Bis(heterocyclic - alkoxide) Lewis base catalysts and methods thereof

Abstract

The present disclosure relates to bis (heterocycle-alkoxide) Lewis base catalysts.The catalyst, catalyst system and method of the present disclosure can provide high temperature ethylene polymerization, propylene polymerization or copolymerization, because bis (heterocycle-alkoxide) Lewis base catalysts can be stable and have good activity at high polymerization temperature.The stable catalyst with good activity can provide polymer with high molecular weight or have the formation of polymer as low as very low molecular weight compared with conventional catalyst, and the ability of preparing the polymer of increased amount in a given reactor.Therefore, the present disclosure illustrates that the highly active catalyst of the polymer with controlled molecular weight and or robust isotacticity can be produced simultaneously by operating at high reactor temperature.

Description

[0001] Inventor: John R.Hagadorn, Irene C.Cai, Hua Zhou, Jo Ann M.Canich

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 085,766, filed September 30, 2020, the disclosure of which is incorporated herein by reference.

[0004] field

[0005] The present disclosure relates to bis(heterocyclic-olate) Lewis base transition metal complexes, including bis(thiophen-3-olate) Lewis base transition metal complexes, and other related complexes, catalyst systems containing such complexes, and polymerization processes using the catalyst systems to produce olefin polymers, such as ethylene-based polymers and / or propylene-based polymers.

[0006] background

[0007] Olefin polymerization catalysts have very large purposes in industry and polyolefins are widely used commercially due to their robust physical properties. Therefore, there is interest in finding new catalyst systems that improve the market value of catalysts and allow the production of polymers with improved properties. Physical properties (such as transition temperature, viscosity etc.) and mechanical properties (such as strength, stiffness and toughness) are affected by the molecular weight of polymers, so catalyst systems that change molecular weight etc. are desirable.

[0008] Low molecular weight polyolefins such as low density polyethylene (LDPE) or ultra-low molecular weight polyethylene such as polyethylene wax are one of the most versatile products in the chemical industry, can be used for multiple products and application, and are widely used in hot melt adhesives and softening agents, or for wax and wax additive production.Yet, development can operate under high reactor temperatures for the production of interested controlled molecular weight polyolefins and the highly active catalyst still has challenge.On the other hand, polyolefins with high molecular weight such as high molecular weight polyethylene (HMWPE) or ultra-high molecular weight polyethylene (UHMWPE) have valuable mechanical properties conventionally.

[0009] In addition, the procatalyst (neutral, unactivated complex) should be thermally stable at and above ambient temperature because they are often stored for long periods of time before use. The performance of a given catalyst is closely affected by reaction conditions such as monomer concentration and temperature. From this perspective, solution processes that benefit from operating at temperatures above 120°C are particularly challenging for catalyst development. At such high reactor temperatures, it is often difficult to maintain high catalyst activity and high molecular weight capacity because both properties generally decrease with increasing reactor temperature. Due to the need for a variety of polyolefin products, from high density polyethylene (HDPE) to lower density materials such as low density polyethylene and elastomers (e.g., thermoplastic elastomers (TPE), ethylene-propylene-diene (EPDM)), many different catalyst systems may be required because a single catalyst will not be able to address all the needs for producing these different polyolefin products. The stringent and varied requirements required to develop and produce new polyolefin products make determining the appropriate catalyst for a given product and production process a highly challenging task.

[0010] There is a need for new and improved catalysts, catalyst systems and methods for the polymerization of olefins to achieve polymer properties such as narrow (e.g., low) polydispersity indexes while controlling the molecular weight of the polymer (e.g., high or low molecular weight as desired). In addition, there remains a need to develop highly active catalysts that can operate at high reactor temperatures (e.g., catalysts with high stability and good activity at high polymerization temperatures) while producing polymers with controlled molecular weights. In the case of polypropylene, there is also a need to provide catalysts and methods for isotactic polypropylene having one or more of the aforementioned properties.

[0011] References of interest include: WO 2018 / 236863, WO 2018 / 236996, WO 2020 / 132244, WO 2020 / 167799, US 7,030,256, US 2020 / 0255556, US 2020 / 0255555, US 2020 / 0254431, US 2020 / 0255553, Baier, M. et al. (2014) “Post-Metallocenes in the Industrial Production of Poly-Polyefins,” Angew. Chem. Int. Ed., Vol. 53, pp. 9722-9744, KR 2018 / 022137, WO 2016 / 172110, USSN filed February 11, 2020 62 / 972,962, USSN 62 / 972,953 filed on February 11, 2020, USSN 62 / 972,943 filed on February 11, 2020, USSN 62 / 972,936 filed on February 11, 2020, 16 / 788,124 filed on February 11, 2020, and USSN 15 / 744,478 filed on January 12, 2018.

[0012] Overview

[0013] The present disclosure relates to catalyst compounds represented by formula (I):

[0014]

[0015] in:

[0016] M is a Group 3, 4 or 5 metal;

[0017] Each A 1 and A 2 are independently an aromatic group, a substituted aromatic group, or an alkenediyl group;

[0018] Heterocyclic ring fragment-(Z 1 Z 2 )- and –(Z 3 Z 4 )-independently selected from –(Z 5 Z 6 )-or–(Z 6 Z 5 )-, where Z 5 Selected from oxygen, sulfur, S(O), S(O)2 and N(R 50 ), and Z 6 Selected from nitrogen and C(R 51 ), where each R 50 and R51 are independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom;

[0019] R 4 and R 5 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom;

[0020] J is a heterocyclic Lewis base;

[0021] Each Q 1 and Q 2 independently selected from oxygen, sulfur, N(R 30 ) or P(R 30 ), where R 30 It is C1-C 40 Hydrocarbon, substituted C1-C 40 a hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom;

[0022] L is a Lewis base, optionally any two L groups are joined together to form a bidentate Lewis base;

[0023] X is an anionic ligand, optionally the X group is joined to an L group to form a monoanionic bidentate group, or optionally any two X groups are joined together to form a dianionic ligand;

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

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

[0026] n+m is not greater than 4, such as 1, 2, 3 or 4;

[0027] In yet another embodiment, the present disclosure provides a catalyst system comprising an activator and a catalyst of the present disclosure.

[0028] In yet another embodiment, the present disclosure provides a polymerization process comprising a) contacting one or more olefin monomers with a catalyst system comprising: i) an activator and ii) a catalyst of the present disclosure.

[0029] In yet another embodiment, the present disclosure provides polyolefins formed by the catalyst systems and / or methods of the present disclosure.

[0030] In another class of embodiments, the present disclosure provides a process for producing an ethylene alpha-olefin copolymer comprising reacting ethylene and at least one C3-C4 copolymer in at least one continuous stirred tank reactor or loop reaction.20 α-olefins are contacted with the catalyst system of the present disclosure to polymerize ethylene and at least one C3-C 20 α-olefins.

[0031] In another class of embodiments, the present disclosure provides a process for producing a propylene alpha-olefin copolymer comprising reacting propylene and at least one ethylene and / or at least one C4-C4 copolymer in at least one continuous stirred tank reactor or loop reactor. 20 The α-olefins are contacted with the catalyst system of the present disclosure to polymerize propylene and at least one of ethylene and / or C4-C 20 α-olefins.

[0032] In at least one embodiment, the catalyst compound is represented by formula (I), wherein the compound is characterized by a tridentate dianionic ligand coordinated to the metal to form a pair of eight-membered metallocyclic rings. In at least one embodiment, the catalyst compound represented by formula (I) has the following structure, wherein M, Q 1 , containing Z 1 Z 2 Ring, A 1 The ring formed by M, Q 2 , containing Z 3 Z 4 Ring, A 2 The ring formed with J is an eight-membered ring.

[0033] BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Attachment Figure 1 ( Figure 1 ) shows the general synthetic route of the bis(heterocycle-alcohol) Lewis base ligands and bis(heterocycle-alkoxide) Lewis base complexes of the present invention.

[0035] Attachment Figure 2 ( Figure 2 ) shows the synthetic route of 2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-phenylthiophen-3-ol) and transition metal complexes.

[0036] Details

[0037] The present disclosure provides catalyst compounds, catalyst systems including such catalyst compounds and uses thereof, wherein the catalyst compounds include a bis(heterocycle-alkoxide) Lewis base tridentate ligand coordinated to a transition metal center to form two eight-membered rings. In at least one embodiment, the central Lewis base fragment (of a bis(heterocycle-alkoxide) Lewis base tridentate ligand) is a heterocyclic ring with 5 or 6 ring atoms, which may include one or more heteroatoms, for example, at least one of which is nitrogen. The five-membered heterocycle may be, for example, azole. The six-membered heterocycle may be, for example, pyridine.

[0038] The catalyst compound of the present disclosure can be a zirconium or hafnium-containing compound having two heterocyclic ring-alkoxides, such as two thiophene-3-alkoxides or substituted thiophene-3-alkoxides, attached to a central Lewis base. In another embodiment, the present disclosure relates to a polymerization process for producing a polyolefin polymer from a catalyst system comprising one or more olefin polymerization catalysts, at least one activator, and an optional support. The polyolefin polymer can be an ethylene-containing polymer and / or a propylene-containing polymer and / or a polymer containing a higher alpha-olefin.

[0039] Bis (heterocycle-alkoxide) Lewis base tridentate ligand is a type of tridentate ligand that can use heterocycle (as neutral Lewis base) such as azole or pyridine group.These ligands and transition metal are coordinated in " tridentate " mode, this means that ligand and metal center form three different keys.The feature of bis (heterocycle-alkoxide) Lewis base complex is for example that ligand combines and forms two eight-membered metal rings in tridentate mode.There is the ligand coordinated with metal in this way, complex is considered to be chiral (i.e. lacking symmetrical mirror plane).Not subject to theoretical constraint, it is believed that when using these catalysts for the production of polypropylene and C3 and other polymers of higher alpha-olefins, chirality is conducive to the production of polyolefins with high isotacticity.

[0040] The catalysts, catalyst systems and methods of the present disclosure can provide high temperature ethylene polymerization, propylene polymerization, ethylene alpha-olefin (e.g., ethylene-1-butene) copolymerization or propylene alpha-olefin copolymerization because the Lewis base catalyst can be stable at high polymerization temperatures and has good activity at high polymerization temperatures. Stable catalysts with good activity can provide the formation of polymers and the ability to prepare increased amounts of polymers in a given reactor compared to conventional catalysts because polymerization generally occurs at higher rates at higher temperatures. In addition, stable catalysts with good activity can also provide the formation of polymers with low molecular weight (e.g., Mw is about 10,500 g / mol or less) to very low molecular weight (e.g., Mw is about 6,000 g / mol or less).

[0041] For the purposes of this disclosure, the new numbering scheme for the periodic table groups as described in Chemical And Engineering News, Vol. 63(5), p. 27 (1985) is used. Thus, a "Group 4 metal" is an element from Group 4 of the periodic table such as Hf, Ti, or Zr.

[0042] The following abbreviations may be used herein: Me is methyl, Et is ethyl, Ph is phenyl, Bn is benzyl, tBu is tert-butyl, MAO is methylaluminoxane, NMR is nuclear magnetic resonance, t is time, s is seconds, h is hours, psi is pounds per square inch, psig is pounds per square inch gauge, equiv is equivalent, It is angstrom, and RPM is revolutions per minute.

[0043] Description of the invention Transition metal complexes are described. The term complex is used to describe molecules wherein an auxiliary ligand is coordinated to a central transition metal atom. The ligand is bulky and stably attached to the transition metal, thereby maintaining its influence during, for example, polymerization in the use of a catalyst. The ligand can be coordinated to the transition metal by covalent bonds and / or electron donation or intermediate bonds. Transition metal complexes are activated conventionally using activators to produce their polymerization or oligomeric functions, without being bound by theory, and the activator is believed to produce cations as a result of removing anionic groups (commonly referred to as leaving groups) from the transition metal.

[0044] As used herein, "olefin polymerization catalyst(s)" refers to any catalyst capable of coordination addition polymerization, such as an organometallic complex or compound, in which successive monomers are added to the monomer chain at an organometallic active center.

[0045] The terms "substituent," "radical," "group," and "moiety" are used interchangeably.

[0046] "Conversion" is the amount of monomer converted to polymer product and is reported as mol% and is calculated based on polymer yield and the amount of monomer fed to the reactor.

[0047] "Catalyst productivity" is a measure of the mass of polymer produced using a known amount of polymerization catalyst. Typically, "catalyst productivity" is expressed in units such as (g polymer) / (g catalyst) or (g polymer) / (mmol catalyst). If no units are specified, "catalyst productivity" is expressed in units of (g polymer) / (g catalyst). To calculate catalyst productivity, only the weight of the transition metal component of the catalyst is used (i.e., omitting the activator and / or co-catalyst). For batch and semi-batch polymerizations, "catalyst activity" is a measure of the mass of polymer produced using a known amount of polymerization catalyst / unit time. Typically, "catalyst activity" is expressed in units such as (g polymer) / (mmol catalyst) / hour or (kg polymer) / (mmol of catalyst) / hour. If no units are specified, "catalyst activity" is expressed in units of (g polymer) / (mmol catalyst) / hour.

[0048] The term "heteroatom" refers to any element of 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" can include the aforementioned elements with attached hydrogens, such as BH, BH2, SiH2, OH, NH, NH2, etc. The term "substituted heteroatom" describes a heteroatom in which one or more of these hydrogen atoms is replaced by a hydrocarbyl group or substituted hydrocarbyl group(s). The term "monovalent heteroatom" refers to a non-carbon element of Groups 13-17, which may (or may not) have attached hydrogens that can form a single covalent bond, such as, but not limited to -F, -Cl, -Br, -I, -OH, -SH, -NH2, -PH2, -SiH3, -GeH3, -BH2. The term "heteroatom-bonded monovalent group" refers to partially substituted non-carbon Group 13-16 elements that can form a single covalent bond, such as but not limited to -O(R*), -OS(O)2(R*), -OS(O)2CF3, -S(R*), -N(R*)2, -NH(R*), -P(R*)2, -PH(R*), -Si(R*)3, -SiH(R*)2, -SiH2(R*), -Ge(R*)3, -B(R*)2, -BH(R*), wherein R* is a hydrocarbon group or a substituted hydrocarbon group, such as but not limited to alkaryl, alkaryl, alkenyl, alkynyl, cycloalkyl, etc., and wherein two or more adjacent R* can be joined together to form a cyclic or polycyclic structure.

[0049] "Olefins," or as they are also called, "alkene" are linear, branched, or cyclic compounds of carbon and hydrogen with at least one double bond. For the purposes of this specification and the appended claims, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such a polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 35% to 55% by weight, it is understood that the monomer (mer) units in the copolymer are derived from ethylene in the polymerization reaction, and the derived units are present at 35% to 55% by weight based on the weight of the copolymer. A "polymer" has two or more identical or different monomeric units. A "homopolymer" is a polymer having identical monomeric units. A "copolymer" is a polymer having two or more monomeric units that are different from each other. A "terpolymer" is a polymer having three monomeric units that are different from each other. "Different" as used in reference to monomeric units means that the monomeric units differ from each other by at least one atom or are isomerically different. Therefore, as used herein, the definition of copolymer includes terpolymers. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50 mol% of ethylene-derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50 mol% of propylene-derived units, and the like. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50 mol% of ethylene-derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50 mol% of propylene-derived units, and the like.

[0050] The term "α-olefin" refers to an olefin having a terminal carbon-carbon double bond in its structure ((R 1 R 2 )-C=CH2, where R 1 and R 2 can be independently hydrogen or any hydrocarbon group; for example, R 1 is hydrogen and R 2 is an alkyl group). A "linear α-olefin" is an α-olefin as defined above wherein R 1 is hydrogen, and R 2 is hydrogen or a linear alkyl group.

[0051] For purposes of this disclosure, ethylene shall be considered an alpha-olefin.

[0052] As used herein, and unless otherwise specified, the term "C n" means a hydrocarbon(s) having n carbon atoms per molecule, where n is a positive integer. The term "hydrocarbon" means a class of compounds containing hydrogen bonded to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds having different values of n. Likewise, "C m -C y "A group or compound is a group or compound containing carbon atoms whose total number is within the range my. Thus, C1-C 50 An alkyl group refers to an alkyl group containing a total number of carbon atoms in the range of 1-50.

[0053] Unless otherwise indicated (e.g., the definitions of “substituted hydrocarbyl,” “substituted aryl,” etc.), the term “substituted” means that at least one hydrogen atom has been replaced by at least one non-hydrogen group, e.g., a hydrocarbyl group, a heteroatom or a heteroatom-containing group, e.g., a halogen (e.g., Br, Cl, F, or I), or at least one functional group, e.g., -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, wherein each R* is independently a hydrocarbyl or a halohydrocarbyl group, and two or more R* can be joined together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted into the hydrocarbyl ring.

[0054] The term "substituted hydrocarbyl" means a hydrocarbyl group in which at least one hydrogen atom of the hydrocarbyl group has been replaced with at least one heteroatom (e.g., a halogen, such as Br, Cl, F, or I) or 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, wherein each R* is independently a hydrocarbyl or a halohydrocarbyl group, and two or more R* can be joined together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom is inserted into the hydrocarbyl ring. The term "hydrocarbyl-substituted phenyl" means a phenyl group having 1, 2, 3, 4, or 5 hydrogen groups replaced by hydrocarbyl or substituted hydrocarbyl groups. For example, a "hydrocarbyl-substituted phenyl" group can be represented by the formula: where R a 、R b 、R c 、R d and R eEach of which can be independently selected from hydrogen, C1-C 40 Hydrocarbon or C1-C 40 Substituted hydrocarbon group, heteroatom or heteroatom-containing group (provided that R a 、R b 、R c 、R d and R e At least one of them is not H), or R a 、R b 、R c 、R d and R e Two or more of these can be joined together to form C4-C 62 Cyclic or polycyclic hydrocarbon ring structures, or combinations thereof.

[0055] The term "substituted phenyl" means a phenyl group having one or more hydrogen radicals replaced by a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

[0056] The term "substituted carbazole" means a carbazole group having one or more hydrogen groups replaced by a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

[0057] The term "substituted naphthyl" means a naphthyl group having one or more hydrogen groups replaced with a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a group containing a heteroatom.

[0058] The term "substituted anthracenyl" means anthracenyl groups having one or more hydrogen groups replaced with a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

[0059] The term "substituted fluorenyl" means a fluorenyl group having one or more hydrogen radicals replaced with a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

[0060] The term "substituted benzyl" means a benzyl group having one or more hydrogen radicals replaced by a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a group containing a heteroatom. For example, a substituted benzyl group is represented by the formula:

[0061]

[0062] where R a’ 、R b’ 、R c’ 、R d’ and R e’ and Z are each independently selected from hydrogen, C1-C 40 Hydrocarbon or C1-C 40 Substituted hydrocarbon group, heteroatom or heteroatom-containing group (provided that R a’ 、Rb’ 、R c’ 、R d’ and R e’ and at least one of Z is not H), or R a’ 、R b’ 、R c’ 、R d’ and R e’ and two or more of Z may join together to form C4-C 62 Cyclic or polycyclic ring structures, or combinations thereof.

[0063] The terms "alkoxy" and "alkoxide" refer to an alkyl or aryl group bonded to an oxygen atom, such as an alkyl ether or aryl ether group / residue attached to an oxygen atom and may include groups wherein the alkyl / aryl group is C1-C 10 The alkyl groups may be straight chain, branched or cyclic. The alkyl groups may be saturated or unsaturated. Examples of suitable alkoxy groups may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and phenoxy.

[0064] The term "alkenyl" means a straight, branched or cyclic hydrocarbon group having one or more double bonds. These alkenyl groups may be optionally substituted. Examples of suitable alkenyl groups may include vinyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, including substituted analogs thereof.

[0065] The tertiary hydrocarbon group of ring type is defined as the tertiary hydrocarbon group that forms at least one ester ring (non-aromatic) ring.The tertiary hydrocarbon group of ring type is also referred to as alicyclic tertiary hydrocarbon group.When hydrocarbon group is an alkyl group, the tertiary hydrocarbon group of ring type is also referred to as tertiary alkyl group or alicyclic tertiary alkyl group.The example of the tertiary hydrocarbon group of ring type comprises 1-adamantyl, 1-methylcyclohexyl, 1-methylcyclopentyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclododecyl, bicyclo [3.3.1] nonyl-1-base, bicyclo [2.2.1] heptyl-1-base, bicyclo [2.3.3] hexamethylene-1-base, bicyclo [1.1.1] penta-1-base, bicyclo [2.2.2] pungent-1-base etc.The tertiary hydrocarbon group of ring type can be illustrated by formula B: where R A is a hydrocarbyl group or a substituted hydrocarbyl group, each R D are independently hydrogen or a hydrocarbyl group or a substituted hydrocarbyl group, w is an integer from 1 to about 30, and R A , and one or more R D , and two or more R D They may optionally be bonded to each other to form additional rings.

[0066] When the cyclic tertiary hydrocarbyl group contains more than one alicyclic ring, it can be referred to as a polycyclic tertiary hydrocarbyl group, or if the hydrocarbyl group is an alkyl group, it can be referred to as a polycyclic tertiary alkyl group.

[0067] The terms "alkyl group" and "alkyl" are used interchangeably in this disclosure. For the purposes of this disclosure, an "alkyl group" is defined as a C1-C 100 Alkyl groups, which may be linear, branched or cyclic. Examples of such groups may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, including substituted analogs thereof. A substituted alkyl group is a group in which at least one hydrogen atom of the alkyl group has been replaced by at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom or a heteroatom-containing group, such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, or -PbR*3, and each R* is independently a hydrocarbyl or halogenated hydrocarbyl group, and two or more R* can be joined together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted into the hydrocarbyl ring.

[0068] The term "aryl" or "aryl group" means an aromatic ring and substituted variants thereof, for example, phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl means an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom, for example, N, O, or S.

[0069] As used herein, and unless otherwise specified, the term "aromatic" refers to unsaturated heterocycles or unsaturated cyclic hydrocarbons having a delocalized conjugated π system, and pseudoaromatic heterocycles, which are heterocycles having properties and structures similar to aromatic heterocyclic ligands (almost planar), but which are not aromatic by definition (Huckel's law). Preferred aromatic compounds include unsaturated cyclic hydrocarbons, typically C6 unsaturated cyclic hydrocarbons.

[0070] The term "substituted aryl" means an aryl group having one or more hydrogen radicals replaced by a hydrocarbyl group, a substituted hydrocarbyl group, a monovalent heteroatom, or a monovalent group in combination with a heteroatom.

[0071] The term "alkenediyl" refers to a divalent -C(R j )=C(R j )-group, wherein each R jindependently selected from hydrogen, C1-C 40 Alkyl or substituted C1-C 40 Alkyl, C6-C 40 Aryl or substituted C6-C 40 Aryl, monovalent heteroatom, monovalent group combined with heteroatom, and wherein adjacent R j The groups may be joined to form a ring.

[0072] The term "aralkyl" means an aryl group in which a hydrogen has been replaced by an alkyl or substituted alkyl group. For example, 3,5'-di-tert-butyl-phenylindenyl is an indene substituted with an aralkyl group. When an aralkyl group is a substituent on another group, it is bonded to the group through the aryl group.

[0073] The term "alkaryl" means an alkyl group in which a hydrogen has been replaced by an aryl or substituted aryl group. For example, phenethylindenyl is an indene substituted with an ethyl group attached to a phenyl group. When an alkaryl group is a substituent on another group, it is attached to that group through the alkyl group.

[0074] When isomers of a given alkyl, alkenyl, alkoxy, or aryl group exist (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), reference to one member of that group (e.g., n-butyl) explicitly discloses the remaining isomers in that family (e.g., isobutyl, sec-butyl, and tert-butyl). Similarly, reference to an alkyl, alkenyl, alkoxy, or aryl group without specifying a specific isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0075] The term "ring atoms" means atoms that are part of a cyclic ring structure. According to this definition, a benzyl group has 6 ring atoms and tetrahydrofuran has 5 ring atoms.

[0076] A heterocyclic ring is a ring having heteroatoms in the ring structure, in contrast to a heteroatom-substituted ring in which hydrogen atoms on the ring atoms are replaced by heteroatoms. For example, tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles can include pyridine, imidazole, and thiazole.

[0077] The term "azole" means a five-membered heterocyclic compound containing nitrogen, at least one other non-carbon atom (e.g., nitrogen, sulfur, or oxygen) as part of the heterocyclic ring and two double bonds. Azoles are aromatic compounds. Examples of azoles may include pyrazole, imidazole, thiazole, Azoles, isocyanates Azoles and azaphospholes.

[0078] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" are used interchangeably and are defined to mean a group consisting solely of hydrogen and carbon atoms. For example, a hydrocarbyl radical may be C1-C 100 A group which can be linear, branched or cyclic and which can be aromatic or non-aromatic when cyclic. Examples of such groups can include, but are not limited to, alkyl groups such as methyl, ethyl, propyl (e.g., n-propyl, isopropyl, cyclopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (e.g., isopentyl, cyclopentyl), hexyl (e.g., cyclohexyl), octyl (e.g., cyclooctyl), nonyl, decyl (e.g., adamantyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or triacontyl, and aryl groups such as phenyl, benzyl and naphthyl.

[0079] Unless otherwise indicated, as used herein, "low comonomer content" is defined as a polyolefin having less than 8 weight percent comonomer, based on the total weight of the polyolefin. As used herein, "high comonomer content" is defined as a polyolefin having greater than or equal to 8 weight percent comonomer, based on the total weight of the polyolefin.

[0080] 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 percent, and mol% is the mole percent. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., Mw, Mn, Mz) are reported in g / mol.

[0081] Unless otherwise specified, as used herein, "high molecular weight" is defined as a weight average molecular weight (Mw) value of 100,000 g / mol or greater. "Low molecular weight" is defined as an Mw value of less than 100,000 g / mol, for example, 10,500 g / mol or less. "Very low molecular weight" is defined as an Mw value of 6,000 g / mol or less.

[0082] Unless otherwise indicated, all melting points (Tm) are differential scanning calorimetry (DSC) second melts.

[0083] A "catalyst system" is a combination of at least one catalyst compound, at least one or more activators, optional co-activators, and optional support materials. The terms "catalyst compound," "catalyst complex," "transition metal complex," "transition metal compound," "procatalyst compound," and "procatalyst complex" are used interchangeably. When "catalyst system" is used to describe such a pair before activation, it refers to the unactivated catalyst complex (procatalyst) together with the activator and optional co-activator. When it is used to describe such a pair after activation, it refers to the activated complex and the activator or other charge-balancing moieties. The transition metal compound can be neutral (as in a procatalyst) or a charged species with a counterion (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 will be fully understood by those skilled in the art that the ionic form of the component is the form that reacts with the monomer to produce a polymer. A polymerization catalyst system is a catalyst system that can polymerize monomers into polymers. In addition, the catalyst compounds and activators represented by the chemical formulas herein include both neutral and ionic forms of the catalyst compounds and activators.

[0084] In the description herein, the catalyst may be described as a catalyst, a catalyst precursor, a procatalyst compound, a catalyst compound, or a transition metal compound, and these terms may be used interchangeably.

[0085] An "anionic ligand" is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A "Lewis base" is a neutrally charged ligand that donates one or more pairs of electrons to a metal ion. Examples of Lewis bases include ethyl ether, trimethylamine, pyridine, tetrahydrofuran, dimethyl sulfide, and triphenylphosphine. The term "heterocyclic Lewis base" refers to a Lewis base that is also a heterocyclic ring. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, 1,3-azaphosphazoline, and furan.

[0086] The term "continuous" means a system that operates without interruption or stopping. For example, a continuous process to produce a polymer would be one in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

[0087] transition metal complexes

[0088] In at least one embodiment, the present disclosure is directed to catalyst compounds having a bis(heterocycle-alkoxide) Lewis base tridentate ligand, such as a bis(thiophene-3-alkoxide) tridentate ligand, coordinated to a Group 3, 4, or 5 transition metal center to form two eight-membered rings.

[0089] The catalyst compound can be represented by formula (I):

[0090]

[0091] in:

[0092] M is a Group 3, 4 or 5 metal, preferably a Group 4 metal;

[0093] Each A 1 and A 2 are independently an aromatic group, a substituted aromatic group, or an alkenediyl group;

[0094] Heterocyclic ring fragment-(Z 1 Z 2 )- and –(Z 3 Z 4 )-independently selected from –(Z 5 Z 6 )-or–(Z 6 Z 5 )-, where Z 5 Selected from oxygen, sulfur, S(O), S(O)2 and N(R 50 ), and Z 6 Selected from nitrogen and C(R 51 ), where each R 50 and R 51 are independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, or phenyl);

[0095] R 4 and R 5 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group combined with a heteroatom (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, cyclohexyl, phenyl, or carbazolyl);

[0096] J is a heterocyclic Lewis base (e.g., pyridine);

[0097] Each Q 1 and Q 2 independently selected from oxygen, sulfur, N(R 30 ) or P(R 30 ), where R 30 It is C1-C 40 Hydrocarbon, substituted C1-C 40a hydrocarbon group, a monovalent heteroatom, or a monovalent group combined with a heteroatom (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, cyclohexyl, phenyl, or carbazolyl);

[0098] L is a Lewis base, optionally any two L groups are joined together to form a bidentate Lewis base (e.g., ether, amine, phosphine, thioether, ester, Et2O, MeOtBu, Et3N, PhNMe2, MePh2N, tetrahydrofuran, and dimethyl sulfide);

[0099] X is an anionic ligand, optionally the X group is joined to the L group to form a monoanionic bidentate group, or optionally any two X groups are joined together to form a dianionic ligand (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, benzyl, trimethylsilyl, neopentyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, triflate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino);

[0100] n is 1, 2, or 3;

[0101] m is 0, 1, or 2; and

[0102] n+m is not greater than 4, such as 1, 2, 3 or 4;

[0103] In at least one embodiment, the catalyst compound is represented by formula (I), wherein the compound is characterized by a tridentate dianionic ligand comprising three heterocyclic rings, and wherein the tridentate dianionic ligand is coordinated to the metal to form a pair of eight-membered metallocycle rings. In at least one embodiment, the catalyst compound represented by formula (I) has the following structure, wherein M, Q 1 , containing Z 1 Z 2 Ring, A 1 The ring formed by J is an eight-membered ring and is composed of M, Q 2 , containing Z 3 Z 4 Ring, A 2 The ring formed by M, Q and J is an eight-membered ring having the following structure: 1 , containing Z 1 Z 2 Ring, A 1 The ring formed by J is an eight-membered ring, and the ring formed by M, Q 2 , containing Z 3 Z 4 Ring, A 2 The ring formed with J is an eight-membered ring.

[0104] The heterocyclic Lewis base (J) of formula (I) is a bridge A 1 and A 2 The divalent group of the group and coordinates to the metal center M as a neutral 2-electron donor. The Lewis base J can be an aromatic or non-aromatic heterocycle. The heterocyclic Lewis base J can be a heterocyclic Lewis base with 5 or 6 ring atoms. In at least one embodiment, J is a heterocycle containing Group 15, or a heterocycle containing Group 16, for example, J is a nitrogen-containing heterocycle, an oxygen-containing heterocycle, a phosphorus-containing heterocycle, or a sulfur-containing heterocycle. For example, the 5-membered heterocyclic Lewis base can include thiazole, isothiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, thiophene, Azoles, isocyanates Azoles, Oxazoline (e.g. 2- Oxazoline, 3- Oxazoline, 4- oxazoline), oxazolidine, imidazole, furan, thiofuran, pyrrole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, phosphazene, azaphosphazene or isomers thereof, which may be substituted or unsubstituted.

[0105] In at least one embodiment, J is a heterocyclic ring having 5 ring atoms. In at least one embodiment, J is a heterocyclic ring having 6 ring atoms. In alternative embodiments of the present invention, J contains 1, 2 or more ring atoms that are heteroatoms. Preferably, when J is a six-membered ring, the ring contains 1 ring heteroatom, preferably J contains one of S, N, P or O as a ring atom. Alternatively, when J is a five-membered ring, the ring contains at least 1 heteroatom ring atom, preferably J contains at least one of S, N, P or O as a ring atom. Alternatively, J can be a five-membered ring and the ring contains at least 2 heteroatom ring atoms (which can be the same or different), preferably J contains at least two of S, N, P or O as ring atoms (which can be the same or different). In a preferred embodiment, the heterocyclic Lewis base (J) is pyridine or a substituted pyridine.

[0106] Heterocyclic ring fragment-(Z 1 Z 2 )- and –(Z 3 Z 4 )- is each portion of a group referred to in this document as a heterocyclic-ol, such as thiophen-3-ol (when neutrally charged) or a heterocyclic-olate, such as thiophen-3-olate (when deprotonated to form an anion).

[0107] For example, a heterocycle-alcohol group is represented by any of the following formulae:

[0108]

[0109] in represents the connection to the rest of the compound, and wherein Q 1 and Q 2 Selected from OH, SH, NH(R 30 ) or PH(R 30 ) and Z 1 , Z 2 , Z 3 , Z 4 、R 4 、R 5 and R 30 As defined above.

[0110] The heterocycle-alkoxide group is represented by any of the following formulae:

[0111]

[0112] in represents the connection to the rest of the compound, and wherein Q 1 and Q 2 Selected from O, S, N(R 30 ) or P(R 30 ) and Z 1 , Z 2 , Z 3 , Z 4 、R 4 、R 5 and R 30 As defined above.

[0113] In at least one embodiment, the heterocyclic ring fragment (of the heterocyclic-alcohol and heterocyclic-alkoxide groups) -(Z 1 Z 2 )- and –(Z 3 Z 4 )-independently selected from -(SC(R 51 ))-or-(C(R 51 )S)-, where each R 50 and R 51 are independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 In a preferred embodiment, -(Z 1 Z 2 )-is –(C(H)S)- and –(Z 3 Z 4)- is –(C(H)S))-; this is equivalent to Z 1 and Z 3 Each is CH, and Z 2 and Z 4 Each is sulfur.

[0114] In at least one embodiment, A 1 It is expressed by the following formula:

[0115]

[0116] in represents the connection to the catalyst compound, and R 9 、R 10 、R 11 and R 12 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group combined with a heteroatom (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl), or R 9 and R 10 、R 10 and R 11 or R 11 and R 12 One or more of the pairs may join to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms.

[0117] In at least one embodiment, A 2 It is expressed by the following formula:

[0118]

[0119] in represents the connection to the catalyst compound, and R 13 、R 14 、R 15 and R 16 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group combined with a heteroatom (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl), or R 13 and R 14 、R 14 and R 15 or R 15 and R16 One or more of the pairs may join to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms.

[0120] In at least one embodiment, J is represented by the formula:

[0121]

[0122] in represents the connection to the catalyst compound, and R 17 is hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon groups, monovalent heteroatoms or monovalent groups incorporating heteroatoms (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl). E may be oxygen (such that J is azole), sulfur (such that J is thiazole) or N(alkyl) (such that J is imidazole).

[0123] In at least one embodiment, J is represented by the formula:

[0124]

[0125] in represents a connection to the catalyst compound, and Z 7 Selected from nitrogen and C(R 18 ), and Z 8 Selected from nitrogen and C(R 19 ), and R 17 and R 18 and R 19 Each of which is selected from hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, phenyl).

[0126] In at least one embodiment, the catalyst compound represented by formula (I) is represented by formula (II) or formula (III):

[0127]

[0128] in:

[0129] Each Q 1 and Q 2 independently selected from oxygen, sulfur, N(R30 ) or P(R 30 ), where R 30 It is C1-C 40 Hydrocarbon, substituted C1-C 40 a hydrocarbon group, a monovalent heteroatom, or a monovalent group combined with a heteroatom (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, cyclohexyl, phenyl, or carbazolyl);

[0130] Heterocyclic ring fragment-(Z 1 Z 2 )- and –(Z 3 Z 4 )-Selected from–(Z 5 Z 6 )-or–(Z 6 Z 5 )-, where Z 5 Selected from oxygen, sulfur, S(O), S(O)2 and N(R 50 ), and Z 6 Selected from nitrogen and C(R 51 ), where each R 50 and R 51 are independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, cyclohexyl, phenyl);

[0131] Z 7 Selected from nitrogen and C(R 18 );

[0132] Z 8 Selected from nitrogen and C(R 19 );

[0133] E is oxygen, sulfur or N(R 20 );

[0134] R 4 and R 5 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group combined with a heteroatom (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, cyclohexyl, phenyl, or carbazolyl);

[0135] R 9、R 10 、R 11 and R 12 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group combined with a heteroatom (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, cyclohexyl, phenyl, carbazolyl), or R 9 and R 10 、R 10 and R 11 or R 11 and R 12 One or more of the pairs may join to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms;

[0136] R 13 、R 14 、R 15 and R 16 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group combined with a heteroatom (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, cyclohexyl, phenyl, carbazolyl), or R 13 and R 14 、R 14 and R 15 or R 15 and R 16 One or more of the pairs may join to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms;

[0137] R 17 、R 18 、R 19 and R 20 Each of them is hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom or a monovalent group combined with a heteroatom (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, phenyl), or R 17 and R 18 、R 18 and R 19One or more of the pairs may join together to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms;

[0138] M is a Group 3, 4 or 5 metal;

[0139] L is a Lewis base;

[0140] X is an anionic ligand;

[0141] n is 1, 2, or 3;

[0142] m is 0, 1, or 2;

[0143] n+m is not greater than 4;

[0144] Any two L groups can be joined together to form a bidentate Lewis base;

[0145] The X group can be joined to the L group to form a monoanionic bidentate group; and

[0146] Any two X groups can be joined together to form a dianionic ligand.

[0147] The metal M of formula (I), formula (II) or formula (III) may be a Group 3, 4 or 5 metal, for example, M may be a Group 4 metal. Group 4 metals may include zirconium, titanium and hafnium. In a preferred embodiment, M is zirconium or hafnium.

[0148] Group Q of formula (I), formula (II) or formula (III) 1 and Q 2 It can be oxygen, sulfur, N(R 30 ) or P(R 30 ), where R 30 It is C1-C 40 Hydrocarbon, substituted C1-C 40 A hydrocarbon group, a monovalent heteroatom or a monovalent group in combination with a heteroatom (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, phenyl). In a preferred embodiment, Q 1 and Q 2 It's all oxygen.

[0149] Each L of Formula (I), Formula (II) or Formula (III) may be independently selected from ethers, amines, phosphines, thioethers, esters, Et2O, MeOtBu, Et3N, PhNMe2, MePh2N, tetrahydrofuran and dimethyl sulfide, and each X may be independently selected from C1-C 40 Hydrocarbon, substituted C1-C 40Hydrocarbyl, monovalent heteroatom or monovalent group in combination with heteroatom, such as but not limited to methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrogen, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamino, diethylamino, dipropylamino and diisopropylamino. In at least one embodiment, in formula (I), formula (II) or formula (III), n is 2 and each X is independently chloro or methyl.

[0150] R of formula (II) or formula (III) 17 Can be hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon groups, monovalent heteroatoms, or monovalent groups in combination with heteroatoms (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, phenyl). In at least one embodiment, R 17 It's hydrogen.

[0151] E of formula (III) may be selected from oxygen (such that J is azole), sulfur (such that J is thiazole) or N(R 20 )(such that J is imidazole), wherein R 20 is hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon groups, monovalent heteroatoms, or monovalent groups incorporating heteroatoms (e.g., F, Cl, Br, I, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, phenyl). In at least one embodiment, E is selected from sulfur, oxygen, or NMe.

[0152] R of formula (II) or formula (III) 4 and R 5 Each of which can be independently selected from hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, or phosphino (e.g., F, Cl, Br, I, F, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, phenyl). In at least one embodiment, R 4 and R 5 Each is C4-C 40 Cyclic tertiary hydrocarbon groups. For example, R 4 and R 5 Can be independently C1-C 10 Alkyl groups, such as R 4 and R 5Can be tert-butyl or adamantyl. In at least one embodiment, R 4 and R 5 independently selected from unsubstituted phenyl, substituted phenyl, unsubstituted carbazole, substituted carbazole, unsubstituted naphthyl, substituted naphthyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted fluorenyl or substituted fluorenyl, a monovalent heteroatom or a monovalent group in combination with a heteroatom, such as R 4 and R 5 may be independently unsubstituted phenyl or 3,5-di-tert-butylbenzyl. In addition, (1) R 4 Can be C1-C 20 Alkyl (such as R 4 may be tert-butyl) and R 5 It can be an aryl group, or (2) R 5 Can be C1-C 20 Alkyl (such as R 5 may be tert-butyl) and R 4 Alternatively, R 4 and / or R 5 Can be independently a monovalent heteroatom such as R 4 and R 5 It may be a halogen atom (such as Br, Cl, F or I).

[0153] R of formula (II) or formula (III) 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 and R 17 Each of which can independently be hydrogen or C1-C 10 Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, adamantyl), preferably R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 and R 17 R is independently hydrogen, methyl, ethyl, propyl or isopropyl. 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 and R 17is hydrogen. Alternatively, R of formula (II) or formula (III) 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 and R 17 Each of these may independently be hydrogen, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy or trimethylsilyl.

[0154] In at least one embodiment, the catalyst compound of formula (II) is one or more of the following, wherein M = Group 4 metal (eg, Hf, Zr, or Ti); R = halide, C1-C 20 Hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, benzyl, trimethylsilyl, neopentyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino):

[0155]

[0156]

[0157]

[0158]

[0159] In at least one embodiment, the catalyst compound of formula (III) is one or more of the following, wherein M = Group 4 metal (eg, Hf, Zr, or Ti); R = halide, C1-C 20 Hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, adamantyl, benzyl, trimethylsilyl, neopentyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino):

[0160]

[0161]

[0162] In at least one embodiment, one or more different catalyst compounds are present in the catalyst system. One or more different catalyst compounds may be present in the reaction zone in which the process(es) described herein are carried out. The same activator may be used for the transition metal compound, however, two different activators may be used in combination, such as a non-coordinating anion activator and an alumoxane.

[0163] The two transition metal compounds (procatalysts) may be used in any ratio. The molar ratio of the (A) transition metal compound to the (B) transition metal compound may be in the range of (A:B) from 1:1000 to 1000:1, alternatively from 1:100 to 500:1, alternatively from 1:10 to 200:1, alternatively from 1:1 to 100:1, alternatively from 1:1 to 75:1, and alternatively from 5:1 to 50:1. The specific ratio selected will depend on the exact procatalyst selected, the activation method, and the desired end product. In at least one embodiment, when two procatalysts are used, both activated using the same activator, the mole percentages based on the molecular weight of the procatalysts may be 10% to 99.9% A to 0.1% to 90% B, alternatively 25% to 99% A to 0.5% to 75% B, alternatively 50% to 99% A to 1% to 50% B, and alternatively 75% to 99% A to 1% to 10% B.

[0164] Method for preparing catalyst compound

[0165] Methods for preparing the catalysts described herein are described below. Figure 1 The general synthetic routes for preparing the bis(heterocycle-alcohol) Lewis base ligands and bis(heterocycle-alkoxide) Lewis base transition metal complexes of the present invention are described. Catalyst compounds of this type are synthesized as described below (including the examples below), wherein a variety of reaction methods are available to obtain the free ligand in order to join the three fragments (i.e., the heterocycle group, the aryl linker group, and the heterocycle-alcohol, such as the thiophen-3-ol group). Figure 1 The abbreviations used in the following are: p is a protecting group; examples of suitable protecting groups include, but are not limited to, methoxymethyl (MOM), ethoxymethyl, tetrahydropyranyl ether (THP), and benzyl. R is a hydrocarbon group or a monovalent heteroatom or a monovalent group incorporating heteroatoms; examples include phenyl, mesityl, cumyl, methyl, tert-butyl, isopropyl, cyclohexyl, adamantyl, methylcyclohexyl, and carbazolyl. Metal M 1 is a Group 1 or 2 metal or metal halide; examples include lithium, magnesium chloride, and magnesium bromide. Metal M 2is a Group 11 or 12 metal or metal halide; examples include copper, zinc, copper chloride, and zinc chloride. J-Br2 represents a dibrominated heterocyclic Lewis base; examples include 2,6-dibromopyridine, 2,6-dibromo-4-methylpyridine, 2,4-dibromo-1-methyl-1H-imidazole, 2,4-dibromo azole, 2,5-dibromothiophene, 2,5-dibromofuran, 2,5-dibromo-3-hexylthiophene. 1 Z 2 ), the metal M, the anionic ligand X and the heterocycle J are as described above.

[0166] The protected heterocycle-alcohol ( Figure 1 The S1 in (S2) is lithiated to form a lithium derivative S2. This lithium derivative is converted into a boric acid ester (S3) by reacting with 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The Negishi coupling of compound S3 and 2-bromoiodobenzene will form a bromoaromatic derivative S4. The alternative path for S4 will be to slowly add 1-bromo-2-chlorobenzene to compound S2. Derivative S4 can be metallized to form S5 by reacting with butyllithium or magnesium metal. Compound S5 will then be converted into S6 by reacting with a main group metal halide such as zinc chloride or copper chloride. Compound S6 can then be joined with J-Br2 in a Pd- or Ni-catalyzed coupling to form a bis(heterocycle-alcohol) Lewis base ligand after deprotection. Alternatively, compound S5 can be converted into S7 by reacting with 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. S7 can then be converted to S8 via Negishi coupling with J-Br2, followed by deprotection. Once the free ligand is prepared, the free ligand (S8) can be converted to the corresponding transition metal complex (S9) by reaction with a metal-containing reagent. Examples of suitable metal-containing reagents may include metal halides, metal amides, and organometallic compounds. For example, the metal-containing reagent may include ZrCl4, HfCl4, Zr(NMe2)2Cl2(1,2-dimethoxyethane), Hf(NMe2)2Cl2(1,2-dimethoxyethane), Zr(NMe2)4, Hf(NEt2)4, Zr(CH2Ph)4, Hf(CH2Ph)4, or TiCl4. The free ligand may be: i) reacted directly with the metal-containing reagent; or ii) deprotonated by reaction with a main group metal reagent (e.g., BuLi, NaH, iPrMgBr, MeMgBr) and then reacted with a transition metal reagent. Alternatively, the metal halide reagent can be reacted with an alkylating agent, such as an organomagnesium reagent, to form a transition metal organometallic species in situ, which can then react with the free ligand to form the catalyst complex.

[0167] Activator

[0168] The terms "cocatalyst" and "activator" are used interchangeably herein.

[0169] The catalyst system described herein comprises a catalyst complex as described above and an activator such as alumoxane or a non-coordinating anion, and can be formed by combining the catalyst components described herein with an activator (including combining them with a carrier such as silica) in any manner known from the literature. The catalyst system can also be added to solution polymerization or bulk polymerization (in monomer) or produced in solution polymerization or bulk polymerization (in monomer). The catalyst system of the present disclosure can have one or more activators and one, two or more catalyst components. An activator is defined as any such 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 can, for example, include alumoxane, alkyl aluminum, ionizing activators (which can be neutral or ionic) and conventional type cocatalysts. Suitable activators can include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that capture reactive σ-bonded metal ligands, thereby making the metal compound a cation and providing a non-coordinating or weakly coordinating anion such as a non-coordinating anion with charge balance.

[0170] In at least one embodiment, the catalyst system comprises an activator and a catalyst compound of formula (I), (II), or (III). The identity of the activator, in combination with the identity of the catalyst compound of formula (I), (II), or (III), can be used to influence the activity of the catalyst. For example, in the case of polymerization or copolymerization of olefins such as ethylene, when the catalyst compound of formula (I), (II), or (III) is combined with an ionizing / non-coordinating anion activator (e.g., N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate), the catalyst activity of the catalyst compound of formula (I), (II), or (III) can be ≥30,000 gP·mmolcat -1 .h -1 , for example 35,000gP.mmolcat -1 .h -1 or larger, such as 40,000 gP.mmolcat -1 .h -1 or larger, such as 50,000 gP.mmolcat -1 .h -1 or larger, such as 75,000 gP.mmolcat -1 .h -1 or larger, such as 100,000 gP.mmolcat -1 .h-1 or larger, such as 150,000 gP.mmolcat -1 .h -1 or greater, such as 200,000 gP.mmolcat -1 .h -1 or larger, such as 250,000 gP.mmolcat -1 .h -1 or greater, such as 300,000 gP.mmolcat -1 .h -1 or greater, such as 400,000 gP.mmolcat -1 .h -1 or greater (e.g., about 379,906 gP.mmolcat -1 .h -1 ). In addition, when the catalyst compound of formula (I), formula (II) or formula (III) is combined with an aluminoxane activator (such as MAO), the catalyst activity of the catalyst compound of formula (I), formula (II) or formula (III) can be ≤30,000 gP.mmolcat -1 .h -1 , for example, about 50 gP.mmolcat -1 .h -1 - About 30,000gP.mmolcat -1 .h -1 , for example, about 100 gP.mmolcat -1 .h -1 - About 25,000gP.mmolcat -1 .h -1In addition, the characteristics of the activator can be used in combination with the characteristics of the catalyst compound of formula (I), formula (II), or formula (III) to influence the molecular weight of the polymer product and the Tm of the polymer product. For example, when an ionizing / non-coordinating anion activator (e.g., N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate) is combined with a catalyst compound of formula (I), formula (II), or formula (III), a low or very low molecular weight polymer (e.g., <100,000 g / mol, e.g., from about 1,000 g / mol to about 20,000 g / mol, e.g., from about 2,000 g / mol to about 15,000 g / mol) can be formed and can have a Tm value that is less than the Tm value of a polymer formed using an aluminoxane activator (e.g., MAO). In contrast, when an aluminoxane activator (e.g., MAO) is combined with a catalyst compound of Formula (I), Formula (II), or Formula (III), high molecular weight polymers (e.g., ≥100,000 g / mol, e.g., from about 100,000 g / mol to about 3,000,000 g / mol, e.g., from about 500,000 g / mol to about 2,000,000 g / mol) can be formed and can have Tm values that are higher than the Tm values of polymers formed using ionizing / non-coordinating anion activators.

[0171] Aluminoxane activator

[0172] Aluminoxane activators are used as activators in the catalyst systems described herein. Aluminoxanes are typically alkyl ... a”’ )-O- subunit oligomer compound, wherein R a”’ is an alkyl group. Examples of aluminoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable for use as catalyst activators, particularly when the extractable ligand is an alkyl, halo, alkoxy or amino group. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. It may be appropriate to use visually clear methylalumoxane. The turbid or gelled aluminoxane can be filtered to produce a clear solution or the clear aluminoxane can be decanted from the turbid solution. An available aluminoxane is modified methylalumoxane (MMAO) cocatalyst type 3A (available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane Type 3A, encompassed in patent number US 5,041,584, which is incorporated herein by reference). Another useful aluminoxane is solid polymethylaluminoxane as described in US 9,340,630, US 8,404,880, and US 8,975,209, which are incorporated herein by reference.

[0173] When the activator is an alumoxane (modified or unmodified), at least one embodiment selects a maximum activator amount of up to 5,000-fold molar excess Al / M relative to the catalyst compound (per metal catalytic site). The minimum activator to catalyst compound ratio may be a 1:1 molar ratio. Alternative ranges may include 1:1-500:1, alternatively 1:1-200:1, alternatively 1:1-100:1, or alternatively 1:1-50:1.

[0174] In alternative embodiments, little or no alumoxane is used in the polymerization methods described herein. For example, alumoxane may be present at zero mole %, alternatively alumoxane may be present at a molar ratio of aluminum to catalyst compound transition metal of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

[0175] Ionizing / non-coordinating anion activators

[0176] The term "non-coordinating anion" (NCA) means an anion that does not coordinate to the catalyst metal cation or only weakly coordinates to the metal cation, thereby remaining sufficiently unstable to be displaced by a Lewis base. "Compatible" non-coordinating anions are those that will not be degraded to neutrality when the initially formed complex decomposes. In addition, the anion will not transfer anionic substituents or fragments to the cation so that it forms a neutral transition metal compound and neutral by-products from the anion. Non-coordinating anions useful in accordance with the present disclosure are those that are compatible, stabilizing the transition metal cation in the sense of balancing its ionic charge with +1, and yet remain sufficiently unstable to allow displacement during the polymerization process. The ionizing activators useful herein generally comprise NCAs, particularly compatible NCAs.

[0177] The term NCA is also defined as including multi-component activators such as tetrakis (pentafluorophenyl) boric acid N, N-dimethylanilinium that contain NCA, which contain acidic cationic groups and non-coordinating anions. The term NCA is also defined as including neutral Lewis acids such as tris (pentafluorophenyl) boron, which can react with catalysts to form activated species by capturing anionic groups. The NCA coordination is weak enough so that Lewis bases such as olefin monomers can be displaced from the catalyst center. Any metal or metalloid that can form a compatible weak coordination complex can be used or contained in the non-coordinating anion. Suitable metals include but are not limited to aluminum, gold and platinum. Suitable metalloids include but are not limited to boron, aluminum, phosphorus and silicon.

[0178] It is within the scope of the present disclosure to use neutral or ionic ionizing activators. It is also within the scope of the present disclosure to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators. For descriptions of suitable activators, see US 8,658,556 and US 6,211,105.

[0179] The catalyst system of the present disclosure may include at least one non-coordinating anion (NCA) activator. In at least one embodiment, a boron-containing NCA activator represented by the following formula may be used:

[0180] Z d + (A d- )

[0181] Wherein: Z is (LH) or a reducible Lewis acid; L is a Lewis base; H is hydrogen;

[0182] (LH) is a Bronsted acid; A d- It is a non-coordinating anion containing boron having a charge d-; d is 1, 2, or 3.

[0183] Cationic component Z d + A Bronsted acid such as a proton or protonated Lewis base or a reducible Lewis acid can be included that is capable of protonating or abstracting a moiety such as an alkyl or aryl group from a bulky ligand transition metal catalyst precursor to produce a cationic transition metal species.

[0184] Activated cation Z d + It can also be the following structural parts, such as silver, (tropylium), carbon , ferrocene and mixtures such as carbon and ferrocene . Z d + Can be triphenylcarbon The reducible Lewis acid can be a triarylcarbonyl (wherein the aryl group may be substituted or unsubstituted, for example, + ) represented by those wherein Ar is an aromatic group or is replaced by a heteroatom, a C1-C 40 Hydrocarbon or substituted C1-C 40 Hydrocarbyl-substituted aryl groups, such as reducible Lewis acids "Z" may include those represented by the formula: (Ph3C) wherein Ph is a substituted or unsubstituted phenyl group, such as substituted with C1-C 40 Hydrocarbon or substituted C1-C 40Hydrocarbon groups, such as C1-C 20 Alkyl or aryl or substituted C1-C 20 Alkyl or aryl, for example, Z is triphenylcarbonyl .

[0185] When Z d + is the activated cation (L–H) d + When it is a Bronsted acid, it can donate protons to transition metal catalytic precursors to generate transition metal cations, including ammonium, oxygen, 、 , silane and mixtures thereof, for example, ammonium amine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, dioctadecylmethylamine, ammonium amine from triethylphosphine, triphenylphosphine and diphenylphosphine , oxygen from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane , sulfonium from sulfides such as diethyl sulfide, tetrahydrothiophene, and mixtures thereof.

[0186] Anionic component A d- Including having the formula [M k+ Q n ] d- wherein 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 of the Elements, such as boron or aluminum, and Q is independently a hydrogen radical, a bridged or unbridged dialkylamino, a halo, an alkoxy, an aryloxy, a hydrocarbyl, a substituted hydrocarbyl, a halohydrocarbyl, a substituted halohydrocarbyl, and a halo-substituted hydrocarbyl radical, said Q having up to 20 carbon atoms, optionally with the proviso that Q is a halo radical in no more than 1 occurrence. Each Q may be a fluorinated hydrocarbyl radical having 1 to 20 carbon atoms, for example, each Q is a fluorinated aryl radical, and for example, each Q is a pentafluoroaryl radical. Suitable A d- Examples also include diboron compounds as disclosed in US 5,447,895, which is incorporated herein by reference in its entirety.

[0187] Illustrative but non-limiting examples of boron compounds that can be used as activating co-catalysts are the compounds described as (and particularly those specifically listed as) activators in US Pat. No. 8,658,556, which is incorporated herein by reference.

[0188] Ionic Activator Z d + (A d-) can be one or more of the following: N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, dioctadecylmethylammonium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbonyl tetrakis(perfluoronaphthyl)borate , triphenylcarbon tetrakis(perfluorobiphenyl)borate , triphenylcarbon tetrakis(3,5-bis(trifluoromethyl)phenyl)borate or triphenylcarbon tetrakis(perfluorophenyl)borate .

[0189] Alternatively, the activator compound is represented by formula (AI):

[0190] [R 1 R 2 R 3 EH] d + [M k+ Q n ] d- (AI)

[0191] in:

[0192] E is nitrogen or phosphorus, preferably nitrogen;

[0193] 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 when M is B, n is 4);

[0194] R 1 、R 2 and R 3 wherein each is independently hydrogen, optionally substituted C1-C 40 Alkyl (e.g. branched or linear alkyl) or optionally substituted C5-C 50 -aryl (optionally R 1 、R 2 and R 3 Each of which is independently unsubstituted or substituted by at least one of the following: halogen, C5-C 50 Aryl, C6-C 35 Aralkyl, C6-C 35 Alkaryl, and C5-C 50 In the case of aryl groups, C1-C 50 alkyl); wherein R 1 、R 2 and R 3Containing a total of 15 or more carbon atoms (e.g., 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 37 or more carbon atoms, such as 40 or more carbon atoms, such as 45 or more carbon atoms), preferably R 1 、R 2 and R 3 At least one is C3-C 40 Hydrocarbon (e.g. C3-C 40 Alkyl, alternatively such as C7-C 40 alkyl);

[0195] M is an element selected from Group 13 of the Periodic Table of Elements, preferably B or Al, preferably B; and

[0196] Each Q is independently a hydrogen group, a bridged or unbridged dialkylamino group, a halo group, an alkoxy group, an aryloxy group, a hydrocarbyl group, a substituted hydrocarbyl group, a halohydrocarbyl group, a substituted halohydrocarbyl group, or a halo-substituted hydrocarbyl group, preferably a fluorinated aryl group, such as a fluoro-phenyl group or a fluoro-naphthyl group, more preferably a perfluorophenyl group or a perfluoronaphthyl group.

[0197] In any embodiment of Formula (AI), R 1 、R 2 and R 3 Each of which can be independently selected from:

[0198] 1) optionally substituted linear alkyl (e.g., 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-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, or n-triacontyl);

[0199] 2) optionally substituted branched alkyl groups (e.g., alkyl-butyl, alkyl-pentyl, alkyl-hexyl, alkyl-heptyl, alkyl-octyl, alkyl-nonyl, alkyl-decyl, alkyl-undecyl, alkyl-dodecyl, alkyl-tridecyl, alkyl-tetradecyl, alkyl-pentadecyl, alkyl-hexadecyl, alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl, alkyl-eicosyl (including polyalkyl analogs, i.e., dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl, dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl, dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl, dialkyl- trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl, trialkyl-tetradecyl, trialkyl-pentadecyl, trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl, dialkyl-eicosyl, trialkyl-butyl, trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl, trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl, trialkyl-tetradecyl, trialkyl-pentadecyl, trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl and trialkyl-eicosyl, etc.), and isomers thereof, wherein each alkyl group is independently C1-C 40 (or C2-C 30 , or C3-C 20 ) linear, branched or cyclic alkyl groups), preferably the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or triacontyl);

[0200] 3) optionally substituted aralkyl groups, for example (methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, tridecylphenyl, tetradecylphenyl, pentadecylphenyl, hexadecylphenyl, heptadecylphenyl, octadecylphenyl, nonadecylphenyl, eicosylphenyl, heneicosylphenyl, docosylphenyl, tricosylphenyl, tetracosylphenyl, pentacosylphenyl, hexacosylphenyl, heptacosylphenyl, octacosylphenyl, nonacosylphenyl, triacontylphenyl, 3,5,5-trimethylhexylphenyl, dioctylphenyl, 3,3,5-trimethylhexylphenyl, 2,2,3,3,4-pentamethylpentylphenyl, etc.);

[0201] 4) optionally substituted silyl, such as trialkylsilyl, wherein each alkyl group is independently an optionally substituted C1-C 20 Alkyl groups (e.g., trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, trinonylsilyl, tridecylsilyl, tri-undecylsilyl, tri-dodecylsilyl, tri-tridecylsilyl, tri-tetradecylsilyl, tri-pentadecylsilyl, tri-hexadecylsilyl, tri-heptadecylsilyl, tri-octadecylsilyl, tri-nonadecylsilyl, tri-eicosylsilyl);

[0202] 5) optionally substituted alkoxy (e.g., -OR*, wherein R* is an optionally substituted C1-C 20 an alkyl group or an aryl group (e.g., a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a phenyl group, an alkylphenyl group (e.g., a methylphenyl group, a propylphenyl group, etc.), a naphthyl group, or an anthracenyl group);

[0203] 6) halogen (such as Br or Cl); and

[0204] 7) Halogen-containing groups (e.g., bromomethyl, bromophenyl, etc.).

[0205] For more information on activators represented by formula (IA) useful herein, see US 2019-0330139 and US 2019-0330392, which are incorporated herein by reference. Useful activators include N-methyl-4-nonadecylammonium tetrakis(perfluoronaphthalene-2-yl)borate and N-methyl-4-nonadecylammonium tetrakis(perfluorophenyl)borate.

[0206] Bulky activators can also be used herein as non-coordinating anion activators. As used herein, "bulky activator" refers to an anion activator represented by the formula:

[0207]

[0208]

[0209] in:

[0210] Each R A are independently halo, such as fluoro;

[0211] Ar is a substituted or unsubstituted aryl group (eg, a substituted or unsubstituted phenyl group), for example, substituted with C1-C 40Hydrocarbon groups such as C1-C 20 Alkyl or aryl.

[0212] Each R B are independently halogen, C6-C 20 Substituted aromatic hydrocarbon groups or groups having the formula –O-Si-R D silyloxy groups, where R D It is C1-C 20 Hydrocarbyl or hydrocarbylsilyl groups (e.g. R B is a fluoro or perfluorinated phenyl group);

[0213] Each R C It is a halogen, C6-C 20 Substituted aromatic hydrocarbon groups or groups having the formula –O-Si-R D silyloxy groups, where R D It is C1-C 20 Hydrocarbyl or hydrocarbylsilyl groups (e.g. R D is a fluoro group or a C6 perfluoroaromatic hydrocarbon group); wherein R B and R C One or more saturated or unsaturated, substituted or unsubstituted rings (e.g. R B and R C forming a perfluorophenyl ring);

[0214] L is a Lewis base; (L–H) + is a Bronsted acid; d is 1, 2 or 3;

[0215] wherein the anion has a molecular weight greater than 1,020 g / mol; and

[0216] wherein at least three of the substituents on the B atom each have a cubic , optional more than 300 cubic meters Or optionally greater than 500 cubic meters The molecular volume of .

[0217] For example, (Ar3C) d + Can be (Ph3C) d + , wherein Ph is a substituted or unsubstituted phenyl group, for example substituted with C1-C 40 Hydrocarbon or substituted C1-C 40 Hydrocarbon groups, such as C1-C 20 Alkyl or aryl or substituted C1-C 20 Alkyl or aryl.

[0218] "Molecular volume" is used herein as an approximation of the spatial volume of an activator molecule in solution. Comparing substituents having different molecular volumes allows the substituent with a smaller molecular volume to be considered "less bulky" than the substituent with a larger molecular volume. Conversely, a substituent with a larger molecular volume can be considered "more bulky" than a substituent with a smaller molecular volume.

[0219] Molecular volume can be calculated as reported in "A Simple "Back of the Envelope" Method for Estimating the Densities and Molecular Volumes of Liquids and Solids", Journal of Chemical Education, Vol. 71(11), November 1994, pp. 962-964, which is incorporated herein by reference. The following formula is used to calculate the density of a substance in cubic form: Molecular volume (MV): MV = 8.3V s , where V s is the scaled volume. V s is the sum of the relative volumes of the constituent atoms and is calculated from the molecular formula of the substituent using the relative volumes in the table below. For fused rings, each fused ring makes V s A decrease of 7.5%.

[0220] element Relative volume H 1 The first short period, Li to F 2 The second short cycle, Na to Cl 4 The first long cycle, K to Br 5 The second longest period, Rb to I 7.5 The third longest period, Cs to Bi 9

[0221] A list of suitable bulky activators is found in US 8,658,556, which is incorporated herein by reference.

[0222] In another embodiment, one or more of the NCA activators are selected from the activators described in US 6,211,105.

[0223] In at least one embodiment, the activator is selected from one or more of the following: triarylcarbonyl (e.g. triphenylcarbon tetraphenylborate , triphenylcarbon tetrakis(pentafluorophenyl)borate , tetrakis-(2,3,4,6-tetrafluorophenyl) borate triphenylcarbon , triphenylcarbon tetrakis(perfluoronaphthyl)borate , triphenylcarbon tetrakis(perfluorobiphenyl)borate , triphenylcarbon tetrakis(3,5-bis(trifluoromethyl)phenyl)borate ).

[0224] In another embodiment, the activator is selected from one or more of the following: trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate), trialkylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dialkylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate , N,N-dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di(isopropyl)ammonium tetrakis(pentafluorophenyl)borate, (wherein alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl or tert-butyl).

[0225] Suitable activator to catalyst ratios, such as a ratio of all NCA activators to catalysts, can be about a 1:1 molar ratio. Alternative ranges include 0.1:1-100:1, alternatively 0.5:1-200:1, alternatively 1:1-500:1, alternatively 1:1-1000:1. A particularly useful range is 0.5:1-10:1, such as 1:1 to 5:1.

[0226] It is also within the scope of the present disclosure that the catalyst compound may be combined with a combination of alumoxane and NCA (see, for example, US 5,153,157; US 5,453,410; EP 0 573 120 Bl; WO 1994 / 07928 and WO 1995 / 014044, which discuss the use of alumoxanes in combination with ionizing activators).

[0227] Useful chain transfer agents may be hydrogen, alkylaluminoxanes, compounds represented by the formula AlR3, 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, such as diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof.

[0228] Additionally, the catalyst systems of the present disclosure may include a metal hydrocarbenyl chain transfer agent represented by the formula:

[0229] Al(R') 3-v (R”) v

[0230] Each R' can be independently C1-C 30 The hydrocarbyl group and / or each R" may independently be a C4-C5 20 hydrocarbenyl group; and v can be 1-3, e.g., 1-2, e.g., 2-3, e.g., 1, 2, or 3. For more information on metal hydrocarbenyl chain transfer agents, see USSN 15 / 744,478, filed January 12, 2018. Preferably, each R" is represented by the formula: -(CH2)nCH=CH2, wherein n is an integer from 2 to 18.

[0231] In any embodiment of the invention described herein, particularly useful AVTAs include, but are not limited to, isobutyl-di(oct-7-en-1-yl)-aluminum, isobutyl-di(dec-9-en-1-yl)-aluminum, isobutyl-di(non-8-en-1-yl)-aluminum, isobutyl-di(hept-6-en-1-yl)-aluminum, dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum, diisobutyl(dec-8-en-1-yl)aluminum, diisobutyl(dodec-10-en-1-yl)aluminum, etc. Mixtures of one or more AVTAs may also be used. In some embodiments of the present invention, isobutyl-di(oct-7-en-1-yl)-aluminum, isobutyl-di(dec-9-en-1-yl)-aluminum, isobutyl-di(non-8-en-1-yl)-aluminum, isobutyl-di(hept-6-en-1-yl)-aluminum are preferred.

[0232] In embodiments of the invention, the activators described herein have a solubility in methylcyclohexane of greater than 10 mM (or greater than 20 mM, or greater than 50 mM) at 25°C (stirring for 2 hours) and / or a solubility in isohexane of greater than 1 mM (or greater than 10 mM, or greater than 20 mM) at 25°C (stirring for 2 hours).

[0233] The present disclosure relates to catalyst systems comprising a metallocene transition metal compound and an activator compound represented by formula (IA), to the use of such an activator compound for activating a transition metal compound in a catalyst system for polymerizing olefins, and to a process for polymerizing olefins comprising contacting one or more olefins with a catalyst system comprising a metallocene transition metal compound and such an activator compound under polymerization conditions, wherein an aromatic solvent, such as toluene, is absent (e.g., present at 0 mol %, or present at less than 1 mol %). Preferably, the catalyst system, the polymerization reaction, and / or the produced polymer contains no detectable aromatic hydrocarbon solvent, such as toluene.

[0234] The polymers (e.g., polyalphaolefins) produced herein preferably contain 0 ppm (or less than 1 ppm or less than 5 ppm or less than 10 ppm) of aromatic hydrocarbons. Preferably, the polymers (e.g., polyalphaolefins) produced herein contain 0 ppm (or less than 1 ppm or less than 5 ppm or less than 10 ppm) of toluene.

[0235] The catalyst system used herein preferably contains 0 ppm (or less than 1 ppm or less than 5 ppm or less than 10 ppm) of aromatic hydrocarbons. Preferably, the catalyst system used herein contains 0 ppm (or less than 1 ppm or less than 5 ppm or less than 10 ppm) of toluene.

[0236] Optional scavenger or co-activator

[0237] In addition to these activator compounds, scavengers or co-activators can be used. Scavengers are compounds that can be added to promote polymerization by removing impurities. Some scavengers can also serve as activators and can be referred to as co-activators. Co-activators (which are not scavengers) can also be used in conjunction with activators to form active catalysts. In at least one embodiment, co-activators can be pre-mixed with transition metal compounds to form alkylated transition metal compounds. Alkyl aluminum or aluminoxane compounds that can be used as scavengers or co-activators can include, for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octylaluminum, diisobutyl aluminum hydride, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), MMAO-3A, and diethyl zinc.

[0238] Optional support material

[0239] In embodiments herein, the catalyst system may include an inert support material. The support material may be a porous support material such as talc and an inorganic oxide. Other support materials include zeolites, clays, organoclays, or other organic or inorganic support materials, or mixtures thereof.

[0240] The support material can be an inorganic oxide in a finely divided form. Suitable inorganic oxide materials for use in the catalyst systems herein can include Group 2, 4, 13, and 14 metal oxides such as silica, alumina, and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica or alumina can be magnesium oxide, titanium dioxide, zirconium oxide. However, other suitable support materials can be used, such as finely divided functionalized polyolefins such as finely divided polyethylene. Examples of suitable supports can include magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, phyllosilicates, zeolites, talc, and clay. In addition, combinations of these support materials can be used, such as silica-chromium, silica-alumina, and silica-titania. In at least one embodiment, the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica clay, silica / clay, or mixtures thereof.

[0241] Support materials such as inorganic oxides may have a surface area of about 10 m 2 / g-about 700m 2 / g, the pore volume is about 0.1cm 3 / g-approximately 4.0cm 3 / g, and the average particle size is in the range of about 5 μm to about 500 μm. The surface area of the support material can be about 50 m 2 / g-about 500m 2 / g, the pore volume is about 0.5cm 3 / g-about 3.5cm 3 / g, and an average particle size of about 10 μm to about 200 μm. For example, the surface area of the support material is about 100 m 2 / g-about 400m 2 / g, the pore volume is about 0.8cm 3 / g-about 3.0cm 3 / g, and an average particle size of about 5 μm to about 100 μm. The average pore size of the support material useful in the present disclosure is in the range of For example to about and for example to about In at least one embodiment, the support material is a high surface area amorphous silica (surface area = 300 m 2 / gm, pore volume is 1.65cm 3 / gm). For example, suitable silica can be obtained from Davison Chemical Division of WR Race and Company under the trade name DAVISON TM952 or DAVISON TM 955. In other embodiments, DAVISON TM 948. Alternatively, the silica may be, for example, ES-70 which has been calcined (eg, at 875°C). TM Silica (PQ Corporation, Malvern, PA).

[0242] The support material should be dry, i.e., free of absorbed water. Drying of the support material can be achieved by heating or calcining at a temperature of about 100° C. to about 1,000° C., for example, at least 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., and for example, at about 600° C.; and for a time of about 1 minute to about 100 hours, about 12 hours to about 72 hours, or about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups to produce the supported catalyst system of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

[0243] The support material with reactive surface groups (such as hydroxyl groups) is made into slurry in a non-polar solvent and the slurry produced is 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 in a time period within the scope of about 0.5 hours to about 24 hours, about 2 hours to about 16 hours or about 4 hours to about 8 hours. The solution of the catalyst compound is then contacted with the support / activator of separation. In at least one embodiment, the catalyst system of the original position generation load is carried. In the embodiment for selection, the slurry of the support material is first contacted with the catalyst compound in a time period within the scope of about 0.5 hours to about 24 hours, about 2 hours to about 16 hours or about 4 hours to about 8 hours. The slurry of the catalyst compound of the load is then contacted with an activator solution.

[0244] The mixture of catalyst, activator and support is heated from about 0° C. to about 70° C., for example, from about 23° C. to about 60° C., for example, at room temperature. The contact time can be from about 0.5 hours to about 24 hours, for example, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.

[0245] Suitable non-polar solvents are materials in which all reactants used herein (e.g., activators and catalyst compounds) are at least partially soluble and are liquid at the reaction temperature. Non-polar solvents can be alkanes such as isopentane, hexane, n-heptane, octane, nonane, and decane, but various other materials can also be used, including cycloalkanes such as cyclohexane, aromatic compounds such as benzene, toluene, and ethylbenzene.

[0246] Aggregation Method

[0247] The present disclosure relates to a polymerization process in which monomers (e.g., ethylene, propylene) and optional comonomers are contacted with a catalyst system comprising an activator, at least one catalyst compound, and an optional support as described above. The catalyst compound and the activator and the optional support can be combined in any order. The catalyst compound and the activator and / or the optional support can be combined before contacting the monomers. Alternatively, the catalyst compound and the activator can be introduced into a polymerization reactor, respectively, where they react subsequently to form an active catalyst.

[0248] Monomers include 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 isomers thereof. In at least one embodiment, the monomers include ethylene and optional comonomers comprising one or more C3-C 40 Olefins, such as C4-C 20 Olefins, such as C6-C 12 Olefins. C3-C 40 The olefin monomers may be linear, branched or cyclic. 40 The cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups. In another embodiment, the monomers include propylene and optional comonomers comprising one or more ethylene or C4-C 40 Olefins, such as C4-C 20 Olefins, such as C6-C 12 Olefins. C4-C 40 The olefin monomers may be linear, branched or cyclic. 40 The cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups.

[0249] Exemplary C2-C 40The olefin monomers and optional comonomers may include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, ethylidene norbornene, vinyl norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornene, substituted derivatives thereof, and isomers thereof, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives, such as norbornene, norbornadiene, and dicyclopentadiene.

[0250] The polymerization methods of the present disclosure may be carried out in any suitable manner. Any suitable suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process may be used. Such processes may be run in batch, semi-batch, or continuous modes. Homogeneous polymerization processes such as solution processes may be used. (Solution polymerization means a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or a blend thereof. Homogeneous polymerization is a polymerization in which the polymer product is dissolved in the polymerization medium. Suitable systems are generally not turbid, as described in J. Vladimir Oliveira, C. Dariva, and JC Pinto, Ind. Eng. Chem. Res., 2000, Vol. 29, p. 4627.) Bulk homogeneous processes may be used (bulk polymerization means a polymerization process in which the monomer and / or comonomer being polymerized serves as a solvent or diluent, with little or no use of an inert solvent as a solvent or diluent. A small portion of the inert solvent may serve as a support for the catalyst and scavengers.) Typically, bulk polymerization systems contain less than 25% by weight of an inert solvent or diluent, such as less than 10% by weight, such as less than 1% by weight, such as 0% by weight. In embodiments, no solvent or diluent is present or added to the reaction medium (except in small amounts used as a support for the catalyst system or other additives, or in amounts found with the monomers, such as propane in propylene).

[0251] In another embodiment, the process is a slurry process. As used herein, the term "slurry polymerization process" refers to a polymerization process conducted in a hydrocarbon solvent, wherein a supported catalyst is employed and monomers are polymerized on supported catalyst particles at a temperature below the melting point of the polymer produced. At least 95% by weight of the polymer product derived from the supported catalyst is in pelletized form as solid particles (not dissolved in the diluent).

[0252] Suitable diluents / solvents for polymerization may include non-coordinating inert liquids. Examples of diluents / solvents for polymerization may include linear and branched hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as commercially available (Isopar TM ); perhalogenated hydrocarbons, such as perfluorinated C4-C 10 Alkanes, chlorobenzenes, and aromatic compounds and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene and xylene. Suitable solvents can also include liquid olefins, which can serve as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. In at least one embodiment, aliphatic hydrocarbon solvents are used as solvents, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, such as aromatic compounds present in the solvent with less than 1% by weight, such as less than 0.5% by weight, such as less than 0% by weight, based on the weight of the solvent.

[0253] In at least one embodiment, the feed concentration of monomers and comonomers used in the polymerization is 60 volume percent solvent or less, such as 40 volume percent or less, such as 20 volume percent or less, based on the total volume of the feed stream. In at least one embodiment, the polymerization is carried out in a bulk process.

[0254] Polymerization can be carried out at any temperature and / or pressure suitable for obtaining the desired polymer. Typical temperatures and / or pressures include temperatures in the range of about 0°C to about 300°C, such as about 20°C to about 200°C, such as about 35°C to about 160°C, such as about 80°C to about 160°C, such as about 90°C to about 140°C, and pressures in the range of about 0.35 MPa to about 25 MPa, such as about 0.45 MPa to about 6 MPa or about 0.5 MPa to about 4 MPa.

[0255] In suitable polymerizations, the run time of the reaction may be up to 300 minutes, such as from about 5 minutes to 250 minutes, such as from about 10 minutes to 120 minutes, such as from about 20 minutes to 90 minutes, such as from about 30 minutes to 60 minutes. In a continuous process, the run time may be the average residence time of the reactor.

[0256] In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345 kPa), e.g., 0.01 psig-25 psig (0.07 kPa to 172 kPa), e.g., 0.1 psig-10 psig (0.7 kPa to 70 kPa).

[0257] In at least one embodiment, little or no alumoxane is used in the process for producing the polymer. For example, the alumoxane may be present at 0 mol%, alternatively the alumoxane may be present at a molar ratio of aluminum to transition metal of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

[0258] In at least one embodiment, the polymerization is: 1) carried out at a temperature of 0°C to 300°C (e.g., 25°C to 250°C, e.g., 80°C to 160°C, e.g., 100°C to 140°C); 2) carried out at a pressure of atmospheric pressure to 10 MPa (e.g., 0.35 MPa-10 MPa, e.g., 0.45 MPa-6 MPa, e.g., 0.5 MPa-4 MPa); 3) carried out in an aliphatic hydrocarbon solvent (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, decane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; e.g., wherein the aromatic compound is present in the solvent at less than 1 wt %, e.g., less than 0.5 wt %, e.g., at 0 wt %, based on the weight of the solvent); 4) wherein the catalyst system used in the polymerization comprises less than 0.5 mol %, such as 0 mol % alumoxane, alternatively alumoxane is present at a molar ratio of aluminum to transition metal of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1; 5) polymerization occurs in one reaction zone; 6) scavenger (e.g., trialkylaluminum compound) is optionally absent (e.g., present at 0 mol %, or the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, such as less than 50:1, such as less than 15:1, such as less than 10:1); and 7) hydrogen is optionally present at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345 kPa), such as 0.01 psig-25 psig (0.07 kPa to 172 kPa), such as 0.1 psig to 10 psig (0.7 kPa to 70 kPa). In at least one embodiment, the catalyst system used in the polymerization comprises no more than one catalyst compound.

[0259] A "reaction zone" (also referred to as a "polymerization zone") is a vessel, such as a stirred tank reactor or a loop reactor, in which polymerization occurs. 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, each polymerization stage is considered a separate polymerization zone. In at least one embodiment, polymerization occurs in one reaction zone. Room temperature is 23°C unless otherwise stated.

[0260] In at least one embodiment, the present disclosure provides a method for producing an ethylene-based polymer comprising polymerizing ethylene by contacting ethylene with the catalyst system of the present disclosure described above in one or more continuous stirred tank reactors or loop reactors connected 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. to form an ethylene-based polymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 5 psig to about 300 psig, such as about 10 psig to about 250 psig, such as about 30 psig to about 200 psig, such as about 40 psig to about 150 psig, such as about 50 psig to about 100 psig (e.g., 75 psig). In at least one embodiment, the activity of the catalyst is at least 1,000 gP.mmolcat -1 .h -1 , for example, about 1,000 gP.mmolcat -1 .h -1 -500,000gP.mmolcat -1 .h -1 , for example, about 10,000 gP.mmolcat -1 .h -1 -250,000gP.mmolcat -1 .h -1 , for example, about 20,000 gP.mmolcat -1 .h -1 -100,000gP.mmolcat -1 .h -1 or about 500,000 gP.mmolcat -1 .h -1 -2,000,000gP.mmolcat -1 .h -1 , for example, about 600,000 gP.mmolcat -1 .h -1 -1,500,000gP.mmolcat -1 .h -1 , for example, about 800,000 gP.mmolcat-1 .h -1 -1,000,000gP.mmolcat -1 .h -1 .

[0261] In another embodiment, the present disclosure provides a method for producing a propylene-based polymer comprising: polymerizing propylene by contacting propylene with the catalyst system of the present disclosure described above in one or more continuous stirred tank reactors or loop reactors connected 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. to form a propylene-based polymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 10 psig to about 300 psig, such as about 20 psig to about 250 psig, such as about 30 psig to about 200 psig, such as about 40 psig to about 150 psig, such as about 50 psig to about 100 psig (e.g., 75 psig). In at least one embodiment, the activity of the catalyst is at least 50 gP.mmolcat -1 .h -1 , for example 50gP.mmolcat -1 .h -1 - Approximately 500,000 gP.mmolcat -1 .h -1 , for example 100gP.mmolcat -1 .h -1 -About 250,000gP.mmolcat -1 .h -1 , for example 150gP.mmolcat -1 .h -1 - Approximately 150,000 gP.mmolcat -1 .h -1 , or about 500,000 gP.mmolcat -1 .h -1 - Approximately 6,000,000 gP.mmolcat -1 .h -1 , for example, about 750,000 gP.mmolcat -1 .h -1 - Approximately 4,000,000 gP.mmolcat -1 .h -1 , for example, about 1,000,000 gP.mmolcat -1 .h -1 -About 2,000,000gP.mmolcat -1 .h -1 .

[0262] In another embodiment, the present disclosure provides a method for producing an ethylene alpha-olefin copolymer, comprising: reacting ethylene and at least one C3-C4 copolymer in one or more continuous stirred tank reactors or loop reactors connected 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 catalyst system described above to polymerize ethylene and at least one C3-C 20 α-olefins to form ethylene α-olefin copolymers. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 10 psig to about 300 psig, such as about 20 psig to about 250 psig, such as about 30 psig to about 200 psig, such as about 40 psig to about 150 psig, such as about 50 psig to about 100 psig (e.g., 75 psig) or about 150 psig to about 300 psig (e.g., 200 psig). In at least one embodiment, the activity of the catalyst is at least 500 gP.mmolcat -1 .h -1 , for example, about 500 gP.mmolcat -1 .h -1 - Approximately 5,000,000 gP.mmolcat -1 .h -1 , for example, about 10,000 gP.mmolcat -1 .h -1 -About 2,500,000 gP.mmolcat -1 .h -1 , for example, about 20,000 gP.mmolcat -1 .h -1 -About 1,000,000gP.mmolcat -1 .h -1 , or about 5,000,000 gP.mmolcat -1 .h -1 - Approximately 8,000,000 gP.mmolcat -1 .h -1 .

[0263] In another embodiment, the present disclosure provides a method for producing a propylene alpha-olefin copolymer, 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 connected 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. 20The α-olefins are contacted with the catalyst system described above to polymerize propylene and at least one ethylene and / or at least one C4-C 20 α-olefins to form ethylene α-olefin copolymers. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 10 psig to about 300 psig, such as about 20 psig to about 250 psig, such as about 30 psig to about 200 psig, such as about 40 psig to about 150 psig, such as about 50 psig to about 100 psig (e.g., 75 psig) or about 150 psig to about 300 psig (e.g., 200 psig). In at least one embodiment, the activity of the catalyst is at least 500 gP.mmolcat -1 .h -1 , for example, about 500 gP.mmolcat -1 .h -1 - Approximately 5,000,000 gP.mmolcat -1 .h -1 , for example, about 10,000 gP.mmolcat -1 .h -1 -About 2,500,000 gP.mmolcat -1 .h -1 , for example, about 20,000 gP.mmolcat -1 .h -1 -About 1,000,000gP.mmolcat -1 .h -1 , or about 5,000,000 gP.mmolcat -1 .h -1 - Approximately 8,000,000 gP.mmolcat -1 .h -1 .

[0264] In at least one embodiment, the conversion of olefin monomer is at least 10%, based on polymer yield and weight of monomer entering the reaction zone, such as 20% or more, such as 30% or more, such as 50% or more, such as 80% or more.

[0265] In at least one embodiment, little or no alumoxane is used in the process for producing the polymer, for example, the alumoxane is present at 0 mol%, alternatively the alumoxane is present at a molar ratio of aluminum to transition metal of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

[0266] In at least one embodiment, little or no scavenger is used in the process for producing the ethylene polymer. For example, the scavenger (e.g., trialkylaluminum) is present at 0 mol%, alternatively the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, such as less than 50:1, such as less than 15:1, such as less than 10:1.

[0267] Other additives may also be used in the polymerization as needed, such as one or more scavengers, hydrogen, alkyl aluminum or chain transfer agents (e.g., alkyl aluminoxanes, compounds represented by the formula AlR3 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, such as diethyl zinc, methyl aluminoxane, trimethyl aluminum, triisobutyl aluminum, trioctylaluminum or combinations thereof).

[0268] Solution polymerization

[0269] In at least one embodiment, the polymerization process using the catalyst compounds of the present disclosure is a solution polymerization process.

[0270] Solution polymerization is preferably a polymerization process in which at least 90% by weight, preferably at least 95% by weight, preferably at least 100% by weight (based on the weight of the polymer) of the polymer product is dissolved in a liquid polymerization medium (e.g., an inert solvent or monomer(s) or a blend thereof). Solution polymerization can include polymerization in a continuous reactor in which the formed polymer, the supplied starting monomers, and the catalyst material are agitated to reduce or avoid concentration gradients, and in which the monomer acts as a diluent or solvent or a hydrocarbon is used as a diluent or solvent. Suitable processes can be operated at a temperature of about 0°C to about 250°C, such as about 50°C to about 170°C, such as about 80°C to about 150°C, such as about 100°C to about 140°C, and / or at a pressure of about 0.1 MPa or greater, such as 2 MPa or greater. The upper pressure limit is not strictly limited but can be about 200 MPa or less, such as 120 MPa or less, such as 30 MPa or less. Temperature control in the reactor can typically be achieved by reactor cooling to balance the heat of polymerization, which is carried out by reactor jacket or cooling coils to cool the contents of the reactor, automatic refrigeration, pre-cooling the feed, evaporation of the liquid medium (diluent, monomer or solvent), or a combination of all three. Adiabatic reactors with pre-cooled feed can also be used. The purity, type and amount of the solvent can be optimized to achieve maximum catalyst productivity for a particular type of polymerization. The solvent can also be introduced as a catalyst support. Depending on the pressure and temperature, the solvent can be introduced as a gas phase or a liquid phase. Advantageously, the solvent can be maintained in the liquid phase and introduced as a liquid. The solvent can be introduced into the polymerization reactor in the feed.

[0271] The method described herein can be a solution polymerization process, which can be carried out in an intermittent manner (e.g., intermittent, semi-batch) or in a continuous process. Suitable reactors can include a kettle, loop, and tube design. In at least one embodiment, the method is carried out in a continuous manner and uses a double loop reactor configured in series. In at least one embodiment, the method is carried out in a continuous manner and uses a double continuous stirred tank reactor (CSTR) configured in series. In addition, the method can be carried out in a continuous manner and can use a tubular reactor. In another embodiment, the method is carried out in a continuous manner and uses a loop reactor and a CSTR in a series arrangement. The method can also be carried out in an intermittent manner and can use a single stirred tank reactor.

[0272] Polyolefin products

[0273] The present disclosure relates to compositions of matter produced by the methods described herein.

[0274] In at least one embodiment, the methods described herein produce C2-C 20 Olefin homopolymers (such as polyethylene, polypropylene), or C2-C 20 Olefin copolymers (e.g. ethylene-octene, ethylene-propylene) and / or propylene-α-olefin copolymers, e.g. C3-C 20 Copolymers (e.g., propylene-hexene copolymers or propylene-octene copolymers). In at least one embodiment, the methods described herein produce C3-C 20 Isotactic olefin homopolymers, such as isotactic polypropylene, such as highly isotactic polypropylene.

[0275] The term "isotactic" is defined as 13 C NMR analysis has at least 20% or more isotactic pentads. The term "highly isotactic" is defined as 13 CNMR analysis showed 50% or more isotactic pentads. 13C-NMR spectroscopy determines the microstructure of polypropylene, including the concentrations of isotactic and syndiotactic diads ([m] and [r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]). The designation "m" or "r" describes the stereochemistry of adjacent propylene pairs, "m" indicating meso and "r" indicating racemic. The sample is dissolved in d2-1,1,2,2-tetrachloroethane and the spectra are recorded at 125°C using a 100 MHz (or higher) NMR spectrometer. The polymer resonance peak is referenced to mmmm = 21.8 ppm. F. A. Bovey, in POLYMER CONFORMATION AND CONFIGURATION (Academic Press, New York 1969) and J. Randall, in POLYMER SEQUENCE DETERMINATION, 13 C-NMR METHOD (Academic Press, New York, 1977) describes the calculations involved in the characterization of polymers by NMR.

[0276] In at least one embodiment, the ethylene or propylene based polymer (homopolymer) has one or more of the following: an Mw value of 500 g / mol or greater, such as from about 500 g / mol to about 3,000,000 g / mol, such as from about 25,000 g / mol to about 2,000,000 g / mol or from about 3,000,000 g / mol to about 10,000,000 g / mol, such as from about 5,000,000 g / mol to about 7,500,000 g / mol; an Mn value of 500 g / mol or greater, such as from about 500 g / mol to about 2,000,000 g / mol; ,000 g / mol, for example, about 100,000 g / mol to about 1,200,000 g / mol or about 2,000,000 g / mol to about 10,000,000 g / mol, for example, about 5,000,000 g / mol to about 7,500,000 g / mol; and an Mz value of 500 g / mol or greater, for example, about 500 g / mol to about 10,000,000 g / mol, for example, about 100,000 to about 6,000,000 g / mol or about 10,000,000 g / mol to about 25,000,000 g / mol.

[0277] In at least one embodiment, the ethylene or propylene based polymer has an Mw / Mn (PDI) value of 1-20, such as 5-20, such as 10-20, or 1-5, such as 1.5 to about 3.

[0278] In at least one embodiment, the ethylene or propylene based polymer has a melting point (Tm) of at least 50°C, such as from about 50°C to about 150°C, such as from about 100°C to about 140°C, such as from about 120°C to about 140°C, such as from about 130°C to about 140°C.

[0279] For purposes of this invention and the claims thereto, unless otherwise indicated (e.g., in the Examples section below, using Rapid DSC), the melting point (or melting temperature, T ) of a polymer is determined using Differential Scanning Calorimetry (DSC) on a commercially available instrument (e.g., a TA Instruments 2920 DSC). m ). 6-10mg of polymer was sealed in an aluminum pan at room temperature and loaded into the instrument. Melting data (first heating) was obtained by heating the sample to at least 30°C (typically 220°C for polypropylene) above its melting temperature at a heating rate of 10°C / min. The sample was kept at this temperature for at least 5 minutes to destroy its thermal history. Crystallization data was obtained by cooling the sample from the melt to at least 50°C (typically -50°C) less than the crystallization temperature at a cooling rate of 20°C / min. The sample was kept at this temperature for at least 5 minutes and finally heated at 10°C / min to obtain additional melting data (second heating). Endothermic melting transitions (first and second heating) and exothermic crystallization transitions were analyzed according to standard procedures. Unless otherwise stated, the melting temperatures reported are the peak melting temperatures from the second heating. For polymers showing multiple peaks, the melting temperature is defined as the peak melting temperature (rather than the peak occurring at the highest temperature) from the melting trace associated with the maximum endothermic calorimetric response.

[0280] In at least one embodiment, the ethylene or propylene based polymer is an ethylene alpha-olefin copolymer or a propylene alpha-olefin copolymer having one or more of the following: an Mw value of 5,000 g / mol or greater, such as from about 1,000 g / mol to about 3,000,000 g / mol, such as from about 1,000 g / mol to about 500,000 g / mol, such as from about 6,000 g / mol to about 250,000 g / mol, such as from about 7,000 g / mol to about 100,000 g / mol, such as from about 8,000 g / mol to about 50,000 g / mol. 00 g / mol or about 500,000 g / mol to about 3,000,000 g / mol, for example, about 750,000 g / mol to about 2,750,000 g / mol, for example, about 1,000,000 g / mol to about 2,500,000 g / mol, for example, about 1,500,000 g / mol to about 2,000,000 g / mol; Mn value is 1,000 g / mol or greater, for example, about 1,000 g / mol to about 1,500,000 g / mol, for example, about 1,000 g / mol to about 300, 000 g / mol, for example, about 2,500 g / mol to about 200,000 g / mol, for example, about 4,000 g / mol to about 50,000 g / mol or about 300,000 g / mol to 2,000,000 g / mol, for example, about 200,000 g / mol to about 1,750,000, for example, about 300,000 g / mol to about 1,500,000 g / mol, for example, about 400,000 g / mol to about 1,250,000 g / mol; an Mz value of 1,000 g / mol or greater, for example About 1,000 g / mol to about 5,000,000 g / mol, for example about 1,000 g / mol to about 100,000 g / mol, for example about 2,500 g / mol to about 75,000 g / mol, for example about 5,000 g / mol to about 50,000 g / mol, or about 100,000 g / mol to about 10,000,000 g / mol, for example about 200,000 g / mol to about 7,500,000 g / mol, for example about 300,000 g / mol to about 5,000,000 g / mol.

[0281] In at least one embodiment, the ethylene α-olefin copolymer or propylene α-olefin copolymer has a comonomer content of 0.1 wt% to 50 wt%, such as 1 wt% to 10 wt%, such as 5 wt% to 25 wt%, such as 15 wt% to 35 wt%, such as 25 wt% to 50 wt%.

[0282] In at least one embodiment, the ethylene alpha-olefin copolymer or the propylene alpha-olefin copolymer has a Mw / Mn (PDI) value of 1-5, such as 1-4, such as 1-3.

[0283] In at least one embodiment, the ethylene alpha-olefin copolymer or propylene alpha-olefin copolymer has a melting point (Tm) of at least 100°C, such as from about 100°C to about 140°C, such as from about 105°C to about 130°C, such as from about 115°C to about 125°C.

[0284] Thus, the present disclosure can provide highly active catalysts capable of operating at high reactor temperatures while producing polymers having substantially high molecular weight.

[0285] Gel Permeation Chromatography (GPC 4-D)

[0286] For the purposes of the claims, and unless otherwise indicated, the molecular weight moments and distributions (Mw, Mn, Mz, Mw / Mn, etc.), comonomer content, and branching index (g') were determined by using high temperature gel permeation chromatography (PolymerChar GPC-IR) equipped with a multi-channel bandpass filter based infrared detector IR5 having a wavelength covering approximately 2,700 cm, an 18-angle light scattering detector, and a viscometer. -1 - Approximately 3,000cm -1Bandpass region (representing saturated CH stretching vibration). Three Agilent PLgel 10-μm mixed-B LS columns are used to provide polymer separation. Reagent grade 1,2,4-trichlorobenzene (TCB) (from Sigma-Aldrich) containing ~300ppm antioxidant BHT is used as mobile phase with a nominal flow rate of ~1.0mL / min and a nominal injection volume of ~200μL. The entire system including transfer lines, columns and detectors can be accommodated in an oven maintained at ~145°C. A given amount of sample can be weighed and sealed in a standard vial, to which ~10μL mobile marker (heptane) is added. After loading the vial in the autosampler, the oligomer or polymer can be automatically dissolved in an instrument with ~8ml of added TCB solvent at ~160°C under continuous shaking. The sample solution concentration can be from ~0.2mg / ml to ~2.0mg / ml, with lower concentrations being used for higher molecular weight samples. The concentration (c) at each point in the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal (I) using the following equation: c = αI, where α is a mass constant determined using polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatogram within the elution volume to the injected mass (which is equal to the predetermined concentration multiplied by the injection loop volume). The conventional molecular weight (IR MW) is determined by combining a universal calibration relationship with a column calibration performed using a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 M gm / mole. The MW at each elution volume is calculated using the following equation:

[0287]

[0288] Variables with the subscript "PS" represent polystyrene, while those without the subscript represent the test sample. In this method, α PS =0.67 and K PS= 0.000175, α and K for other materials are calculated as in the open literature (see, e.g., Sun, T. et al., Macromolecules 2001, Vol. 34, p. 6812), except that for the purposes of this invention and the claims thereto, α = 0.695 + (0.01 * (propylene weight fraction)) and K = 0.000579 - (0.0003502 * (propylene weight fraction)) for ethylene-propylene copolymers and ethylene-propylene-diene copolymers, α = 0.705 and K = 0.0002288 for linear propylene polymers, α = 0.695 and K = 0.000181 for linear butene polymers, and α = 0.000190 for ethylene-butene copolymers. α is 0.695 and K is 0.000579*(1-0.0087*w2b+0.000018*(w2b)^2) (where w2b is the bulk weight percent of the butene comonomer), for ethylene-hexene copolymers α is 0.695 and K is 0.000579*(1-0.0075*w2b) (where w2b is the bulk weight percent of the hexene comonomer), for ethylene-octene copolymers α is 0.695 and K is 0.000579*(1-0.0077*w2b) (where w2b is the bulk weight percent of the octene comonomer), and for all other linear ethylene polymers α=0.695 and K=0.000579. Unless otherwise noted, concentrations are in g / cm 3 The molecular weight is expressed in units of g / mole, and the intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed in units of dL / g.

[0289] The comonomer composition is determined by the ratio of the IR5 detector intensities corresponding to the CH2 and CH3 channels (calibrated with a series of PE and PP homopolymer / copolymer standards with predetermined nominal values by NMR or FTIR). Specifically, this provides the methyl groups per 1,000 total carbons (CH3 / 1000TC) as a function of molecular weight. The short chain branch (SCB) content per 1000TC (SCB / 1000TC) is then calculated as a function of molecular weight by applying a chain end correction to the CH3 / 1000TC function, assuming that each chain is linear and terminated at each end with a methyl group. The weight percent comonomer is then obtained from the following expression, where f is 0.3, 0.4, 0.6, 0.8, etc. for comonomers C3, C4, C6, C8, etc., respectively:

[0290] w2=f*SCB / 1000TC.

[0291] The bulk composition of the polymers analyzed from GPC-IR and GPC-4D was obtained by considering the entire signal of the CH3 and CH2 channels between the integration limits of the concentration chromatogram. First, the following ratio was obtained:

[0292]

[0293] The same calibration of the CH3 and CH2 signal ratios (as mentioned previously in obtaining CH3 / 1000TC as a function of molecular weight) is then applied to obtain bulk CH3 / 1000TC. Bulk methyl chain ends / 1,000TC (bulk CH3 ends / 1000TC) are obtained by weighting the average chain end correction over the molecular weight range. Then,

[0294] w2b=f*body CH3 / 1000TC

[0295] Main body SCB / 1000TC = main body CH3 / 1000TC - main body CH3 end / 1000TC

[0296] The body SCB / 1000TC is transformed into body w2 in the same manner as described above.

[0297] The LS detector was an 18-angle Wyatt Technology High Temperature DAWN HELEOS II. The LS molecular weight (M) at each point in the chromatogram was determined by analyzing the output of the LS using the Zimm model for static light scattering (Light Scattering from Polymer Solutions, Huglin, MB ed., Academic Press, 1972):

[0298]

[0299] Here, ΔR(θ) is the excess Rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined from IR5 analysis, A2 is the second virial coefficient, P(θ) is the shape factor of the monodisperse random coils, and K o is the optical constant of the system:

[0300]

[0301] where N A is Avogadro's constant, and (dn / dc) is the refractive index increment of the system. The refractive index of TCB at 145°C and λ = 665 nm is n = 1.500. For the analysis of polyethylene homopolymer, ethylene-hexene copolymer, and ethylene-octene copolymer, dn / dc = 0.1048 ml / mg and A2 = 0.0015; for the analysis of ethylene-butene copolymer, dn / dc = 0.1048*(1-0.00126*w2) ml / mg and A2 = 0.0015, where w2 is the weight percent of butene comonomer.

[0302] The specific viscosity is determined using a high temperature Agilent (or Viscotek Corporation) viscometer (which has four capillaries arranged in a Wheatstone bridge configuration, and two pressure sensors). One sensor measures the total pressure drop across the detector, and the other sensor placed between the two sides of the bridge measures the pressure difference. The specific viscosity η of the solution flowing through the viscometer is calculated from their outputs. s From the equation [η] = η s The intrinsic viscosity [η] at each point in the chromatogram is calculated as: / c, where c is the concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as where α ps is 0.67 and K ps It is 0.000175.

[0303] The branching index (g'vis) was calculated using the output of the GPC-IR5-LS-VIS method as follows: Average intrinsic viscosity [η] of the sample avg By the following calculation:

[0304]

[0305] where the sum is taken over all chromatographic slices i between the integration limits.

[0306] Branching index g' vis Defined as Among them, M V is the viscosity average molecular weight based on the molecular weight determined by LS analysis and K and α are for reference linear polymers which, for purposes of this invention and the claims thereto, are α = 0.700 and K = 0.0003931 for ethylene, propylene, diene monomer copolymers, α = 0.705 and K = 0.0002288 for linear propylene polymers, α = 0.695 and K = 0.000181 for linear butene polymers, and α is 0.695 and K = 0.000579*(1 - 0.0087*w2b + 0.0000181 for ethylene-butene copolymers. *(w2b)^2) (where w2b is the bulk weight percent of the butene comonomer), for ethylene-hexene copolymers α is 0.695 and K is 0.000579*(1-0.0075*w2b) (where w2b is the bulk weight percent of the hexene comonomer), for ethylene-octene copolymers α is 0.695 and K is 0.000579*(1-0.0077*w2b) (where w2b is the bulk weight percent of the octene comonomer), and for all other linear ethylene polymers, α=0.695 and K=0.000579. Unless otherwise noted, concentrations are in g / cm 3The molecular weight is expressed in g / mole, the intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed in dL / g. The w2b value is calculated as discussed above. For other linear materials, α and K are calculated as in the published literature (see, for example, Sun, T. et al., Macromolecules 2001, Vol. 34, p. 6812).

[0307] blends

[0308] In another embodiment, the polymers produced herein (e.g., polyethylene or polypropylene) are combined with one or more additional polymers prior to being formed into films, molded parts, or other articles. Other useful 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 process, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resin, ethylene-propylene rubber (EPR), sulfurized EPR, EPDM, block copolymers, styrenic block copolymers, polyamides, polycarbonates, PET resins, cross-linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetals, polyvinylidene fluoride, polyethylene glycol, and / or polyisobutylene.

[0309] In at least one embodiment, the polymer (e.g., polyethylene or polypropylene) is present in the above blend at 10% to 99% by weight, such as 20% to 95% by weight, such as at least 30% to 90% by weight, such as at least 40% to 90% by weight, such as at least 50% to 90% by weight, such as at least 60% to 90% by weight, such as at least 70 to 90% by weight, based on the weight of the polymer in the blend.

[0310] The blends described above can be produced by mixing a polymer of the present disclosure with one or more polymers (as described above), by connecting reactors together in series to prepare a reactor blend, or by using more than one catalyst in the same reactor to produce multiple polymer species. The polymers can be mixed together before being placed in the extruder or can be mixed in the extruder.

[0311] The blends may be formed using conventional equipment and methods, for example, by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as a Banbury mixer, Haake mixer, Brabender internal mixer, or single or twin screw extruder, which may include compounding extruders used directly downstream of the polymerization process and side arm extruders, which may include powders or pellets of the blended resins at the film extruder hopper. Additionally, additives may be included in the blend, in one or more components of the blend, and / or in products formed from the blend, such as films, as desired. Such additives are well known in the art and may include, for example, fillers; antioxidants (e.g., hindered phenols such as IRGANOX® available from Ciba-Geigy); TM 1010 or IRGANOX TM 1076); phosphites (e.g., IRGAFOS available from Ciba-Geigy); TM 168); anti-cling additives; tackifiers such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glyceryl stearates, and hydrogenated rosin; UV stabilizers; heat stabilizers; antiblocking agents; mold release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; talc.

[0312] membrane

[0313] Any of the aforementioned polymers, such as the aforementioned polypropylene or their blends, can be used in various end-use applications. Such applications include, for example, single-layer or multilayer blow molding, extrusion and / or shrink film. These films can be formed by any number of known extrusion or coextrusion techniques, such as blown bubble film processing technology, in which the composition can be extruded in a molten state through an annular die and then expanded to form a uniaxial or biaxially oriented melt, then cooled to form a tubular blown film, which can then be axially cut and expanded to form a flat film. The film can then be unoriented, uniaxially oriented, or biaxially oriented to the same or different extents. One or more layers of the film can be oriented in the horizontal and / or longitudinal directions to the same or different degrees. Uniaxial orientation can be accomplished using conventional cold drawing or hot drawing methods. Biaxial orientation can be accomplished using a tenter frame apparatus or a double bubble method, and biaxial orientation can occur before or after each layer is brought together. For example, a polyethylene layer can be extrusion coated or laminated to an oriented polypropylene layer, or polyethylene and polypropylene can be coextruded together to form a film and then oriented. Likewise, oriented polypropylene can be laminated to oriented polyethylene, or oriented polyethylene can be coated onto polypropylene and then the combination can optionally be oriented even further. For example, the film is oriented in the machine direction (MD) at a ratio of up to 15, such as from about 5 to about 7, and in the transverse direction (TD) at a ratio of up to 15, such as from about 7 to about 9. However, in another embodiment, the film is oriented to the same extent in both the MD and TD directions.

[0314] The film thickness may vary depending on the intended application; however, films having a thickness of 1 μm to 50 μm may be suitable. Films intended for packaging may be 10 μm to 50 μm thick. The sealant layer may have a thickness of 0.2 μm to 50 μm. The sealant layer may be present on both the inner and outer surfaces of the film or may be present only on the inner or outer surface.

[0315] In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwaves.In at least one embodiment, one or both surface layers are modified by corona treatment.

[0316] wax

[0317] Polyolefin waxes such as polyethylene waxes can be prepared using bis(heterocycle-alkoxide) Lewis base catalysts in a solution polymerization process, and they have, for example, low molecular weights ranging from about 250 g / mol to about 5,000 g / mol. The production of polyolefin waxes can be carried out at a temperature of 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 under a reactor pressure of from about 0.5 MPa to about 25 MPa, for example, from about 0.7 MPa to 6 MPa. The production of polyolefin waxes can be carried out in the presence of hydrogen added at a partial pressure of from 0 psig to about 100 psig, for example, from 0 psig to about 40 psig, for example, from 0 psig.

[0318] Aspect List

[0319] This disclosure provides, among other things, the following aspects, each of which may be considered to optionally include any alternative aspects.

[0320] Item 1. A catalyst compound represented by formula (I):

[0321]

[0322] in:

[0323] M is a Group 3, 4 or 5 metal;

[0324] Each A 1 and A 2 are independently an aromatic group, a substituted aromatic group, or an alkenediyl group;

[0325] Heterocyclic ring fragment-(Z 1 Z 2 )- and –(Z 3 Z 4 )-independently selected from –(Z 5 Z 6 )-or–(Z 6 Z 5 )-, where Z 5 Selected from oxygen, sulfur, S(O), S(O)2 and N(R 50 ), and Z 6 Selected from nitrogen and C(R 51 ), where each R 50 and R 51 are independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom;

[0326] R 4 and R 5 Each of which is independently hydrogen, C1-C 40Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom;

[0327] J is a heterocyclic Lewis base;

[0328] Each Q 1 and Q 2 independently selected from oxygen, sulfur, N(R 30 ) or P(R 30 ), where R 30 It is C1-C 40 Hydrocarbon, substituted C1-C 40 a hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom;

[0329] L is a Lewis base;

[0330] X is an anionic ligand;

[0331] n is 1, 2, or 3;

[0332] m is 0, 1, or 2;

[0333] n+m is not greater than 4;

[0334] Any two L groups can be joined together to form a bidentate Lewis base;

[0335] The X group can be joined to the L group to form a monoanionic bidentate group; and

[0336] Any two X groups can be joined together to form a dianionic ligand.

[0337] Item 2. The catalyst compound of Item 1, wherein A 1 It is expressed by the following formula:

[0338]

[0339] in represents a connection to the catalyst compound, and

[0340] R 9 、R 10 、R 11 and R 12 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom or a monovalent group combined with a heteroatom, or R 9 and R 10 、R 10 and R 11 or R 11 and R 12One or more of the pairs may join to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms.

[0341] Item 3. The catalyst compound of Item 1, wherein A 2 It is expressed by the following formula:

[0342]

[0343] in represents a connection to the catalyst compound, and

[0344] R 13 、R 14 、R 15 and R 16 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom or a monovalent group combined with a heteroatom, or R 13 and R 14 、R 14 and R 15 or R 15 and R 16 One or more of the pairs may join to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms.

[0345] Item 4. The catalyst compound of Item 1, wherein the compound features a tridentate dianionic ligand coordinated to the metal to form a pair of eight-membered metallocycle rings.

[0346] Item 5. The catalyst compound of Item 1, wherein J is a Group 15-containing heterocycle, or a Group 16-containing heterocycle.

[0347] Item 6. The catalyst compound of Item 1, wherein J is a nitrogen-containing heterocycle, an oxygen-containing heterocycle, a phosphorus-containing heterocycle, or a sulfur-containing heterocycle.

[0348] Item 7. The catalyst compound of any one of Items 1 to 6, wherein J is selected from pyridine, pyrimidine, pyrazine, thiazole, Azoles, oxazoline, imidazole, furan or thiophene.

[0349] Item 8. The catalyst compound of any one of Items 1 to 6, wherein J is represented by the formula:

[0350]

[0351] in Indicates the connection to the catalyst compound; E is oxygen, sulfur or NR 17 ; Z 7 Selected from nitrogen and C(R 18 );Z 8 Selected from nitrogen and C(R 19 ); and R 17 and R 18 and R 19 Each of which is selected from hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom.

[0352] Item 9. The catalyst compound of Item 1, wherein the catalyst compound represented by formula (I) is represented by formula (II) or formula (III):

[0353]

[0354] in:

[0355] Each Q 1 and Q 2 independently selected from oxygen, sulfur, N(R 30 ) or P(R 30 ), where R 30 It is C1-C 40 Hydrocarbon, substituted C1-C 40 a hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom;

[0356] Heterocyclic ring fragment-(Z 1 Z 2 )- and –(Z 3 Z 4 )-Selected from–(Z 5 Z 6 )-or–(Z 6 Z 5 )-, where Z 5 Selected from oxygen, sulfur, S(O), S(O)2 and N(R 50 ), and Z 6 Selected from nitrogen and C(R 51 ), where each R 50 and R 51 are independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom;

[0357] Z 7 Selected from nitrogen and C(R 18 );

[0358] Z 8 Selected from nitrogen and C(R19 );

[0359] E is oxygen, sulfur or N(R 20 );

[0360] R 4 and R 5 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom;

[0361] R 9 、R 10 、R 11 and R 12 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom or a monovalent group combined with a heteroatom, or R 9 and R 10 、R 10 and R 11 or R 11 and R 12 One or more of the pairs may join to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms;

[0362] R 13 、R 14 、R 15 and R 16 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom or a monovalent group combined with a heteroatom, or R 13 and R 14 、R 14 and R 15 or R 15 and R 16 One or more of the pairs may join to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms;

[0363] R 17 、R 18 、R 19 and R 20 Each of them is hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom or a monovalent group combined with a heteroatom, or R 17 and R 18 、R18 and R 19 One or more of the pairs may join together to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms;

[0364] M is a Group 3, 4 or 5 metal;

[0365] L is a Lewis base;

[0366] X is an anionic ligand;

[0367] n is 1, 2, or 3;

[0368] m is 0, 1, or 2;

[0369] n+m is not greater than 4;

[0370] Any two L groups can be joined together to form a bidentate Lewis base;

[0371] The X group can be joined to the L group to form a monoanionic bidentate group; and

[0372] Any two X groups can be joined together to form a dianionic ligand.

[0373] Item 10. The catalyst compound of Item 9, wherein M is zirconium or hafnium.

[0374] Item 11. The catalyst compound of Item 10, wherein R 9 to R 17 It's hydrogen.

[0375] Item 12. The catalyst compound of Item 11, wherein R 4 and R 5 Each selected from C1-C 40 Hydrocarbon, C1-C 40 A substituted hydrocarbyl or monovalent group containing up to 40 atoms in combination with heteroatoms.

[0376] Item 13. The catalyst compound of Item 12, wherein -(Z 1 Z 2 )- and –(Z 3 Z 4 )-Selected from–(Z 5 Z 6 )-or–(Z 6 Z 5 )-, where Z 5 It's oxygen or sulfur.

[0377] Item 14. The catalyst compound of Item 13, wherein R 4 and R 5Each selected from C4-C 40 A cyclic tertiary hydrocarbon group.

[0378] Item 15. The catalyst compound (II) of Item 9, wherein Z 7 It is C(R 18 ), where R 18 is selected from hydrogen, trifluoromethyl, methoxy, Me2N or a halogen atom.

[0379] Item 16. The catalyst compound of Item 15, wherein Z 8 It is C(R 19 ), where R 18 It's hydrogen.

[0380] Item 17. The catalyst compound of Item 16, wherein R 4 and R 5 Each selected from C4-C 20 Hydrocarbon group.

[0381] Item 18. The catalyst compound of Item 17, wherein R 4 and R 5 Each selected from C6-C 20 Aryl.

[0382] Item 19. The catalyst compound of Item 17, wherein R 4 and R 5 Each selected from C4-C 20 Tertiary hydrocarbon group.

[0383] Item 20. The catalyst compound of Item 19, wherein R 4 and R 5 Each selected from C4-C 20 A cyclic tertiary hydrocarbon group.

[0384] Item 21. The catalyst compound of Item 20, wherein R 4 and R 5 Each is selected from adamantane-1-yl, 3,5-dimethyladamantan-1-yl, and 3,5,7-trimethyladamantan-1-yl.

[0385] Item 22. The catalyst compound of Item 17, wherein R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 and R 17 Each of which is independently hydrogen or C1-C 10 alkyl.

[0386] Clause 23. The catalyst compound of clause 1, wherein the catalyst compound is selected from the group consisting of: wherein M = Zr or Hf; and R = Cl-C 20 Hydrocarbyl, monovalent heteroatom or monovalent group combined with heteroatom:

[0387]

[0388]

[0389]

[0390]

[0391] Clause 24. The catalyst compound of clause 1, wherein the catalyst compound is selected from the group consisting of: wherein M = Zr or Hf; and R = Cl-C 20 Hydrocarbyl, monovalent heteroatom or monovalent group combined with heteroatom:

[0392]

[0393]

[0394] Item 25. A catalyst system comprising an activator and the catalyst compound of any one of items 1 to 24.

[0395] Item 26. The catalyst system of Item 25, further comprising a support material.

[0396] Item 27. The catalyst system of Item 26, wherein the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica clay, silica / clay, or mixtures thereof.

[0397] Item 28. The catalyst system of Item 25, wherein the activator comprises a non-coordinating anion activator.

[0398] Item 29. The catalyst system of Item 25, wherein the activator is represented by the formula:

[0399] Z d + (A d- )

[0400] Wherein Z is (LH) or a reducible Lewis acid, L is a Lewis base, H is hydrogen, (LH) + is a Bronsted acid; A d- is a non-coordinating anion having a charge d-; and d is an integer from 1 to 3.

[0401] Item 30. The catalyst system of Item 25, wherein the activator is represented by the formula:

[0402] [R 1 R 2 R 3 EH] d + [M k+ Q n ] d-

[0403] in:

[0404] E is nitrogen or phosphorus; d is 1, 2, or 3; k is 1, 2, or 3); n is 1, 2, 3, 4, 5, or 6; nk = d; R 1 、R 2 and R 3 wherein each is independently hydrogen, optionally substituted C1-C 40 Alkyl or optionally substituted C5-C 50 -aryl; wherein R 1 、R 2 and R 3 The alkyl radicals together contain 15 or more carbon atoms; M is an element selected from Group 13 of the Periodic Table of Elements; and each Q is independently a hydrogen radical, a bridged or unbridged dialkylamino, a halo, an alkoxy, an aryloxy, a hydrocarbyl, a substituted hydrocarbyl, a halohydrocarbyl, a substituted halohydrocarbyl, or a halo-substituted hydrocarbyl radical.

[0405] Clause 31. The catalyst system of Clause 25, wherein the activator is one or more of:

[0406] N-Methyl-4-nonadecyl-N-octadecylanilinium tetrakis(perfluorophenyl)borate, N-Methyl-4-nonadecyl-N-octadecylanilinium tetrakis(perfluorophenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate,

[0407] Dioctadecylmethylammonium tetrakisperfluoronaphthylborate,

[0408] N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

[0409] triphenylcarbon tetrakis(pentafluorophenyl)borate trimethylammonium tetrakisperfluoronaphthylborate,

[0410] triethylammonium tetrakisperfluoronaphthylborate,

[0411] Tripropylammonium tetrakis(perfluoronaphthyl)borate,

[0412] tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate,

[0413] tri(tert-butyl)ammonium tetrakis(perfluoronaphthyl)borate,

[0414] N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,

[0415] N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,

[0416] N,N-dimethyl-(2,4,6-trimethylanilinium tetrakis(perfluoronaphthyl)boric acid, tetrakis(perfluoronaphthyl)boric acid triphenylcarbon tetrakisperfluoronaphthyl borate triphenyl tetrakis(perfluoronaphthyl)borate triethylsilyltetrakisperfluoronaphthylborate Tetrakis(perfluoronaphthyl)benzene borate (diazo ),

[0417] trimethylammonium tetrakis(perfluorobiphenyl)borate,

[0418] triethylammonium tetrakis(perfluorobiphenyl)borate,

[0419] Tripropylammonium tetrakis(perfluorobiphenyl)borate,

[0420] tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,

[0421] tri(tert-butyl)ammonium tetrakis(perfluorobiphenyl)borate,

[0422] N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,

[0423] N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,

[0424] N,N-dimethyl-(2,4,6-trimethylanilinium tetrakis(perfluorobiphenyl)boric acid, tetrakis(perfluorobiphenyl)boric acid triphenylcarbon tetrakis(perfluorobiphenyl)borate triphenyl tetrakis(perfluorobiphenyl)borate triethylsilyl tetrakis(perfluorobiphenyl)borate Tetrakis(perfluorobiphenyl)benzene borate (diazo ),

[0425] [4-tert-butyl-PhNMe2H][(C6F3(C6F5)2)4B],

[0426] trimethylammonium tetraphenylborate,

[0427] triethylammonium tetraphenylborate,

[0428] Tripropylammonium tetraphenylborate,

[0429] tri(n-butyl)ammonium tetraphenylborate,

[0430] tri(tert-butyl)ammonium tetraphenylborate,

[0431] N,N-dimethylanilinium tetraphenylborate,

[0432] N,N-diethylanilinium tetraphenylborate,

[0433] N,N-dimethyl-(2,4,6-trimethylphenylammonium tetraphenylboronic acid, tetraphenylboronic acid triphenylcarbon tetraphenylborate triphenyl tetraphenyl borate triethylsilyl tetraphenylborate Tetraphenylboronic acid benzene (diazo ),

[0434] trimethylammonium tetrakis(pentafluorophenyl)borate,

[0435] triethylammonium tetrakis(pentafluorophenyl)borate,

[0436] tripropylammonium tetrakis(pentafluorophenyl)borate,

[0437] tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

[0438] tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

[0439] N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

[0440] N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,

[0441] N,N-dimethyl-(2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)boric acid, tetrakis(pentafluorophenyl)boric acid triphenylcarbon tetrakis(pentafluorophenyl)borate triphenyl tetrakis(pentafluorophenyl)borate triethylsilyltetrakis(pentafluorophenyl)borate benzene tetrakis(pentafluorophenyl)borate (diazo ),

[0442] trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0443] triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0444] Tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0445] Tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0446] Dimethyl(tert-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0447] N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0448] N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0449] N,N-dimethyl-(2,4,6-trimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0450] Tetrakis(2,3,4,6-tetrafluorophenyl)boric acid

[0451] triphenylcarbon tetrakis(2,3,4,6-tetrafluorophenyl)borate

[0452] triphenyl tetrakis(2,3,4,6-tetrafluorophenyl)borate

[0453] triethylsilyl tetrakis(2,3,4,6-tetrafluorophenyl)borate

[0454] benzene tetrakis(2,3,4,6-tetrafluorophenyl)boronic acid (diazo ),

[0455] trimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0456] triethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0457] Tripropylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0458] Tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0459] tri(tert-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0460] N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0461] N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0462] N,N-dimethyl-(2,4,6-trimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid,

[0463] Tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid

[0464] triphenylcarbon tetrakis(3,5-bis(trifluoromethyl)phenyl)borate

[0465] triphenyl tetrakis(3,5-bis(trifluoromethyl)phenyl)borate

[0466] triethylsilyl tetrakis(3,5-bis(trifluoromethyl)phenyl)borate

[0467] benzene tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid ),

[0468] Di(isopropyl)ammonium tetrakis(pentafluorophenyl)borate,

[0469] Dicyclohexylammonium tetrakis(pentafluorophenyl)borate,

[0470] Tri(o-tolyl)tetrakis(pentafluorophenyl)borate

[0471] Tris(2,6-dimethylphenyl)tetrakis(pentafluorophenyl)borate

[0472] triphenylcarbon tetrakis(pentafluorophenyl)borate

[0473] 1-(4-(tris(pentafluorophenyl)boronic acid)-2,3,5,6-tetrafluorophenyl)pyrrolidine

[0474] Tetrakis(pentafluorophenyl)borate,

[0475] 4-(tris(pentafluorophenyl)boronic acid)-2,3,5,6-tetrafluoropyridine, and

[0476] triphenylcarbon tetrakis(3,5-bis(trifluoromethyl)phenyl)borate

[0477] Item 32. The catalyst system of Item 25, further comprising a metal hydrocarbenyl chain transfer agent represented by the formula:

[0478] Al(R') 3-v (R”) v

[0479] Wherein each R' is independently C1-C 30 Hydrocarbyl group; each R" is independently C4-C having a terminal vinyl group 20 a hydrocarbenyl group; and v is 1-3.

[0480] Item 33. The catalyst system of Item 25, wherein the activator comprises an alkylaluminoxane.

[0481] Item 34. The catalyst system of Item 33, wherein the aluminoxane is present in a molar ratio of aluminum to transition metal of the catalyst compound of 100:1 or greater.

[0482] Clause 35. A process for producing an ethylene-based polymer, comprising: polymerizing ethylene by contacting ethylene with the catalyst system of any one of Clauses 25 to 34 in one or more continuous stirred tank reactors or loop reactors connected 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.

[0483] Clause 36. The process of Clause 35, wherein the ethylene-based polymer has an Mw value of 2,000 to 3,000,000 g / mol, an Mn value of 1,000 to 2,000,000 g / mol, an Mz value of 10,000 to 10,000,000 g / mol, and an Mw / Mn of 1 to 5.

[0484] Clause 37. The process of Clause 35, wherein the ethylene-based polymer has a melting point of 110°C to 150°C.

[0485] Clause 38. A process for producing a propylene-based polymer, comprising: polymerizing propylene by contacting propylene with the catalyst system of Clause 25 in one or more continuous stirred tank reactors or loop reactors connected 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.

[0486] Clause 39. The process of Clause 38, wherein the propylene-based polymer has an Mw value of 500-15,000 g / mol, an Mn value of 500-15,000 g / mol, an Mz value of 500-20,000 g / mol, and an Mw / Mn of 1-5.

[0487] Clause 40. The process of Clause 38, wherein the propylene-based polymer has a melting point of 50°C to 150°C.

[0488] Clause 41. A method for producing an ethylene alpha-olefin copolymer, comprising: reacting ethylene and at least one C3-C4 copolymer in one or more continuous stirred tank reactors or loop reactors connected 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 catalyst system of clause 25 to polymerize ethylene and at least one C3-C 20 α-olefins.

[0489] Clause 42. The process of Clause 41, wherein the ethylene α-olefin copolymer has a comonomer content of 0.1 to 50 weight percent, an Mw value of 1,000-3,000,000 g / mol, and an Mz value of 1,000-10,000,000 g / mol, an Mn value of 1,000-1,000,000 g / mol, and an Mw / Mn ratio of 1-5.

[0490] Clause 43. The process of Clause 41, wherein the ethylene alpha-olefin copolymer has a melting point of 100°C to 140°C.

[0491] Clause 44. A method for producing a propylene alpha-olefin copolymer comprising: reacting propylene and at least one ethylene or at least one C3-C4 copolymer in one or more continuous stirred tank reactors or loop reactors connected 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 The α-olefin is contacted with the catalyst system of clause 25 to polymerize propylene and at least one ethylene or at least one C4-C 20 α-olefins.

[0492] Clause 45. The process of Clause 44, wherein the propylene alpha-olefin copolymer has a comonomer content of 0.1 to 35 weight percent, an Mw value of 1,000-3,000,000 g / mol, and an Mz value of 1,000-10,000,000 g / mol, an Mn value of 1,000-1,000,000 g / mol, and an Mw / Mn ratio of 1-5.

[0493] Clause 46. The process of Clause 44, wherein the propylene alpha-olefin copolymer has a melting point of 100°C to 140°C. Example

[0494] The following are examples of complexes of the present invention (M = Group 4 metal; R = halide, C1-C 20 Hydrocarbon):

[0495]

[0496]

[0497]

[0498]

[0499] Chemicals and reagents:

[0500] 4-Bromo-3-hydroxythiophene-2-carboxylic acid methyl ester [95201-93-7] can be prepared using the procedures described in WO 2002 / 38572 and Tetrahedron Letters 2011, 52, 1288-1291 and Tetrahedron Letters 2017, 58, 2537-2541. 4-Bromothiophene-3-ol (Compound A) can be prepared from 4-bromo-3-hydroxythiophene-2-carboxylic acid methyl ester using the procedures described in WO 2018 / 236863. Zr(NMe2)Cl2(DME) can be prepared using the method described in Organometallics (2000), 19(2), 127-134. Solvents and the following chemicals were purchased from commercial sources (Sigma Aldrich, Alfa Aesar, TCI): 4-bromothiophen-3-ol, 1,2-dimethoxyethane (DME), sodium hydride, chloro(methoxy)methane (MOM-Cl), phenylboronic acid, sodium carbonate, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( i PrOB(pin)), tetrakistriphenylphosphine palladium, 2-bromoiodobenzene, butyl lithium, methylmagnesium bromide, hydrochloric acid.

[0501]

[0502] Prophetic synthesis of 3-bromo-4-(methoxymethoxy)thiophene (Compound B). Sodium hydride (13.4 mmol) was added to a stirred mixture of tetrahydrofuran (100 mL) and 4-bromothiophene-3-ol (Compound A) (2.00 g, 11.2 mmol) over 30 minutes. After stirring overnight, chloro(methoxy)methane (1.08 g, 13.4 mmol) was added dropwise. After several hours, the volatiles were evaporated and the residue was extracted with diethyl ether (100 mL). The solution was filtered through Celite and then evaporated to produce the product. Yield: 95%.

[0503]

[0504]

[00155] Prophetic Synthesis of 3-(Methoxymethoxy)-4-phenylthiophene (Compound C). A round-bottom flask was charged with 3-bromo-4-(methoxymethoxy)thiophene (3.36 g, 15.1 mmol), phenylboronic acid (1.91 g, 15.7 mmol), sodium carbonate (4.15 g, 39.2 mmol), dioxane (180 mL), and water (90 mL). The mixture was sparged with nitrogen for 50 minutes, then solid Pd(PPh3)4 (0.905 g, 0.783 mmol) was added. The mixture was sparged for an additional 40 minutes, then rapidly stirred and heated in an oil bath maintained at 100°C. After 20 hours, the volatiles were evaporated to provide the crude product, which was purified using column chromatography. Yield: 70%.

[0505]

[0506] Prophetic synthesis of (3-(methoxymethoxy)-4-phenylthiophen-2-yl)lithium (Compound D). To 3-(methoxymethoxy)-4-phenylthiophene (2.90 g, 13.2 mmol) was added hexane (50 mL) to form a mixture. A hexane solution of butyllithium (13.2 mmol, approximately 8 mL) was added dropwise over 15 minutes. 1,2-Dimethoxyethane (1.5 mL) was then added. The volatiles were evaporated to provide the product. Yield: 90%.

[0507]

[0508]

[0146] Prophetic synthesis of 2-(3-(methoxymethoxy)-4-phenylthiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Compound E). Toluene (100 mL) and (3-(methoxymethoxy)-4-phenylthiophen-2-yl)lithium (1.86 g, 8.24 mmol) were combined to form a mixture. The mixture was cooled to -40 °C and iPrOB(pin) (2.41 g, 13.0 mmol) was added. The mixture was allowed to slowly warm to ambient temperature. After 16 hours, the mixture was transferred to a separatory funnel and extracted with water (4 x 50 mL) and then brine (20 mL). The organics were dried over MgSO4, filtered and evaporated to afford the product. The product was purified using column chromatography. Yield: 85%.

[0509]

[0510]

[00155] Prophetic synthesis of 2-(2-bromophenyl)-3-(methoxymethoxy)-4-phenylthiophene (Compound F, Method 1). Toluene (50 mL) was added to (3-(methoxymethoxy)-4-phenylthiophen-2-yl)lithium (2.18 g, 9.64 mmol) to form a suspension. A solution of 1-bromo-2-chlorobenzene (1.87 g, 9.74 mol) in toluene (25 mL) was added dropwise over 2 hours. After an additional 2 hours, the mixture was transferred to a separatory funnel and extracted with water (3 x 50 mL) and then brine (20 mL). The organics were dried over MgSO4, filtered, and evaporated to provide the product. The product was purified using column chromatography. Yield: 85%.

[0511]

[00155] Prophetic synthesis of 2-(2-bromophenyl)-3-(methoxymethoxy)-4-phenylthiophene (Compound F, Method 2). A round-bottom flask was charged with 2-(3-(methoxymethoxy)-4-phenylthiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.23 g, 15.1 mmol), 2-dibromoiodobenzene (6.41 g, 22.7 mmol), sodium carbonate (4.15 g, 39.2 mmol), dioxane (180 mL) and water (90 mL). The mixture was sparged with nitrogen for 50 minutes, then solid Pd(PPh3)4 (0.905 g, 0.783 mmol) was added. The mixture was sparged for an additional 40 minutes, then rapidly stirred and heated in an oil bath maintained at 100°C. After 20 hours, the volatiles were evaporated to provide the crude product, which was purified using column chromatography. Yield: 70%.

[0512]

[0513] Prophetic Synthesis of (2-(3-(methoxymethoxy)-4-phenylthiophen-2-yl)phenyl)lithium (Compound G). Hexanes (100 mL) and 2-(2-bromophenyl)-3-(methoxymethoxy)-4-phenylthiophene (3.09 g, 8.24 mmol) were combined to form a mixture. The mixture was cooled to -20°C, and then a solution of butyllithium in hexanes (approximately 3.3 mL, 8.65 mmol) was added dropwise over 10 minutes. The mixture was slowly warmed to 0°C over one hour. The mixture was stirred for an additional hour, and then the volatiles were evaporated to provide the product. Yield: 90%.

[0514]

[0515]

[00156] Prophetic Synthesis of 2-(2-(3-(methoxymethoxy)-4-phenylthiophen-2-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Compound H). Toluene (100 mL) and (2-(3-(methoxymethoxy)-4-phenylthiophen-2-yl)phenyl)lithium (2.49 g, 8.24 mmol) were combined to form a mixture. The mixture was cooled to -40 °C and iPrOB(pin) (2.41 g, 13.0 mmol) was added. The mixture was allowed to slowly warm to ambient temperature. After 16 hours, the mixture was transferred to a separatory funnel and extracted with water (4 x 50 mL) followed by brine (20 mL). The organics were dried over MgSO4, filtered, and evaporated to afford the product. The product was purified using column chromatography. Yield: 85%.

[0516]

[0517]

[00155] Prophetic Synthesis of 2,6-bis(2-(3-(methoxymethoxy)-4-phenylthiophen-2-yl)phenyl)pyridine (Compound I). A round-bottom flask was charged with 2-(2-(3-(methoxymethoxy)-4-phenylthiophen-2-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.98 g, 7.06 mmol), 2,6-dibromopyridine (0.794 g, 3.35 mmol), Na2CO3 (1.87 g, 17.6 mmol), dioxane (100 mL), and water (50 mL). The mixture was sparged with nitrogen for 30 minutes, then solid Pd(PPh3)4 (0.407 g, 0.353 mmol) was added. The mixture was sparged for an additional 30 minutes, then stirred and heated in an oil bath maintained at 100°C. After 17 hours, the mixture was cooled to ambient temperature and the volatiles were evaporated to a residue. The residue was extracted with ether (200 mL) and the mixture was transferred to a separatory funnel and extracted with water (4×50 mL) and then brine (20 mL). The organics were dried over MgSO 4 , filtered and evaporated to provide the product. Yield: 90%.

[0518]

[0519] Prophetic Synthesis of 2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-phenylthiophen-3-ol) (Compound J). Methanol (60 mL), tetrahydrofuran (60 mL), concentrated HCl (5 mL), and 2,6-bis(2-(3-(methoxymethoxy)-4-phenylthiophen-2-yl)phenyl)pyridine (3.35 mmol) were combined and the mixture was heated to 60°C for 16 hours. The volatiles were then evaporated and the residue was extracted with ether (100 mL) and water (50 mL) and then charged to a separatory funnel. The aqueous layer was removed and the organics were extracted with water (4 x 50 mL) and then brine (2 x 10 mL). The organics were dried over MgSO4 and then evaporated to yield the product. The product was purified using column chromatography. Yield: 70%.

[0520]

[0521] Prophetic synthesis of [2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-phenylthiophen-3-ol)]zirconium dichloride (Compound K). To ZrCl2(NMe2)2(dimethoxyethane) (0.696 g, 2.04 mmol) was added toluene (60 mL) to form a solution. A solution of 2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-phenylthiophen-3-ol) (1.18 g, 2.04 mmol) dissolved in toluene (20 mL) was then added dropwise over 20 minutes. The mixture was heated to 80°C for 4 hours and then cooled to ambient temperature. The mixture was filtered and then evaporated to provide the product. Yield: 80%.

[0522]

[0523] Prophetic synthesis of [2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-phenylthiophen-3-ol)]zirconium dimethyl (Compound L). To [2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-phenylthiophen-3-ol)]zirconium dichloride (Compound K, 1.27 g, 1.71 mmol) was added toluene (80 mL) to form a mixture. The mixture was cooled to -20°C and MeMgBr (1.6 mL, 5.14 mmol in diethyl ether) was added over 10 minutes. The mixture was slowly warmed to ambient temperature over one hour. After an additional 12 hours, the volatiles were evaporated under reduced pressure. The solid was extracted with toluene (50 mL) and filtered. The volatiles were evaporated to provide the product. Purification can be performed by trituration with cold hexanes. Yield: 80%.

[0524] General olefin polymerization process

[0525] Solvents, polymer grade toluene and / or isohexane, were supplied by ExxonMobil Chemical Co. and purified through the following series of columns: two 500 cm 3 Oxyclear cylinders, then filled with dry Two 500 cm2 molecular sieves (8-12 mesh, Aldrich Chemical Company) were connected in series. 3 Column and packed with dry Two 500 cm2 molecular sieves (8-12 mesh, Aldrich Chemical Company) were connected in series. 3 column.

[0526] 1-Octene (98%) (Aldrich Chemical Company) was dried by filtration through basic alumina (Aldrich Chemical Company, Brockman Basic 1) after stirring overnight on Na-K alloy. Tri(n-octyl)aluminum (TNOA) was purchased from Aldrich Chemical Company or Akzo Nobel and used as received.

[0527] Polymerization grade ethylene was further purified by passing it through the following series of columns: 500 cm 3 Oxyclear cylinders, then filled with dry Molecular sieves (8-12 mesh, Aldrich Chemical Company) 500 cm 3 Column and packed with dry Molecular sieves (8-12 mesh, Aldrich Chemical Company) 500 cm 3 column.

[0528] Polymer grade propylene was further purified by passing it through the following series of columns: 2250 cm 3 Oxyclear cylinder, followed by a cylinder filled with Molecular sieves (8-12 mesh, Aldrich Chemical Company) at 2250 cm 3 Column, then two in series are filled with Molecular sieves (8-12 mesh, Aldrich Chemical Company) 500 cm 3 Column, 500 cm packed with Selexsorb CD (BASF)3 The column was then filled with Selexsorb COS (BASF) to form a 500 cm 3 column.

[0529] N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (also referred to as Activator 1) was purchased from WR Grace and Co. Methylaluminoxane (MAO, also referred to as Activator 2) was purchased from WR Grace and Co. as a 10 wt% solution in toluene. All complexes and activators were added to the reactor as diluent solutions in toluene. The concentrations of the solutions of activator, scavenger, and complex added to the reactor were selected so that between 40 microliters and 200 microliters of solution were added to the reactor to ensure accurate delivery.

[0530] Reactor Description and Preparation. Polymerizations were performed in an inert atmosphere (N2) dry box using an autoclave equipped with an external heater for temperature control, a glass insert (the internal volume of the reactor was 23.5 mL for C2 and C2 / C8 runs and 22.5 mL for C3 runs), a septum inlet, a regulated supply of nitrogen, ethylene, and propylene, and a disposable polyetheretherketone mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110°C or 115°C for 5 hours and then at 25°C for 5 hours.

[0531] Ethylene polymerization (PE) or ethylene / 1-octene copolymerization (EO)

[0532] The reactor was prepared as described above and then purged with ethylene. Toluene (solvent, unless otherwise specified), optional 1-octene (0.1 mL when used), and optional MAO were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to process temperature (typically 80° C.) and ethylene was added to process pressure (typically 75 psig = 618.5 kPa or 200 psig = 1480.3 kPa) while stirring at 800 RPM. An optional scavenger solution (e.g., TNOA in isohexane) was then added to the reactor via syringe under process conditions. An optional non-coordinating activator (e.g., N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate) solution (in toluene) was added to the reactor via syringe under process conditions, followed by a precatalyst (i.e., complex or catalyst) solution (in toluene) added to the reactor via syringe under process conditions. Ethylene was admitted to the autoclave (using a computer-controlled solenoid valve) during polymerization to maintain the reactor gauge pressure (+ / - 2 psi). The reactor temperature was monitored and typically maintained within + / - 1° C. The polymerization was stopped by adding approximately 50 psi of an O / Ar (5 mol% O) gas mixture (greater than the reactor pressure) to the autoclave for approximately 30 seconds. The polymerization was quenched after the addition of a predetermined cumulative amount of ethylene or for a maximum polymerization time of 30 minutes. The reactor was cooled and vented. The polymer was isolated after removal of the solvent under reduced pressure. The yield reported includes the total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer / mmol of transition metal compound / hour of reaction time (g / mmol / hr).

[0533] Propylene polymerization

[0534] The reactor was prepared as described above, then heated to 40°C and purged with propylene gas at atmospheric pressure. Toluene (solvent, unless otherwise specified), optional MAO, and liquid propylene (1.0 mL) were added via syringe. The reactor was then heated to the process temperature (70°C or 100°C) while stirring at 800 RPM. An optional scavenger solution (e.g., TNOA in isohexane) was then added to the reactor via syringe under process conditions. An optional non-coordinating activator (e.g., N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate) solution (in toluene) was then added to the reactor via syringe under process conditions, followed by a procatalyst (i.e., complex or catalyst) solution (in toluene) added to the reactor via syringe under process conditions. The reactor temperature was monitored and typically maintained within + / - 1°C. The polymerization was stopped by adding approximately 50 psi of an O2 / Ar (5 mol% O2) gas mixture (greater than the reactor pressure) to the autoclave for approximately 30 seconds. The polymerization was quenched based on a predetermined pressure loss of approximately 8 psi or for a maximum polymerization time of 30 minutes. The reactor was cooled and vented. The polymer is isolated after removal of the solvent under reduced pressure. The yield to be reported includes the total weight of the polymer and the residual catalyst. Catalyst activity is usually reported as grams of polymer / mmol of transition metal compound / hour of reaction time (g / mmol / hr).

[0535] Polymer characterization

[0536] For analytical testing, polymer sample solutions were 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) in a shaker oven at 165°C for approximately 3 hours. Typical concentrations of the polymer in solution were between 0.1 mg / mL and 0.9 mg / mL, with a BHT concentration of 1.25 mg BHT / mL of TCB. The samples were cooled to 135°C for testing.

[0537] High temperature size exclusion chromatography was performed using an automated "Fast GPC" system as described in U.S. Patent Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388, each of which is incorporated herein by reference. The molecular weight (weight average molecular weight (Mw) and number average molecular weight (Mn)) and molecular weight distribution (MWD = Mw / Mn), which is sometimes also referred to as the polydispersity index (PDI) of the polymer, were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) between 5,000 and 3,390,000). The samples were run using three Polymer Laboratories: PLgel 10 μm Mixed-B 300×7.5 mm columns in series (250 μL of polymer solution in TCB was injected into the system) at an eluent flow rate of 2.0 mL / min (135° C. sample temperature, 165° C. oven / column). No column diffusion correction was used. The HPLC-MS / MS / MS data available from Symyx Technologies were used. Data analysis was performed using Automation Studio software or Automation Studio software available from Freeslate. Molecular weights obtained are relative to linear polystyrene standards.

[0538] Rapid differential scanning calorimetry (Rapid-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 minutes 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. The melting point was collected during the heating process.

[0539] Samples for infrared analysis were prepared by depositing the stabilized polymer solution onto a silanized wafer (Part No. S10860, Symyx). By this method, between approximately 0.12 mg and 0.24 mg of polymer were deposited onto the wafer unit. The samples were then analyzed on a Bruker Equinox 55 FTIR spectrometer equipped with a specular reflectance sample accessory from Pikes' MappIR. The 2 cm -1 The resolution was 32 scans collected to cover 5,000 cm -1 Up to 500cm -1 Spectral range of the spectrum.

[0540] For ethylene-1-octene copolymer, the -1 The copolymer weight percent was determined by measuring the methyl deformation band at -4,321 cm -1 The normalized peak height is compared with the peak height from 1 The respective calibration curves for the H NMR data were correlated to predict the wt% copolymer content over a concentration range of 2 wt% to 35 wt% for octene. Typically, an R of 0.98 or greater was achieved. 2 Correlation. Values reported below 4.1 wt% are outside the calibration range.

[0541] Polymerization Example

[0542] The following are the specific conditions described for prophetic polymerizations using catalysts of the present invention, such as Catalyst L. Catalyst L is an active catalyst for olefin polymerization when activated using N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (Activator 1) or MAO (Activator 2), respectively.

[0543] General conditions for ethylene homopolymerization using Activator 1: Catalyst complex = 25 nmol, Activator 1 = 27.5 nmol, ethylene = 75 psig, Al(n-octyl)3 = 500 nmol, temperature = 80°C, total volume = 5 mL, solvent = toluene. Complex L (when activated with Activator 1) forms an active catalyst capable of polymerizing ethylene to form polyethylene. The melting point of the polyethylene samples ranges from 123°C to 138°C.

[0544] General conditions for ethylene homopolymerization using Activator 2: Catalyst complex = 25 nmol, Activator 2 = 0.0125 mmol, ethylene = 75 psig, total volume = 5 mL, solvent = toluene. Complex L (when activated with Activator 2) forms an active catalyst capable of polymerizing ethylene to form polyethylene. The melting point of the polyethylene samples ranged from 123°C to 138°C.

[0545] General conditions for ethylene-octene copolymerization using Activator 1: Catalyst complex = 25 nmol, Activator 1 = 27.5 nmol, 0.1 mL octene, Al(n-octyl)3 = 500 nmol, temperature = 80°C, total volume = 5 mL, solvent = toluene. Complex L (when activated with Activator 1) forms an active catalyst capable of polymerizing ethylene and octene to form ethylene-octene copolymers. The melting points of the ethylene-octene copolymer samples range from 60°C to 125°C.

[0546] General conditions for ethylene-octene copolymerization using Activator 2: Complex L = 25 nmol, Activator 2 = 0.0125 mmol, 0.1 mL octene, Temperature = 80°C, Total Volume = 5 mL, Solvent = Toluene. Complex L (when activated with Activator 2) forms an active catalyst capable of polymerizing ethylene and octene to form ethylene-octene copolymers. The melting points of the ethylene-octene copolymer samples range from 60°C to 125°C.

[0547] General conditions for propylene homopolymerization using Activator 1: Catalyst complex = 25 nmol, Activator 1 = 27.5 nmol, propylene = 1 mL, Al(n-octyl)3 = 500 nmol, total volume = 5 mL, solvent = isohexane. Complex L (when activated with Activator 1) forms an active catalyst capable of polymerizing propylene to form polypropylene. The melting point of the polypropylene samples ranges from 85°C to 165°C.

[0548] General conditions for propylene homopolymerization using Activator 2: Catalyst complex = 40 nmol, Activator 2 = 0.025 mmol, propylene = 1 mL, total volume = 5 mL, solvent = toluene. Complex L (when activated with Activator 2) forms an active catalyst capable of polymerizing propylene to form polypropylene. The melting point of the polypropylene samples ranged from 85°C to 165°C.

[0549] Non-prophetic embodiments

[0550] The following are examples of complexes that embody the advances of this technology:

[0551]

[0552] General considerations for synthesis:

[0553] Unless otherwise noted, all reagents were purchased from a commercial supplier (Sigma Aldrich) and used as received. 3-Bromo-4-(ethoxymethoxy)thiophene was prepared using the procedure described in WO2018 / 236863. 2,6-Bis(2-bromophenyl)pyridine was prepared using the procedure described in WO2020 / 167821. The solvent was sparged with N2 and the reaction mixture was stirred for 2 h. All chemical operations were performed under nitrogen atmosphere unless otherwise stated. (70 mesh–230 mesh) Flash column chromatography was performed using the specified solvent system. NMR spectra were recorded on a Bruker 400 and / or 500 NMR, with chemical shifts referenced to the residual solvent peak. All anhydrous solvents were purchased from Fisher Chemical and degassed and dried over molecular sieves before use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and degassed and dried over molecular sieves before use. The spectral range was obtained at 400 MHz or 500 MHz using solutions prepared by dissolving approximately 10 mg of sample in C6D6, CD2Cl2, CDCl3, D8-toluene, or other deuterated solvents. 1 H NMR spectral data. The chemical shifts (δ) presented are relative to the residual protium in the deuterated solvent and are located at 7.15 ppm, 5.32 ppm, 7.24 ppm, and 2.09 ppm for C6D6, CD2Cl2, CDCl3, and D8-toluene, respectively.

[0554] Synthesis of ligands and catalysts

[0555]

[0556] 3-(Ethoxymethoxy)-4-isobutylthiophene. To a solution of ZnCl2 (0.69 g, 5 mmol) in tetrahydrofuran (10 mL) was slowly added a pentane solution of tert-butyl lithium (2.98 mL, 1.7 M, 5 mmol). The reaction mixture was stirred at ambient temperature for 5 minutes. Subsequently, 3-bromo-4-(ethoxymethoxy)thiophene (0.8 g, 3.4 mmol) and Pd (P t Bu3)2 (140 mg, 0.17 mmol). The reaction mixture was stirred at 70°C overnight and then concentrated to dryness. The resulting mixture was slurried in toluene and hexane. The supernatant was then purified by flash chromatography on silica gel (10%-20% dichloromethane in hexane). Yield 0.54 g (75%) of a clear oil. 1 H NMR (CDCl3, 400MHz): δ6.80 (d, J = 3.3Hz, 1H), 6.50 (d, J = 3.2Hz, 1H), 5.16 (s, 2H), 3.71 (q, J = 7.1Hz, 2 H), 2.38 (d, J = 7.1Hz, 2H), 1.90 (dt, J = 13.5, 6.7Hz, 1H), 1.24 (t, J = 7.1Hz, 3H), 0.91 (d, J = 6.7Hz, 6H).

[0557]

[0558] 2,6-bis(2-(3-(ethoxymethoxy)-4-isobutylthiophen-2-yl)phenyl)pyridine. To a solution of 3-(ethoxymethoxy)-4-isobutylthiophene (0.52 g, 2.43 mmol) in tetrahydrofuran (10 mL) was added a hexane solution of n-butyllithium (0.22 mL, 11 M, 2.43 mmol). The reaction mixture was stirred at ambient temperature for 30 minutes. ZnCl2 (0.35 g, 2.43 mmol) was then added and the reaction was stirred for 5 minutes. 2,6-bis(2-bromophenyl)pyridine (0.45 g, 1.16 mmol) and Pd(P) were subsequently added. t Bu3)2 (78 mg, 0.09 mmol). The reaction mixture was stirred at 70°C overnight and then concentrated to dryness. The mixture was then slurried in toluene. The supernatant was then purified by flash chromatography on silica gel (25% dichloromethane and 2%-5% acetone in hexane). Yield 0.6 g (79%) of a clear oil. 1 H NMR (CDCl3, 400MHz): δ7.66–7.58(m,2H),7.55–7.49(m,2H),7.44–7.34(m,4H),7.28–7.21(m,1H),7.02(d,J=7.7Hz,2H),6.77(s,2H), 4.75 (s, 4H), 3.42 (q, J = 7.0Hz, 4H), 2.32 (d, J = 7.1Hz, 4H), 1.82 (dt, J = 13.5, 6.8Hz, 2H), 0.95 (t, J = 7.2Hz, 6H), 0.86 (d, J = 6.6Hz, 12H).

[0559]

[0560] 2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-isobutylthiophen-3-ol). To a solution of 2,6-bis(2-(3-(ethoxymethoxy)-4-isobutylthiophen-2-yl)phenyl)pyridine (0.6 g, 0.9 mmol) in 1,4-dioxane / CHCl (180 mL, 1:2) was added concentrated HCl (40 mL) under nitrogen. The reaction mixture was stirred for 24 hours and then basified with NaOH (aqueous solution). The organics were extracted from the aqueous layer with CHCl (2×50 mL), combined, and dried over solid MgSO. All solvents were subsequently removed under vacuum in an inert atmosphere (N) glove box. The resulting dark red amorphous foam was dissolved in CHCl (5 mL), filtered through a pad of silica gel, and rinsed with CHCl (4×20 mL). The dichloromethane was then removed under vacuum. The product was slurried in 5 mL of pentane for 10 minutes.The pure product was collected by filtration as a white solid (0.22 g, 45%).1 HNMR(CDCl3,400MHz)δ8.73(s,2H),7.76(t,J=7.8Hz,1H),7.55–7.37(m,8H),7.33(d,J=7.8Hz ,2H),6.63(s,2H),2.10(d,J=7.0Hz,4H),1.45(dt,J=13.5,6.7Hz,2H),0.64(d,J=6.5Hz,12H).

[0561] [2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-isobutylthiophene-3-ol)]dibenzyl hafnium (catalyst 1). Toluene (3 mL) was added to tetrabenzyl hafnium (40 mg, 0.07 mmol) and 2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-isobutylthiophene-3-ol) (40 mg, 0.07 mmol). The reaction mixture was stirred for 1 hour. The volatiles were evaporated and the crude product was stirred in pentane (2 mL) for 15 minutes. The product was collected by filtration as a yellow solid (42 mg, 62%). 1 HNMR(CD2Cl2,400MHz)δ7.83(t,J=7.8Hz,1H),7.74–7.49(m,6H),7.28(d,J=7.8Hz ,2H),7.21–7.13(m,2H),6.99–6.89(m,4H),6.82(s,2H),6.69(t,J=7.3Hz,2H),6. 43(d,J=7.6Hz,4H),2.25(d,J=7.0Hz,4H),1.87(dt,J=13.5,6.7Hz,2H),0.97(d,J =11.8Hz, 2H), 0.92 (d, J = 6.6Hz, 6H), 0.85 (d, J = 6.4Hz, 6H), 0.77 (d, J = 12.2Hz, 2H).

[0562] [2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-isobutylthiophene-3-ol)]dibenzylzirconium (catalyst 2). Toluene (3 mL) was added to tetrabenzylzirconium (59 mg, 0.13 mmol) and 2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-isobutylthiophene-3-ol) (70 mg, 0.13 mmol). The reaction mixture was stirred for 1 hour. The volatiles were evaporated and the crude product was stirred in pentane (2 mL) for 15 minutes. The product was collected by filtration as a yellow solid (80 mg, 76%). 1HNMR(CD2Cl2,400MHz)δ7.82(t,J=7.8Hz,1H),7.69–7.49(m,6H),7.25(d,J=7.5Hz, 2H),7.16(d,J=7.8Hz,2H),6.92(t,J=7.5Hz,4H),6.81(s,2H),6.71(t,J=7.4Hz,2H) ,6.42(d,J=7.6Hz,4H),2.30(d,J=7.0Hz,4H),1.90(dt,J=13.4,6.8Hz,2H),1.31(d, J=11.1Hz, 2H), 1.00 (d, J=11.2Hz, 2H), 0.93 (d, J=6.7Hz, 6H), 0.87 (d, J=6.6Hz, 6H).

[0563]

[0564] To a solution of p-fluorophenyl bromide (0.875 g, 5 mmol) in diethyl ether (20 mL) was added a hexane solution of n-butyl lithium (0.45 mL, 11 M, 5 mmol). The reaction mixture was stirred for 30 minutes and then concentrated to dryness. The crude product was slurried in 5 mL of hexane and stirred for 15 minutes. The product was collected by filtration as a yellow solid (0.21 g, 41%). 1 H NMR (THF-d8, 400MHz) δ7.74 (s, 2H), 6.56 (s, 2H).

[0565]

[0566] 3-(Ethoxymethoxy)-4-(4-fluorophenyl)thiophene. To a solution of p-fluorophenyllithium (0.20 g, 1.8 mmol) in tetrahydrofuran (10 mL) was slowly added ZnCl2 (0.24 g, 1.8 mmol). The reaction mixture was stirred at ambient temperature for 5 minutes. Subsequently, 3-bromo-4-(ethoxymethoxy)thiophene (0.39 g, 1.6 mmol) and Pd(P) were added. t Bu3)2 (42 mg, 0.09 mmol). The resulting mixture was stirred at 70°C overnight and then concentrated to dryness. The mixture was then slurried in toluene and hexane. The supernatant was then purified by flash chromatography on silica gel (20% dichloromethane in hexane). Yield 0.41 g (75%) of a clear oil. 1H NMR(CDCl3,400MHz)δ7.58(dd,J=8.7,5.5Hz,2H),7.20(d,J=3.5Hz,1H),7.08(t,J=8.8H z, 2H), 6.71 (d, J = 3.5Hz, 1H), 5.20 (s, 2H), 3.72 (q, J = 7.1Hz, 2H), 1.24 (t, J = 7.1Hz, 3H). 19 F NMR (CDCl3, 376MHz) δ-115.33.

[0567]

[0568] 2,6-bis(2-(3-(ethoxymethoxy)-4-(4-fluorophenyl)thiophen-2-yl)phenyl)pyridine. To a solution of 3-(ethoxymethoxy)-4-(4-fluorophenyl)thiophene (0.30 g, 1.2 mmol) in tetrahydrofuran (5 mL) was added a hexane solution of n-butyllithium (0.11 mL, 11 M, 1.2 mmol). The reaction mixture was stirred at ambient temperature for 30 minutes. ZnCl2 (0.24 g, 1.8 mmol) was then added and the reaction was stirred for 5 minutes. 2,6-bis(2-bromophenyl)pyridine (0.21 g, 0.54 mmol) and Pd(P) were subsequently added. t Bu3)2 (54 mg, 0.06 mmol). The resulting mixture was stirred at 70°C overnight and then concentrated to dryness. The mixture was then slurried in toluene. The supernatant was then purified by flash chromatography on silica gel. Yield 0.19 g (21%) of a clear oil. 1 H NMR(CDCl3,400MHz)δ7.66–7.57(m,4H),7.52–7.39(m,9H),7.23(d,J=7.8Hz,2H),7.14( s, 2H), 7.05 (t, J = 8.5Hz, 4H), 4.62 (s, 4H), 3.11 (q, J = 7.0Hz, 4H), 0.72 (t, J = 7.0Hz, 6H). 19 F NMR (CDCl3, 376MHz) δ-115.07.

[0569]

[0570] 2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-(4-fluorophenyl)thiophen-3-ol). To a solution of 2,6-bis(2-(3-(ethoxymethoxy)-4-(4-fluorophenyl)thiophen-2-yl)phenyl)pyridine (0.19 g, 0.26 mmol) in 1,4-dioxane / CHCl (60 ml, 1:2) was added concentrated HCl (15 mL) under nitrogen. The reaction mixture was stirred for 24 hours and then basified with NaOH (aqueous solution). The organics were extracted from the aqueous layer with CHCl (2 x 30 mL), combined, and dried over solid MgSO. All solvents were subsequently removed under vacuum in an inert atmosphere (N) glove box. The resulting dark red amorphous foam was dissolved in CHCl (5 mL), suction filtered through a silica gel pad, and rinsed with CHCl (4 x 5 mL). The dichloromethane was then removed under vacuum. The product was slurried in 2 mL of pentane for 10 minutes.The pure product was collected by filtration as a white solid (0.15 g, 94%). 1 H NMR(CDCl3,400MHz)δ8.71(s,2H),7.78(t,J=7.8Hz,1H),7.53(t,J=3.7Hz,6H),7.43(td,J=7.9 ,6.7,3.8Hz,2H),7.36(d,J=7.8Hz,2H),7.19–7.09(m,4H),7.02(s,2H),6.90(t,J=8.7Hz,4H). 19 F NMR (CDCl3, 376MHz) δ-115.67.

[0571] [2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-fluorophenylthiophene-3-ol)]dibenzyl hafnium (catalyst 3). Toluene (3 mL) was added to tetrabenzyl hafnium (44 mg, 0.08 mmol) and 2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-(4-fluorophenyl)thiophene-3-ol) (50 mg, 0.08 mmol). The reaction mixture was stirred for 4 hours and then concentrated to dryness. The crude product was dissolved in a minimum amount of dichloromethane. Pentane (2 mL) was added and the resulting mixture was stirred for 15 minutes. The product was collected by filtration as a yellow solid. 1H NMR(CD2Cl2,400MHz)δ7.83(t,J=7.8Hz,1H),7.67(dd,J=8.9,3.4Hz,4H),7.60(td,J=7.6,1.3Hz,2H),7.33–7.02(m, 14H), 6.94–6.84 (m, 4H), 6.68 (t, J = 7.3Hz, 2H), 6.34 (d, J = 7.6Hz, 4H), 1.40 (d, J = 12.0Hz, 2H), 0.15 (d, J = 12.3Hz, 2H). 19 F NMR (CD2Cl2, 376MHz) δ-116.15.

[0572] [2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-fluorophenylthiophene-3-ol)]dibenzyl zirconium (catalyst 4). Toluene (3 mL) was added to tetrabenzyl zirconium (37 mg, 0.08 mmol) and 2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-(4-fluorophenyl)thiophene-3-ol) (50 mg, 0.08 mmol). The reaction mixture was stirred for 4 hours and then concentrated to dryness. The crude product was dissolved in a minimum amount of dichloromethane. Pentane (2 mL) was added and the resulting mixture was stirred for 15 minutes. The product was collected by filtration as a yellow solid. 1 H NMR(CD2Cl2,400MHz)δ7.79(t,J=7.8Hz,1H),7.71–7.58(m,4H),7.53(t,J=7.6Hz,2H),7.29–6.98(m,14H),6. 89–6.77(m,4H),6.65(t,J=7.4Hz,2H),6.28(d,J=7.8Hz,4H),1.56(d,J=11.3Hz,2H),0.42(d,J=11.3Hz,2H). 19 FNMR (CD2Cl2, 376MHz) δ-116.14.

[0573]

[0574] 3-(1-adamantyl)-4-(ethoxymethoxy)thiophene. Tetrahydrofuran (7 mL) was added to anhydrous lithium chloride (108 mg, 2.6 mmol) and magnesium powder (113 mg, 4.6 mmol). 1,2-dibromoethane (5 mol%) and TMSCl (5 mol%) were added to activate the magnesium powder. Zinc dichloride (350 mg, 2.6 mmol) and 1-bromoadamantane (0.5 g, 2.3 mmol) in tetrahydrofuran (2.6 ml) were then added. The reaction mixture was then stirred at ambient temperature overnight. 3-bromo-4-(ethoxymethoxy)thiophene (0.5 g, 2.1 mmol) and Pd (P) were then added. t Bu3)2 (85 mg, 0.1 mmol). The resulting mixture was stirred at 70°C overnight. The crude product was purified by flash chromatography on silica gel (30% dichloromethane and 2% acetone in hexanes). Yield 0.19 g (29%) of a white solid. 1 H NMR (CDCl3, 400MHz) δ6.76 (d, J = 3.4Hz, 1H), 6.53 (d, J = 3.5Hz, 1H), 5.18 (s, 2H), 3.73 (q, J = 7.1Hz, 2H), 2.01 (br, 8H), 1.75 (br, 6H), 1.25 (t, J = 7.0Hz, 3H).

[0575]

[0576] 2,6-bis[2-[4-(1-adamantyl)-3-(ethoxymethoxy)-2-thienyl]phenyl]pyridine. To a solution of 3-(1-adamantyl)-4-(ethoxymethoxy)thiophene (0.25 g, 0.8 mmol) in diethyl ether (5 ml) was added a hexane solution of n-butyllithium (0.078 mL, 11 M, 0.8 mmol). The reaction mixture was stirred at ambient temperature for 1 hour and then concentrated to dryness. ZnCl2 (93 mg, 0.7 mmol) and tetrahydrofuran (5 mL) were then added and the reaction mixture was stirred for 5 minutes. 2,6-bis(2-bromophenyl)pyridine (0.12 g, 0.3 mmol) and Pd(P) were subsequently added. t Bu3)2 (30 mg, 0.03 mmol). The resulting mixture was stirred at 70°C overnight. The crude product was purified by flash chromatography on silica gel (25% dichloromethane and 3% acetone in hexanes). Yield 0.20 g (57%) of a white solid. 1H NMR (CDCl3, 400MHz) δ7.52 (s, 2H), 7.39 (s, 2H), 7.32 (t, J = 7.8Hz, 1H), 6.94 (d, J = 7.8Hz, 2H), 6. 74(s,2H),4.74(s,4H),3.44(q,J=7.2Hz,4H),1.93(s,6H),1.71(s,8H),0.98(t,J=7.1Hz,6H).

[0577]

[0578] 2,2'-(Pyridine-2,6-diylbis(2,1-phenylene))bis(4-(1-adamantyl)thiophen-3-ol). To a solution of 2,6-bis[2-[4-(1-adamantyl)-3-(ethoxymethoxy)-2-thienyl]phenyl]pyridine (0.20 g, 0.25 mmol) in 1,4-dioxane / CHCl (60 ml, 1:2) was added concentrated HCl (15 mL) under nitrogen. The reaction mixture was stirred for 24 hours and then basified with NaOH (aqueous solution). The organics were extracted from the aqueous layer with CHCl (2 x 30 mL), combined, and dried over solid MgSO. All solvents were subsequently removed under vacuum in an inert atmosphere (N) glove box. The resulting dark red amorphous foam was dissolved in CHCl (5 mL), suction filtered through a pad of silica gel, and rinsed with CHCl (4 x 5 mL). The dichloromethane was then removed under vacuum. The product was slurried in 2 mL of pentane for 10 minutes.The pure product was collected by filtration as a white solid (0.15 g, 94%). 1 H NMR (CDCl3, 400MHz) δ8.82(s,2H),7.77(t,J=7.8Hz,1H),7.57–7.37(m,8H),7.32(d,J=7.8Hz,2H),6.58(s,2H),1.86(s,6H),1.60(s,24H).

[0579] [2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-(1-adamantyl)thiophen-3-ol)]dibenzylhafnium (catalyst 5). Toluene (3 mL) was added to tetrabenzylhafnium (39 mg, 0.07 mmol) and 2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-(1-adamantyl)thiophen-3-ol) (50 mg, 0.07 mmol). The reaction mixture was stirred for 4 hours and then concentrated to dryness. The crude product was dissolved in a minimum amount of dichloromethane. Pentane (2 mL) was added and the resulting mixture was stirred for 15 minutes. The product was collected by filtration as a yellow solid.

[0580] [2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-(1-adamantyl)thiophen-3-ol)]dibenzylzirconium (Catalyst 6). Toluene (3 mL) was added to tetrabenzylzirconium (33 mg, 0.07 mmol) and 2,2'-(pyridine-2,6-diylbis(2,1-phenylene))bis(4-(1-adamantyl)thiophen-3-ol) (50 mg, 0.07 mmol). The reaction mixture was stirred for 4 hours and then concentrated to dryness. The crude product was dissolved in a minimum amount of dichloromethane. Pentane (2 mL) was added and the resulting mixture was stirred for 15 minutes. The product was collected by filtration as a yellow solid.

[0581] General olefin polymerization process

[0582] Solvents, polymer grade toluene and / or isohexane, were supplied by ExxonMobil Chemical Co. and purified through the following series of columns: two 500 cm 3 Oxyclear cylinders, then filled with dry Two 500 cm2 molecular sieves (8-12 mesh, Aldrich Chemical Company) were connected in series. 3 Column and packed with dry Two 500 cm2 molecular sieves (8-12 mesh, Aldrich Chemical Company) were connected in series. 3 column.

[0583] 1-Octene (98%) (Aldrich Chemical Company) was dried by filtration through basic alumina (Aldrich Chemical Company, Brockman Basic 1) after stirring overnight on Na-K alloy. Tri(n-octyl)aluminum (TNOA) was purchased from Aldrich Chemical Company or Akzo Nobel and used as received.

[0584] Polymerization grade ethylene was further purified by passing it through the following series of columns: 500 cm 3 Oxyclear cylinders, then filled with dry Molecular sieves (8-12 mesh, Aldrich Chemical Company) 500 cm 3 Column and packed with dry Molecular sieves (8-12 mesh, Aldrich Chemical Company) 500 cm3 column.

[0585] Polymer grade propylene was further purified by passing it through the following series of columns: 2250 cm 3 Oxyclear cylinder, followed by a cylinder filled with Molecular sieves (8-12 mesh, Aldrich Chemical Company) at 2250 cm 3 Column, then two in series are filled with Molecular sieves (8-12 mesh, Aldrich Chemical Company) 500 cm 3 Column, 500 cm packed with Selexsorb CD (BASF) 3 The column was then filled with Selexsorb COS (BASF) to form a 500 cm 3 column.

[0586] N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (also referred to as Activator 1) was purchased from WR Grace and Co. All complexes and activators were added to the reactor as diluent solutions in toluene. The concentrations of the solutions of activator, scavenger, and complex added to the reactor were selected so that between 40 microliters and 200 microliters of solution were added to the reactor to ensure accurate delivery.

[0587] Reactor Description and Preparation. Polymerizations were performed in an inert atmosphere (N2) dry box using an autoclave equipped with an external heater for temperature control, a glass insert (the internal volume of the reactor was 23.5 mL for C2 and C2 / C8 runs and 22.5 mL for C3 runs), a septum inlet, a regulated supply of nitrogen, ethylene, and propylene, and a disposable polyetheretherketone mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110°C or 115°C for 5 hours and then at 25°C for 5 hours.

[0588] Ethylene polymerization (PE) or ethylene / 1-octene copolymerization (EO)

[0589] The reactor was prepared as described above and then purged with ethylene. Toluene (solvent, unless otherwise specified), optional 1-octene (0.1 mL when used), and optional MAO were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to process temperature (typically 80° C.) and ethylene was added to process pressure (typically 75 psig = 618.5 kPa or 200 psig = 1480.3 kPa) while stirring at 800 RPM. An optional scavenger solution (e.g., TNOA in isohexane) was then added to the reactor via syringe under process conditions. An optional non-coordinating activator (e.g., N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate) solution (in toluene) was added to the reactor via syringe under process conditions, followed by a precatalyst (i.e., complex or catalyst) solution (in toluene) added to the reactor via syringe under process conditions. Ethylene was admitted to the autoclave (using a computer-controlled solenoid valve) during polymerization to maintain the reactor gauge pressure (+ / - 2 psi). The reactor temperature was monitored and typically maintained within + / - 1° C. The polymerization was stopped by adding approximately 50 psi of an O / Ar (5 mol% O) gas mixture (greater than the reactor pressure) to the autoclave for approximately 30 seconds. The polymerization was quenched after the addition of a predetermined cumulative amount of ethylene or for a maximum polymerization time of 30 minutes. The reactor was cooled and vented. The polymer was isolated after removal of the solvent under reduced pressure. The reported yield includes the total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer / mmol of transition metal compound / hour of reaction time (g / mmol / hr).

[0590] Propylene polymerization

[0591] The reactor was prepared as described above, then heated to 40°C and purged with propylene gas at atmospheric pressure. Toluene (solvent, unless otherwise specified) and liquid propylene (1.0 mL) were added via syringe. The reactor was then heated to the process temperature (70°C or 100°C) while stirring at 800 RPM. An optional scavenger solution (e.g., TNOA in isohexane) was then added to the reactor via syringe under process conditions. An optional non-coordinating activator (e.g., N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate) solution (in toluene) was then added to the reactor via syringe under process conditions, followed by a precatalyst (i.e., complex or catalyst) solution (in toluene) added to the reactor via syringe under process conditions. The reactor temperature was monitored and typically maintained within + / - 1°C. The polymerization was stopped by adding approximately 50 psi of an O2 / Ar (5 mol% O2) gas mixture (greater than the reactor pressure) to the autoclave for approximately 30 seconds. The polymerization was quenched based on a predetermined pressure loss of approximately 8 psi or for a maximum polymerization time of 30 minutes. The reactor was cooled and vented. The polymer is isolated after removal of the solvent under reduced pressure. The reported yield includes the total weight of the polymer and the residual catalyst. Catalyst activity is usually reported as grams of polymer / mmol of transition metal compound / hour of reaction time (g / mmol / hr).

[0592] Polymer characterization

[0593] For analytical testing, polymer sample solutions were 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) in a shaker oven at 165°C for approximately 3 hours. Typical concentrations of polymer in solution were between 0.1 mg / mL and 0.9 mg / mL, with a BHT concentration of 1.25 mg BHT / mL of TCB. Samples were cooled to 135°C for testing.

[0594] High temperature size exclusion chromatography was performed using an automated "Fast GPC" system as described in U.S. Patent Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388, each of which is incorporated herein by reference. The molecular weight (weight average molecular weight (Mw) and number average molecular weight (Mn)) and molecular weight distribution (MWD = Mw / Mn), which is sometimes also referred to as the polydispersity index (PDI) of the polymer, were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) between 5,000 and 3,390,000). The samples were run using three Polymer Laboratories: PLgel 10 μm Mixed-B 300×7.5 mm columns in series (250 μL of polymer solution in TCB was injected into the system) at an eluent flow rate of 2.0 mL / min (135° C. sample temperature, 165° C. oven / column). No column diffusion correction was used. The HPLC-MS / MS / MS data available from Symyx Technologies were used. Data analysis was performed using Automation Studio software or Automation Studio software available from Freeslate. Molecular weights obtained are relative to linear polystyrene standards.

[0595] Rapid differential scanning calorimetry (Rapid-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 minutes 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. The melting point was collected during the heating process.

[0596] Samples for infrared analysis were prepared by depositing the stabilized polymer solution onto a silanized wafer (Part No. S10860, Symyx). By this method, between approximately 0.12 mg and 0.24 mg of polymer were deposited onto the wafer unit. The samples were then analyzed on a Bruker Equinox 55 FTIR spectrometer equipped with a specular reflectance sample accessory from Pikes' MappIR. The 2 cm -1 The resolution was 32 scans collected to cover 5,000 cm -1 Up to 500cm -1 Spectral range of the spectrum.

[0597] For ethylene-1-octene copolymer, the -1 The copolymer weight percent was determined by measuring the methyl deformation band at -4,321 cm -1 The normalized peak heights are compared with those from 1 A single calibration curve of H NMR data was correlated to predict wt% copolymer content over a concentration range of 2 wt% to 35 wt% for octene. Typically, an R of 0.98 or greater was achieved. 2 Correlation. Values reported below 4.1 wt% are outside the calibration range.

[0598] Polymerization Example

[0599] Table 1 below illustrates ethylene polymerization results obtained using catalyst complexes 1 through 4. General conditions: catalyst complex = 25 nmol, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator = 1.1 equivalents, 75 psig ethylene, Al(n-octyl)3 = 500 nmol, temperature = 80°C, total volume = 5 mL.

[0600] Table 1

[0601]

[0602] Table 1 (continued)

[0603]

[0604] Table 2 illustrates the ethylene-octene copolymerization results obtained using Catalysts 1 to 4. General Conditions: Catalyst complex = 25 nmol, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator = 27.5 nmol, 0.1 mL octene, Al(n-octyl)3 = 500 nmol, temperature = 80°C, total volume = 5 mL, ethylene = 75 psi.

[0605] Table 2

[0606]

[0607]

[0608] Table 2 (continued)

[0609]

[0610] Table 3 illustrates the ethylene-octene copolymerization results obtained using Catalysts 1 to 4. General Conditions: Catalyst complex = 25 nmol, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator = 27.5 nmol, 0.1 mL octene, Al(n-octyl)3 = 500 nmol, temperature = 80°C, total volume = 5 mL, ethylene = 200 psi.

[0611] Table 3

[0612]

[0613]

[0614] Table 3 (continued)

[0615]

[0616] Blank cells in the table above indicate insufficient amounts of polymer (ie, <0.01 g) to allow further characterization of molecular weight, PDI, Tm, etc.

[0617] Table 4 shows the propylene polymerization results obtained for catalysts 1 to 4. General conditions: catalyst complex = 25 nmol, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator = 1.1 molar equivalents relative to catalyst complex, propylene = 1 mL, Al(n-octyl)3 = 500 nmol, total volume = 5 mL.

[0618] Table 4

[0619]

[0620]

[0621] Table 5 shows the propylene polymerization results obtained for catalysts 1 to 4. General conditions: catalyst complex = 40 nmol, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator = 1.1 molar equivalents relative to catalyst complex, propylene = 1 mL, Al(n-octyl)3 = 500 nmol, total volume = 5 mL.

[0622] Table 5

[0623]

[0624] In general, the catalysts, catalyst systems, and methods of the present disclosure can provide high temperature ethylene polymerization, propylene polymerization, or ethylene-α-olefin copolymerization because the bis(heterocycle-alkoxide) Lewis base catalysts are stable and have good activity at high polymerization temperatures. Stable catalysts with good activity provide the formation of polymers with high molecular weights, polymers with low to very low molecular weights, and the ability to produce increased amounts of polymer in a given reactor compared to conventional catalysts.

[0625] Thus, the present disclosure illustrates highly active catalysts capable of operating at high reactor temperatures while producing polymers with controlled molecular weight and / or robust isotacticity.

[0626] Unless otherwise specified, the phrases "consisting essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether or not specifically mentioned in the specification, as long as such steps, elements, or materials do not affect the basic and novel characteristics of the present disclosure, and further, they do not exclude impurities and variations normally associated with the elements and materials used.

[0627] For the purpose of brevity, only certain ranges are explicitly disclosed herein. However, the range from any lower limit can be combined with any upper limit to record the range that is not explicitly stated, and the range from any lower limit can be combined with any other lower limit to record the range that is not explicitly stated, and in the same manner, the range from any upper limit can be combined with any other upper limit to record the range that is not explicitly stated. In addition, even if not explicitly stated, each point or individual value between its endpoints is included in the scope. Therefore, each point or individual value can serve as its own lower limit or upper limit, combined with any other point or individual value or any other lower limit or upper limit, to record the range that is not explicitly stated.

[0628] All documents described herein are incorporated herein by reference, including any priority documents and / or test procedures, as long as they do not contradict this article. As is apparent from the general description and specific embodiments above, although the form of the present disclosure has been set forth and described, various changes can be made without departing from the spirit and scope of the present disclosure. Therefore, it is not intended to limit the present disclosure thereby. Similarly, for the purposes of U.S. law, the term "comprising" is considered to be synonymous with the term "including". Similarly, whenever a composition, element or group of elements is preceded by the conjunction "comprising", it should be understood that we also consider the same composition or group of elements with the conjunction "essentially consisting of...", "consisting of...", "selected from the group consisting of..." or "is" in front of the record of the composition, one or more elements, and vice versa.

[0629] While this disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised that do not depart from the scope and spirit of this disclosure.

Claims

1. A catalyst compound represented by formula (I): in: M is a Group 4 metal; Each A 1 and A 2 are independently an aromatic group, a substituted aromatic group, or an alkenediyl group; Heterocyclic ring fragment-(Z 1 Z 2 )- and –(Z 3 Z 4 )-independently selected from –(Z 5 Z 6 )-or–(Z 6 Z 5 )-, where Z 5 Selected from oxygen, sulfur, S(O), S(O)2 and N(R 50 ), and Z 6 Selected from nitrogen and C(R 51 ), where each R 50 and R 51 are independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom; R 4 and R 5 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom; J is a heterocyclic Lewis base; Each Q 1 and Q 2 independently selected from oxygen, sulfur, N(R 30 ) or P(R 30 ), where R 30 It is C1-C 40 Hydrocarbon, substituted C1-C 40 a hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom; L is a Lewis base, optionally any two L groups are joined together to form a bidentate Lewis base; X is an anionic ligand, optionally the X group is joined to an L group to form a monoanionic bidentate group, or optionally any two X groups are joined together to form a dianionic ligand; n is 1, 2, or 3; m is 0, 1, or 2; and n+m is not greater than 4.

2. The catalyst compound according to claim 1, wherein A 1 It is expressed by the following formula: in represents a connection to the catalyst compound, and R 9 、R 10 、R 11 and R 12 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom or a monovalent group combined with a heteroatom, or R 9 and R 10 、R 10 and R 11 or R 11 and R 12 One or more of the pairs may join to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms.

3. The catalyst compound according to claim 1, wherein A 2 It is expressed by the following formula: in represents a connection to the catalyst compound, and R 13 、R 14 、R 15 and R 16 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom or a monovalent group combined with a heteroatom, or R 13 and R 14 、R 14 and R 15 or R 15 and R 16 One or more of the pairs may join to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms.

4. The catalyst compound of claim 1, wherein the catalyst compound is characterized by a tridentate dianionic ligand coordinated to the metal to form a pair of eight-membered metallocycle rings. The catalyst compound according to claim 1 , wherein J is a Group 15-containing heterocycle or a Group 16-containing heterocycle. The catalyst compound according to claim 1 , wherein J is one of a nitrogen-containing heterocycle, an oxygen-containing heterocycle, a phosphorus-containing heterocycle, and a sulfur-containing heterocycle.

7. The catalyst compound according to any one of claims 1 to 6, wherein J is selected from pyridine, pyrimidine, pyrazine, thiazole, Azoles, One of oxazoline, imidazole, furan or thiophene.

8. The catalyst compound according to any one of claims 1 to 6, wherein J is represented by the following formula: in Indicates the connection to the catalyst compound; E is oxygen, sulfur or NR 17 ; Z 7 Selected from nitrogen and C(R 18 );Z 8 Selected from nitrogen and C(R 19 ); and R 17 and R 18 and R 19 Each of which is selected from hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom.

9. The catalyst compound according to claim 1, wherein the catalyst compound represented by formula (I) is represented by formula (II) or formula (III): in: Each Q 1 and Q 2 independently selected from oxygen, sulfur, N(R 30 ) or P(R 30 ), where R 30 It is C1-C 40 Hydrocarbon, substituted C1-C 40 a hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom; Heterocyclic ring fragment-(Z 1 Z 2 )- and –(Z 3 Z 4 )-Selected from–(Z 5 Z 6 )-or–(Z 6 Z 5 )-, where Z 5 Selected from oxygen, sulfur, S(O), S(O)2 and N(R 50 ), and Z 6 Selected from nitrogen and C(R 51 ), where each R 50 and R 51 are independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom; Z 7 Selected from nitrogen and C(R 18 ); Z 8 Selected from nitrogen and C(R 19 ); E is oxygen, sulfur or N(R 20 ); R 4 and R 5 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom, or a monovalent group incorporating a heteroatom; R 9 、R 10 、R 11 and R 12 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom or a monovalent group combined with a heteroatom, or R 9 and R 10 、R 10 and R 11 or R 11 and R 12 One or more of the pairs may join to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 13 、R 14 、R 15 and R 16 Each of which is independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom or a monovalent group combined with a heteroatom, or R 13 and R 14 、R 14 and R 15 or R 15 and R 16 One or more of the pairs may join to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; R 17 、R 18 、R 19 and R 20 Each of them is hydrogen, C1-C 40 Hydrocarbon, C1-C 40 a substituted hydrocarbon group, a monovalent heteroatom or a monovalent group combined with a heteroatom, or R 17 and R 18 、R 18 and R 19 One or more of the pairs may join together to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms; M is a Group 4 metal; L is a Lewis base; X is an anionic ligand; n is 1, 2, or 3; m is 0, 1, or 2; n+m is not greater than 4; Any two L groups can be joined together to form a bidentate Lewis base; The X group can be joined to the L group to form a monoanionic bidentate group; and Any two X groups can be joined together to form a dianionic ligand.

10. The catalyst compound of claim 9, wherein M is zirconium or hafnium.

11. The catalyst compound according to claim 10, wherein R 9 to R 17 It's hydrogen.

12. The catalyst compound according to claim 11, wherein R 4 and R 5 Each selected from C1-C 40 Hydrocarbon, C1-C 40 A substituted hydrocarbon group or a monovalent group containing up to 40 atoms of combined heteroatoms, wherein -(Z 1 Z 2 )- and –(Z 3 Z 4 )-Selected from–(Z 5 Z 6 )-or–(Z 6 Z 5 )-, where Z 5 It is oxygen or sulfur.

13. The catalyst compound according to claim 12, wherein R 4 and R 5 Each selected from C4-C 40 A cyclic tertiary hydrocarbon group.

14. The catalyst compound (II) according to claim 9, wherein Z 7 It is C(R 18 ), where R 18 is selected from hydrogen, trifluoromethyl, methoxy, Me2N or halogen atoms, wherein Z 8 It is C(R 19 ), where R 19 is hydrogen, where R 4 and R 5 Each selected from C4-C 20 hydrocarbon group, tertiary hydrocarbon group or cyclic tertiary hydrocarbon group, and wherein R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 and R 17 Each of which is independently hydrogen or C1-C 10 alkyl.

15. The catalyst compound according to claim 1, wherein R 4 and R 5 Each selected from C6-C 20 an aromatic group, a tertiary hydrocarbon group or a cyclic tertiary hydrocarbon group.

16. The catalyst compound according to claim 15, wherein R 4 and R 5 Each is selected from adamantane-1-yl, 3,5-dimethyladamantan-1-yl, and 3,5,7-trimethyladamantan-1-yl.

17. The catalyst compound of claim 1, wherein the catalyst compound is selected from the group consisting of: wherein M = Zr or Hf; and R = Cl-C 20 Hydrocarbyl, monovalent heteroatom or monovalent group combined with heteroatom:

18. The catalyst compound of claim 1, wherein the catalyst compound is selected from the group consisting of: wherein M = Zr or Hf; and R = Cl-C 20 Hydrocarbyl, monovalent heteroatom or monovalent group combined with heteroatom:

19. A catalyst system comprising an activator and the catalyst compound of claim 1.

20. A method of producing an ethylene-based polymer comprising: Ethylene is polymerized by contacting ethylene with the catalyst system of claim 19 in one or more continuous stirred tank reactors or loop reactors connected 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.

21. The method of claim 20, wherein the ethylene-based polymer has an Mw value of 2,000 to 3,000,000 g / mol, an Mn value of 1,000 to 2,000,000 g / mol, an Mz value of 10,000 to 10,000,000 g / mol, and an Mw / Mn ratio of 1 to 5.

22. The method of claim 20, wherein the ethylene-based polymer has a melting point of 110°C to 150°C.

23. A method of producing a propylene-based polymer comprising: Propylene is polymerized by contacting propylene with the catalyst system of claim 19 in one or more continuous stirred tank reactors or loop reactors connected 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.

24. The method of claim 23, wherein the propylene-based polymer has an Mw value of 500-15,000 g / mol, an Mn value of 500-15,000 g / mol, an Mz value of 500-20,000 g / mol, and an Mw / Mn ratio of 1-5.

25. The method of claim 23, wherein the propylene-based polymer has a melting point of 50°C to 150°C.

26. A method for producing an ethylene α-olefin copolymer, comprising: The method comprises the steps of: reacting ethylene and at least one C3-C4 hydrocarbon in one or more continuous stirred tank reactors or loop reactors connected 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 catalyst system of claim 19 to polymerize ethylene and at least one C3-C 20 α-olefins.

27. The method of claim 26, wherein the ethylene α-olefin copolymer has a comonomer content of 0.1 to 50 weight percent, an Mw value of 1,000-3,000,000 g / mol, and an Mz value of 1,000-10,000,000 g / mol, an Mn value of 1,000-1,000,000 g / mol, and an Mw / Mn ratio of 1-5.

28. The method of claim 26, wherein the ethylene alpha-olefin copolymer has a melting point of 100°C to 140°C.

29. A method for producing a propylene α-olefin copolymer, comprising: The method comprises the steps of: reacting propylene and at least one ethylene or at least one C3-C4 hydrocarbon in one or more continuous stirred tank reactors or loop reactors connected 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 catalyst system of claim 19 to polymerize propylene and at least one ethylene or at least one C4-C 20 α-olefins.

30. The method of claim 29, wherein the propylene alpha-olefin copolymer has a comonomer content of 0.1 to 35 wt%, an Mw value of 1,000-3,000,000 g / mol, and an Mz value of 1,000-10,000,000 g / mol, an Mn value of 1,000-1,000,000 g / mol, and an Mw / Mn ratio of 1-5.

31. The method of claim 29, wherein the propylene alpha-olefin copolymer has a melting point of 100°C to 140°C.

Images