl group with C1-C2 substituted aryl groups. 40 Hydrocarbon group or substituted C1-C 40 Hydrocarbon groups (e.g., C1-C) 20 Alkyl or aryl or substituted C1-C 20 Alkyl or aryl substitution, for example, Z is triphenylcarbazide. When Z d + To activate the cation (LH) d + When present, it can be a Brønsted acid, capable of donating protons to transition metal catalytic precursors to generate transition metal cations, including ammonium, oxonium, phosphoronium, silaneonium and mixtures thereof, such as methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, ammonium from octadecylmethylamine, phosphoronium from triethylphosphine, triphenylphosphine and diphenylphosphine, oxonium from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, and matte from sulfides such as diethyl sulfide, tetrahydrothiophene and mixtures thereof.

[0263] Anionic component A d- Including those with the formula [M] k+ Q n ] d- Those, where k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (e.g., 1, 2, 3, or 4); nk = d; M is an element selected from Group 13 of the periodic table, such as boron or aluminum, and Q is independently a hydrogen group, a bridged or non-bridged dialkylamino group, a halogroup, an alkoxy group, an aryloxy group, a hydrocarbon group, a substituted hydrocarbon group, a haloalkyl group, a substituted haloalkyl group, and a halogen-substituted hydrocarbon group, wherein Q has at most 20 carbon atoms, provided that the number of times Q is a halogroup does not exceed 1. Each Q can be a fluorinated hydrocarbon group having 1-20 carbon atoms, for example, each Q is a fluorinated aryl group, and for example, each Q is a pentafluorinated aryl group. Suitable A d- Examples also include diboron compounds such as those disclosed in U.S. Patent No. 5,447,895, which is incorporated herein by reference in its entirety.

[0264] Illustrative but non-limiting examples of boron compounds that can be used as activation cocatalysts are compounds described (and particularly enumerated) as activators in U.S. Patent No. 8,658,556, which is incorporated herein by reference.

[0265] Ionic stoichiometric activator Z d + ( A d- ) It can be one or more of the following compounds:

[0266] N,N-Dimethylphenylamine tetra(perfluorophenyl)borate, N,N-Dimethylphenylamine tetra(perfluoronaphthyl)borate, bis(octadecylmethylammonium tetra(perfluorophenyl)borate, N,N-Dimethylphenylamine tetra(perfluorobiphenyl)borate, N,N-Dimethylphenylamine tetra(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbazide tetra(perfluoronaphthyl)borate, triphenylcarbazide tetra(perfluorobiphenyl)borate, triphenylcarbazide tetra(3,5-bis(trifluoromethyl)phenyl)borate or triphenylcarbazide tetra(perfluorophenyl)borate.

[0267] Alternatively, the activator compound is represented by formula (AI):

[0268] [R 1 R 2 R 3 EH] d + [M k+ Q n ] d- (AI)

[0269] in:

[0270] E is either nitrogen or phosphorus, with nitrogen being preferred;

[0271] d is 1, 2 or 3 (preferably 3); k is 1, 2 or 3 (preferably 3); n is 1, 2, 3, 4, 5 or 6 (preferably 4, 5 or 6); nk = d (preferably d is 1, 2 or 3; k is 3; n is 4, 5 or 6, preferably n is 4 when M is B);

[0272] R 1 R 2 and R 3 Each is independently H, or an optional substituted C1-C 40 Alkyl (e.g., branched or linear alkyl) or optionally substituted C6-C 50 Aryl (optional R) 1 R 2 and R 3 Each is independently unsubstituted or substituted with at least one of the following: halogen, C6-C 50 Aryl, C7-C 35 Arylalkyl, C7-C 35 alkyl aryl and in C6-C 50 In the case of aryl, C1-C50 Alkyl); wherein R 1 R 2 and R 3 Together comprising 15 or more carbon atoms (e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 37 or more carbon atoms, e.g., 40 or more carbon atoms, e.g., 45 or more carbon atoms), preferably R 1 R 2 and R 3 At least one of them is C3-C 40 Hydrocarbon groups (e.g., C3-C) 40 Alkyl, optionally C7-C 40 alkyl);

[0273] M is an element selected from Group 13 of the periodic table, such as B or Al, and

[0274] Each Q is independently a hydrogen group, a bridged or unbridged dialkylamino group, a halogen group, an alkoxy group, an aryloxy group, a hydrocarbon group, a substituted hydrocarbon group, a halogenated hydrocarbon group, a substituted halogenated hydrocarbon group, or a halogenated hydrocarbon group, such as a fluoroaryl group, such as a fluorophenyl group, or a fluoronaphthyl group, such as a perfluorophenyl group, or a perfluoronaphthyl group.

[0275] In some implementations of the formula (AI), R 1 R 2 and R 3 Each is independently selected from substituted linear alkyl groups, substituted branched alkyl groups, substituted aryl alkyl groups, substituted silyl alkyl groups, substituted alkoxy groups, halogen groups, halogen-containing groups, and combinations thereof.

[0276] In some embodiments, the substituted linear alkyl group may include, but is not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-heptadecyl, n-heptadecyl, n-heptadecyl, n-heptadecyl, n-heptadecyl, n-heptadecyl, n-heptadecyl, n-heptadecyl, n-heptadecyl, n-heptadecyl, n-heptadecyl, n-heptadecyl, and any of their isomers.

[0277] In some embodiments, the substituted branched alkyl groups may include, but are not limited to, alkylbutyl, alkylpentyl, alkylhexyl, alkylheptyl, alkyloctyl, alkylnonyl, alkyldecyl, alkylundecyl, alkyldodecyl, alkyltridecyl, alkyltetradecyl, alkylpentadecanyl, alkylhexadecyl, alkylheptadecyl, alkylheptadecyl, alkyloctadecyl, alkylnonadecanyl, alkyleicosyl and their isomers. In some embodiments, the substituted branched alkyl group is a polyalkyl analogue, such as dialkylbutyl, dialkylpentyl, dialkylhexyl, dialkylheptyl, dialkyloctyl, dialkylnonyl, dialkyldecyl, dialkylundecyl, dialkyldodecyl, dialkyltridecyl, dialkyltetradecyl, dialkylpentadedecyl, dialkylhexadecyl, dialkylheptadecyl, dialkyloctadecyl, dialkylnonadedecyl, dialkylbutanedecyl, trialkylpentyl, trialkylhexanedecyl, trialkylhexadecyl, trialkylhexadecyl, trialkyloctadecyl, trialkyloctadecyl, trialkylheptadecyl, trialkyloctadecyl, trialkyloctadecyl, trialkyleicosyl, and isomers thereof. In some embodiments, the substituted branched alkyl group is independently C1-C1. 40 Linear, branched or cyclic alkyl groups, such as C2-C 30 Linear, branched or cyclic alkyl groups, such as C3-C 20 Linear, branched, or cyclic alkyl groups. In some embodiments, the substituted branched alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecanyl, triadecyl, and their isomers.

[0278] In some embodiments, the substituted arylalkyl groups include methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, tridecylphenyl, tetradecylphenyl, pentadecylphenyl, hexadecylphenyl, heptadecanylphenyl, heptadecanylphenyl, octadecylphenyl, nonadecanylphenyl, eicosylphenyl, dodecylphenyl, tridecylphenyl, tetradecylphenyl, pentadecylphenyl, hexadecylphenyl, heptadecanylphenyl, octadecylphenyl, nonadecanylphenyl, triadecylphenyl, 3,5,5-trimethylhexylphenyl, dioctylphenyl, 3,3,5-trimethylhexylphenyl, 2,2,3,3,4-pentamethylpentylphenyl, and their isomers.

[0279] In some embodiments, the substituted silyl groups include trialkylsilyl groups, wherein each alkyl group is independently substituted C1-C. 20 Alkyl groups, such as trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, trinonylsilyl, tridecylsilyl, triundecylsilyl, tridodecylsilyl, tridecaylsilyl, tritetradecylsilyl, tridecylsilyl, tritetradecylsilyl, tridecylsilyl, tridecylsilyl, tridecylsilyl, tridecylsilyl, trihexadecylsilyl, trihexadecylsilyl, triheptadecylsilyl, trioctadecylsilyl, trinonylsilyl, trieicosylsilyl and their isomers.

[0280] In some implementations, the substituted alkoxy group can be represented by the formula -OR It means that R Including the replacement of C1-C 20 Alkyl or aryl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, phenyl, naphthyl, anthracene, and combinations thereof. In some embodiments, R It may include alkylphenyl groups, such as methylphenyl, propylphenyl and their isomers.

[0281] In some embodiments, the halogens include Br and Cl. In some embodiments, the halogen-containing groups include bromomethyl and bromophenyl.

[0282] In some implementations, the NCA may include one or more of the following:

[0283] N,N-Di(hydrogenated tallowyl)methylammonium [tetra(perfluorophenyl)borate],

[0284] N-Methyl-4-nonadecanyl-N-octadecylphenylammonium [tetra(perfluorophenyl)borate],

[0285] N-Methyl-4-hexadecyl-N-octadecylphenylammonium [tetra(perfluorophenyl)borate],

[0286] N-Methyl-4-tetradecyl-N-octadecylphenylammonium [tetra(perfluorophenyl)borate],

[0287] N-Methyl-4-dodecyl-N-octadecylphenylammonium [tetra(perfluorophenyl)borate],

[0288] N-Methyl-4-decyl-N-octadecylphenylammonium [tetra(perfluorophenyl)borate],

[0289] N-Methyl-4-octyl-N-octadecylphenylammonium [tetra(perfluorophenyl)borate],

[0290] N-Methyl-4-hexyl-N-octadecylphenylammonium [tetra(perfluorophenyl)borate],

[0291] N-Methyl-4-butyl-N-octadecylphenylammonium [tetra(perfluorophenyl)borate],

[0292] N-Methyl-4-octadecyl-N-decylphenylammonium [tetra(perfluorophenyl)borate],

[0293] N-Methyl-4-nonadecanyl-N-dodecylphenylammonium [tetra(perfluorophenyl)borate],

[0294] N-Methyl-4-nonadecanyl-N-tetradecylphenylammonium [tetra(perfluorophenyl)borate],

[0295] N-Methyl-4-nonadecanyl-N-hexadecylphenylammonium [tetra(perfluorophenyl)borate],

[0296] N-Ethyl-4-nonadecanyl-N-octadecylphenylammonium [tetra(perfluorophenyl)borate],

[0297] N-Methyl-N,N-di-octadecylammonium [tetra(perfluorophenyl)borate],

[0298] N-Methyl-N,N-di-hexadecylammonium [tetra(perfluorophenyl)borate],

[0299] N-Methyl-N,N-di-tetradecylammonium [tetra(perfluorophenyl)borate],

[0300] N-Methyl-N,N-di-dodecylammonium [tetra(perfluorophenyl)borate],

[0301] N-Methyl-N,N-didecylammonium [tetra(perfluorophenyl)borate],

[0302] N-Methyl-N,N-dioctylammonium [tetra(perfluorophenyl)borate],

[0303] N-Ethyl-N,N-di-octadecylammonium [tetra(perfluorophenyl)borate],

[0304] N,N-Di(octadecyl)tolueneammonium [tetra(perfluorophenyl)borate],

[0305] N,N-Di(hexadecyl)tolueneammonium [tetra(perfluorophenyl)borate],

[0306] N,N-Di(tetradecyl)tolueneammonium [tetra(perfluorophenyl)borate],

[0307] N,N-Di(dodecyl)tolueneammonium [tetra(perfluorophenyl)borate],

[0308] N-Octadecyl-N-hexadecyl-tolueneammonium [tetra(perfluorophenyl)borate],

[0309] N-Octadecyl-N-hexadecyl-tolueneammonium [tetra(perfluorophenyl)borate],

[0310] N-Octadecyl-N-tetradecyl-tolueneammonium [tetra(perfluorophenyl)borate],

[0311] N-Octadecyl-N-dodecyl-tolueneammonium [tetra(perfluorophenyl)borate],

[0312] N-Octadecyl-N-decyl-tolueneammonium [tetra(perfluorophenyl)borate],

[0313] N-Hexadecyl-N-tetradecyl-tolueneammonium [tetra(perfluorophenyl)borate],

[0314] N-Hexadecyl-N-dodecyl-tolueneammonium [tetra(perfluorophenyl)borate],

[0315] N-Hexadecyl-N-decyl-tolueneammonium [tetra(perfluorophenyl)borate],

[0316] N-Tetradecyl-N-dodecyl-tolueneammonium [tetra(perfluorophenyl)borate],

[0317] N-Tetradecyl-N-decyl-tolueneammonium [tetra(perfluorophenyl)borate],

[0318] N-Dodecyl-N-decyl-tolueneammonium [tetra(perfluorophenyl)borate],

[0319] N-Methyl-N-octadecylphenylammonium [tetra(perfluorophenyl)borate],

[0320] N-Methyl-N-hexadecylphenylammonium [tetra(perfluorophenyl)borate],

[0321] N-Methyl-N-tetradecylphenylammonium [tetra(perfluorophenyl)borate],

[0322] N-Methyl-N-dodecylphenylammonium [tetra(perfluorophenyl)borate],

[0323] N-methyl-N-decylphenylammonium [tetra(perfluorophenyl)borate], and

[0324] N-Methyl-N-octylphenylammonium [tetra(perfluorophenyl)borate].

[0325] NCA activator

[0326] In some embodiments, the activator is selected from one or more triarylcarbium compounds, including triphenylcarbium tetraphenylborate, triphenylcarbium tetra(pentafluorophenyl)borate, triphenylcarbium tetra(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbium tetra(perfluoronaphthyl)borate, triphenylcarbium tetra(perfluorobiphenyl)borate, and triphenylcarbium tetra(3,5-bis(trifluoromethyl)phenyl)borate.

[0327] In another embodiment, the activator is selected from one or more of the following: trialkylammonium tetra(pentafluorophenyl)borate, N,N-dialkylphenylammonium tetra(pentafluorophenyl)borate, di-octadecylmethylammonium tetra(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylphenylammonium)tetra(pentafluorophenyl)borate, trialkylammonium tetra(2,3,4,6-tetrafluorophenyl)borate, N,N-dialkylphenylammonium tetra(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetra(perfluoronaphthyl)borate, N,N-dialkylphenylammonium tetra(perfluoronaphthyl)borate, trialkyl ... Fluorophenyl) borates, N,N-dialkylphenylammonium tetra(perfluorophenyl) borates, trialkylammonium tetra(3,5-bis(trifluoromethyl)phenyl) borates, N,N-dialkylphenylammonium tetra(3,5-bis(trifluoromethyl)phenyl) borates, N,N-dialkyl-(2,4,6-trimethylphenylammonium) tetra(3,5-bis(trifluoromethyl)phenyl) borates, di(isopropyl)ammonium tetra(pentafluorophenyl) borates, N-methyl-4-nonadecanyl-N-octadecylphenylammonium tetra(perfluoronaphth-2-yl) borates, N-methyl-4-nonadecanyl-N-octadecylphenylammonium tetra(perfluorophenyl) borates.

[0328] Suitable activator-to-catalyst ratios for catalyst systems with NCA activators can be approximately 1:1 molar ratio. In some embodiments, the activator-to-catalyst ratio is approximately 0.1:1 to approximately 100:1, for example, approximately 0.5:1 to approximately 200:1, for example, approximately 1:1 to approximately 500:1, for example, approximately 1:1 to approximately 1000:1. In some embodiments, the activator-to-catalyst ratio is approximately 0.5:1 to approximately 10:1, for example, approximately 1:1 to approximately 5:1.

[0329] In some embodiments, any one or more catalyst compounds, one or more aluminoxanes, one or more NCAs, and one or more activators can be combined in any amount or ratio to form a catalyst system to produce the desired results, such as, but not limited to, polymers having the desired structure, molecular weight, physical properties, thermal properties, and combinations thereof.

[0330] Optional scavengers and co-catalysts

[0331] In some embodiments, the catalyst system may include scavengers and / or co-activators. In some embodiments, alkyl aluminum and aluminum oxane compounds may be used as scavengers and / or co-activators, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), MMAO-3A, ​​diethylzinc, and combinations thereof.

[0332] Optional carrier material

[0333] In some implementations, the catalyst system may include an inert support material. The support material may be a porous support material, such as talc and inorganic oxides. Other support materials include zeolites, clays, organoclays, other organic or inorganic support materials, and combinations thereof.

[0334] In some embodiments, the support material may be a finely dispersed inorganic oxide. Suitable inorganic oxide materials for use in catalyst systems include Group 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides may be used alone or in combination with silica or alumina, including magnesium oxide, titanium oxide, zirconium oxide, and combinations thereof. Other suitable support materials may include finely dispersed functionalized polyolefins, such as finely dispersed polyethylene. Examples of suitable supports include magnesium oxide, titanium oxide, zirconium oxide, montmorillonite, layered silicates, zeolites, talc, clay, and combinations thereof. In some embodiments, combinations of these support materials may be used, such as silica-chromium, silica-alumina, and silica-titanium oxide. In at least one embodiment, the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica-clay, silica / clay, and combinations thereof.

[0335] In some implementations, the carrier material has a thickness of approximately 10m. 2 / g to approximately 700m 2 / g surface area, approximately 0.1cm 3 / g to approximately 4.0cm 3 The pore volume is approximately 5 μm / g, and the average particle size is approximately 500 μm to approximately 500 μm. The surface area of ​​the support material can be approximately 50 m². 2 / g to approximately 500m 2 / g, pore volume approximately 0.5cm³ 3 / g to approximately 3.5cm 3 / g, and the average particle size is from about 10 μm to about 200 μm. For example, the surface area of ​​the support material is about 100 m². 2 / g to approximately 400m 2 / g, pore volume is approximately 0.8cm³3 / g to approximately 3.0cm 3 / g, with an average particle size of about 5 μm to about 100 μm. In some embodiments, the average pore size is about 10 Å to about 1000 Å, for example about 50 Å to about 500 Å, and for example about 75 Å to about 350 Å. In at least one embodiment, the support material is amorphous silica with a high surface area of ​​about 300 μm. 2 / g surface area and approximately 1.65cm 3 / g pore volume.

[0336] The support material should be dry, i.e., free of absorbed water. In some embodiments, the support material is dried by heating or calcining at about 100°C to about 1,000°C, for example, about 600°C. When the support material is silica, it is heated to at least 200°C, for example, about 200°C to about 850°C, for example, about 600°C. The support material is dried for about 1 minute to about 100 hours, for example, about 12 hours to about 72 hours, for example, about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups to produce a supported catalyst system. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

[0337] A support material with reactive surface groups is slurried in a nonpolar solvent and then contacted with a solution of a catalyst compound and an activator. In at least one embodiment, the slurry of the support material is first contacted with the activator for a period of about 0.5 hours to about 24 hours, for example, about 2 hours to about 16 hours, or for example, about 4 hours to about 8 hours. Then, the solution of the catalyst compound is contacted with the separated support / activator. In at least one embodiment, a supported catalyst system is generated in situ. In some embodiments, the slurry of the support material is first contacted with the catalyst compound for a period of about 0.5 hours to about 24 hours, for example, about 2 hours to about 16 hours, or for example, about 4 hours to about 8 hours. Then, the slurry of the supported catalyst compound is contacted with the activator solution.

[0338] 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 components of the mixture are brought into contact for about 0.5 hours to about 24 hours, for example, about 2 hours to about 16 hours, for example, about 4 hours to about 8 hours.

[0339] A suitable nonpolar solvent is a material in which all reactants (e.g., activators and catalyst compounds) used herein are at least partially soluble and are liquid at the reaction temperature. Nonpolar solvents can be alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials may also be used, including cycloalkanes (e.g., cyclohexane) and aromatic compounds (e.g., benzene, toluene, and ethylbenzene).

[0340] Aggregation methods

[0341] The polymerization methods disclosed herein relate to the introduction of monomers and / or comonomers into a catalyst system comprising an activator and one or more catalyst compounds. The catalyst compounds and activators can be combined in any order. The catalyst compounds and activators can be combined prior to contact with the monomers. Alternatively, the catalyst compounds and activators can be introduced separately into the polymerization reactor, where they subsequently react to form an active catalyst.

[0342] In some embodiments, the monomer includes substituted or unsubstituted C2-C. 40 α-olefins, such as C2-C 20 α-olefins, such as C2-C 12 α-olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and their isomers. In at least one embodiment, the monomer comprises ethylene and optionally a comonomer, said comonomer comprising one or more C3-C... 40 Alkenes, such as C4-C 20 Alkenes, such as C6-C 12 Alkenes, such as 1-octene. C3-C 40 Olefin monomers can be linear, branched, or cyclic. (C3-C) 40 Cyclic olefins can be tensioned or non-tensioned, monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups. In another embodiment, the monomer comprises propylene and optionally a comonomer, said comonomer comprising one or more ethylene or C4-C... 40 Alkenes, such as C4-C 20 Alkenes, such as C6-C 12 Alkenes. C4-C 40 Olefin monomers can be linear, branched, or cyclic. (C4-C) 40 Cyclic alkenes can be tensile or non-tensile, monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups.

[0343] In some embodiments, the monomers and optional comonomers include one or more of the following: ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, their substituted derivatives and 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, ethylidene norbornene, vinyl norbornene, norbornene, norbornadiene and their corresponding homologues and derivatives, such as norbornene, norbornadiene and dicyclopentadiene.

[0344] The polymerizations disclosed herein can be carried out via any suitable polymerization technique, such as suspension polymerization, homogeneous polymerization, bulk polymerization, solution polymerization, slurry polymerization, and / or gas-phase polymerization. Such methods can be operated in batch, semi-batch, or continuous modes. In some embodiments, a bulk homogeneous method is used, wherein no solvent or diluent is present or added to the reaction medium. In some embodiments, a slurry method is used. As used herein, the term "slurry polymerization method" means a polymerization method carried out in a hydrocarbon solvent, wherein a supported catalyst is used, and the monomer is polymerized on supported catalyst particles at a temperature below the melting point of the resulting polymer.

[0345] In some embodiments, the polymerization method employs any one or more suitable diluents and solvents, which may be noncoordinate inert liquids, including straight-chain and branched hydrocarbons, cyclic and alicyclic hydrocarbons, and aromatic and alkyl-substituted aromatic compounds. In some embodiments, suitable solvents may also include one or more liquid olefins serving as monomers and / or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In at least one embodiment, an aliphatic hydrocarbon solvent is used as the solvent, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof, cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In other embodiments, the solvent is not aromatic, for example, the presence of an aromatic compound in the solvent is 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. In some embodiments, straight-chain and branched hydrocarbons may include, but are not limited to, any one or more of the following: isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and combinations thereof. In some embodiments, cyclic and acyclic hydrocarbons may include, but are not limited to, any one or more of the following: cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, perhalogenated hydrocarbons, perfluorinated C4-C hydrocarbons. 10 Alkanes, chlorobenzenes, and combinations thereof. In some embodiments, aromatic and alkyl-substituted aromatic compounds may include, but are not limited to, any one or more of the following: benzene, toluene, mesitylene, xylene, and combinations thereof.

[0346] In at least one embodiment, the feed concentration of the monomer and comonomer used for polymerization is 60 vol% solvent or less, for example 40 vol% or less, for example 20 vol% or less, based on the total volume of the feed stream. In at least one embodiment, polymerization is carried out using a bulk method.

[0347] Polymerization can be carried out at any temperature and / or pressure suitable for obtaining the desired polymer. In some embodiments, the temperature is from about 0°C to about 300°C, for example from about 20°C to about 200°C, for example from about 35°C to about 160°C, for example from about 80°C to about 160°C, for example from about 90°C to about 140°C. In some embodiments, the pressure is from about 0.1 MPa to about 25 MPa, for example from about 0.45 MPa to about 6 MPa, or from about 0.5 MPa to about 4 MPa.

[0348] In some implementations, suitable polymerization may have run times of about 300 minutes or less, such as about 5 minutes to 250 minutes, about 10 minutes to 120 minutes, about 20 minutes to 90 minutes, or about 30 minutes to 60 minutes. In continuous processes, run time can be considered as the average residence time of the reactor.

[0349] In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 0.001 psig to about 50 psig (about 0.007 kPa to about 345 kPa), for example about 0.01 psig to about 25 psig (about 0.07 kPa to about 172 kPa), for example about 0.1 psig to about 10 psig (about 0.7 kPa to about 70 kPa).

[0350] In at least one embodiment, the polymerization method uses a small amount or no aluminoxane. In some embodiments, the aluminoxane may be present at zero molar percentage. In some embodiments, the aluminoxane may be present at a molar ratio of aluminum to transition metal of less than about 500:1, for example less than about 300:1, for example less than about 100:1, for example less than about 1:1.

[0351] In at least one embodiment, polymerization is carried out at a temperature of about 0°C to about 300°C, for example, about 25°C to about 250°C, for example, about 80°C to 160°C, for example, about 100°C to about 140°C. In at least one embodiment, polymerization is carried out at a pressure range of about atmospheric pressure to about 10 MPa, for example, about 0.35 MPa to about 10 MPa, for example, about 0.45 MPa to about 6 MPa, for example, about 0.5 MPa to 4 MPa. In some embodiments, polymerization is carried out in one or more aliphatic, cyclic, and alicyclic hydrocarbon solvents, said hydrocarbon solvents including isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In some embodiments, the aromatic compound is present in the solvent in less than about 1% by weight, for example, less than about 0.5% by weight, for example, about 0% by weight, based on the weight of the solvent. In some embodiments, the catalyst system used in the polymerization comprises less than about 0.5 mol% of an aluminum oxane, for example, about 0 mol%. In some embodiments, the aluminum oxane is present in the catalyst system at a molar ratio of aluminum to transition metal of less than about 500:1, for example, less than about 300:1, for example, less than about 100:1, for example, less than about 1:1. In some embodiments, the polymerization is carried out in a reaction zone. In some embodiments, a scavenger is present in the catalyst system at a molar ratio of scavenger metal to transition metal of less than about 100:1, for example, less than about 50:1, for example, less than about 15:1, for example, less than about 10:1. In some embodiments, hydrogen is present in the polymerization reactor at a partial pressure range of about 0.001 psig to about 50 psig (about 0.007 kPa to about 345 kPa), for example, about 0.01 psig to about 25 psig (about 0.07 kPa to about 172 kPa), for example, about 0.1 psig to about 10 psig (about 0.7 kPa to about 70 kPa). In at least one embodiment, the catalyst system used in the polymerization comprises no more than one catalyst compound. A "reaction zone," also known as a "polymerization zone," is a container in which polymerization takes place, such as 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 is carried out in one reaction zone.

[0352] In at least one embodiment, this disclosure provides a method for producing vinyl polymers, wherein ethylene is polymerized by contacting a catalyst system with one or more continuous stirred tank reactors or loop reactors at a reactor pressure of about 0.05 MPa to about 1,500 MPa and a reactor temperature of about 30°C to about 230°C. In some embodiments, one or more continuous stirred tank reactors or loop reactors are in series, in parallel, or a combination of both. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure ranging from about 5 psig to about 300 psig, for example from about 10 psig to about 250 psig, for example from about 20 psig to about 200 psig, for example from about 30 psig to about 150 psig, for example from about 50 psig to 100 psig, for example from about 75 psig. In at least one embodiment, the catalyst activity is at least about 1,000 g P·mmolcat. -1 ·h -1 For example, approximately 1,000 g P·mmolcat -1 ·h -1 Approximately 10,000,000 gP·mmolcat -1 ·h -1 For example, approximately 1,500 g P·mmolcat -1 ·h -1 Approximately 8,000,000 gP·mmolcat -1 ·h -1 For example, approximately 1,800 gP·mmolcat -1 ·h -1 Approximately 1,000,000 gP·mmolcat -1 ·h -1 In at least one embodiment, the catalyst has an activity of about 10,000 gP·mmolcat. -1 ·h -1 Approximately 8,000,000 gP·mmolcat -1 ·h -1 .

[0353] In another embodiment, this disclosure provides a method for producing a propylene-based polymer, comprising: polymerizing propylene to form a propylene-based polymer by contacting propylene with the catalyst system of this disclosure described above in one or more continuous stirred tank reactors or loop reactors (in series or in parallel) at a reactor pressure of 0.5 MPa to 1,500 MPa and a reactor temperature of 30°C to 230°C. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 10 psig to about 300 psig, for example about 20 psig to about 250 psig, for example about 30 psig to about 200 psig, for example about 40 psig to about 150 psig, for example about 50 psig to about 100 psig (e.g., 75 psig). In at least one embodiment, the catalyst activity is at least 1,000 g P·mmolcat. -1 ·h -1 For example, 1,000 gP·mmolcat -1 ·h -1 Approximately 1,000,000 gP·mmolcat -1 ·h -1 For example, 2,000 gP·mmolcat -1 ·h -1 Approximately 3,000 gP·mmolcat -1 ·h -1 10,000 gP·mmolcat available -1 ·h -1 Approximately 750,000 gP·mmolcat -1 ·h -1 For example, 50,000 gP·mmolcat -1 ·h -1 Approximately 500,000 gP·mmolcat -1 ·h -1 For example, 100,000 gP·mmolcat -1 ·h -1 Approximately 250,000 gP·mmolcat -1 ·h -1 Approximately 1,000,000 gP·mmolcat is available as an option. -1 ·h -1 Approximately 6,000,000 gP·mmolcat -1 ·h -1 For example, approximately 2,000,000 gP·mmolcat -1 ·h -1 Approximately 4,000,000 gP·mmolcat -1 ·h -1.

[0354] In another embodiment, this disclosure provides a method for producing ethylene α-olefin copolymers, comprising: reacting ethylene and at least one C3-C4 copolymer in one or more continuous stirred tank reactors or loop reactors (in series or in parallel) at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30°C to 230°C. 20 α-olefins are contacted with the above catalyst system to react ethylene and at least one C3-C 20 α-olefin polymerization is performed to form an ethylene-α-olefin copolymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 10 psig to about 300 psig, for example about 20 psig to about 250 psig, for example about 30 psig to about 200 psig, for example about 40 psig to about 150 psig, for example about 50 psig to about 100 psig (e.g., 75 psig), and optionally about 150 psig to about 300 psig (e.g., 200 psig). In at least one embodiment, the catalyst has an activity of at least 1,000 g P·mmolcat. -1 ·h -1 For example, approximately 1,000 g P·mmolcat -1 ·h -1 Approximately 10,000,000 gP·mmolcat -1 ·h -1 For example, approximately 1,500 g P·mmolcat -1 ·h -1 Approximately 8,000,000 gP·mmolcat -1 ·h -1 For example, approximately 1,800 gP·mmolcat -1 ·h -1 Approximately 1,000,000 gP·mmolcat -1 ·h -1 The available selection is approximately 10,000 gP·mmolcat. -1 ·h -1 Approximately 8,000,000 gP·mmolcat -1 ·h -1 .

[0355] In another embodiment, this disclosure provides a method for producing propylene α-olefin copolymers, the method comprising: reacting propylene and at least one ethylene and / or at least one C3-C4 copolymer in one or more continuous stirred tank reactors or loop reactors (in series or in parallel) at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30°C to 230°C.20 α-olefins are contacted with the above catalyst system to react propylene with at least one ethylene and / or at least one C4-C 20 α-olefin polymerization is performed to form an ethylene-α-olefin copolymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 10 psig to about 300 psig, for example about 20 psig to about 250 psig, for example about 30 psig to about 200 psig, for example about 40 psig to about 150 psig, for example about 50 psig to about 100 psig (e.g., 75 psig), and optionally about 150 psig to about 300 psig (e.g., 200 psig). In at least one embodiment, the catalyst has an activity of at least 1,000 g P·mmolcat. -1 ·h -1 For example, approximately 1,000 g P·mmolcat -1 ·h -1 Approximately 10,000,000 gP·mmolcat -1 ·h -1 For example, approximately 1,500 g P·mmolcat -1 ·h -1 Approximately 8,000,000 gP·mmolcat -1 ·h -1 For example, approximately 1,800 gP·mmolcat -1 ·h -1 Approximately 1,000,000 gP·mmolcat -1 ·h -1 The available selection is approximately 10,000 gP·mmolcat. -1 ·h -1 Approximately 8,000,000 gP·mmolcat -1 ·h -1 .

[0356] In at least one embodiment, the conversion rate of the olefin monomer is at least about 10%, based on the polymer yield and the weight of the monomer entering the reaction zone, for example about 20% or higher, for example about 30% or higher, for example about 50% or higher, for example about 80% or higher.

[0357] In at least one embodiment, the polymer is produced using a small amount or no aluminoxane in the process. In some embodiments, the aluminoxane is present in a molar ratio of aluminum to transition metal of less than about 500:1, for example less than about 300:1, for example less than about 100:1, for example less than about 1:1.

[0358] In at least one embodiment, a small amount or no scavenger is used in the process to produce the ethylene polymer. In some embodiments, the scavenger is present in a molar ratio of scavenger metal to transition metal of less than about 100:1, for example less than about 50:1, for example less than about 15:1, for example less than about 10:1.

[0359] Other additives may also be used in the polymerization, such as one or more scavengers, hydrogen, alkylaluminum, or chain transfer agents. In at least one embodiment, the additive includes alkylaluminoxanes, diethylzinc, methylaluminoxanes, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof. In at least one embodiment, the alkylaluminoxane is represented by the formula AIR3 or ZnR2, wherein each R is independently a C1-C8 aliphatic group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, or isomers thereof, or combinations thereof.

[0360] Solution polymerization

[0361] In at least one embodiment, the polymerization method using the catalyst compound of this disclosure is a solution polymerization method.

[0362] Solution polymerization is a polymerization method in which a polymer is dissolved in a liquid polymerization medium (e.g., an inert solvent or monomers (one or more) or blends thereof). Solution polymerization is typically homogeneous. Homogeneous polymerization is polymerization in which the polymer product is dissolved in the polymerization medium. Such a system is non-turbid. Solution polymerization can involve polymerization in a continuous reactor, in which the formed polymer, starting monomer, and supplied catalyst material are agitated to reduce or avoid concentration gradients. In some embodiments, the monomer is used as a diluent or solvent. In some embodiments, a hydrocarbon is used as a diluent or solvent. Suitable methods can be operated at temperatures ranging from about 0°C to about 250°C, for example from about 50°C to about 170°C, for example from about 80°C to about 150°C, for example from about 100°C to about 140°C, and / or at pressures ranging from about 0.1 MPa to about 200 MPa, for example from about 0.1 MPa to about 120 MPa, for example from about 2 MPa to about 30 MPa. Temperature control within the reactor is achieved by balancing the heat of polymerization with reactor cooling, which may involve cooling the reactor contents using a reactor jacket or cooling coils, automatic refrigeration, pre-cooling the feed, vaporization of the liquid medium, or a combination thereof. An adiabatic reactor with a pre-cooled feed may also be used. The purity, type, and amount of solvent can be optimized for a specific type of polymerization to achieve maximum catalyst productivity. In some embodiments, the solvent is introduced as a catalyst support. In some embodiments, depending on pressure and temperature, the solvent may be introduced as a gaseous or liquid phase. Advantageously, the solvent can be maintained in a liquid phase and introduced as a liquid. The solvent may be introduced into the polymerization reactor in the feed.

[0363] In some embodiments, the polymerization method is a solution polymerization method, which can be carried out in a batch or continuous process. Suitable reactors may include kettle, loop, and tube designs. In at least one embodiment, the method is carried out continuously, wherein a dual loop reactor configured in series is used. In at least one embodiment, the method is carried out continuously, wherein one or more dual continuous stirred tank reactors (CSTRs) configured in series are used, wherein the method may be carried out continuously using a tubular reactor. In another embodiment, the method is carried out continuously, wherein a loop reactor and a CSTR configured in series are used. The process can also be carried out batch, wherein a single stirred tank reactor may be used.

[0364] Polyolefin products

[0365] The polymers disclosed herein can be formed via any one or more methods disclosed herein. In some embodiments, the formed polymer comprises a homopolymer of polyethylene and / or polypropylene. In some embodiments, the formed polymer comprises a copolymer of ethylene or propylene, wherein the respective monomers are mixed with C3-C4 polymers. 20 One or more copolymers of α-olefins.

[0366] In at least one embodiment, the polyethylene homopolymer has a weight-average molecular weight (Mw) of about 50,000 g / mol to about 1,500,000 g / mol, for example, about 80,000 g / mol to about 1,300,000 g / mol, for example, about 100,000 g / mol to about 1,200,000 g / mol. In at least one embodiment, the polyethylene homopolymer formed using any one or more catalyst systems has a melt temperature (Tm) of about 129°C to about 137°C, for example, about 131°C to about 136°C, for example, about 132°C to about 135°C. In at least one embodiment, the polyethylene homopolymer formed using any one or more catalyst systems has a polydispersity index (PDI) of about 1.4 to about 25.0, for example, about 1.5 to about 20.0, for example, about 1.6 to about 18.0, for example, about 1.7 to about 15.0, for example, about 1.8 to about 10.0, for example, about 1.9 to about 5.0, for example, about 2.0 to about 3.0.

[0367] In some embodiments, different catalyst systems are used to form the polyethylene copolymer. The polyethylene copolymer may have a Mw of about 20,000 g / mol to about 1,500,000 g / mol, for example about 30,000 g / mol to about 1,200,000 g / mol, for example about 40,000 g / mol to about 1,000,000 g / mol. In at least one embodiment, the polyethylene copolymer may have a PDI of about 1.2 to about 35.0, for example about 1.4 to about 10, for example about 1.8 to about 9, for example about 1.9 to about 6, for example about 2 to about 2.5. In at least one embodiment, the polyethylene copolymer may have a Tm of about 65°C to about 130°C, for example about 67°C to about 127°C, for example about 107.5°C.

[0368] In at least one embodiment, the polypropylene homopolymer has a Mw of about 2,000 g / mol to about 600,000 g / mol, for example about 2,500 g / mol to about 500,000 g / mol, for example about 30,000 g / mol to about 500,000 g / mol, for example about 60,000 g / mol to about 300,000 g / mol. In at least one embodiment, the polypropylene homopolymer has a PDI of about 1.40 to about 3.0, for example about 1.5 to about 2.5, for example about 1.6 to about 2.3, for example about 1.7 to about 2.0. In at least one embodiment, the polypropylene homopolymer has a Tm of about 100°C to about 150°C, for example about 109°C to about 147°C.

[0369] blends

[0370] In another embodiment, the polymer produced herein (e.g., polyethylene or polypropylene) is combined with one or more additional polymers before being molded into films, molded parts, or other articles. Other available polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymers of propylene and ethylene and / or butene and / or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethyl methacrylate, or any other polymer that can be polymerized by a high-pressure free radical method, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resin, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymers, styrene block copolymers, polyamide, polycarbonate, PET resin, cross-linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1-ester, polyacetal, polyvinylidene fluoride, polyethylene glycol, and / or polyisobutylene.

[0371] In at least one embodiment, based on the weight of the polymer in the blend, the polymer (e.g., polyethylene or polypropylene) is present in the blend at 10% to 99% by weight, for example, 20% to 95% by weight, for example, at least 30% to 90% by weight, for example, at least 40% to 90% by weight, for example, at least 50% to 90% by weight, for example, at least 60% to 90% by weight, for example, at least 70% to 90% by weight.

[0372] The above-described blends can be produced by mixing the polymers of this disclosure with one or more polymers (as described above) in reactors connected in series, or by using more than one catalyst in the same reactor to produce multiple polymers. The polymers can be mixed together before being fed into an extruder, or they can be mixed in the extruder.

[0373] Blends can be formed using conventional equipment and methods, such as by dry mixing the components and subsequently melt-mixing them in a mixer, or by directly mixing the components together in a mixer, such as a Banbury mixer, Haake mixer, Brabender internal mixer, or a single-screw or twin-screw extruder, which may include compounding extruders and side-arm extruders used directly downstream of the polymerization process, and may include blending resin powder or granules at the hopper of a film extruder. Additionally, additives may be included as needed in the blend, in one or more components of the blend, and / or in the product (e.g., a film) formed from the blend. Such additives are well known in the art and may include, for example: fillers; antioxidants (e.g., IRGANOX, available from Ciba-Geigy). TM 1010 or IRGANOX TM 1076); phosphites (e.g., IRGAFOS available from Ciba-Geigy) TM 168); anti-blocking additives; tackifiers, such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glyceryl stearates and hydrogenated rosin; UV stabilizers; heat stabilizers; anti-caking agents; release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; talc.

[0374] membrane

[0375] Any of the aforementioned polymers, such as the aforementioned polypropylene or blends thereof, can be used in a variety of end-use applications. Such applications include, for example, single-layer or multi-layer blown, extruded, and / or shrink films. These films can be formed by any number of known extrusion or co-extrusion techniques (e.g., blown bubble film processing techniques), wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uniaxially or biaxially oriented melt, which is then cooled to form a tubular blown film, which can then be axially cut and unfolded to form a flat film. The film can subsequently be non-oriented, uniaxially oriented, or biaxially oriented to the same or different degrees. One or more layers of the film can be oriented to the same or different degrees in the transverse and / or longitudinal directions. Uniaxial orientation can be accomplished by using conventional cold stretching or hot stretching methods. Biaxial orientation can be accomplished by using tenter frame equipment or a bifoaming method, and can be performed before or after the individual layers are combined together. For example, a polyethylene layer can be extruded, coated, or laminated onto an oriented polypropylene layer, or polyethylene and polypropylene can be co-extruded together into a film and then oriented. Similarly, oriented polypropylene can be laminated onto oriented polyethylene, or oriented polyethylene can be coated onto polypropylene, and then optionally the combination can be further oriented. For example, the film can be oriented in the longitudinal (MD) direction at a ratio of up to 15, for example, about 5 to about 7, and in the transverse (TD) direction at a ratio of up to 15, for example, about 7 to about 9. However, in another embodiment, the film is oriented to the same extent in both the MD and TD directions.

[0376] The thickness of the membrane can vary depending on the intended application; however, a thickness of 1 μm to 50 μm may be suitable. Membranes intended for packaging can be 10 μm to 50 μm thick. The thickness of the sealing layer can be 0.2 μm to 50 μm. The sealing layer can be present on both the inner and outer surfaces of the membrane, or it can exist only on the inner or outer surface.

[0377] In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave treatment. In at least one embodiment, one or two of the surface layers are modified by corona treatment.

[0378] wax

[0379] Low molecular weight polyolefin waxes, such as polyethylene waxes, having a molecular weight of about 250 g / mol to about 5,000 g / mol, can be prepared, for example, by solution polymerization using a Lewis base catalyst. The production of polyolefin waxes can be carried out at temperatures ranging from about 50°C to about 220°C, for example from about 100°C to about 200°C, for example from about 120°C to about 160°C. The production of polyolefin waxes can be carried out at reactor pressures ranging from about 0.5 MPa to about 25 MPa, for example from about 0.7 MPa to about 6 MPa. The production of polyolefin waxes can be carried out in the presence of added hydrogen at partial pressures ranging from 0 psig to about 100 psig, for example from 0 psig to about 40 psig, for example.

[0380] experiment

[0381] Precatalyst Synthesis

[0382] General information

[0383] All reactions using compounds sensitive to oxygen and moisture were carried out in a glove box under an argon atmosphere or using the Schlenk technique. 2-Bromo-4-methyl-6-phenylphenol [US 2004 / 014950], 2-Bromo-4-methyl-6-(3,5-di-tert-butylphenyl)phenol [JP 2015 / 193612], 1-Bromo-3-(tert-butyl)-2-(methoxymethoxy)-5-methylbenzene, 1-(3-bromo-2-(methoxymethoxy)-5-methylphenyl)adamantane, 2-(2-(methoxymethoxy)-5-methyl-3-(9-methyl-9-fluorenyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane [US 11,214,634], 2-(2-allyloxy-3-(tert-butyl)-5-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane [WO 2021 / 048030], 2,7-di-tert-butyl-9-(2-(methoxymethoxy)-5-methylphenyl)-9 H -Carbazole [WO 2018 / 122693], bis(4,4,5,5-tetramethyl-1,3,2-dioxane-2-yl)methane [ Org.Lett. , 2014, 16

[6342] Prepared as described in the literature. The preparation was carried out using the method described by Hata and colleagues from 1,1-dibromo-2-methylprop-1-ene, THF-Et2O. n Preparation of 2,2'-(2-methylprop-1-en-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane) from BuLi and bis(pinacolyl)diborane Angew.Chem.Int.Ed. , 2001, 40

[790] . All other reagents are available from commercial chemical suppliers.

[0384] Preparation of ligands

[0385] 2-Methylquinoline-8-yltrifluoromethanesulfonate

[0386]

[0387] A solution of trifluoromethanesulfonic anhydride (21.3 g, 75.4 mmol) in 20 mL of dry dichloromethane was added dropwise to a solution of 2-methylquinoline-8-ol (10.0 g, 62.9 mmol) and pyridine (9.9 g, 126 mmol) in 150 mL of dry dichloromethane. The mixture was warmed to room temperature and stirred for 1 hour. The mixture was then washed with an aqueous solution of NaHCO3, dried over Na2SO4, and the solvent was evaporated under reduced pressure to give 18.1 g (99%) of the product as a white crystalline powder. 1 H NMR (400MHz, CDCl3): δ 8.06(d, J =8.5Hz, 1H), 7.77 (dd, J =8.1Hz, J =1.1Hz, 1H), 7.56 (dd, J =7.6Hz, J =1.1Hz, 1H), 7.46 (dd, J =8.1Hz, J =7.6Hz, 1H), 7.37 (d, J =8.5Hz, 1H), 2.78(s, 3H).

[0388] 2-(bromomethyl)quinoline-8-yltrifluoromethanesulfonate

[0389]

[0390] A mixture of 2-methylquinoline-8-yltrifluoromethanesulfonate (18.1 g, 62.2 mmol), N-bromosuccinimide (NBS, 18.8 g, 106 mmol), and azobisisobutyronitrile (AIBN, 1.07 g, 6.53 mmol) in 200 mL of dry CCl4 was heated to reflux under an argon atmosphere for 36 hours. The reaction mixture was cooled to room temperature, filtered, and the filtrate was evaporated under reduced pressure. The product was separated from the residue by column chromatography (silica gel 60, 40-63 μm, eluent: hexane / dichloromethane = 7 / 3, v / v). Yield: 7.50 g (31%) of the product as a white crystalline powder. 1 H NMR (400MHz, CDCl3): δ 8.22(d, J =8.5Hz, 1H), 7.84 (d, J =7.9Hz, 1H), 7.70 (d, J =8.5Hz, 1H), 7.62 (d, J =7.1Hz, 1H), 7.56 (dd, J =7.9Hz, J =7.1Hz, 1H), 4.73 (s, 2H).

[0391] 2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yltrifluoromethanesulfonate

[0392]

[0393] Add dropwise to a solution of 2,6-diisopropylaniline (3.3 g, 18.4 mmol) in 100 mL of THF at 0 °C. n A solution of BuLi in hexane (2.5 M, 6.44 mL, 16.12 mmol). The reaction mixture was stirred at this temperature for 30 min and cooled to -78 °C, and a solution of 2-(bromomethyl)quinoline-8-yltrifluoromethanesulfonate (5.7 g, 15.35 mmol) in THF (20 mL) was added dropwise. The mixture was slowly warmed to room temperature, poured into 300 mL of water, and the product was extracted with 3 × 100 mL of dichloromethane. The combined organic phases were dried over Na₂SO₄, and the solvent was evaporated under reduced pressure. The product was separated by column chromatography (silica gel 60, 40–60 μm, elution: hexane / EtOAc = 10 / 1, v / v). Yield: 4.9 g (68%) of the product as a white crystalline powder. 1 H NMR (400MHz, CDCl3): δ 8.19(d, J =8.4Hz, 1H), 7.86 (d, J =8.3Hz, 1H), 7.63 (d, J =7.6Hz, 1H), 7.55 (dd, J =8.3Hz, J =7.6Hz, 1H), 7.48 (d, J =8.4Hz, 1H), 7.10-7.15(m, 3H), 4.53(br.s, 1H), 4.43(s, 2H), 3.50(sept, J =6.8Hz, 2H), 1.25(d, J =6.8Hz, 12H).

[0394] 2-(2-Allyloxy-3-tert-butyl-5-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxane

[0395]

[0396] Add dropwise to a solution of 2-(allyloxy)-1-bromo-3-(tert-butyl)-5-methylbenzene (24.6 g, 86.7 mmol) in anhydrous THF (500 mL) at -78 °C n A solution of BuLi in hexane (2.45 M, 35.4 mL, 86.7 mmol). The reaction mixture was stirred at this temperature for 1 hour. Then, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxane (19.3 g, 104 mmol) was added in one dose, and the mixture was stirred overnight at room temperature. Next, water (200 mL) was added, the organic layer was separated, and the aqueous layer was extracted with dichloromethane (2 × 100 mL). The combined organic extracts were dried over Na₂SO₄, and the solvent was evaporated under reduced pressure. The residue was recrystallized from methanol to give 20.4 g (72%) of the product as a pale yellow crystalline solid. 1 H NMR (400MHz, CDCl3): δ 7.39 (m, 1H), 7.22 (m, 1H), 6.17 (m, 1H), 5.43 (m, 1H), 5.25 (m, 1H), 4.45 (m, 2H), 2.29 (s, 3H), 1.38 (s, 9H), 1.35 (s, 12H).

[0397] 2-(2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yl)-4-methyl-6-tert-butylphenol

[0398]

[0399] A mixture of 2-(2-allyloxy-3-(tert-butyl)-5-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane (1.31 g, 3.97 mmol), 2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yltrifluoromethanesulfonate (1.76 g, 3.78 mmol), Cs₂CO₃ (3.1 g, 9.44 mmol), water (20 mL), dioxane (35 mL), and Pd(PPh₃)₄ (0.220 g, 0.189 mmol) was stirred at 105 °C for 10 hours. The reaction mixture was then poured into 200 mL of water, and the product was extracted with 3 × 100 mL of dichloromethane. The combined extracts were dried over Na₂SO₄ and the solvent was evaporated under reduced pressure. Column chromatography on silica gel 60 (40-63 μm, eluent: hexane / EtOAc / Et3N = 100 / 10 / 1, volume ratio) yielded 920 mg (51%) of the product as a yellow solid. 1 H NMR (400MHz, CDCl3): δ 9.80 (br s, 1H), 8.29 (d, J =8.4Hz, 1H), 7.84-7.87(m, 2H), 7.65-7.68(m, 1H), 8.59(d, J =8.4Hz, 1H), 7.21(d, J =2.0Hz, 1H), 7.05-7.12(m, 4H), 4.40(s, 2H), 3.85(br s, 1H), 3.26(sept, J =6.8Hz, 2H), 2.37(s, 3H), 1.46(s, 9H), 1.15(d, J =6.8Hz, 12H).

[0400] 2-(2-Allyloxy-3-phenyl-5-methylphenyl)4,4,5,5-Tetramethyl-1,3,2-dioxacyclopentaborane

[0401]

[0402] A mixture of 2-bromo-4-methyl-6-phenylphenol (4.0 g, 15.2 mmol), allyl bromide (2.76 g, 22.8 mmol), and anhydrous K₂CO₃ (4.2 g, 30.4 mmol) in 50 mL of acetone was stirred for 10 hours at 50 °C. The reaction mixture was poured into 300 mL of water, and the product was extracted with 3 × 100 mL of dichloromethane. The combined extracts were dried over Na₂SO₄ and the solvent was evaporated under reduced pressure. The resulting 2-(allyloxy)-1-bromo-3-phenyl-5-methylbenzene (4.60 g) was used without further purification. The solution of the above-obtained 2-(allyloxy)-1-bromo-3-phenyl-5-methylbenzene (4.60 g, 15.18 mmol) in 100 mL of THF was added dropwise at -78 °C. n A 2.5 M solution of BuLi in hexane (6.42 mL, 16.04 mmol). The reaction mixture was stirred at this temperature for 30 minutes. Then, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxane (3.69 g, 19.9 mmol) was added in one dose, and the reaction mixture was warmed to ambient temperature. The reaction mixture was then poured into 300 mL of water, and the product was extracted with 3 × 100 mL of dichloromethane. The combined extracts were dried over Na₂SO₄ and the solvent was evaporated under reduced pressure. Yield: 5.25 g (99%) of the product as a colorless oil. 1 H NMR (400MHz, CDCl3): δ 7.58 (d, J =7.2Hz, 2H), 7.49(s, 1H), 7.34-7.39(m, 1H), 7.30(d, J =7.2Hz, 2H), 7.24(s, 1H), 5.74-5.86(m, 1H), 4.97-5.06(m, 2H), 3.99(d, J =5.8Hz, 2H), 2.34(s, 3H), 1.35(s, 12H).

[0403] 2-(2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yl)-4-methyl-6-phenylphenol

[0404]

[0405] The mixture of 2-(2-allyloxy-5-methyl-3-phenylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxane (1.79 g, 5.92 mmol), 2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yltrifluoromethanesulfonate (2.30 g, 4.94 mmol), Cs₂CO₃ (4.02 g, 12.34 mmol), water (10 mL), dioxane (20 mL), and Pd(PPh₃)₄ (0.285 g, 0.247 mmol) was stirred at 105 °C for 10 hours. The reaction mixture was then poured into 100 mL of water, and the product was extracted with 3 × 30 mL of dichloromethane. The combined extracts were dried over Na₂SO₄, and the solvent was evaporated under reduced pressure. Column chromatography on silica gel 60 (40-63 μm, eluent: hexane / EtOAc / Et3N = 100 / 10 / 1, volume ratio) yielded 607 mg (25%) of the product as a yellow solid. 1 H NMR (400MHz, CDCl3): δ 9.72 (br s, 1H), 8.31 (d, J =8.4Hz, 1H), 7.90(d, J =7.7Hz, 2H), 7.67-7.71(m, 1H), 7.62-7.65(m, 2H), 7.60(d, J =8.4Hz, 1H), 7.32-7.36(m, 2H), 7.26-7.30(m, 2H), 7.21(d, J =2.1Hz, 1H), 7.02-7.10(m, 3H), 4.37(s, 2H), 3.4(br s, 1H), 3.23(sept, J =6.9Hz, 2H), 2.41(s, 3H), 1.10(d, J =6.9Hz, 12H).

[0406] 2-(2-Allyloxy-3-(3,5-di-tert-butylphenyl)-5-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane

[0407]

[0408] A mixture of 2-bromo-4-methyl-6-(3,5-di-tert-butylphenyl)phenol (4.0 g, 10.7 mmol), allyl bromide (1.94 g, 16.0 mmol), and anhydrous K₂CO₃ (4.2 g, 30.4 mmol) in 50 mL of acetone was stirred for 10 hours at 50 °C. The reaction mixture was poured into 300 mL of water, and the product was extracted with 3 × 100 mL of dichloromethane. The combined extracts were dried over Na₂SO₄, and the solvent was evaporated under reduced pressure. The resulting 2-(allyloxy)-1-bromo-3-(3,5-di-tert-butylphenyl)-5-methylbenzene (4.40 g) was used without further purification. A 2.5 M solution of BuLi in hexane (4.50 mL, 11.25 mmol) was added dropwise to a solution of 2-(allyloxy)-1-bromo-3-(3,5-di-tert-butylphenyl)-5-methylbenzene (4.40 g, 10.6 mmol) in 100 mL of THF at -78 °C. The reaction mixture was stirred at this temperature for 30 min. Then, 2-isopropoxy-4,4,5,5,-tetramethyl-1,3,2-dioxane (2.59 g, 13.93 mmol) was added in a single addition, and the reaction mixture was warmed to room temperature. The reaction mixture was then poured into 300 mL of water, and the product was extracted with 3 × 100 mL of dichloromethane. The combined extracts were dried over Na₂SO₄, and the solvent was evaporated under reduced pressure. Yield: 4.85 g (99%) of the product as a white crystalline powder. 1 H NMR (400MHz, CDCl3): δ 7.49(d, J =2.0Hz, 1H), 7.39-7.41(m, 2H), 7.35-7.38(m, 1H), 7.26(s, 1H), 5.76-5.86(m, 1H), 4.96-5.06(m, 2H), 3.99(d, J =5.8Hz, 2H), 2.35(s, 3H), 1.36(s, 12H), 1.34(s, 18H).

[0409] 2-(2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yl)-4-methyl-6-(3,5-di-tert-butylphenyl)phenol

[0410]

[0411] A mixture of 2-(2-allyloxy-5-methyl-3-(3,5-di-tert-butylphenyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane (0.70 g, 1.51 mmol), 2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yltrifluoromethanesulfonate (0.50 g, 1.07 mmol), Cs₂CO₃ (1.03 g, 3.15 mmol), water (5 mL), dioxane (10 mL), and Pd(PPh₃)₄ (0.070 g, 0.061 mmol) was stirred at 105 °C for 10 hours. The reaction mixture was then poured into 100 mL of water, and the product was extracted with 3 × 20 mL of dichloromethane. The combined extracts were dried over Na₂SO₄, and the solvent was evaporated under reduced pressure. Column chromatography on silica gel 60 (40-63 μm, eluent: hexane / EtOAc / Et3N = 100 / 10 / 1, volume ratio) yielded 401 mg (61%) of the product as a yellow solid. 1 H NMR (400MHz, CDCl3): δ 9.23 (s, 1H), 8.29 (d, J =8.4Hz, 1H), 7.87-7.93(m, 2H), 7.66-7.70(m, 1H), 7.57(d, J =8.4Hz, 1H), 7.45 (d, J =1.8Hz, 2H), 7.97(t, J =1.8Hz, 1H), 7.27 (d, J =1.9Hz, 1H), 7.22(d, J =1.9Hz, 1H), 7.00-7.07(m, 3H), 4.36(s, 2H), 3.97(br s, 1H), 3.20(sept, J =6.8Hz, 2H), 2.42(s, 3H), 1.31(s, 18H), 1.07(d, J =6.8Hz, 12H).

[0412] 2-(2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yl)-4-methyl-6-(9-methyl-9-fluorenyl)phenol

[0413]

[0414] 2-(2-(methoxymethoxy)-5-methyl-3-(9-methyl-9-fluorenyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxane (2.35 g, 5.14 mmol), 2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yltrifluoromethanesulfonate (2.0 g, 4.29 mmol), Cs₂CO₃ (3.5 g, 10.71 mmol), water (10 mL), dioxane (16 mL), and Pd(PPh₃)₄ (0.25 g, 0.214 mmol) were stirred at 105 °C for 10 hours. The reaction mixture was then poured into 100 mL of water, and the product was extracted with 3 × 20 mL of dichloromethane. The combined extracts were dried over Na₂SO₄, and the solvent was evaporated under reduced pressure. The residue was dissolved in a mixture of 40 mL of THF and 40 mL of MeOH, and 2.2 mL of 12 M HCl was added to the resulting solution. The mixture was stirred at 60 °C for 10 hours, cooled to room temperature, poured into 300 mL of 3% NaHCO3 aqueous solution, and extracted with 3 × 100 mL of dichloromethane. The combined extracts were dried over Na2SO4, and the solvent was evaporated under reduced pressure. Column chromatography on silica gel 60 (40-60 μm, eluent: hexane / EtOAc / Et3N = 100 / 10 / 1, v / v) yielded 2.2 g (85%) of the product as a yellow solid. 1 H NMR (400MHz, CDCl3): δ 8.93 (s, 1H), 8.14 (d, J =8.5Hz, 1H), 7.76 (dd, J =7.3Hz, J =1.4Hz, 1H), 7.73 (dd, J =8.5Hz, J =1.4Hz, 1H), 7.61-7.65(m, 2H), 7.59(s, 1H), 7.52-7.56(m, 2H), 7.23-7. 26(m, 2H), 7.13-7.17(m, 4H), 6.99-7.07(m, 4H), 3.85(s, 2H), 3.06(sept, J =6.8Hz, 2H), 2.46(s, 3H), 1.85(s, 3H), 1.15(d, J =6.8Hz, 12H).

[0415] 2-(2-(methoxymethoxy)-5-methyl-3-(2,7-di-tert-butylcarbazole-9-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxane

[0416]

[0417] Dissolve 2,7-di-tert-butyl-9-(2-(methoxymethoxy)-5-methylphenyl)carbazole in dry diethyl ether (500 mL) and heat at 0 °C. n BuLi (2.5 M in hexane, 13.0 mL, 32.0 mmol) was added dropwise to the solution. The cooling bath was then removed, and the resulting mixture was stirred overnight at room temperature. 2-Isopropoxy-4,4,5,5-Tetramethyl-1,3,2-dioxane (8.80 mL, 7.54 g, 41.0 mmol) was added dropwise to the mixture at -80 °C, and the mixture was warmed to room temperature and stirred overnight at that temperature. Water (1000 mL) was added to the mixture, and the organic layer was separated. The aqueous layer was extracted with diethyl ether (3 × 100 mL); the combined organic extracts were washed with brine, dried over Na₂SO₄, and the solvent was evaporated under reduced pressure. The residue was purified by rapid chromatography on silica gel 60 (40-63 μm, eluent: hexane / EtOAc = 20 / 1, v / v). Yield: 6.70 g (45%, 85% purity) of the product as a white solid. 1 H NMR (400MHz, CDCl3) δ 7.99-7.94(m, 2H), 7.76-7.73(m, 1H), 7.32-7.27(m, 3H), 7.12-7.08(m, 2H), 4.66(s, 2H), 2.48(s, 3H), 2.41(s, 3H), 1.41(s, 12H), 1.37(s, 18H).

[0418] 2-(2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yl)-4-methyl-6-(2,7-di-tert-butylcarbazole-9-yl)phenol

[0419]

[0420] A mixture of 2-(2-(methoxymethoxy)-5-methyl-3-(2,7-di-tert-butylcarbazole-9-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxane (2.86 g, 5.14 mmol), 2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yltrifluoromethanesulfonate (2.00 g, 4.29 mmol), Cs₂CO₃ (3.50 g, 10.71 mmol), water (10 mL), dioxane (16 mL), and Pd(PPh₃)₄ (0.25 g, 0.214 mmol) was stirred at 105 °C for 10 hours. The reaction mixture was then poured into 100 mL of water, and the product was extracted with 3 × 20 mL of dichloromethane. The combined extracts were dried over Na₂SO₄, and the solvent was evaporated under vacuum. The residue was dissolved in a mixture of 40 mL THF and 40 mL MeOH, and 2.2 mL of 12 M HCl was added to the resulting solution. The mixture was stirred at 60 °C for 10 hours, cooled to room temperature, and poured into 300 mL of 3% NaHCO3 aqueous solution. The product was extracted with 3 × 100 mL of dichloromethane. The combined extracts were dried over Na2SO4 and the solvent was evaporated under reduced pressure. Column chromatography on silica gel 60 (40–63 μm; eluent: hexane / EtOAc / Et3N = 100 / 10 / 1, v / v) yielded 2.0 g (67%) of the product as a yellow solid. 1 H NMR (400MHz, CDCl3): δ10.20 (s, 1H), 8.32 (d, J=8.5Hz, 1H), 8.02 (dd, J=7.3Hz, J=1.3 Hz, 1H), 7.97 (d, J=8.2Hz, 2H), 7.92 (dd, J=8.2Hz, J=1.3Hz, 1H), 7.69-7.75 (m, 2H), 7 .44 (dd, J=2.2Hz, J=0.6Hz, 1H), 7.34 (dd, J=2.2Hz, J=0.6Hz, 1H), 7.26 (d, J=1.7Hz, 1 H), 7.24(d, J=1.7Hz, 1H), 7.21-7.23(m, 2H), 6.98-7.02(m, 3H), 4.27(s, 2H), 3.54(br s, 1H), 3.08 (sept, J=6.9Hz, 2H), 2.46 (s, 3H), 1.27 (s, 18H), 0.99 (d, J1=6.9Hz, 12H).

[0421] N- ((6-bromopyridin-2-yl)methylene)-2,6-diisopropylaniline

[0422]

[0423] Under an argon atmosphere, 85.0 g (457 mmol) of 6-bromopyridine-2-carboxaldehyde and 80.9 g (457 mmol) of 2,6-diisopropylaniline in 1000 mL of ethanol were heated to reflux for 8 hours. The resulting solution was evaporated to dryness, and the solid was recrystallized from 200 mL of methanol. Yield: 113.5 g (72%) of product, as a yellow crystalline solid. 1 H NMR (CDCl3): δ 8.24-8.26 (m, 2H), 7.68-7.72 (m, 1H), 7.59-7.61 (m, 1H), 7.10-7.18 (m, 3H), 2.91 (sept, J=6.8Hz, 2H), 1.16 (d, J=6.8Hz, 12H).

[0424] N- ((6-bromopyridin-2-yl)methyl)-2,6-diisopropylaniline

[0425]

[0426] Under an argon atmosphere, 113.5 g (329 mmol) of methanol was added to 1000 mL of methanol. N- A mixture of ((6-bromopyridin-2-yl)methylene)-2,6-diisopropylaniline, 33.2 g (526 mmol) of NaBH3CN, 9 mL of glacial acetic acid, and 1000 mL of methanol was heated to reflux for 12 hours. The mixture was cooled to room temperature, poured into 1000 mL of water, and extracted with 3 × 200 mL of ethyl acetate. The combined extracts were dried over Na2SO4 and the solvent was evaporated under reduced pressure. The residue was purified by rapid chromatography on silica gel 60 (40–63 μm; eluent: hexane / EtOAc = 10 / 1, v / v). Yield: 104 g (91%) of product as a yellow oil. 1 H NMR (CDCl3): δ7.51-7.55 (m, 1H), 7.41-7.43 (m, 1H), 7.31-7.33 (m, 1H), 7.08-7.15 (m, 3H), 4.21 (s, 2H), 3.96 (br s, 1H), 3.36 (sept, J=6.8Hz, 2H), 1.26 (d, J=6.8Hz, 12H).

[0427] 2-(3-(tert-butyl)-2-(methoxymethoxy)-5-methylbenzyl)-4,4,5,5-tetramethyl-1,3,2-dioxane

[0428]

[0429] At room temperature, 770 mg (2.88 mmol) of bis(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)methane, 500 mg (1.44 mmol) of 1-bromo-3-(tert-butyl)-2-(methoxymethoxy)-5-methylbenzene and 74 mg (0.144 mmol) of Pd(P t Bu3)2 was added dropwise to a solution of 15 mL dioxane with 0.360 mL of 8N KOH aqueous solution (2.88 mmol). The resulting mixture was stirred overnight at this temperature and then poured into 30 mL of water. The crude product was extracted with 3 × 20 mL dichloromethane. The combined organic extracts were dried with Na2SO4 and the solvent was evaporated to near dryness under reduced pressure. The residue was purified by rapid chromatography on silica gel 60 (40–63 μm; eluent: hexane / dichloromethane = 10 / 1, v / v). The product was obtained in a yield of 307 mg (61%) as a yellow oil. 1 H NMR (CDCl3, 400MHz): δ 6.94 (d, J=1.8Hz, 1H), 6.86 (d, J=1.8Hz, 1H), 4.98 (s, 2H), 3.64 (s, 3H), 2.26 (s, 3H), 2.25 (s, 2H), 1.40 (s, 9H), 1.25 (s, 12H).

[0430] 2-(tert-butyl)-6-((6-(((2,6-diisopropylphenyl)amino)methyl)pyridin-2-yl)methyl)-4-methylphenol

[0431]

[0432] 500 mg (1.44 mmol) of 2-(3-(tert-butyl)-2-(methoxymethoxy)-5-methylbenzyl)-4,4,5,5-tetramethyl-1,3,2-dioxane and 600 mg (1.72 mmol) of N A solution of 1.41 g (4.31 mmol) of cesium carbonate and 40 mg (0.08 mmol) of Pd (P2O3) in 8 mL of dioxane was subsequently added. tBu3) and 2 mL of water. The mixture was stirred at 95 °C for 12 hours, cooled to room temperature, and diluted with 50 mL of water. 50 mL of diethyl ether was added to the resulting mixture, the organic layer was separated, and washed with brine. The resulting solution was dried with Na2SO4 and the solvent was evaporated under reduced pressure. 10 mL of THF, 10 mL of methanol, and 0.7 mL of 12NHCl were added to the residue in succession. The mixture was stirred at 60 °C overnight, then poured into 30 mL of water, and sodium carbonate aqueous solution was added until pH≈7. The resulting mixture was extracted with dichloromethane (3 × 20 mL), and the combined organic extracts were dried with Na2SO4 and the solvent was evaporated under reduced pressure. The residue was purified by rapid chromatography on silica gel 60 (40-63 μm, eluent: hexane / EtOAc / Et3N = 100 / 10 / 1, v / v). Yield: 510 mg (79%) of product as a white solid. 1 H NMR (CDCl3, 400MHz): δ 11.3 (br s, 1H), 7.67 (t, J =7.7Hz, 1H), 7.30 (d, J =7.7Hz, 1H), 7.24 (d, J =7.4Hz, 1H), 7.11-7.13(m, 3H), 6.99(d, J =1.9Hz, 1H), 6.90(d, J =1.9Hz, 1H), 4.13(s, 2H), 4.09(s, 2H), 3.28(sept, J =6.8Hz, 2H), 2.26(s, 3H), 1.44(s, 9H), 1.22(d, J =6.8Hz, 12H).

[0433] 3-(adamantane-1-yl)-2-(methoxymethoxy)-5-methylbenzaldehyde

[0434]

[0435] At -78°C, 11.5 mL of [amount of solution] was added dropwise to a solution of 10.0 g (27.5 mmol) of 1-(3-bromo-2-(methoxymethoxy)-5-methylphenyl)adamantane in 250 mL of THF. nBuLi (28.8 mmol, 2.5 M in hexane). The resulting suspension was stirred at this temperature for 1 hour, and then 3.01 g (41.0 mmol) of N,N-dimethylformamide (DMF) was added in a single batch. The resulting mixture was heated to -10 °C and quenched with 100 mL of 2N citric acid aqueous solution. The mixture was extracted with 150 mL of dichloromethane, the organic extract was washed with 100 mL of water and 100 mL of brine, dried with Na2SO4, and the solvent was evaporated under reduced pressure. The residue was ground with 20 mL of n-pentane, the precipitate was filtered through a sand filter, washed with 2 × 10 mL of n-pentane, and dried under vacuum. Yield: 7.10 g (83%) of the product as a pale yellow crystalline solid. 1 H NMR (CDCl3, 400MHz): δ 10.19 (s, 1H), 7.51 (d, J =2.2Hz, 1H), 7.35 (d, J =2.2Hz, 1H), 5.02(s, 2H), 3.65(s, 3H), 2.34(s, 3H), 2.08-2.13(m, 9H), 1.79(br s, 3H). 13 C NMR (CDCl3, 100MHz): δ 191.5, 158.3, 143.4, 134.2, 133.6, 130.6, 126.9, 102.6, 57.6, 41.5, 37.1, 36.8, 28.9, 20.9.

[0436] (3-(adamantane-1-yl)-2-(methoxymethoxy)-5-methylphenyl)(6-(((2,6-diisopropylphenyl)amino)methyl)pyridin-2-yl)methanol

[0437]

[0438] At -45°C, 2.00 g (5.75 mmol) N 2.3 mL of 1-((6-bromopyridin-2-yl)methyl)-2,6-diisopropylaniline was added dropwise to a solution of 24 mL of hexane-toluene mixture (2:1, v / v). n BuLi (5.75 mmol, 2.5 M in hexane). The resulting mixture was heated to -10 °C, stirred at this temperature for 5 minutes, cooled to -60 °C, and 20 mL of diethyl ether was added. Then, it was cooled to -90 °C, and 6.72 mL of [unspecified ingredient] was added dropwise. tBuLi (12.1 mmol, 1.8 M in pentane). The resulting suspension was warmed to -75 °C and a solution of 2.35 g (7.40 mmol) of 3-(adamantane-1-yl)-2-(methoxymethoxy)-5-methylbenzaldehyde in 5 mL of toluene was added in a single batch. The mixture was warmed to -10 °C and quenched with 150 mL of water. 150 mL of dichloromethane was added to the resulting two-phase mixture, the organic layer was separated, washed with 100 mL of water and 100 mL of brine, dried over Na2SO4, and the solvent was evaporated under reduced pressure. Volatile impurities were distilled off using a Kugelrohr apparatus (0.1 mbar, 150 °C). The residue was purified by rapid chromatography on silica gel 60 (40-63 μm, eluent: hexane / EtOAc = 10 / 1, v / v). Yield: 2.22 g (66%) of the product as a pale yellow viscous oil. 1 H NMR (CDCl3, 400MHz): δ 7.62(t, J =7.7Hz, 1H), 7.12-7.25(m, 5H), 7.06(d, J =1.8Hz, 1H), 6.77(d, J =1.8Hz, 1H), 6.30(d, J =3.2Hz, 1H), 5.40(d, J =3.4Hz, 1H), 5.27 (d, J =5.3Hz, 1H, AB), 5.20(d, J =5.3Hz, 1H, AB), 4.25(s, 2H), 4.09(br.s, 1H), 3.71(s, 3H), 3.39(sept, J =6.9Hz, 1H), 2.21(s, 3H), 2.08-2.20(m, 9H), 1.82(br.s, 6H), 1.28(d, J =6.9Hz, 12H). 13 C NMR (CDCl3, 100MHz): δ 160.7, 156.3, 152.7, 142.73, 142.67, 142.1, 137.0, 136.6, 133.2, 127.6, 127.0, 123.5, 123.2, 120.1, 119.9, 101.1, 68.4, 57.1, 56.1, 41.4, 37.0, 36.6, 28.8, 27.5, 23.9, 23.81, 23.79, 20.8.

[0439] 2-(adamantane-1-yl)-6-((6-(((2,6-diisopropylphenyl)amino)methyl)pyridin-2-yl)methyl)-4-methylphenol

[0440]

[0441] 1.01 g (1.72 mmol) of (3-(adamantane-1-yl)-2-(methoxymethoxy)-5-methylphenyl)(6-((((2,6-diisopropylphenyl)amino)methyl)pyridin-2-yl)methanol was added in a single batch to a mixture of 30 mL acetic acid and 7 mL concentrated HI. The resulting suspension was heated to 95 °C until the starting material was completely dissolved (approximately 20 minutes). The resulting solution was cooled to room temperature and poured into 500 mL of an aqueous solution of NaHCO3 (70 g) and Na2SO3 (6 g). 150 mL of diethyl ether was added to the resulting two-phase mixture, the organic layer was separated and washed with 100 mL of water and 100 mL of brine, dried with Na2SO4, and passed through a short silica gel pad. The filtrate was evaporated under reduced pressure. The residue was ground with 55 mL of a methanol-dichloromethane mixture (10:1 v / v). Dichloromethane was carefully evaporated from this mixture under reduced pressure. The precipitate obtained by filtration on a sand filter cartridge was washed with 2 × 5 mL of methanol and dried under vacuum. Yield: 590 mg (66%) of product as a white crystalline powder. 1 H NMR (CDCl3, 400MHz): δ 11.11(s, 1H), 7.67(t, J =7.7Hz, 1H), 7.32 (d, J =7.7Hz, 1H), 7.23 (d, J =7.6Hz, 1H), 7.12-7.14(s, 3H), 6.95(d, J =1.8Hz, 1H), 6.90(d, J =1.8Hz, 1H), 4.18(s, 2H), 4.08(s, 2H), 3.42(br.s, 1H), 3.23(sept, J =6.9Hz, 1H), 2.27(s, 3H), 2.19(br.s, 6H), 2.06(br.s, 3H), 1.72-1.84(m, 6H), 1.21(d, J =6.9Hz, 12H). 13 C NMR (CDCl3, 100MHz): δ161.3, 158.5, 152.9, 142.9, 142.1, 139.0, 138.7, 128.5, 128.3, 127.5, 126.4, 124.3, 123.6, 121.0, 119.9, 56.7, 41.5, 40.6, 37.1, 37.0, 29.1, 27.7, 24.2, 20.8.

[0442] 2-(1-(3-(adamantane-1-yl)-2-(methoxymethoxy)-5-methylphenyl)-2-methylprop-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxane

[0443]

[0444] To a solution of 3.98 g (9.65 mmol) of (3-iodo-2-(methoxymethoxy)-5-methylphenyl)adamantane, 3.12 g (10.2 mmol) of 2,2'-(2-methylprop-1-en-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane), and 352 mg (0.48 mmol) of (1,1'-bis(diphenylphosphine)ferrocene)PdCl2 in 200 mL of THF, 9.7 mL of KOH aqueous solution (29 mmol, 3 M) was added dropwise. The mixture was stirred overnight at room temperature and then poured into 200 mL of water. 150 mL of dichloromethane was added to the resulting two-phase mixture, the organic layer was separated, washed with 100 mL of water and 100 mL of brine, dried over Na2SO4, and the solvent was evaporated under reduced pressure. The residue was dissolved in 150 mL of n-hexane, the resulting mixture was filtered (G4), and the filtrate was evaporated under reduced pressure to give 4.66 g (quantitative, 96% purity) of product as a red viscous oil, which was used in the next step without further purification. 1 H NMR (CDCl3, 400MHz): δ 6.94 (d, J =2.0Hz, 1H), 6.69(d, J =2.0Hz, 1H), 5.04(d, J =4.7Hz, 1H, AB), 4.68(d, J =4.7Hz, 1H, AB), 3.58 (s, 3H), 2.27 (s, 3H), 2.14 (br.s, 6H), 2.08 (br.s, 3H), 2.07 (s, 3H), 1.77 (br.s, 6H), 1.72 (s, 3H), 1.26 (s, 12H).

[0445] 2-(adamantane-1-yl)-6-(1-(6-(((2,6-diisopropylphenyl)amino)methyl)pyridin-2-yl)-2-methylprop-1-en-1-yl)-4-methylphenol

[0446]

[0447] At room temperature, 3.00 g (6.44 mmol) of 2-(1-(3-(adamantane-1-yl)-2-(methoxymethoxy)-5-methylphenyl)-2-methylprop-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxane and 1.86 g (5.36 mmol) were reacted. N- To a solution of ((6-bromopyridin-2-yl)methyl)-2,6-diisopropylaniline and 240 mg (0.33 mmol) (1,1'-bis(diphenylphosphine)ferrocene)PdCl2 in 45 mL of 1,4-dioxane, 7.5 mL of hydrated KOH (22.5 mmol, 3 M) was added dropwise. The mixture was stirred overnight at room temperature and then poured into 200 mL of water. 150 mL of dichloromethane was added to the resulting two-phase mixture, the organic layer was separated, washed with 100 mL of water and 100 mL of brine, dried over Na2SO4, and the solvent was evaporated under reduced pressure. The residue was purified by rapid chromatography on silica gel 60 (40-63 μm, eluent: dichloromethane). The solvent was evaporated under reduced pressure, and the residue was dissolved in 80 mL of a THF-methanol mixture (1:1, v / v), to which 2 mL of concentrated HCl was added. The resulting solution was stirred overnight at 60 °C and then poured into 150 mL of water. Add 150 mL of dichloromethane to the resulting two-phase mixture, separate the organic layer, wash with 100 mL of water and 100 mL of brine, dry with Na2SO4 and evaporate under reduced pressure. Crystals obtained from the crystallization residue in n-pentane were filtered through a sand filter (G4), washed with 2 × 10 mL of n-pentane and dried under vacuum to give 1.71 g (57%) of product as white crystals. 1 H NMR (CDCl3, 400MHz): δ 10.58 (s, 1H), 7.67 (t, J =7.7Hz, 1H), 7.28 (d, J =7.7Hz, 1H), 7.19(d, J =7.7Hz, 1H), 7.08-7.13(m, 3H), 6.95(s, 1H), 6.74(s, 1H), 3.48(br.s, 1H), 3.21(sept, J=6.8Hz, 2H), 2.25(s, 3H), 2.11-2.24(m, 6H), 2.04(br.s, 3H), 1.84(s, 3H), 1.74-1.82(m, 6H), 1.70(s, 3H), 1.20(d, J =6.8Hz, 6H), 1.18(d, J =6.8Hz, 6H). 13 C NMR (CDCl3, 100MHz): δ 160.6, 157.7, 151.1, 142.5, 138.3, 137.3, 136.0, 133.4, 130.0, 128.1, 127.6, 126.1, 123.8, 123.2, 122.1, 119.5, 56.4, 40.2, 36.8, 36.6, 28.8, 27.3, 23.9, 23.8, 21.6, 21.2, 20.4.

[0448] Preparation of transition metal complexes

[0449] Complex 1-HfCl2

[0450]

[0451] 2-(2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yl)-4-methyl-6-tert-butylphenol (747 mg, 1.55 mmol) was dissolved in toluene (70 mL), followed by the addition of Hf(NMe2)4 (551 mg, 1.55 mmol). The reaction mixture was stirred overnight at 100 °C. The evaporation was then evaporated under vacuum, and the residue was dissolved in toluene (70 mL), followed by the addition of Me2SiCl2 (1.0 mL, 7.75 mmol). The reaction mixture was stirred overnight at 55 °C, and then the evaporation was evaporated under reduced pressure. Recrystallization of the residue from the toluene / hexane mixture gave 904 mg (80%) of the complex 1-HfCl2 as a white solid. 1 HNMR (400MHz, CD2Cl2): δ 8.54(d, J =8.3Hz, 1H), 8.02 (dd, J 1 = 7.8 Hz J 2=1.6Hz, 1H), 7.88(m, 1H), 7.81(m, 1H), 7.50(d, J=8.3Hz, 1H), 7.29(m, 1H), 7.18(s, 3H), 6.63(br.s, 1H), 5.18(br.s, 2H), 3.46(m, 2H), 2.30(s, 3H), 1.56(s, 9H), 1.25(d, J =6.8Hz, 6H), 1.21(d, J =6.8Hz, 6H).

[0452] Complex 1-HfMe2

[0453]

[0454] The complex 1-HfCl2 (500 mg, 0.7 mmol) was dissolved in dry dichloromethane (50 mL), and a solution of MeMgBr in diethyl ether (500 μL, 2.9 M) was added to the solution at room temperature. The mixture was stirred overnight at room temperature. The evaporation was carried out under reduced pressure, the residue was extracted with hot hexane, and the extract was filtered through a short diatomaceous earth mat. The filtrate was evaporated, and the residue was dried under vacuum to give the complex 1-HfMe2 (300 mg, 62%) as a white solid. 1 H NMR (400MHz, CD2Cl2): δ 8.43(d, J =8.4Hz, 1H), 7.94(m, 1H), 7.82(m, 1H), 7.73(m, 1H), 7.48(d, J =8.3Hz, 1H), 7.29(m, 1H), 7.15-7.24(m, 3H), 6.62(m, 1H), 5.78(m, 1H), 4.44(m, 1H), 3.84(m, 1H), 3.63(m, 1H), 2.31(s, 3H), 1.62(s, 9H), 1.19-1.35(m, 12H), -0.26(s, 3H), -0.90(s, 3H). 13 C NMR (100MHz, CD2Cl2), 166.4, 156.8, 149.0, 146.7, 146.0, 145.8, 141.8, 138.1, 138.0, 136.3, 133.4, 131.3, 129.1, 128.4, 127.8, 127.7, 125.5, 124.4, 123.9, 119.6, 67.0, 56.2, 44.8, 35.3, 30.6, 28.1, 27.5, 26.2, 24.8, 24.5, 20.9.

[0455] Complex 2-HfCl2

[0456]

[0457] 2-(2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yl)-4-methyl-6-phenylphenol (607 mg, 1.2 mmol) was dissolved in toluene (50 mL), followed by the addition of Hf(NMe2)4 (430 mg, 1.2 mmol). The reaction mixture was stirred overnight at 100 °C. The evaporation was then evaporated under reduced pressure, and the residue was dissolved in toluene (50 mL), followed by the addition of Me2SiCl2 (0.8 mL, 6.0 mmol). The reaction mixture was stirred overnight at 55 °C, the evaporation was evaporated under reduced pressure, and the residue was recrystallized from a toluene / hexane mixture to give the complex 2-HfCl2 (300 mg, 33%) as a white solid. 1 H NMR (400MHz, CDCl3): δ 8.47(d, J =8.5Hz, 1H), 8.02 (d, J =7.8Hz, 1H), 7.90(m, 1H), 7.81(m, 1H), 7.71(d, J =7.3Hz, 2H), 7.56(s, 1H), 7.49(d, J =8.6Hz, 1H), 7.28-7.33(m, 3H), 7.19-7.26(m, 2H), 7.10-7.13(m, 2H), 5.27(m, 2H), 3.48(m, 2H), 2.50(s, 3H), 1.22(d, J =6.5Hz, 6H), 1.14(d, J =5.4Hz, 6H).

[0458] Complex 3-HfCl2

[0459]

[0460] 2-(2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yl)-4-methyl-6-(3,5-di-tert-butylphenyl)phenol (380 mg, 0.62 mmol) was dissolved in toluene (50 mL), followed by the addition of Hf(NMe2)4 (220 mg, 0.62 mmol). The reaction mixture was stirred overnight at 100 °C. The evaporation was then distilled off under reduced pressure, and the residue was dissolved in toluene (50 mL), followed by the addition of Me2SiCl2 (0.4 mL, 3.1 mmol). The reaction mixture was stirred overnight at 55 °C, and the evaporation was then distilled off under reduced pressure. The residue was recrystallized from a toluene / hexane mixture to give the complex 3-HfCl2 (200 mg, 37%) as a white solid.1 H NMR (400MHz, CDCl3): δ 8.44(d, J =8.5Hz, 1H), 7.98 (m, 1H), 7.88 (m, 1H), 7.79 (m, 1H), 7.45 (m, 4H), 7.31 (m, 1H), 7.24-7.2 7(m, 1H), 7.19(m, 1H), 7.10(m, 2H), 3.46(br.s, 2H), 2.47(s, 3H), 1.30(s, 18H), 1.20(d, J =6.8Hz, 6H), 1.13(d, J =5.8Hz, 6H). 13 C NMR (100MHz, CDCl3) δ 164.7, 149.6, 149.3, 144.2, 141.5, 137.7, 136.7, 136.2, 135.1, 134.7, 129.0, 128.8, 128.2, 127.8, 125.9, 125.3, 124.1, 123.8, 121.6, 118.7, 66.3, 34.8, 31.5, 27.8, 25.3, 24.8, 22.6, 21.0, 14.1.

[0461] Complex 3-HfMe2

[0462]

[0463] The complex 3-HfCl2 (100 mg, 0.12 mmol) was dissolved in dry dichloromethane, and a solution of MeMgBr in diethyl ether (88 μL, 2.9 M) was added to the solution at room temperature. The resulting mixture was stirred overnight at room temperature. The evaporation was then evaporated under reduced pressure, the residue was extracted with hot hexane, and the extract was filtered through a short diatomaceous earth mat. The filtrate was evaporated, and the residue was dried under vacuum to give the complex 3-HfMe2 (82 mg, 56%) as a white solid. 1 H NMR (400MHz, CDCl3): δ 8.03(d, J =1.7Hz, 2H), 7.68 (dd, J 1 = 7.2 Hz J 2=1.6Hz, 1H), 7.64(m, 1H), 7.59(t, J =1.8Hz, 1H), 7.48 (d, J=8.4Hz, 1H), 7.30(m, 1H), 7.21(m, 3H), 7.10(m, 1H), 6.83(d, J =2.1Hz, 1H), 6.60(d, J =8.4Hz, 1H), 5.30 (m, 1H), 5.06 (m, 1H), 4.17 (m, 1H), 3.51 (m, 1H), 2.31 (s, 3H), 1 .49 (m, 3H), 1.48 (s, 18H), 1.34 (m, 6H), 1.17 (m, 3H), -0.12 (s, 3H), -0.23 (s, 3H).

[0464] Complex 4-HfCl2

[0465]

[0466] 2-(2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yl)-4-methyl-6-(9-methyl-9-fluorenyl)phenol (1.0 g, 1.66 mmol) was dissolved in toluene (100 mL) and then Hf(NMe2)4 (589 mg, 1.66 mmol) was added. The reaction mixture was stirred overnight at 100 °C. The evaporation was then evaporated under reduced pressure, and the residue was dissolved in toluene (100 mL) and then Me2SiCl2 (1.0 mL, 8.3 mmol) was added. The reaction mixture was stirred overnight at 55 °C, and then the evaporation was evaporated under reduced pressure, and the residue was recrystallized from a toluene / hexane mixture to give the complex 4-HfCl2 (650 mg, 46%) as a white solid. 1 H NMR (400MHz, CDCl3): δ 8.49(d, J =8.4Hz, 1H), 7.98(m, 1H), 7.70-7.76(m, 3H), 7.53-7.69(m, 2H), 7.52(d, J =8.5Hz, 1H), 7.27-7.35(m, 2H), 7.15-7.24(m, 6H), 6.99(br.s, 1H), 6.48(d, J =1.9Hz, 1H), 5.31(br.s, 2H), 3.71(br.s, 2H), 2.35(s, 3H), 2.03(s, 3H), 1.34(d, J =6.8Hz, 6H), 1.28(d, J =6.8Hz, 6H).

[0467] Complex 4-HfMe2

[0468]

[0469] The complex 4-HfCl2 (500 mg, 0.59 mmol) was dissolved in dry dichloromethane (50 mL), and a solution of MeMgBr in diethyl ether (0.51 mL, 2.9 M) was added to the solution at room temperature. The resulting mixture was stirred overnight at room temperature. The evaporation was then evaporated under reduced pressure, the residue was extracted with toluene, and filtered through a short diatomaceous earth mat. The filtrate was evaporated under reduced pressure, and the residue was recrystallized from a toluene / hexane mixture to give the complex 4m (200 mg, 43%) as yellow crystals. 1 H NMR (400MHz, CDCl3): δ 8.41(d, J =8.3Hz, 2H), 7.91 (dd, J =8.0Hz, J =1.2Hz, 1H), 7.83 (dd, J =7.2Hz, J =1.3Hz, 1H), 7.75(br.s, 1H), 7.71(m, 1H), 7.60(br.s, 1H), 7.48(d, J =8.3Hz, 1H), 7.44(br.s, 2H), 7.31(br.s, 2H), 7.28(m, 1H), 7.18-7.22(m, 3H), 6.65(d, J =1.9Hz, 1H), 6.59 (d, J =1.9Hz, 1H), 5.86(m, 1H), 4.49(m, 1H), 3.81(sept, J =6.8Hz, 2H), 2.47(s, 3H), 2.02(s, 3H), 1.23-1.31(m, 12H), -0.17(s, 3H), -0.82(s, 3H). 13 C NMR (100MHz, CDCl3) δ 166.0, 157.6, 154.8, 148.2, 146.4, 145.1, 141.1, 137.8, 136.0, 134.5, 132.6, 131.9, 130.8, 129.0, 128.7, 128.2, 128.0, 127.4, 127.0, 125.2, 125.1, 124.1, 123.6, 120.1, 119.7, 119.0, 66.7, 57.3, 56.3, 45.2, 27.8, 27.6, 27.2, 25.9, 24.5, 20.4.

[0470] Complex 5-HfMe3

[0471]

[0472] A solution of MeMgBr in diethyl ether (3.4 mL, 2.9 M) and a solution of 2-(2-(((2,6-diisopropylphenyl)amino)methyl)quinoline-8-yl)-4-methyl-6-(2,7-di-tert-butylcarbazole-9-yl)phenol (750 mg, 1.07 mmol) in toluene (20 mL) were successively added to a suspension of HfCl4 (349 mg, 1.07 mmol) in toluene (50 mL). The reaction mixture was stirred overnight at room temperature. Then, hexane (50 mL) was added to the mixture, and the resulting suspension was filtered through a diatomaceous earth sieve. The filtrate was evaporated under reduced pressure, and the residue was dissolved in toluene and filtered through a diatomaceous earth sieve. The filtrate was evaporated under reduced pressure, and the residue was recrystallized from the toluene / hexane mixture to give the complex 5-HfMe3 (510 mg, 52%) as a white solid. 1 H NMR (400MHz, C6D6): δ 8.08(d, J =8.1Hz, 2H), 7.92(s, 2H), 7.65(dd, J =7.0Hz, J =1.6Hz, 1H), 7.46 (d, J =1.8Hz, 1H), 7.39 (d, J =8.3Hz, 2H), 7.37(br.s, 2H), 7.14-7.23(m, 2H), 7.01(m, 3H), 6.77(d, J =1.9Hz, 1H), 6.54 (d, J =8.3Hz, 1H), 5.26 (m, 1H), 4.50 (m, 1H), 3.87 (m, 1H), 3.19 (m, 1H), 2.19 (s, 3 H), 1.10-1.51 (m, 30H), 0.49 (br.s, 3H), -0.42 (br.s, 3H), -0.83 (br.s, 3H).

[0473] Complex 6-HfMe2

[0474]

[0475] To a suspension of 576 mg (1.80 mmol) HfCl4 in 50 mL of dry toluene, 3.02 mL (8.10 mmol, 2.7 M) of MeMgBr in diethyl ether was added in a single addition. The resulting mixture was stirred for 10 min, and 800 mg (1.00 mmol) of a solution of 2-(tert-butyl)-6-((6-((((2,6-diisopropylphenyl)amino)methyl)pyridin-2-yl)methyl)-4-methylphenol in 10 mL of dry toluene was added dropwise over 5 min. The reaction mixture was stirred overnight at room temperature, and then the solvent was evaporated to near dryness under reduced pressure. The solid residue was extracted with 2 × 20 mL of hot toluene, the combined extracts were filtered through a short diatomaceous earth sachet, and the filtrate was evaporated under reduced pressure. The resulting solid was washed with 10 × 2 mL of n-pentane and dried under vacuum. Yield: 610 mg (49%) of the complex 6-HfMe2, as a white solid. 1 H NMR (C6D6, 400MHz): δ 7.25-7.33 (m, 3H), 7.19 (d, J =2.1Hz, 1H), 6.85 (d, J =2.0Hz, 1H), 6.65(t, J =7.6Hz, 1H), 6.44 (d, J =7.6Hz, 1H), 6.16 (d, J =8.0Hz, 1H), 4.82-4.94(m, 2H, AB), 4.54(d, J =13.1Hz, 1H, AB), 4.36 (sept, J =6.9Hz, 1H), 3.46 (sept, J =6.9Hz, 1H), 3.23(d, J =13.1Hz, 1H, AB), 2.29(s, 3H), 1.62(d, J =6.9Hz, 3H), 1.61(s, 9H), 1.36(d, J =6.9Hz, 6H), 1.28 (d, J =6.9Hz, 3H), 0.74 (s, 3H), 0.41 (s, 3H). 13 C NMR (CDCl3, 100MHz): δ163.1, 159.5, 158.3, 149.0, 145.3, 144.8, 139.5, 137.8, 128.7, 127.7, 127.5, 127.0, 125.0, 123.9, 123.8, 122.2, 118.9, 67.7, 55.0, 47.4, 40.0, 34.7, 29.8, 29.7, 27.7, 27.5, 26.9, 26.3, 25.2, 24.3, 20.84, 20.82.

[0476] Complex 7-HfMe2

[0477]

[0478] To a suspension of 153 mg (0.48 mmol) HfCl4 in 50 mL of dry toluene, 0.695 mL (2.02 mmol, 2.9 M) of MeMgBr in diethyl ether was added in a single addition. The resulting mixture was stirred for 10 minutes, and 250 mg (0.48 mmol) of a solution of 2-(adamantane-1-yl)-6-((6-((((2,6-diisopropylphenyl)amino)methyl)pyridin-2-yl)methyl)-4-methylphenol in 10 mL of dry toluene was added dropwise over 5 minutes. The reaction mixture was stirred overnight at room temperature, and then the solvent was evaporated under reduced pressure. The residue was extracted with 2 × 20 mL of hot toluene, the combined extracts were filtered through a short diatomaceous earth sachet, and the filtrate was evaporated under reduced pressure. The residue was washed with 10 × 2 mL of n-pentane and dried under vacuum. Yield: 252 mg (72%) of the complex 7-HfMe2, as a white solid. 1 H NMR (C6D6, 400MHz): δ 7.24-7.33 (m, 3H), 7.18 (d, J =1.9Hz, 1H), 6.87 (d, J =1.9Hz, 1H), 6.68(t, J =7.8Hz, 1H), 6.45 (d, J =7.2Hz, 1H), 6.15(d, J =7.2Hz, 1H), 4.83-4.96(m, 2H, AB), 4.54(d, J =13.2Hz, 1H, AB), 4.39 (sept, J =6.9Hz, 1H), 3.47 (sept, J =6.9Hz, 1H), 3.24 (d, J=13.2Hz, 1H, AB), 2.42-2.51(m, 3H), 2.32-2.38(m, 3H), 2.34(s, 3H), 2.15(br.s, 3H), 1.92-2.00(m, 3H), 1.71-1.80(m, 3H), 1.62(d, J =6.9Hz, 3H), 1.40(d, J =6.9Hz, 3H), 1.34(d, J =6.9Hz, 3H), 1.28 (d, J =6.9Hz, 3H), 0.76 (s, 3H), 0.44 (s, 3H). 13 C NMR (C6D6, 100MHz): δ 163.2, 160.0, 159.9, 150.0, 145.9, 145.1, 139.6, 139.0, 129.7, 129.2, 128.9, 128.5, 128.3, 126.1, 124.8, 124.7, 122.0, 118.7, 68.6, 57.5, 48.3, 41.5, 40.6, 38.0, 37.7, 29.9, 28.7, 28.3, 27.6, 27.3, 25.7, 25.2, 21.5.

[0479] Complex 7-ZrMe2

[0480]

[0481] 0.695 mL (2.02 mmol, 2.9 M) of MeMgBr in diethyl ether was added in a single addition to a suspension of 112 mg (0.48 mmol) ZrCl4 in 50 mL of dry toluene at room temperature. The resulting mixture was stirred for 10 min, and 250 mg (0.48 mmol) of a solution of 2-(adamantane-1-yl)-6-((6-((((2,6-diisopropylphenyl)amino)methyl)pyridin-2-yl)methyl)-4-methylphenol in 10 mL of dry toluene was added dropwise over 5 min. The reaction mixture was stirred overnight at room temperature and then evaporated under reduced pressure. The residue was extracted with 2 × 20 mL of hot toluene, the combined extracts were filtered through a short diatomaceous earth stencil, and the filtrate was evaporated under vacuum. The residue was washed with 10 × 2 mL of n-pentane and dried under vacuum. Yield: 233 mg (76%) of the complex 7-ZrMe2 as a white solid. 1 H NMR (C6D6, 400MHz): δ 7.21-7.33 (m, 3H), 7.16 (d, J =1.9Hz, 1H), 6.87 (d, J= 1.9 Hz, 1H), 6.68 (t, J = 7.7 Hz, 1H), 6.47 (d, J = 7.5 Hz, 1H), 6.16 (d, J = 7.5 Hz, 1H), 4.68-4.84 (m, 2H, AB), 4.50 (d, J = 13.3 Hz, 1H, AB), 4.47 (sept, J = 6.9 Hz, 1H), 3.39 (sept, J = 6.9 Hz, 1H), 3.26 (d, J = 13.3 Hz, 1H, AB), 2.46-2.51 (m, 3H), 2.32-2.39 (m, 3H), 2.33 (s, 3H), 2.14 (br.s, 3H), 1.92-2.00 (m, 3H), 1.73-1.80 (m, 3H), 1.64 (d, J = 6.9 Hz, 3H), 1.38 (d, J = 6.9 Hz, 3H), 1.35 (d, J = 6.9 Hz, 3H), 1.27 (d, J = 6.9 Hz, 3H), 0.92 (s, 3H), 0.61 (s, 3H). 13 ¹³C NMR (C₆D₆, 100 MHz): δ 162.7, 159.9, 159.4, 150.0, 145.4, 144.7, 139.5, 138.4, 129.7, 129.3, 128.9, 128.5, 128.3, 126.2, 126.0, 124.8, 121.8, 118.6, 68.4, 49.3, 41.5, 41.0, 39.4, 38.0, 37.6, 30.0, 28.8, 28.4, 27.5, 27.2, 25.7, 25.1, 21.5.

[0482] Complex 8-HfMe₂

[0483]

[0484] At room temperature, 0.760 mL (2.80 mmol, 3.7 M) of MeMgBr in diethyl ether was added in a single addition to a suspension of 290 mg (0.62 mmol) of HfCl4 in 50 mL of dry toluene. The resulting mixture was stirred for 10 minutes, and 350 mg (0.48 mmol) of a solution of 2-(adamantane-1-yl)-6-(1-(6-((((2,6-diisopropylphenyl)amino)methyl)pyridin-2-yl)-2-methylprop-1-en-1-yl)-4-methylphenol in 10 mL of dry toluene was added dropwise for 1 minute. The reaction mixture was stirred overnight at room temperature, and the solvent was evaporated under reduced pressure. The residue was extracted with 2 × 20 mL of hot toluene, the combined extracts were filtered through a short diatomaceous earth pad, and the filtrate was evaporated under reduced pressure. The residue was washed with 10 × 2 mL of n-pentane and dried under vacuum to give 395 mg (83%) of the complex 8-HfMe2 as a beige solid. 1 H NMR (CD2Cl2, 400MHz): δ 7.86(t, J =7.7Hz, 1H), 7.12-7.30(m, 5H), 7.04(d, J =1.9Hz, 1H), 6.85 (d, J =1.9Hz, 1H), 5.07 (d, J =20.6Hz, 1H, AB), 4.94(d, J =20.6Hz, 1H, AB), 4.19 (sept, J =6.9Hz, 1H), 3.18 (sept, J =6.9Hz, 1H), 2.27(s, 3H), 2.20-2.29(m, 3H), 2.10-2.16(m, 3H), 2.02(br.s, 3H), 1.79-1.85(m, 3H), 1.64-1.75(m, 3H), 1.70(s, 3H), 1.57(s, 3H), 1.41(d, J =6.9Hz, 3H), 1.30(d, J =6.9Hz, 3H), 1.14(d, J =6.9Hz, 3H), 1.12(d, J =6.9Hz, 3H), 0.11(s, 3H), -0.31(s, 3H). 13 CNMR (CD2Cl2, 100MHz): δ164.0, 160.5, 159.2, 151.0, 146.0, 145.4, 140.1, 138.8, 138.7, 132.8, 131.6, 129.0, 128.7, 128.2, 125.1, 124.23, 124.18, 123.3, 119.5, 68.3, 55.4, 48.6, 41.2, 37.7, 37.5, 29.8, 28.2, 27.9, 27.2, 27.0, 25.2, 24.8, 21.9, 21.6.

[0485] Complex 8-ZrMe2

[0486]

[0487] To a suspension of 145 mg (0.62 mmol) ZrCl4 in 50 mL of dry toluene, 0.760 mL (2.80 mmol, 3.7 M) of MeMgBr in diethyl ether was added in a single addition. The resulting mixture was stirred for 10 minutes, and a solution of 350 mg (0.48 mmol) of 2-(adamantane-1-yl)-6-(1-(6-(((2,6-diisopropylphenyl)amino)methyl)pyridin-2-yl)-2-methylprop-1-en-1-yl)-4-methylphenol in 10 mL of dry toluene was added dropwise for 1 minute. The reaction mixture was stirred overnight at room temperature, and the solvent was evaporated under reduced pressure. The residue was extracted with 2 × 20 mL of hot toluene, the combined extracts were filtered through a short diatomaceous earth pad, and the filtrate was evaporated under reduced pressure. The residue was washed with 10 × 2 mL of n-pentane and dried under vacuum to give 370 mg (87%) of the complex 8-ZrMe2 as a beige solid. 1 H NMR (CD2Cl2, 400MHz): δ 7.84(t, J =7.7Hz, 1H), 7.10-7.28(m, 5H), 7.04(d, J =1.9Hz, 1H), 6.85 (d, J =1.9Hz, 1H), 4.96 (d, J =20.8Hz, 1H, AB), 4.82(d, J =20.8Hz, 1H, AB), 4.29(sept, J =6.9Hz, 1H), 3.12(sept, J=6.9Hz, 1H), 2.23-2.31(m, 3H), 2.27(s, 3H), 2.11-2.20(m, 3H), 2.03(br.s, 3H), 1.80-1.87(m, 3H), 1.66-1.73(m, 3H), 1.71(s, 3H), 1.55(s, 3H), 1.43(d, J =6.9Hz, 3H), 1.31(d, J =6.9Hz, 3H), 1.13(d, J =6.9Hz, 3H), 1.12(d, J =6.9Hz, 3H), 0.29 (s, 3H), -0.10 (s, 3H). 13 CNMR (CD2Cl2, 100MHz): δ 163.5, 160.4, 158.6, 151.3, 145.4, 144.9, 140.0, 138.6, 138.2, 133.1, 132.0, 129.1, 128.1, 127.8, 125.1, 124.3, 124.2, 123.0, 119.4, 68.1, 47.4, 41.3, 39.3, 37.8, 37.5, 29.8, 28.2, 28.0, 27.1, 27.0, 25.2, 24.7, 21.8, 21.6.

[0488] Aggregate Examples

[0489] A solution of the precatalyst was prepared using toluene (ExxonMobil Chemical - anhydrous, stored under N2) (98%). The precatalyst solution was typically 0.5 mmol / L.

[0490] Solvents, polymerization-grade toluene, and / or isohexane were supplied by ExxonMobil Chemical Co. and purified by passing through a series of columns: two 500cc Oxyclear tubes in series from Labclear (Oakland, Calif.), followed by two 500cc columns in series packed with dry 3Å molecular sieves (8-12 mesh; Aldrich Chemical Company), and two 500cc columns in series packed with dry 5Å molecular sieves (8-12 mesh; Aldrich Chemical Company).

[0491] 1-Octenene (C8; 98%, Aldrich Chemical Company) was dried by stirring overnight on NaK and then filtering through alkaline alumina (Aldrich Chemical Company, Brockman Basic 1).

[0492] Polymer-grade ethylene (C2) was used and further purified by passing it through a series of columns: a 500cc Oxyclear tube from Labclear (Oakland, Calif.), followed by a 500cc column packed with dry 3Å molecular sieves (8-12 mesh; Aldrich Chemical Company), and a 500cc column packed with dry 5Å molecular sieves (8-12 mesh; Aldrich Chemical Company).

[0493] Polymer-grade propylene (C3) was used and further purified by passing it through a series of columns: a 2250cc Oxiclear tube from Labclear, followed by a 2250cc column packed with 3Å molecular sieves (8-12 mesh; Aldrich Chemical Company), then two 500cc columns in series packed with 5Å molecular sieves (8-12 mesh; Aldrich Chemical Company), then a 500cc column packed with Selexsorb CD (BASF), and finally a 500cc column packed with Selexsorb COS (BASF).

[0494] Activation of the precatalyst was performed using methylaluminoxane (MAO, 10 wt% in toluene, Albemarle Corp.; ActID=M) or dimethylphenylammonium tetra(perfluorophenyl)borate (Boulder Scientific or Albemarle Corp.; ActID=D). MAO was used as a 0.5 wt% or 1.0 wt% solution in toluene. The micromolar numbers of MAO reported in the experimental section are based on the micromolar numbers of aluminum in MAO. The molecular weight of MAO is 58.0 g / mol. Dimethylphenylammonium tetra(perfluorophenyl)borate was typically used as a 0.5 mmol / L solution in toluene.

[0495] For polymerization operations using dimethylphenylammonium tetra(perfluorophenyl)borate, tri-n-octylaluminum (TnOAl, pure, AkzoNobel) is used as a scavenger before introducing the activator and pre-catalyst into the reactor. TnOAl is typically used as a 5 mmol / L solution in toluene.

[0496] Reactor description and preparation :

[0497] Polymerization was carried out in an autoclave equipped with an external heater for temperature control, a glass insert (reactor internal volume = 23.5 mL for C2 and C2 / C8; 22.5 mL for C3 operation), a diaphragm inlet, controlled nitrogen, ethylene, and propylene supply, and a disposable PEEK mechanical stirrer (800 RPM) in an inert atmosphere (N2) drying chamber. The autoclave was prepared by purging with dry nitrogen at 110°C or 115°C for 5 hours, followed by purging at 25°C for 5 hours.

[0498] Ethylene polymerization (PE) or ethylene / 1-octene copolymerization (EO) :

[0499] Prepare the reactor as described above, then purge with ethylene. For MAO (Act ID=M) activation, add toluene, 1-octene (0.100 mL for use), and activator (MAO) via syringe at room temperature and atmospheric pressure. Then bring the reactor to the process temperature (80°C) and charge with ethylene to the process pressure (75 psig = 618.5 kPa or 200 psig = 1480.3 kPa) while stirring at 800 RPM. Then add the pre-catalyst solution to the reactor via syringe under process conditions. For dimethylphenylammonium tetrafluorophenylborate (Act ID=D) activation, add toluene, 1-octene (100 μL for use), and tris(n-octyl)aluminum scavenger (TnOAl, 0.5 μmol) via syringe at room temperature and atmospheric pressure. The reactor was then brought to the process temperature (80°C) and charged with ethylene to the process pressure (75 psig = 618.5 kPa or 200 psig = 1480.3 kPa) while stirring at 800 RPM. The activator solution, followed by the pre-catalyst solution, was then injected into the reactor via a syringe under process conditions. During polymerization, ethylene was introduced into the autoclave (using a computer-controlled solenoid valve) to maintain the reactor gauge pressure (+ / - 2 psig). The reactor temperature was monitored and typically maintained within + / - 1°C. Polymerization was stopped by adding approximately 50 psi of compressed dry air gas mixture to the autoclave for approximately 30 seconds. Polymerization was quenched after the predetermined cumulative amount of ethylene had been added (maximum quenching value psid) or after a maximum of 30 minutes of polymerization time. The reactor was then cooled and vented. The polymer was separated after removing the solvent under vacuum. The reported yield includes the total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer per mmol of transition metal compound per hour of reaction time (g / mmol·hr). The ethylene homopolymerization and ethylene / 1-octene copolymerization operations are summarized in Table 1.

[0500] Polypropylene (PP) :

[0501] Prepare the reactor as described above, then heat it to 40°C and purge it with propylene gas at atmospheric pressure. For MAO activation, add toluene or isohexane, MAO, and liquid propylene (1.0 mL) via a syringe. Then heat the reactor to the process temperature (70°C or 100°C) while stirring at 800 RPM. Add the pre-catalyst solution via a syringe while the reactor is under process conditions. For dimethylphenylammonium tetrafluorophenyl borate activation, add toluene or isohexane, liquid propylene (1.0 mL), and tris(n-octyl)aluminum scavenger (TnOAl, 0.5 μmol) via a syringe. Then bring the reactor to the process temperature (70°C or 100°C) while stirring at 800 RPM. Inject the activator solution, followed by the pre-catalyst solution, into the reactor via a syringe under process conditions. Monitor the reactor temperature and typically maintain it within + / - 1°C. Stop the polymerization by adding a mixture of approximately 50 psi of compressed dry air to the autoclave for approximately 30 seconds. The polymerization was quenched based on a predetermined pressure loss of 8 psid (maximum quenching value) or a maximum of 30 minutes. The reactor was then cooled and evacuated. The polymer was separated after the solvent was removed under vacuum. The actual quenching time (s) is reported as quenching time (s). The reported yield includes the total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer per mmol of transition metal compound per hour of reaction time (g / mmol·hr). Examples of propylene homopolymerization are reported in Table 2.

[0502] Polymer characterization

[0503] For analytical testing, a polymer sample solution was prepared by dissolving the polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity, from Sigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%, from Aldrich) at 165°C for approximately 3 hours. Typical polymer concentrations in the solution ranged from 0.1 to 0.9 mg / mL, and BHT concentrations were 1.25 mg BHT / mL TCB. The sample was then cooled to 135°C for testing.

[0504] High-temperature size exclusion chromatography was performed using an automated “rapid GPC” system as described in U.S. Patents 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388, each of which is incorporated herein by reference. Molecular weight (weight-average molecular weight (Mw) and number-average molecular weight (Mn)) and molecular weight distribution (MWD = Mw / Mn), also known as polymer polydispersity (PDI), were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector (ELSD) and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) from 5,000 to 3,390,000). Alternatively, samples were measured by gel permeation chromatography using a Symyx Technology GPC equipped with a dual-wavelength infrared detector and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) 580 to 3,039,000). Samples were run using three Polymer Laboratories: PLgel 10μm Mixed-B 300x7.5mm columns in tandem at an elution rate of 2.0 mL / min (sample temperature 135°C, oven 165°C / column) (injecting 250 μL of polymer solution from TCB into the system). Column diffusion correction was not employed. Epoch, available from Symyx Technologies, was used. ® Numerical analysis can be performed using Automation Studio software available from Freeslate. The obtained molecular weights are relative to linear polystyrene standards. Molecular weight data are reported in Tables 1 and 2 under the headings Mn, Mw, Mz, and PDI as defined above.

[0505] Differential scanning calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point of the polymer. The sample was pre-annealed at 220 °C for 15 min and then allowed to cool to room temperature overnight. The sample was 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 heating. The results are reported in Tables 1 and 2 under the heading Tm (°C).

[0506] Samples for infrared analysis were prepared by depositing a stabilized polymer solution onto a silanized wafer (part number S10860, Symyx). Approximately 0.12 to 0.24 mg of polymer was deposited on the wafer unit using this method. The samples were then analyzed on a Brucker Equinox 55FTIR spectrometer equipped with a Pikes' MappIR specular reflection sample accessory. The analysis was performed at 2 cm⁻¹. -1 Data was collected at a resolution of 32 scans covering a depth of 5000 cm. -1 Up to 500cm -1 The spectrum of the spectral range.

[0507] For ethylene-1-octene copolymer, measurements were taken at ~1375 cm⁻¹. -1 The methyl deformation at the position determines the weight percentage of octene in the copolymer. This is achieved through combination and overtone bands (~4321 cm⁻¹). -1 The peak height of this band is normalized (at the location), which corrects for path length differences. The normalized peak height is then compared with that from... 1 Individual calibration curves of H NMR data were correlated to predict the wt% octene content in the concentration range of ~2 wt% to 35 wt% octene. Typically, an R-value of 0.98 or greater is achieved. 2 Relevance. These figures are reported in Table 1 under heading C8 weight %

[0508] The aggregation results are collected in Tables 1 and 2 below. “Ex#” represents the instance number. Under the Ex# column heading, the following abbreviations are defined:

[0509] PE = Polyethylene, EO = Ethylene-1-octene copolymer, PP = Polypropylene, CPE = Comparative Polyethylene, CEO = Comparative Ethylene-1-octene copolymer

[0510] CPP = Comparative polypropylene. Examples beginning with "C", such as CPP and CPE, are comparative examples. "Cat ID" indicates the precatalyst used in the experiment. The corresponding number indicates that the precatalyst (also referred to as a precatalyst, complex, or compound) is located in the synthesis experiment section. "Cat (μmol)" is the amount of precatalyst added to the reactor. For all experiments using dimethylphenylammonium tetra(perfluorophenyl)borate (Act ID = D), the molar ratio of activator / precatalyst is 1.1. For all experiments using MAO (Act ID = M) as the activator, a molar ratio of 500 Al / M is used unless otherwise specified. T (°C) is the polymerization temperature, typically maintained within ±1°C. "Yield" is the polymer yield and is not corrected for catalyst residue. "Quenching time (s)" is the actual duration of the polymerization run in seconds. For ethylene-based polymerization runs, "Quenching value (psid)" is the set maximum (conversion) amount of ethylene absorption in the experiment. If the polymerization quenching time is less than the set maximum time, polymerization continues until the set maximum amount of ethylene absorption is reached. For propylene homopolymer operation, the quench value represents the maximum set pressure loss (conversion) of propylene (for PP operation) during polymerization. Activity is reported as grams of polymer per mmol of catalyst per hour.

[0511] Table 1. Examples of ethylene homopolymerization and ethylene / 1-octene copolymerization

[0512] General reaction conditions The total solvent volume, including catalyst, activator, and diluent, is 5.0 ml toluene (for ethylene homopolymerization) and 4.9 ml toluene (for ethylene-octene copolymerization), with 0.1 mL 1-octene (shown in the table in microliters (µL)); 25 nmol pre-catalyst and 500 equivalents of Act ID M or 1.1 equivalents of Act ID D; polymerization temperature of 80 °C; ethylene absorption at 75 or 200 psi; when using 75 psi ethylene, the quenching value is set to 20 psid ethylene absorption, and when using 200 psi ethylene, the quenching value is set to 15 psid ethylene absorption, or a maximum time of 30 minutes. This indicates that the reported FTIR value is outside the calibration range.

[0513] Table 1

[0514]

[0515]

[0516] Table 1- (Continued)

[0517]

[0518]

[0519] Table 1- (Continued)

[0520]

[0521]

[0522] Table 1– (Continued)

[0523]

[0524]

[0525] Table 1- (Continued)

[0526]

[0527]

[0528] Table 1– (Continued)

[0529]

[0530]

[0531] Table 1– (Continued)

[0532]

[0533] Table 2: Examples of Propylene Polymerization

[0534] General reaction conditions Total solvent volume including catalyst, activator, and diluent: 4.1 ml solvent; 1.0 ml propylene; pre-catalyst amount and activator dosage listed in the table; TnOAl (500 nmol) used when using ActID D; polymerization carried out at 70°C or 100°C as indicated; quenching set to 8 psi loss or a maximum time of 30 minutes.

[0535] Table 2

[0536]

[0537] Table 2- (Continued)

[0538]

[0539] Table 2- (Continued)

[0540]

[0541] Table 2– (Continued)

[0542]

[0543] Table 2– (Continued)

[0544]

[0545] Table 2- (Continued)

[0546]

[0547] In general, the catalyst compounds of this disclosure having phenolic-heterocyclic-amino ligands coordinated with Group 4 transition metals can form catalyst compounds having five-membered rings in addition to seven-membered rings. The catalyst compounds of this disclosure can provide high molecular weight polymers with high catalytic activity, which can be used in commercial polymer production.

[0548] Unless otherwise stated, the phrases "consist essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether or not they are specifically mentioned in this specification, provided that such steps, elements, or materials do not affect the essential and novel features of this disclosure. Furthermore, they do not exclude impurities and variations commonly associated with the elements and materials used.

[0549] For the sake of brevity, only certain ranges are explicitly disclosed in this document. However, a range derived from any lower limit can be combined with any upper limit to describe an unspecified range, and a range derived from any lower limit can be combined with any other lower limit to describe an unspecified range; similarly, a range derived from any upper limit can be combined with any other upper limit to describe an unspecified range. Furthermore, a range includes every point or individual value between its endpoints, even if not explicitly stated. Thus, each point or individual value can serve as its own lower or upper limit, combined with any other point or individual value or any other lower or upper limit, to describe an unspecified range.

[0550] All references cited herein are incorporated herein by reference, including any priority documents and / or testing procedures, provided they are not inconsistent with this text. As will be apparent from the foregoing general description and specific embodiments, various modifications may be made without departing from the spirit and scope of this disclosure, despite the form described and illustrated herein. Therefore, this disclosure is not intended to be limited thereto. Similarly, for the purposes of U.S. law, the term “comprising” is considered synonymous with the term “including.” Likewise, whenever the transitional phrase “comprising” precedes a composition, element, or group of elements, it should be understood that we also contemplate the same composition or group of elements preceding the description of the composition, element, or plurality of elements with the transitional phrases “substantially constitutes,” “consisting of,” “selected from,” or “is,” and vice versa.

[0551] Although this disclosure has been described with respect to various embodiments and examples, those skilled in the art who benefit from this disclosure will understand that other embodiments can be devised without departing from the scope and spirit of this disclosure.

Claims

1. A catalyst comprising: Chemical structure represented by formula (I): (I) in: M is a transition metal from Group 3, 4, 5 or 6, or a lanthanide metal; A 2 Selected from unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, and substituted heteroaryl groups; J is a heterocyclic Lewis base; E 1 Selected from unsubstituted hydrocarbon groups, substituted hydrocarbon groups, unsubstituted silyl hydrocarbon groups, and substituted silyl hydrocarbon groups; E 2 Selected from unsubstituted hydrocarbon groups, substituted hydrocarbon groups, unsubstituted silyl hydrocarbon groups, and substituted silyl hydrocarbon groups; J and E 2 Optional fusion to form one or more unsubstituted hydrocarbon rings, substituted hydrocarbon rings, unsubstituted heterocycles, or substituted heterocycles; Each L is an independent Lewis base; Each X is an anionic ligand independently; n is 1, 2, or 3; m is 0, 1, or 2; n+m is 4 or less; R 1 Selected from unsubstituted C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, unsubstituted C1-C 40 Heteroatom-containing groups and substituted C1-C 40 Groups containing heteroatoms; Any two L groups can bond together to form a bidentate Lewis base; The X group can combine with the L group to form a monoanionic bidentate group; and Any two X groups can join together to form a bianionic ligand group.

2. The catalyst according to claim 1, wherein L is independently selected from ethers, amines, phosphines, thioethers, and esters.

3. The catalyst according to claim 2, wherein L is independently selected from Et2O, MeO t Bu, Et3N, PhNMe2, MePh2N, tetrahydrofuran, and dimethyl sulfide.

4. The catalyst according to claim 1, wherein X is independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydroxyl, chlorine, fluorine, bromine, iodine, trifluoromethanesulfonate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino.

5. The catalyst according to any one of claims 1 to 4, wherein E 1 Selected from C(R) 15 (R) 16 ) and Si(R 15 (R) 16 ), where R 15 and R 16 Independently selected from hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms and C1-C 40 Groups containing heteroatoms.

6. The catalyst according to any one of claims 1 to 5, wherein R 1 It is selected from methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, isopropylphenyl, diisopropylphenyl, triisopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, tri-tert-butylphenyl, methylisopropylphenyl, methyl-tert-butylphenyl, ethyl-isopropylphenyl, ethyl-tert-butylphenyl, methylnaphthyl, ethylnaphthyl, isopropylnaphthyl and tert-butylnaphthyl.

7. The catalyst according to any one of claims 1 to 6, wherein A 2 It can be represented by the following structure: Where R 11 R 12 R 13 and R 14 Each is independently selected from hydrogen, unsubstituted C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom, substituted C1-C 40 Heteroatom-containing groups and unsubstituted C1-C 40 Groups containing heteroatoms.

8. The catalyst according to claim 7, wherein R 11 R 12 R 13 and R 14 Each is independently selected from hydrogen, substituted C1-C 30 Hydrocarbon groups and unsubstituted C1-C 30 Hydrocarbon group.

9. The catalyst according to claim 7, wherein R 11 Selected from unsubstituted C1-C 30 Alkyl, substituted C1-C 30 Alkyl, unsubstituted C5-C 30 Cycloalkyl and substituted C5-C 30 cycloalkyl, unsubstituted C1-C 30 Groups containing heteroatoms, substituted C1-C 30 Groups containing heteroatoms, unsubstituted C6-C 30 Aryl and substituted C6-C 30 Aryl.

10. The catalyst according to claim 8, wherein R 13 It is unsubstituted C1-C 20 Hydrocarbon group.

11. The catalyst according to any one of claims 1 to 10, wherein J is selected from: (IA), (IB), and (IC) Where E 3 Selected from O, S and N(R) 10 ), R 2 R 3 R 4 R 5 and R 10 Each is independently selected from hydrogen, unsubstituted C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom, unsubstituted C1-C 30 Heteroatom-containing groups and substituted C1-C 30 Groups containing heteroatoms, where R 2 and R 3 Or R 3 and R 4 One or more pairs of them can join to form one or more hydrocarbon rings, substituted hydrocarbon rings, unsubstituted heterocycles, or substituted heterocycles, each having 5, 6, 7, or 8 ring atoms.

12. The catalyst according to claim 11, wherein R 2 R 3 R 4 and R 5 Each is independently selected from hydrogen, unsubstituted C1-C 40 Hydrocarbon groups and substituted C1-C 40 Hydrocarbon group.

13. The catalyst according to claims 1 to 12, wherein E 2 Selected from C(R) 25 (R) 26 ), Si(R) 25 (R) 26 ) and C = C(R 25 (R) 26 ), where R 25 and R 26 Independently selected from hydrogen, unsubstituted C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom, unsubstituted C1-C 40 Heteroatom-containing groups and substituted C1-C 40 Groups containing heteroatoms, where R 25 and R 26 One or more pairs can join to form one or more unsubstituted hydrocarbon rings, substituted hydrocarbon rings, unsubstituted heterocycles or substituted heterocycles, each having 5, 6, 7 or 8 ring atoms.

14. The catalyst according to any one of claims 1 to 13, wherein E 2 It is bonded to J to form a fused ring structure selected from unsubstituted hydrocarbon rings, substituted hydrocarbon rings, unsubstituted heterocycles, and substituted heterocycles.

15. The catalyst according to claim 14, wherein the fused ring structure is represented by formula (1D) or (1E): (1D) or (1E) in: E 3 Selected from O, S and N(R) 10 ), where R 2 R 3 R 4 R 5 R 6 R 7 R 8 and R 10 Each is selected from hydrogen, unsubstituted C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom, substituted C1-C 40 Heteroatom-containing groups and substituted C1-C 40 Groups containing heteroatoms.

16. The catalyst according to claim 15, wherein R 2 R 3 R 4 R 5 R 6 R 7 and R 8 Each is hydrogen.

17. The catalyst according to claim 15, wherein R 2 and R 3 R 3 and R 4 R 6 and R 7 R 7 and R 8 and R 3 and R 6 One or more pairs of hydrocarbon rings fused together to form unsubstituted or substituted hydrocarbon rings.

18. The catalyst according to claim 1, wherein the catalyst is selected from:

19. A method for producing polyolefins, the method comprising: By using one or more C2-C 20 α-olefin monomers and catalyst systems are introduced into a reactor to polymerize one or more C2-C... 20 α-olefin monomers to form polyolefin polymers, the catalyst system comprising an activator and a catalyst compound according to any one of claims 1-18.

20. The method of claim 19, wherein one or more C2-C 20 α-olefin monomers include ethylene.

21. The method of claim 19, wherein one or more C2-C 20 α-olefin monomers include propylene.

22. The method of claim 19, wherein one or more C2-C 20 α-olefin monomers include ethylene and C3-C 12 α-olefins.

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