Restricted geometry metal-ligand complexes and their use in polymerization of olefins

Abstract

The metal-ligand complex may comprise a transition metal atom or a lanthanide metal atom and a ligand having a structure represented by Formula 1: # imgabs0 # wherein R1, R2, R5 and R6 are independently hydrogen or a C1-C14 hydrocarbon group; r3 and R4 are independently hydrogen or a C1-C14 hydrocarbyl group, or R3 and R4 are linked together to form an optionally substituted 6-membered aromatic ring; r5 is hydrogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C30 aryl, heteroaryl, or CN, with the proviso that if the transition metal atom is Ti or Zr and R3 and R4 are joined together to form an optionally substituted 6-membered aromatic ring, or if the transition metal atom is Ti or Zr and R1 to R4 are both H, then R5 is C3-C10 cycloalkyl, C6-C30 aryl, heteroaryl, or CN; and Z is a bridging atom. The catalyst system may include at least one activator and one or more metal-ligand complexes.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 355,249, filed on June 24, 2022, the disclosure of which is incorporated herein by reference. Technical Field

[0002] The present disclosure relates to olefin polymerization and constrained geometry metal-ligand complexes for olefin polymerization. Background Art

[0003] Many catalysts for olefin polymerization have been developed, many of which are based on metal-ligand complexes. The selection of catalysts can allow customization of various polyolefin properties, such as molecular weight, branching, stereoregularity, crystallinity, melt index and similar features. Activators such as aluminoxanes and non-coordinating anion activators are usually used in conjunction with metal-ligand complexes to promote polymerization.

[0004] Metal-ligand complexes with restricted geometry can be used to promote olefin polymerization. Some of these metal-ligand complexes can include a π-bonded ligand bridged to a second ligand, each of which is at least bidentately bonded to the metal atom. Additional ligands can complete the coordination sphere of the metal atom. The bridge between the π-bonded ligand and the second ligand can produce a smaller angle (bite angle) between the π-bonded ligand and the second ligand. The smaller angle can provide a more active catalyst platform than the catalyst platform that may exist in other catalyst systems (such as Ziegler-Natta catalysts, non-bridged metallocenes and other single-site catalysts). Representative metal-ligand complexes with restricted geometry by means of a single atom bridge between a π-bonded ligand and a pyrrole ligand are described in CN112552436, CN112552434, CN112552433, CN112552429 and CN112552428. Although many metal-ligand complexes with constrained geometries have been developed, there remains a need to further develop new complexes suitable for producing polyolefins with tailored properties (including specific molecular weight ranges, molecular weight distributions, stereoregularity, or similar features) at a given reaction temperature. Summary of the invention SUMMARY OF THE INVENTION

[0005] In various aspects, the present disclosure provides one or more metal-ligand complexes comprising: a transition metal atom or a lanthanide metal atom and a ligand having a structure represented by Formula 1 Where: R 1 and R 2 are independently hydrogen or C1 -C 14 Hydrocarbon; R 3 and R 4 are independently hydrogen or C 1 -C 14 Hydrocarbyl, or R 3 and R 4 are joined together to form an optionally substituted 6-membered aromatic ring; R 5 It is hydrogen, C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 30 aryl, heteroaryl or CN, provided that if the transition metal atom is Ti or Zr and R 3 and R 4 are connected together to form a 6-membered aromatic ring, then R 5 It is C 3 -C 10 Cycloalkyl, C 6 -C 30 aryl, heteroaryl or CN, or if the transition metal atom is Ti or Zr and R 1 -R 4 All are H, then R 5 It is C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 30 Aryl, heteroaryl or CN; R 6 and R 7 are independently hydrogen or C 1 -C 14 A hydrocarbon group; and Z is a bridging atom.

[0006] In other various aspects, the present disclosure provides a catalyst system. The catalyst system comprises: at least one activator, and a metal-ligand complex comprising a transition metal atom or a lanthanide metal atom and a ligand having a structure represented by Formula 1 Where: R 1 and R 2 are independently hydrogen or C 1 -C 14 Hydrocarbon; R 3 and R 4 are independently hydrogen or C 1 -C 14 Hydrocarbyl, or R 3 and R 4are joined together to form an optionally substituted 6-membered aromatic ring; R 5 It is hydrogen, C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 30 aryl, heteroaryl or CN, provided that if the transition metal atom is Ti or Zr and R 3 and R 4 are connected together to form a 6-membered aromatic ring, then R 5 It is C 3 -C 10 Cycloalkyl, C 6 -C 30 aryl, heteroaryl or CN, or if the transition metal atom is Ti or Zr and R 1 -R 4 All are H, then R 5 It is C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 30 Aryl, heteroaryl or CN; R 6 and R 7 are independently hydrogen or C 1 -C 14 A hydrocarbon group; and Z is a bridging atom.

[0007] In yet other various aspects, the present disclosure provides an olefin polymerization process comprising: providing an olefinic feed, and contacting a catalyst system with the olefinic feed under polymerization reaction conditions. The catalyst system comprises: at least one activator, and a metal-ligand complex comprising a transition metal atom or a lanthanide metal atom and a ligand having a structure represented by Formula 1, Where: R 1 and R 2 are independently hydrogen or C 1 -C 14 Hydrocarbon; R 3 and R 4 are independently hydrogen or C 1 -C 14 Hydrocarbyl, or R 3 and R 4 are joined together to form an optionally substituted 6-membered aromatic ring; R 5 It is hydrogen, C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C6 -C 30 aryl, heteroaryl or CN, provided that if the transition metal atom is Ti or Zr and R 3 and R 4 are connected together to form a 6-membered aromatic ring, then R 5 It is C 3 -C 10 Cycloalkyl, C 6 -C 30 aryl, heteroaryl or CN, or if the transition metal atom is Ti or Zr and R 1 -R 4 All are H, then R 5 It is C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 30 Aryl, heteroaryl or CN; R 6 and R 7 are independently hydrogen or C 1 -C 14 A hydrocarbon group; and Z is a bridging atom.

[0008] These and other features and properties of the disclosed complexes, systems and / or methods of the present disclosure, as well as advantageous applications and / or uses thereof, will become apparent from the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The following drawings are included to illustrate certain aspects of the disclosure and should not be viewed as exclusive embodiments. As will occur to those of ordinary skill in the art upon reading this disclosure, the disclosed subject matter is capable of numerous modifications, alterations, combinations, and equivalents in form and function.

[0010] In order to assist one of ordinary skill in the relevant art in making and using the subject matter of the present invention, reference is made to the accompanying drawings, in which:

[0011] Figure 1 The X-ray crystal structure of the metal-ligand complex having the formula 3-Ti is shown.

[0012] Figure 2A and 2B An alternative view of the X-ray crystal structure of a metal-ligand complex having the formula 3'-Nd is shown.

[0013] Figure 3A and 3B An alternative view of the X-ray crystal structure of a metal-ligand complex having the formula 10-La is shown. DETAILED DESCRIPTION OF THE INVENTION

[0014] The present disclosure relates to olefin polymerization and constrained geometry metal-ligand complexes for olefin polymerization.

[0015] The present disclosure provides constrained geometry metal-ligand complexes that are capable of polymerizing olefin monomers to form high molecular weight polyolefins with improved co-monomer incorporation relative to other types of catalysts. Specific constrained geometry ligands disclosed herein include various bridged cyclopentadienyl-pyrrole ligands, which are described in further detail below. Advantageously, constrained geometry ligands can incorporate a wide range of catalytically active metals, including lanthanides such as neodymium and lanthanum. definition

[0016] All numerical values ​​in the detailed description and claims herein are modified by "about" or "approximately" relative to the indicated value, and take into account experimental error and deviation that would be expected by one of ordinary skill in the art. Unless otherwise indicated, room temperature is about 23°C.

[0017] As used in this disclosure and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. The term "and / or" used in phrases such as "A and / or B" is intended herein to include "A and B," "A or B," "A," and "B."

[0018] For the purposes of this disclosure, a new numbering scheme for the groups of the periodic table of the elements is used. In the numbering scheme, the groups (columns) are numbered sequentially from 1 to 18 from left to right, excluding f-block elements (lanthanides and actinides). Under this scheme, the term "transition metal" refers to any atom from Groups 3-12 of the periodic table, including lanthanides and actinides. Ti, Zr, and Hf are, for example, Group 4 transition metals.

[0019] As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, Mz is the z average molecular weight, wt% is the weight percentage, and mol% is the mole percentage. 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, and Mz) are expressed in g / mol (g·mol -1 The procedure used to analyze the polymer and determine its molecular weight is as follows.

[0020] "Olefins", or "olefins", are linear, branched or cyclic compounds of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims thereto, when a polymer or copolymer is referred to as containing an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 35% to 55% by weight, it is understood that the monomer 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 monomer units that are the same or different. A "homopolymer" is a polymer containing the same monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. A "terpolymer" is a polymer having three monomer units that are different from each other. Therefore, the definition of copolymer as used herein includes terpolymers and the like. The term "different" used in reference to monomer units indicates that the monomer units differ from each other by at least one atom or are isomerically different. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50 mole % ethylene-derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50 mole % propylene-derived units, and so forth.

[0021] The terms "group," "radical," and "substituent" are used interchangeably herein.

[0022] The term "hydrocarbon" refers to a class of compounds having hydrogen bonded to carbon, and encompasses mixtures of saturated hydrocarbon compounds, unsaturated hydrocarbon compounds, and hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds with different numbers of carbon atoms. The term "Cn" refers to hydrocarbons (one or more) or hydrocarbon groups having n carbon atoms (one or more) per molecule or group, wherein n is a positive integer. Such hydrocarbon compounds can be one or more of linear, branched, cyclic, acyclic, saturated, unsaturated, aliphatic or aromatic. Cyclic hydrocarbons used herein may be referred to as "carbocycles", which include saturated, unsaturated and partially unsaturated carbocyclic compounds and aromatic carbocyclic compounds. The term "heterocycle" refers to a carbocycle containing at least one ring heteroatom.

[0023] 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 and having at least one unfilled valency position when removed from the parent compound. Preferred hydrocarbyl radicals are C alkyl radicals which may be linear or branched. 1 -C 100Examples of such groups include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and / or the like. The term "hydrocarbon group having 1 to about 100 carbon atoms" refers to a group selected from a linear or branched C 1 -C 100 The structural part of the alkyl group.

[0024] The term "optionally substituted" means that the hydrocarbon or hydrocarbon group can be unsubstituted or substituted. For example, the term "optionally substituted hydrocarbon group" means replacing at least one hydrogen atom or carbon atom in the hydrocarbon group with a heteroatom or heteroatom functional group. Unless otherwise specified as explicitly unsubstituted, any hydrocarbon group herein can be optionally substituted. The term "optionally substituted" means that the group can be unsubstituted or substituted. For example, the term "optionally substituted hydrocarbon group" means replacing at least one hydrogen atom or carbon atom in the hydrocarbon group with a heteroatom or heteroatom-containing group. Unless otherwise specified, any hydrocarbon group herein can be optionally substituted. For example, the term "substituted" means that at least one hydrogen atom has been replaced by at least a non-hydrogen group, such as a hydrocarbon group, a heteroatom or heteroatom-containing group, such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group, such as -NR* 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 、-SR*、-BR* 2 、-SiR*、-SiR* 3 , -GeR*, -GeR* 3 、-SnR*、-SnR* 3 , -PbR* 3 , and similar group replacements, wherein each R* is independently a hydrocarbon group or a halocarbyl radical, and two or more R* can be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted into the ring structure.

[0025] The terms "hydrocarbyl radical," "hydrocarbyl," and "hydrocarbyl group" are used interchangeably in this application. Likewise, the terms "group," "radical," and "substituent" are used interchangeably and are defined to refer to a group consisting solely of hydrogen and carbon atoms. Preferred hydrocarbyl groups are C 1 -C 100The term "radical" refers to a radical which may be linear, branched or cyclic, and when cyclic, may be aromatic or non-aromatic. Examples of such radicals include, but are not limited to, alkyls such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc., aryl such as phenyl, benzyl, naphthyl, etc.

[0026] A substituted hydrocarbyl group is one in which at least one of the hydrogen atoms of the hydrocarbyl group has been replaced by a heteroatom or heteroatom-containing group, such as a halogen (eg, 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*、-SiR* 3 , -GeR*, -GeR* 3 、-SnR*、-SnR* 3 , -PbR* 3 The invention also provides a group of substituted R*, wherein each R* is independently a hydrocarbon group or a halocarbon group, and two or more R* can be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted into the hydrocarbon ring.

[0027] Cyclopentadiene and fused cyclopentadienes (e.g., indene, tetrahydroindene, and fluorene) can complex metal atoms via π-bonding. Substituted cyclopentadienyl, indenyl, tetrahydroindenyl, or fluorenyl is a cyclopentadienyl, indenyl, tetrahydroindenyl, or fluorenyl group in which at least one hydrogen atom has been replaced by at least one non-hydrogen group such as a hydrocarbon group, a heteroatom or heteroatom-containing group such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group such as -NR*. 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 、-SR*、-BR* 2 、-SiR*、-SiR* 3 , -GeR*, -GeR* 3 、-SnR*、-SnR* 3 , -PbR* 3 The invention also provides an alternative, wherein each R* is independently a hydrocarbon group or a halocarbon group, and two or more R* can be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted into the ring structure.

[0028] A halocarbyl group (also referred to as a halocarbyl, a halocarbyl group, or a halocarbyl substituent) is a group in which one or more hydrocarbyl hydrogen atoms have been replaced by at least one halogen (e.g., F, Cl, Br, I) or a halogen-containing group. A substituted halocarbyl group is a group in which at least one halocarbyl hydrogen or halogen atom has been replaced by at least one functional group such as NR*. 2 、OR*、SeR*、TeR*、PR* 2 、AsR* 2 , SbR* 2 , SR*, BR* 2 、SiR* 3 ,GeR* 3 、SnR* 3 , PbR* 3 or a group in which at least one non-carbon atom or group has been inserted into a halocarbon group, such as --O--, --S--, --Se--, --Te--, --N(R*)--, =N---, --P(R*)--, =P--, --As(R*)--, =As--, --Sb(R*)--, =Sb--, --B(R*)--, =B--, --Si(R*) 2 --、--Ge(R*) 2 --、--Sn(R*) 2 --、--Pb(R*) 2 --, wherein R * is independently a hydrocarbon radical or a halocarbon radical, provided that at least one halogen atom remains on the original halocarbon radical. In addition, two or more R * can be joined together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure.

[0029] A hydrocarbylsilyl group, also known as a silylcarbonyl group, is a group in which one or more of the hydrocarbyl hydrogen atoms has been replaced by at least one SiR* 3 or at least one -Si(R*) 2 - a group inserted into a hydrocarbon group, wherein R* is independently a hydrocarbon group or a halocarbon group, and two or more R* can be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure. The silylcarbon group can be bonded via a silicon atom or a carbon atom.

[0030] A substituted silyl carbonyl is one in which at least one hydrogen atom has been replaced by at least one functional group such as -NR* 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 、-SR*、-BR* 2 , -GeR*3 、-SnR* 3 , -PbR* 3 or a silyl carbon group in which at least one non-hydrocarbon atom or group has been inserted into the silyl carbon group, such as --O--, --S--, --Se--, --Te--, --N(R*)--, =N--, --P(R*)--, =P--, --As(R*)--, =As--, --Sb(R*)--, =Sb--, --B(R*)--, =B--, -Ge(R*) 2 --、--Sn(R*) 2 --、--Pb(R*) 2 --, etc., wherein R* is independently a hydrocarbon group or a halogenated carbon group, and two or more R* can be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

[0031] Germylcarbyl (also known as germylcarbyl, germylcarbyl group or germylcarbyl substituent) is a group in which one or more hydrocarbyl hydrogen atoms have been replaced by at least one germanium-containing GeR*. 3 or at least one -Ge(R*) 2 - has been inserted into a hydrocarbyl group, wherein R* is independently a hydrocarbyl group or a halogenated carbyl group, and two or more R* may be joined together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure. The germyl carbyl group may be bonded via a germanium atom or a carbon atom.

[0032] A substituted germyl carbonyl is one in which at least one hydrogen atom has been replaced by at least one functional group such as NR* 2 、OR*、SeR*、TeR*、PR* 2 、AsR* 2 , SbR* 2 , SR*, BR* 2 、SiR* 3 、SnR* 3 , PbR* 3 a germanyl carbon group substituted with the above-mentioned alkyl group, or a germanyl carbon group in which at least one non-hydrocarbon atom or group has been inserted into the germanyl group, such as --O--, --S--, --Se--, --Te--, --N(R*)--, =N--, --P(R*)--, =P--, --As(R*)--, =As--, --Sb(R*)--, =Sb--, --B(R*)--, =B--, --Si(R*) 2 --、--Sn(R*) 2 --、--Pb(R*)2 --, etc., wherein R* is independently a hydrocarbon group or a halogenated carbon group, and two or more R* can be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

[0033] The terms "alkyl group" and "alkyl" are used interchangeably throughout this application. For the purposes of this application, "alkyl" is defined as a C alkyl group which may be linear, branched or cyclic. 1 -C 100 Alkyl. 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, and the like. Substituted alkyl is an alkyl 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 hydrocarbon group, a heteroatom or heteroatom-containing group such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group such as -NR*. 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 、-SR*、-BR* 2 、-SiR*、-SiR* 3 , -GeR*, -GeR* 3 、-SnR*、-SnR* 3 , -PbR* 3 wherein each R* is independently a hydrocarbon group or a halocarbon group, and two or more R* may be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted into the hydrocarbon ring.

[0034] The term "branched alkyl" means that the alkyl group contains a tertiary or quaternary carbon (a tertiary carbon is a carbon atom bonded to three other carbon atoms, and a quaternary carbon is a carbon atom bonded to four other carbon atoms). For example, 3,5,5-trimethylhexylphenyl is an alkyl (hexyl) group having three methyl branches (thus, one tertiary carbon and one quaternary carbon) and is therefore a branched alkyl group bonded to a phenyl group.

[0035] The term "alkenyl" refers to a linear, branched or cyclic hydrocarbon radical having one or more carbon-carbon double bonds. These alkenyls may be substituted. Examples of suitable alkenyls may include vinyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, etc.

[0036] The term "aralkenyl" refers to an aryl group in which a hydrogen has been replaced with an alkenyl or substituted alkenyl group. For example, styrylindenyl is an indene substituted with an aralkenyl (styryl).

[0037] The term "alkoxy" or "aryloxide" refers to an alkyl group bonded to an oxygen atom, such as an alkyl ether or aryl ether group, and may include groups in which the alkyl group is C 1 -C 10 The alkyl radicals may be linear, branched or cyclic alkyl radicals. The alkyl radicals may be saturated or unsaturated. Examples of suitable alkoxy radicals and radicals may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and the like.

[0038] The term "aryloxy" or "aryloxide" refers to an aryl group bonded to an oxygen atom, such as an aryl ether group / group, wherein the term aryl is as defined herein. Examples of suitable aryloxy groups may include phenoxy and the like.

[0039] The term "aryl" or "aryl group" refers to a carbon-containing aromatic ring, such as a phenyl or fused phenyl. Likewise, a heteroaryl refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O or S. The term "aromatic" as used herein also refers to a quasi-aromatic heterocycle, which is a heterocyclic substituent having properties and structure (almost planar) similar to aromatic heterocyclic ligands, but which is not aromatic by definition.

[0040] A heterocycle refers to a cyclic group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom such as N, O or S. A heterocycle is a ring with heteroatoms in the ring structure, as opposed to a heteroatom-substituted ring in which hydrogens on a ring atom are replaced by heteroatoms. For example, tetrahydrofuran is a heterocycle, and 4-N,N-dimethylaminophenyl is a heteroatom-substituted ring.

[0041] Substituted heterocycle refers to a heterocyclic group in which at least one hydrogen atom of the heterocyclic group has been replaced by at least one non-hydrogen group, such as a hydrocarbon group, a heteroatom or a heteroatom-containing group, such as a halogen (e.g., Br, Cl, F or I) or at least one functional group, such as -NR*. 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 、-SR*、-BR* 2 、-SiR*、-SiR* 3 , -GeR*, -GeR* 3 、-SnR*、-SnR* 3 , -PbR* 3 The like are substituted, wherein each R* is independently a hydrocarbon group or a halogenated carbon group.

[0042] Substituted aryl is an aryl group wherein at least one hydrogen atom of the aryl group has been replaced by at least one non-hydrogen group, such as a hydrocarbon group, a heteroatom or heteroatom-containing group, such as a halogen (e.g., Br, Cl, F or I), or at least one functional group, such as -NR*. 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 、-SR*、-BR* 2 、-SiR*、-SiR* 3 , -GeR*, -GeR* 3 、-SnR*、-SnR* 3 , -PbR* 3 substituted, wherein each R* is independently a hydrocarbon group or a halogenated carbon group, and two or more R* may be linked together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted into the hydrocarbon ring. For example, 3,5-dimethylphenyl is a substituted aryl group.

[0043] The term "substituted phenyl" or "substituted phenyl group" refers to a phenyl group having one or more hydrogen groups replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom or a heteroatom-containing group such as a halogen (e.g., Br, Cl, F, or I) or at least one functional group such as -NR*. 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 、-SR*、-BR* 2 、-SiR*、-SiR* 3 , -GeR*, -GeR* 3 、-SnR*、-SnR* 3 , -PbR* 3 The substituted phenyl group is represented by the following formula: Where R a1 , R a2 , R a3 , R a4 and R a5 Each of which is independently selected from hydrogen, C 1 -C 40 Hydrocarbon or C 1 -C 40 Substituted hydrocarbon groups, heteroatoms such as halogens or heteroatom-containing groups (provided that R a1 , R a2, R a3 , R a4 and R a5 At least one of them is not H), or R a1 , R a2 , R a3 , R a4 and R a5 Two or more of them are connected together to form C 4 -C 62 Cyclic or polycyclic ring structures, or combinations thereof. Fused bicyclic and polycyclic aromatic rings are included within the definition of substituted phenyl.

[0044] The term "substituted naphthyl" refers to a naphthyl group having one or more hydrogen groups replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0045] "Fluorophenyl" or a "fluorophenyl group" is a phenyl group substituted with one, two, three, four or five fluorine atoms.

[0046] The term "substituted fluorenyl" refers to a fluorenyl group having one or more hydrogen groups replaced with a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

[0047] The term "aralkyl" refers to an aryl group in which a hydrogen has been replaced with an alkyl or substituted alkyl group. For example, 3,5'-di-tert-butylphenylindenyl is an indene substituted with an aralkyl group. When an aralkyl group is a substituent on another group, it is bonded to the group via the aryl group. For example, the aryl moiety can be bonded to E.

[0048] The term "alkaryl" refers to an alkyl group in which a hydrogen has been replaced with an aryl or substituted aryl group. For example, phenethylindenyl is an indene substituted with an ethyl group bonded to a phenyl group. When an alkaryl group is a substituent on another group, it is bonded to the group via the alkyl group.

[0049] Unless otherwise indicated, a reference to an alkyl, alkenyl, alcoholate, or aryl group without specifying a particular isomer (eg, butyl) specifically discloses all isomers (eg, n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0050] The term "ring atoms" refers to atoms belonging to a cyclic ring structure. Accordingly, benzyl has 6 ring atoms and tetrahydrofuran has 5 ring atoms.

[0051] As used herein and unless otherwise specified, the term "Cn" refers to hydrocarbon(s) containing n carbon atoms(s) per molecule, where n is a positive integer.

[0052] The term "hydrocarbon" refers to 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 in total from m to y. Therefore, C 1 -C 50 Alkyl refers to an alkyl group containing 1 to 50 carbon atoms in total.

[0053] A "catalyst system" is a combination of at least one catalyst compound, at least one activator, an optional co-activator, and an optional support material. When "catalyst system" is used to describe such a pairing prior to activation, it refers to the unactivated catalyst complex (procatalyst) together with the activator and, optionally, the co-activator. When it is used to describe such a pairing 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 purposes of this disclosure and the claims thereto, when a catalyst system is described as comprising a neutral stable form of a component, it will be 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.

[0054] As used herein, "complex" or "metal-ligand complex" may also be referred to as catalyst precursor, procatalyst, catalyst, catalyst compound, transition metal compound or transition metal complex. These terms may be used interchangeably.

[0055] In the description herein, catalysts can be described as catalyst precursors, procatalyst compounds, catalyst compounds or transition metal compounds, and these terms are used interchangeably. A polymerization catalyst system is a catalyst system that can polymerize monomers into polymers. An "anionic ligand" is a negatively charged ligand that provides one or more pairs of electrons to a metal atom (e.g., a transition metal atom or a lanthanide metal atom). A "neutral donor ligand" is an electrically neutral ligand that provides one or more pairs of electrons to a metal atom (e.g., a transition metal atom or a lanthanide metal atom).

[0056] The term "metallocene" describes an organometallic compound having at least one π-bonded cyclopentadienyl moiety or substituted cyclopentadienyl moiety, such as substituted or unsubstituted cyclopentadienyl (Cp) and / or indenyl (Ind) and more often two (or three) π-bonded cyclopentadienyl moieties or substituted cyclopentadienyl moieties, such as substituted or unsubstituted Cp and / or Ind.

[0057] The term "post-metallocene" describes transition metal complexes that do not have any π-coordinated cyclopentadienyl anion donor (or the like) and that can be used to polymerize olefins when combined with common activators.

[0058] The following abbreviations may be used herein: Me is methyl, Et is ethyl, Pr is propyl, cPR is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu is n-butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl, MAO is methylaluminoxane, dme is 1,2-dimethoxyethane, p-tBu is p-tert-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is tri(n-octyl)aluminum, p-Me is p-methyl, Bz and Bn are benzyl (i.e., CH 2 Ph), THF (also known as thf) is tetrahydrofuran, RT is room temperature (and is 23° C. unless otherwise stated), tol is toluene, EtOAc is ethyl acetate, Cbz is carbazole, and Cy is cyclohexyl.

[0059] "Catalyst productivity" is a measure of the mass of polymer produced using a known amount of a 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., activators and / or co-catalysts are omitted). "Catalyst activity" is a measure of the mass of polymer produced per unit time using a known amount of a polymerization catalyst for batch and semi-batch polymerizations. To calculate catalyst productivity, only the weight of the transition metal component of the catalyst is used (i.e., activators and / or co-catalysts are omitted). Typically, "catalyst activity" is expressed in units such as (g polymer) / (mmol catalyst) / hour or (kg polymer) / (mmol catalyst) / hour. If no units are specified, "catalyst activity" is expressed in units of (g polymer) / (mmol catalyst) / hour.

[0060] "Conversion" is the percentage of monomer converted to polymer product in a polymerization and is reported as a % and is calculated based on polymer yield, polymer composition and the amount of monomer fed to the reactor. Ligands and Metal-Ligand Complexes

[0061] The metal-ligand complex of the present disclosure may include a transition metal atom or a lanthanide metal atom and a ligand having a structure represented by Formula 1 below. In formula 1, R 1 and R 2 are independently hydrogen or C 1 -C 40 The optionally substituted hydrocarbon, halocarbon, silylcarbonyl, aminocarbonyl, germylcarbonyl, oxyhydrocarbon, halo or silyloxy radicals are more preferably independently hydrogen or C 1 -C 40 optionally substituted hydrocarbon groups, or more preferably independently hydrogen or C 1 -C 14 Hydrocarbon; R 3 and R 4 are independently hydrogen or C 1 -C 40 The optionally substituted hydrocarbon, halocarbon, silylcarbonyl, aminocarbonyl, germylcarbonyl, oxyhydrocarbon, halo or silyloxy radicals are more preferably independently hydrogen or C 1 -C 40 The optionally substituted hydrocarbon group is, or more preferably independently, hydrogen or C 1 -C 14 Hydrocarbon, or R 3 and R 4 are joined together to form an optionally substituted 6-membered aromatic ring; R 5 It is hydrogen, C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 30 aryl, heteroaryl or CN, provided that if the transition metal atom is Ti or Zr and R 3 and R 4 are connected together to form a 6-membered aromatic ring, then R 5 It is C 3 -C 10 Cycloalkyl, C 6 -C 30 aryl, heteroaryl or CN, or if the transition metal atom is Ti or Zr and R 1 -R 4 All are H, then R 5 It is C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 30 Aryl, heteroaryl or CN; R 6 and R 7 are independently hydrogen or C 1 -C 40The optionally substituted hydrocarbon, halocarbon, silylcarbonyl, aminocarbonyl, germylcarbonyl, oxyhydrocarbon, halo or silyloxy radicals are more preferably independently hydrogen or C 1 -C 40 optionally substituted hydrocarbon groups, or more preferably independently hydrogen or C 1 -C 14 and Z is a bridging atom, preferably a carbon atom. The ligand having a structure represented by Formula 1 may be at least bidentately bonded to a transition metal atom or a lanthanide metal atom in the metal-ligand complex disclosed herein.

[0062] In some embodiments, the metal-ligand complex may have a structure represented by Formula 1A below: In Formula 1A, M is a transition metal atom or a lanthanide metal atom, X is independently a leaving group, or two Xs are attached to and bonded to M to form a metallocycle ring, a chelating ligand, a diene ligand, or an alkylidene group. Other variables are defined as further defined herein.

[0063] In Formula 1A, X is independently a leaving group, wherein each X group may be the same or different. Examples of suitable leaving groups X include, but are not limited to, C 1 To C 20 The leaving group X may be a hydrocarbon group (e.g., an alkyl or aryl group), a hydride group, an amide group, an alkoxide group, a sulfide group, a phosphide group, a halide group, an amine group, a phosphine group, an ether group, or any combination thereof. The leaving group X may be in a deprotonated or protonated (neutral) form. Preferably, one or more of the leaving groups X are halide groups, aryl groups, C 1 To C 20 In some embodiments, the X group is a alkyl, amino or a combination thereof. More preferably, one or more X groups are amino (e.g., dimethylamino, diethylamino or dimethylsilylamino). In the context of leaving groups, the term "amino" refers to an amine compound that has been deprotonated to leave a negative charge on nitrogen. Therefore, dimethylamine can be deprotonated to form a dimethylamino ligand. Optionally, two of the X groups can be connected to and bonded to M to form a metal cyclization ring, a chelated ligand, a diene ligand or an alkylidene group.

[0064] Optionally, the metal-ligand complex may include a second ligand complexed with the transition metal atom or lanthanide metal atom. For example, the metal-ligand complex may include a solvent or a Lewis base complexed with the transition metal atom or lanthanide metal atom M as the second ligand. Exemplary solvents and Lewis bases may include representative members of the X group discussed above. More specific examples may include, but are not limited to, tertiary phosphines (PR 3 ), phosphine oxide (OPR 3 ), tertiary amine (NR 3 ), pyridine, DMAP, THF and other ether solvents, etc.

[0065] In more specific embodiments, the transition metal atom or lanthanide metal atom may include a Group 4 metal (e.g., titanium (Ti), zirconium (Zr), or hafnium (Ha); chromium (Cr) and / or a lanthanide metal (e.g., gadolinium (Gd), neodymium (Nd), or lanthanum (La)). In a more specific example, the transition metal atom or lanthanide metal atom may be hafnium, chromium, neodymium, or lanthanum.

[0066] In 1 and 1A, Z is a bridging group. Examples of suitable bridging groups Z include, but are not limited to: R' 2 C. R′ 2 Si, R′ 2 Ge, R′ 2 CCR′ 2 , R′ 2 CCR′ 2 CR′ 2 , R′ 2 CCR′ 2 CR′ 2 CR′ 2 , R′C═CR′, R′C═CR′CR′ 2 , R′ 2 CCR′═CR′CR′ 2 , R′C═CR′CR′═CR′, R′C═CR′CR′ 2 CR′ 2 , R′ 2 CSiR′ 2 , R′ 2 SiSiR′ 2 , R 2 CSiR′ 2 CR′ 2 , R′ 2 SiCR′ 2 SiR′ 2 、R′C═CR′SiR′ 2 , R′ 2 CGeR′ 2 , R′ 2 GeGeR′ 2、R′ 2 CGeR′ 2 CR′ 2 、R′ 2 GeCR′ 2 GeR′ 2 、R′ 2 SiGeR′ 2 、R′C═CR′GeR′ 2 、R′B、R′ 2 C-BR′、R′ 2 C-BR′-CR′ 2 、R′ 2 C-O-CR′ 2 、R′ 2 CR′ 2 C-O-CR′ 2 CR′ 2 、R′ 2 C-O-CR′ 2 CR′ 2 、R′ 2 C-O-CR′═CR′、R′ 2 C-S-CR′ 2 、R′ 2 CR′ 2 C-S-CR′ 2 CR′ 2 、R′ 2 C-S-CR′ 2 CR′ 2 、R′ 2 C-S-CR′═CR′、R′ 2 C-Se-CR′ 2 、R′ 2 CR′ 2 C-Se-CR′ 2 CR′ 2 、R′ 2 C-Se-CR 2 CR′ 2 、R′ 2 C-Se-CR′═CR′、R′ 2 C-N═CR′、R′ 2 C-NR′-CR′ 2 、R′ 2 C-NR′-CR′ 2 CR′ 2 、R′ 2 C-NR′-CR′═CR′、R′ 2 CR′ 2 C-NR′-CR′ 2 CR′ 2 、R′2 CP═CR′ and R′ 2 C-PR′-CR′ 2 , where R′ is hydrogen or C 1 -C 20 A hydrocarbon, substituted hydrocarbon, halocarbon, substituted halocarbon, silylcarbon or germylcarbon substituent. Optionally, two or more adjacent R's may be linked to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. Particularly suitable examples of bridging groups Z include R' 2 Si (more preferably, R' is methyl) and CR' 2 (More preferably, R' is H). That is, in a particular example, Z can be CH 2 .

[0067] In Formulas 1 and 1A, R 1 and R 2 and / or R 6 and R 7 can independently be hydrogen or C 1 -C 40 Optionally substituted hydrocarbon, halocarbon, silylcarbyl, aminocarbyl, germylcarbyl, oxyalkyl, halo or siloxy. 1 and R 2 and / or R 6 and R 7 are independently hydrogen or C 1 -C 40 More preferably, R 1 and R 2 and / or R 6 and R 7 are independently hydrogen or C 1 -C 14 An optionally substituted hydrocarbon group. Still more preferably, R 1 and R 2 and / or R 6 and R 7 are independently hydrogen, C 1 -C 10 Alkyl or C 6 -C 10 Aryl. Exemplary R 1 and / or R 2 and / or R 6 and R 7 The groups may include, but are not limited to, hydrogen, optionally substituted C 1 -C 10alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl) and optionally substituted phenyl. In a specific example, R 6 and R 7 It can all be hydrogen.

[0068] In Formulas 1 and 1A, R 3 and R 4 can independently be hydrogen or C 1 -C 40 An optionally substituted hydrocarbon group, a halocarbon group, a silylcarbon group, an aminocarbon group, a germylcarbon group, an oxyhydrocarbon group, a halo group or a siloxy group. 3 and R 4 are independently hydrogen or C 1 -C 40 More preferably, R 3 and R 4 are independently hydrogen or C 1 -C 14 Optionally, R 3 and R 4 can be linked together to form an optionally substituted carbocyclic or heterocyclic ring. 3 and R 4 An optionally substituted alicyclic, aromatic or heteroaromatic ring may be formed. 3 and R 4 An optionally substituted 6-membered aromatic ring may be formed wherein R 5 Can be C 1 -C 10 Alkyl or C 6 -C 30 In addition, R 3 and R 4 A fused ring with one or more additional fused rings may be formed. 3 and / or R 4 The group may include, but is not limited to, hydrogen, optionally substituted C 1 -C 10 Alkyl (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl) and optionally substituted phenyl.

[0069] In Formulas 1 and 1A, R 5 It is hydrogen, C 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 6 -C 30 Preferably, R 5 It is hydrogen, C 1 -C10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 30 In various embodiments, if the transition metal atom is Ti or Zr, and R 3 and R 4 are connected together to form a 6-membered aromatic ring, then R 5 It is C 3 -C 10 Cycloalkyl, C 6 -C 30 In other various embodiments, if the transition metal atom is Ti or Zr and R 1 -R 4 All are H, then R 5 It is C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 30 In more specific embodiments of any of the foregoing, R 5 It may be tert-butyl or optionally substituted phenyl.

[0070] The ligand having the structure represented by Formula 1 can also be represented by the following Formula 2, wherein Cp represents the optionally substituted cyclopentadienyl moiety of the ligand, Pyr represents the optionally substituted pyrrolidinyl moiety of the ligand, and Z is as defined above. The optionally substituted cyclopentadienyl moiety includes, but is not limited to, a fused cyclopentadienyl ring, such as an indenyl ring. The optionally substituted cyclopentadienyl moiety of the optionally substituted pyrrolidinyl moiety of the ligand may be substituted with one or more substituents described in more detail above.

[0071] Specific examples of the structure that may be present in the cyclopentadienyl (Cp) portion of Formula 2 include, but are not limited to, those having a structure represented by the following formula (the wavy line indicates bonding to Z):

[0072] Specific examples of structures that may be present in the pyrrolidinyl (Pyr) portion of Formula 2 include, but are not limited to, those having a structure represented by the following formula (the wavy line represents a bond to Z or a metal-ligand bond from the pyrrolidinyl nitrogen atom):

[0073] Specific examples of the ligand defined by Formula 2 may include, but are not limited to, those defined by the following Formulas 3-9.

[0074] Specific examples of the metal-ligand complex defined by Formula 1A may include, but are not limited to, those having a structure represented by the following formula: Optionally, a solvent or a Lewis base may be attached within the coordination sphere of M.

[0075] In more specific examples, the present disclosure provides metal-ligand complexes having structures represented by the following formulas 3-M to 9-M, wherein M represents a metal complexed by a ligand in Formula 1A, particularly a ligand represented by Formula 3-9: In any of the above specific examples, M can be, for example, Ti, Zr or Hf. For the purpose of the following discussion, such metal-ligand complexes may be referred to as 3-Ti, 3-Zr, 3-Hf, 4-Ti, 4-Zr, 4-Hf, 5-Ti, 5-Zr, 5-Hf, 6-Ti, 6-Zr, 6-Hf, 7-Ti, 7-Zr, 7-Hf, 8-Ti, 8-Zr, 8-Hf, 9-Ti, 9-Zr and 9-Hf.

[0076] In other more specific examples, the present disclosure provides metal-ligand complexes having structures represented by the following formulae 3'-M to 9'-M, wherein M represents the metal in Formula 1A complexed by a ligand, particularly a ligand of Formula 3-9, and THF. In any of the above specific examples, M can be, for example, La or Nd. For the purposes of the following discussion, such metal-ligand complexes may be referred to as Formula 3'-Nd, Formula 3'-La, Formula 4'-Nd, Formula 4'-La, Formula 5'-Nd, Formula 5'-La, Formula 6'-Nd, Formula 6'-La, Formula 7'-Nd, Formula 7'-La, Formula 8'-Nd, Formula 8'-La, Formula 9'-Nd, and Formula 9'-La.

[0077] In other specific examples, the ligand may form a dimeric metal-ligand complex. Exemplary dimeric metal-ligand complexes may have structures represented by the following Formulas 10-12. In any of Formulas 10-12, M may be La.

[0078] Scheme 1 below shows a general synthetic route that can be used to prepare the ligands and metal-ligand complexes of the present disclosure using a multi-step synthesis. Scheme 1 shows an exemplary scalable synthetic route for ligands having 2-aryl substituted pyrroles, which can be obtained via commercially available N-Boc-2-pyrrole boronic acid (Boc = 2-tert-butoxycarbonyl). In Scheme 1, reaction step (i) is a cross-coupling reaction, wherein "Ar" is an aryl group and "X" is a leaving group (e.g., a halide). For example, reaction step (i) can be a Suzuki-Miyaura cross-coupling reaction using a palladium or nickel catalyst. Reaction step (ii) is an ester deprotection reaction to form a 2-aryl substituted pyrrole. Reaction step (iii) is a formylation reaction, wherein the 2-aryl substituted pyrrole is functionalized with a formyl group. In reaction step (iv), the 2-aryl substituted pyrrole is functionalized with an indenyl group to form a bridging structure of the ligand. Reaction step (v) is the reduction of the alkylidene group to form a CH 2 The reaction step (vi) forms a metal-ligand complex from the ligand. As shown in Scheme 1, the metal compound may comprise a metal M and one or more amino leaving groups X (e.g., NMe 2 ). Solution 1

[0079] Scheme 2 below shows another general synthetic route that can be used to prepare the ligands and metal-ligand complexes of the present disclosure using a multi-step synthesis. Scheme 2 shows an exemplary scalable synthetic route for ligands having 2-alkyl substituted pyrroles. In reaction step (i), the pyrrole can be functionalized with a precursor of a formyl group, followed by alkylation with an alkyl group in step (ii). In reaction step (iii), the 2-alkyl substituted pyrrole is functionalized with an indenyl group to form a bridged structure of the ligand. Reaction step (iv) is the reduction of the alkylidene group to form a CH 2 The reaction step (v) forms a metal-ligand complex from the ligand. As shown in Scheme 2, the metal compound may comprise a metal M and one or more amino leaving groups X (e.g., NMe 2 ). Solution 2

[0080] Catalyst system of the present disclosure may comprise at least one activator and one or more above-mentioned metal-ligand complexes.Polymerization process of the present disclosure may comprise contacting olefinic feed with catalyst system under suitable polymerization reaction conditions.Not subject to the constraint of any theory or mechanism, at least one activator may react with metal-ligand complex to promote the loss of ligand, thereby opening the coordination site where olefin polymerization may occur.Especially, it is believed that at least one activator removes at least one leaving group to form catalytically active species.

[0081] In some embodiments, the catalyst systems described herein may comprise one metal-ligand complex rather than using two or more different metal-ligand complexes. For the purposes of this disclosure, a metal-ligand complex is considered different from another if the two complexes differ by at least one atom.

[0082] In other embodiments, two or more different metal-ligand complexes may be present in various catalyst systems described herein. In some embodiments, two or more different metal-ligand complexes may be present in the reaction zone where the polymerization process described herein occurs. When two or more metal-ligand complexes are used in one reactor as a mixed catalyst system, the two or more metal-ligand complexes are preferably selected so that they are compatible. Simple screening methods known to those of ordinary skill in the art (e.g., by 1 H or 13 C NMR) can be used to determine whether two or more metal-ligand complexes are compatible. It is preferred to use the same activator for the metal-ligand complexes, however, two different activators, such as a non-coordinating anion activator and an alumoxane, can be used in combination. If one or more of the metal-ligand complexes contains a leaving group X ligand that is not a hydrogen, hydrocarbyl, or substituted hydrocarbyl group, the alumoxane can be contacted with the transition metal compound prior to the addition of the non-coordinating anion activator.

[0083] A variety of metal-ligand complexes can be used in any ratio in the catalyst system or polymerization process. The preferred molar ratio of (A) metal-ligand complex to (B) metal-ligand complex is in the range of 1:1000-1000:1, or 1:100-500:1, or 1:10-200:1, or 1:1-100:1, or 1:1-75:1, or 5:1-50:1 (A:B). The specific ratio selected will depend on the precise procatalyst selected, the activation method, and the desired end product. In a particular embodiment, when two procatalysts are used, both of which are activated with the same activator, useful mole percentage values ​​based on the molecular weight of the procatalysts are 10% to 99.9% A to 0.1% to 90% B, or 25% to 99% A to 0.5% to 50% B, or 50% to 99% A to 1% to 25% B, or 75% to 99% A to 1% to 10% B.

[0084] The terms "co-catalyst" and "activator" are used interchangeably herein. The catalyst system described herein generally comprises a metal-ligand complex as described above and an activator such as aluminoxane or a non-coordinating anion, and can be formed by combining the catalyst components described herein with an activator in any manner known in the literature, including combining them with a carrier such as silica. The catalyst system can also be added to 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 metal-ligand complexes. An activator is defined as any compound that can activate any of the above-mentioned catalyst compounds by converting a neutral metal compound into a catalytically active metal compound cation. Non-limiting activators include, for example, aluminoxanes, alkyl aluminums, ionizing activators (which can be neutral or ionic), and co-catalysts of conventional types. Preferred activators generally include aluminoxane compounds, modified aluminoxane compounds, and ionizing anion precursor compounds which abstract reactive, sigma-bonded metal ligands, thereby cationizing the metal compound and providing a charge balancing non-coordinating or weakly coordinating anion, e.g., a non-coordinating anion.

[0085] Aluminoxane activators are used as activators in the catalyst systems described herein. Aluminoxanes are generally oligomeric compounds containing -Al(R)-O- subunits, wherein R is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, especially when the extractable ligand is an alkyl, halide, alkoxy or amino (amide). Mixtures of different aluminoxanes and modified aluminoxanes can also be used. Visually transparent methylaluminoxane can be preferably used. Turbid or gel aluminoxanes can be filtered to prepare a transparent solution or transparent aluminoxanes can be decanted from the turbid solution. Useful aluminoxanes are modified methylaluminoxane (MMAO) cocatalyst 3A type (commercially available from Akzo Chemicals, Inc. under the trade name modified methylaluminoxane 3A type) covered by U.S. Patent No. US 5,041,584. Another useful aluminoxane is the solid polymethylaluminoxane described in US Pat. Nos. 9,340,630; 8,404,880 and 8,975,209.

[0086] When the activator is an aluminoxane (modified or unmodified), some embodiments select a maximum activator amount typically at up to 5000-fold molar excess (Al / M) relative to the catalyst compound (per metal catalytic site). The minimum activator to catalyst compound ratio is a 1:1 molar ratio. Alternative preferred ranges include 1:1-500:1, or 1:1-200:1, or 1:1-100:1, or 1:1-50:1.

[0087] In an alternative embodiment, little or no alumoxane is used in the polymerization process described herein. Preferably, the alumoxane is present at 0 mol%, or the alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal of less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1:1.

[0088] Other suitable activators for the catalyst may include compounds containing non-coordinating anions, especially borane and borate compounds. Particularly useful borane and borate compounds containing non-coordinating anions or similar entities include, for example, B(C 6 F 5 ) 3 、[PhNMe 2 H] + [B(C 6 F 5 ) 4 ] - 、[Ph 3 C] + [B(C 6 F 5) 4 ] - and [PhNMe 2 H] + [B(C 10 F 7 ) 4 ] - .

[0089] The term "non-coordinating anion" (NCA) refers to an anion that is not coordinated to the cation or is only weakly coordinated to the cation, thereby maintaining an anion that is sufficiently unstable to be replaced by a neutral Lewis base. The term NCA is defined as including an activator containing multi-component NCA, such as tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium and tetrakis (heptafluoronaphthyl) borate N, N-dimethylanilinium, which contain acidic cationic groups and non-coordinating anions. The term NCA is also defined as including neutral Lewis acids that can form activated species (an activated species) by the extraction of anionic groups and catalyst reactions, such as tris (pentafluorophenyl) boron. Typically, NCA coordination is weak enough so that a neutral Lewis base such as an olefinic or acetylenic unsaturated monomer can be displaced from the catalyst center. Any metal or metalloid that can form a compatible, weakly coordinated complex can be used or included in a 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. The term non-coordinating anion includes neutral activators, ionic activators, and Lewis acid activators.

[0090] "Compatible" non-coordinating anions are those that do not degrade to neutrality when the initially formed complex decomposes. In addition, the anion does not transfer anionic substituents or fragments to the cation, causing it to form a neutral transition metal compound and neutral byproducts from the anion. Non-coordinating anions that can be used according to the present invention are anions that are compatible, stabilizing the transition metal cation in the sense of balancing its ionic charge at +1, yet remaining sufficiently unstable to allow displacement during the polymerization process. Ionizing activators useful herein typically comprise NCAs, especially compatible NCAs.

[0091] It is within the scope of the present invention to use an ionizing activator (neutral or ionic). It is also within the scope of the present invention to use a neutral or ionic activator alone or in combination with an aluminoxane or modified aluminoxane activator. For a description of useful activators, see US 8,658,556 and US 6,211,105.

[0092] It is within the scope of the present disclosure to use ionizing, neutral or ionic activators, such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, triperfluorophenylborane metalloid precursors or triperfluoronaphthylborane metalloid precursors, polyhalogenated heteroborane anions (WO 1998 / 043983), boric acid (U.S. Pat. No. 5,942,459), or any combination thereof. It is also within the scope of the present disclosure to use neutral or ionic activators, alone or in combination with aluminoxane activators.

[0093] The catalyst system of the present disclosure may include at least one non-coordinating anion (NCA) activator. In a preferred embodiment, a boron-containing NCA activator represented by Formula 13 may be used, Z d + (A d- ) Formula 13 wherein Z is (LH) or a reducible Lewis acid; L is a neutral Lewis base; H is hydrogen; (LH) is a Bronsted acid; A d- is a boron-containing non-coordinating anion having a charge d-; d is 1, 2 or 3.

[0094] Cationic component Z d + A Bronsted acid may be included, such as a proton or protonated Lewis base or a reducible Lewis acid, which is capable of protonating or abstracting a moiety from a metal-ligand complex to provide a cationic metal-ligand complex.

[0095] Cationic component Z d + It can also be silver, (tropylium), carbon (carbonium), ferrocene (ferrocenium) and mixtures thereof, preferably carbon and ferrocene Suitable reducible Lewis acids include any triarylcarbonyl (wherein the aryl group may be substituted or unsubstituted, for example, 3 C + ) wherein Ar is an aromatic group or is substituted by a heteroatom, C 1 To C 40 Hydrocarbon or substituted C 1 To C 40 Preferably, the reducible Lewis acid defined as "Z" in Formula 5 above includes those represented by the following formula: (Ph 3 C), wherein Ph is substituted or unsubstituted phenyl, preferably C 1 To C 40Hydrocarbyl substituted, or substituted C 1 To C 40 Hydrocarbyl, preferably C 1 To C 20 Alkyl or aromatic or substituted C 1 -C 20 An alkyl or aromatic group, and preferably Z d + It is triphenyl carbon

[0096] When Z d + It is an activating cation (LH) d + When it is preferably a Bronsted acid, it is capable of donating protons to the transition metal catalyst precursor to generate transition metal cations, including ammonium, oxygen phosphorus Silane and mixtures thereof, preferably methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline, ammonium p-nitro-N,N-dimethylaniline; phosphorus derived from triethylphosphine, triphenylphosphine and diphenylphosphine From ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and di Oxygen of alkane Sulfonium derived from thioethers, such as diethyl sulfide and tetrahydrothiophene, and mixtures thereof.

[0097] Anionic component A d- Including having the formula [M k+ G] d- Those wherein k is 1, 2 or 3; g is 1, 2, 3, 4, 5 or 6 (preferably 1, 2, 3 or 4); gk=d; M is an element selected from Group 13 of the Periodic Table, preferably boron or aluminum, and G is independently hydrogen, a bridged or unbridged dialkylamino, a halide, an alkoxy, an aryloxide, a hydrocarbon, a substituted hydrocarbon, a halocarbon, a substituted halocarbon, and a halocarbon, said G having up to 20 carbon atoms, provided that G is a halide no more than once. Preferably, each G is a fluorinated hydrocarbon group containing 1 to 20 carbon atoms, more preferably, each G is a fluorinated aryl group, and most preferably, each G is a pentafluoroaryl group. Suitable A d- Examples also include diboron compounds as disclosed in US Pat. No. 5,447,895, which is incorporated herein by reference in its entirety with respect to the diboron compounds disclosed therein.

[0098] Illustrative but non-limiting examples of boron compounds useful as activators are the compounds described as activators (and particularly those specifically listed as activators) in US Pat. No. 8,658,556, which is incorporated herein by reference with respect to the boron compounds disclosed therein.

[0099] Most preferably, the activator Z d + (A d- ) is one or more of the following: N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbon tetrakis(perfluoronaphthyl)borate Tetrakis(perfluorobiphenyl) borate triphenylcarbon triphenylcarbon tetrakis(3,5-bis(trifluoromethyl)phenyl)borate or triphenylcarbon tetrakis(perfluorophenyl)borate In any embodiment, the non-coordinating anion can be selected from the group consisting of: N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbon tetrakis(perfluoronaphthyl)borate, Tetrakis(perfluorobiphenyl) borate triphenylcarbon triphenylcarbon tetrakis(3,5-bis(trifluoromethyl)phenyl)borate Triphenylcarbon tetrakis(perfluorophenyl)borate [Me 3 NH + ][B(C 6 F 5 ) 4- ], 1-(4-(tris(pentafluorophenyl)boronic acid)-2,3,5,6-tetrafluorophenyl)pyrrolidine [Me 3 NH + ][B(C 6 F 5 ) 4- ], 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidine salt, sodium tetrakis(pentafluorophenyl)borate, potassium tetrakis(pentafluorophenyl)borate, and 4-(tris(pentafluorophenyl)boronic acid)-2,3,5,6-tetrafluoropyridine Preferably, the non-coordinating anion may be N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate.

[0100] Bulky activators may also be used as NCAs herein. As used herein, "bulky activator" refers to an anionic activator represented by the following Formula 14 or 15. In equations 14 and 15, each R 1a Ar is a substituted or unsubstituted aryl group (preferably a substituted or unsubstituted phenyl group), preferably substituted with C 1 To C 40 Hydrocarbyl, preferably C 1 To C 20 an alkyl group or an aromatic group; each R 2a are independently halogen, C 6 To C 20 Substituted aromatic hydrocarbon or -O-Si-R a silyloxy, where R a It is C 1 To C 20 Hydrocarbyl or hydrocarbyl silyl (preferably R 2a is a fluoro group or a perfluorinated phenyl group); each R 3a Is a halogen, C 6 To C 20 Substituted aromatic hydrocarbon or -O-Si-R a silyloxy, where R a It is C 1 To C 20 Hydrocarbyl or hydrocarbyl silyl (preferably, R 3a Is fluorine or C 6 perfluorinated aromatic hydrocarbon group); wherein R 2a and R 3a Can form one or more saturated or unsaturated substituted or unsubstituted rings (preferably, R 2a and R 3a forming a perfluorinated phenyl ring); and L is a neutral Lewis base; (LH) + is a Bronsted acid; d is 1, 2 or 3; wherein the anion has a molecular weight greater than 1020 g / mol; wherein at least three of the substituents on the B atom each have a molecular weight greater than 250 cubic More than 300 cubic meters or more than 500 cubic meters The molecular volume is as follows.

[0101] Preferably, (Ar 3 C) d + Yes (Ph 3 C) d + , wherein Ph is a substituted or unsubstituted phenyl group, preferably substituted with C 1To C 40 Hydrocarbon or substituted C 1 To C 40 Hydrocarbyl, preferably C 1 To C 20 Alkyl or aromatic or substituted C 1 To C 20 Alkyl or aromatic group.

[0102] "Molecular volume" is used herein as an approximation of the spatial volume of an activator molecule in solution. Comparison of substituents having different molecular volumes allows substituents having smaller molecular volumes to be considered "less bulky" than substituents having larger molecular volumes. Conversely, substituents having larger molecular volumes can be considered "bulkier" than substituents having smaller molecular volumes. 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. Molecular volume (MV) (in cubic units) ) Use the following formula to calculate: 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 Table 1 below. For fused rings, V s 7.5% reduction / fused ring. The calculated total MV of an anion is the sum of the MVs of each substituent, e.g., the MV of perfluorophenyl is The calculated total MV of tetrakis(perfluorophenyl)borate is four times or Table 1 element Relative volume H 1 First short term, Li to F 2 Second short term, Na to Cl 4 First term, K to Br 5 Second long term, Rb to I 7.5 The third long term, Cs to Bi 9 For a list of particularly useful bulky activators, reference may be made to US Patent No. 8,658,556, which is incorporated herein by reference for its disclosure regarding bulky activators.

[0103] In any embodiment, the NCA activator can be an activator as described in U.S. Pat. No. 6,211,105. The ratio of NCA activator to catalyst can be from about 1:1 molar ratio to about 1000:1 molar ratio, including from about 0.1:1 to about 100:1, from about 0.5:1 to about 200:1, from about 1:1 to about 500:1, or from about 1:1 to about 1000:1. A particularly useful range is from about 0.5:1 to about 10:1, preferably from about 1:1 to about 5:1.

[0104] It is also within the scope of the present disclosure that the metal-ligand complex can be activated with a combination of alumoxane and NCA (see, for example, US Pat. Nos. 5,153,157 and 5,453,410; EP 0 573 120 Bl and International Patent Application Publications WO 1994 / 007928 and WO 1995 / 014044 which discuss the use of alumoxanes in combination with ionizing activators).

[0105] In addition to the activator compound, a scavenger or co-activator may be used. Alkyl aluminum or organoaluminum compounds that may be used as scavengers or co-activators include, for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexylaluminum, tri-n-octylaluminum, ethylaluminum dichloride, diethylaluminum chloride, and diethylzinc.

[0106] Chain transfer agents may also be used in the compositions and / or methods described herein. Useful chain transfer agents are typically alkylaluminoxanes, i.e., compounds of the formula AlR 3 , ZnR 2 A compound represented by (wherein each R is independently C 1 -C 8 Aliphatic groups, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or isomers thereof) or combinations thereof, for example diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum or combinations thereof.

[0107] In any embodiment, the catalyst system suitable for the method and system disclosed herein can be arranged on a solid support. The solid support can allow catalytic reaction to be carried out under heterogeneous conditions, such as polymerization of olefinic feed. In a more specific embodiment, the solid support can be silicon dioxide. Other suitable solid supports may include, but are not limited to, aluminum oxide, magnesium chloride, talc, inorganic oxides or chlorides (including one or more metals from the 2nd, 3rd, 4th, 5th, 13th or 14th group of the periodic table of elements), and polymers such as polystyrene, or functionalized and / or cross-linked polymers. Other inorganic oxides that can be suitably used as solid supports include, for example, titanium oxide, zirconium oxide, boron oxide, zinc oxide, magnesium oxide or any combination thereof. The combination of inorganic oxides can also be suitably used as solid supports. The exemplary combination of suitable inorganic oxides includes, but is not limited to, silicon dioxide-aluminum oxide, silicon dioxide-titania, silicon dioxide-zirconium oxide, silicon dioxide-boron oxide, etc.

[0108] In any embodiment, aluminoxane or other suitable activator can be arranged on silica or another suitable solid support before combining with the metal-ligand complex disclosed herein. The metal-ligand complex disclosed herein can be arranged on silica or another suitable support before combining with aluminoxane or other suitable activator. When the activator and solid support are combined with the metal-ligand complex, the resulting catalyst system can be arranged on the solid support. Catalyst systems with different catalytic properties can be obtained, depending on whether the metal-ligand complex or the activator is first loaded on the solid support.

[0109] In any embodiment, the aluminoxane, such as MAO, can be mixed in an inert solvent, such as toluene, and then slurried with a solid support, such as silica. The aluminoxane deposition on the solid support can be carried out at a temperature of about 60° C. to 120° C., or about 80° C. to 120° C., or about 100° C. to 120° C. Deposition at temperatures below 60° C., including room temperature deposition, may also be effective.

[0110] In various embodiments, the catalyst system may include an inert support material. Preferably, the support material is a porous support material, such as talc and inorganic oxides. Other support materials include zeolites, clays, organoclays or any other organic or inorganic support materials, or mixtures thereof.

[0111] Preferably, the support material is an inorganic oxide in finely dispersed form. Suitable inorganic oxide materials for use in the catalyst system herein include metal oxides of Groups 2, 4, 13 and 14 such as silicon dioxide, aluminum oxide and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silicon dioxide or aluminum oxide are magnesium oxide, titanium oxide, zirconium oxide and the like. However, other suitable support materials can be used, for example, finely dispersed functionalized polyolefins such as finely dispersed polyethylene. Particularly useful supports include magnesium oxide, titanium oxide, zirconium oxide, montmorillonite, phyllosilicate, zeolite, talc, clay and the like. In addition, combinations of these support materials can be used, for example, silicon dioxide-chromium, silicon dioxide-alumina, silicon dioxide-titania and the like. Preferred support materials include Al 2 O 3 、ZrO 2 、SiO 2 , and combinations thereof, more preferably SiO 2 、Al 2 O 3 or SiO 2 / Al 2 O 3 .

[0112] In any embodiment, a solid support suitable for use in the present disclosure may have a diameter of from about 10 to about 700 m 2 / g surface area, a pore volume of about 0.1 to about 4.0 cc / g, and an average particle size of about 5 to about 500 μm. More preferably, the surface area of ​​the support material is about 50 to about 500 m 2 / g, the pore volume is in the range of about 0.5 to about 3.5 cc / g, and the average particle size is in the range of about 10 to about 200 μm. Most preferably, the surface area of ​​the support material is about 100 m 2 / g to about 400m 2 / g, the pore volume is in the range of about 0.8cc / g to about 3.0cc / g, and the average particle size is in the range of about 5μm to about 100μm. The average pore size of the support material that can be used in the present invention is in the range of Preferably 50-approximately Most preferably 75 to about In some embodiments, the support material is high surface area, amorphous silica (surface area = 300 m 2 / gm; pore volume is 1.65cm 3 / gm). Preferred silica is available from Davison Chemical Division of W.R. Grace and Company under the trade name DAVISON TM 952 or DAVISONTM 955 sales. In other embodiments, DAVISON TM 948.

[0113] The support material may be free of adsorbed water. Drying of the support material may be carried out by heating or calcining at about 100°C to about 1000°C, preferably at least about 600°C. When the support material is silica, it is heated to at least 200°C, preferably about 200°C to about 850°C, most preferably about 600°C; and maintained for a period 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 may have at least some reactive hydroxyl groups (OH) to prepare the supported catalyst system of the present invention. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

[0114] In a non-polar solvent, a support material with reactive surface groups (usually hydroxyl groups) is slurried and the resulting slurry is contacted with a solution of a catalyst compound and an activator. In some embodiments, the slurry of the support material is first contacted with the activator for about 0.5 hour to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. Then the solution of the catalyst compound is contacted with the isolated support / activator. In some embodiments, a supported catalyst system is generated in situ. In an optional embodiment, the slurry of the support material is first contacted with the catalyst compound for about 0.5 hour to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. Then the slurry of the catalyst compound of the load is contacted with the activator solution.

[0115] The mixture of catalyst, activator and support is heated at about 0° C. to about 70° C., preferably at about 23° C. to about 60° C., preferably at room temperature. The contact time is generally about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours.

[0116] Suitable non-polar solvents are materials in which all of the reactants used herein, i.e., the activator and catalyst compounds, are at least partially soluble and are liquid at the reaction temperature. Preferred non-polar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, but various other materials may also be employed, including cycloalkanes, such as cyclohexane, aromatic compounds, such as benzene, toluene, and ethylbenzene.

[0117] Various embodiments described herein further relate to polymerization methods, wherein monomers (such as ethylene or propylene) and optionally one or more comonomers are contacted with a catalyst system comprising an activator and at least one metal-ligand complex, as described above. The metal-ligand complex and the activator can be combined in any order, and are typically combined prior to contact with the monomers. Suitable polymerization conditions for carrying out the polymerization reaction are provided below.

[0118] Monomers useful herein include substituted or unsubstituted C 2 -C 40 α-olefins, preferably C 2 -C 20 α-olefins, preferably C 2 -C 12 α-olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In a preferred embodiment, the monomers include propylene and one or more optional comonomers, the comonomers including one or more ethylene or C 4 To C 40 Olefins, preferably C 4 To C 20 Olefins, or preferably C 6 To C 12 Olefins. 4 To C 40 The olefin monomers may be linear, branched or cyclic. 4 To C 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 preferred embodiment, the monomers include ethylene and optional comonomers including one or more C 3 To C 40 Olefins, preferably C 4 To C 20 Olefins, or preferably C 6 To C 12 Olefins. 3 To C 40 The olefin monomers may be linear, branched or cyclic. 3 To C 40 The cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups.

[0119] Exemplary C 2 To C 40Olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof and isomers thereof, preferably 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 corresponding homologs and derivatives, preferably norbornene, norbornadiene and dicyclopentadiene.

[0120] In some embodiments, one or more dienes may be present in the polymers prepared herein at up to 10 wt %, preferably 0.00001 to 1.0 wt %, preferably 0.002 to 0.5 wt %, even more preferably 0.003 to 0.2 wt %, based on the total weight of the composition. In some embodiments, 500 ppm or less, preferably 400 ppm or less, preferably 300 ppm or less of diene is added to the polymerization. In other embodiments, at least 50 ppm or 100 ppm or more or 150 ppm or more of diene is added to the polymerization.

[0121] Preferred diene monomers useful in the various embodiments described herein may include any hydrocarbon structure having at least two unsaturated bonds, preferably C 4 To C 30, wherein at least two unsaturated bonds are readily incorporated into the polymer by stereospecific or non-stereospecific catalyst(s). It is further preferred that the diene monomer is selected from α,ω-diene monomers (i.e., divinyl monomers containing two terminal olefin groups). More preferably, the diene monomer is a linear divinyl monomer, very preferably, those containing 4 to 30 carbon atoms. Examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, eicosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, and particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weight polybutadiene (Mw less than 1000 g / mol). Preferred cyclic dienes include cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing dienes with or without substituents at various ring positions.

[0122] The polymerization process of various embodiments described herein can be carried out in any manner known in the art. Any suspension, homogeneous, bulk, solution, slurry or gas phase polymerization process known in the art can be used. These methods can be operated in batch, semi-batch or continuous mode. The term "continuous" refers to a system that operates without interruption or stopping. For example, a continuous method for producing a polymer or oligomer may be a method in which reactants are continuously introduced into one or more reactors and the polymer or oligomer product is continuously taken out. Homogeneous polymerization methods and slurry methods can be used. Homogeneous polymerization methods are defined as methods in which at least 90% by weight of the product is soluble in the reaction medium. Particularly preferred bulk homogeneous methods. Bulk methods are defined as methods in which the monomer concentration in all raw materials of the reactor is 70% by volume or higher. Alternatively, neither solvent nor diluent is present in or added to the reaction medium (except for a small amount used as a carrier for a catalyst system or other additives, or the amount usually found with the monomer (e.g., propane in propylene)). Alternatively, the method can be a slurry method. The term "slurry polymerization method" used herein refers to a polymerization method in which a supported catalyst is used and the monomers are polymerized on the supported catalyst particles. At least 95% by weight of the oligomer product derived from the supported catalyst is in granular form as solid particles (not dissolved in the diluent). A heterogeneous process is defined as a process in which the catalyst system is not soluble in the reaction medium.

[0123] Other additives may also be used in the polymerization as desired, such as one or more scavengers, promoters, modifiers, chain transfer agents (e.g., diethyl zinc), hydrogen, aluminum alkyls or silanes. Useful chain transfer agents are typically alkylaluminoxanes, i.e., alkyl groups of the formula AlR 3 , ZnR 2 A compound represented by (wherein each R is independently C 1 -C 8 aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or isomers thereof) or a combination thereof; for example, diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride or a combination thereof.

[0124] Suitable diluents / solvents for the polymerization include non-coordinating inert liquids. Examples include: straight chain and branched hydrocarbons (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and / or mixtures thereof); cyclic and alicyclic hydrocarbons (e.g., cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and / or mixtures thereof, such as commercially available (Isopar TM )); perhalogenated hydrocarbons (e.g., perfluorinated C 4-10 The solvent may be selected from the group consisting of alkylene, chlorobenzene, and aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins that may optionally serve as monomers or comonomers, such as, but not limited to, ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and / or mixtures thereof. In a preferred embodiment, aliphatic hydrocarbon solvents (such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and / or mixtures thereof) or cyclic and alicyclic hydrocarbons (such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and / or mixtures thereof) may be used. In any embodiment, the solvent may be substantially free of any aromatic compounds. For example, aromatic compounds may be present in the solvent in an amount of less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0% by weight, based on the weight of the solvent. In any embodiment, the feed stream may include about 60% by volume or less, about 40% by volume or less, or 20% by volume or less of diluent / solvent, based on the total volume of the feed stream. This includes 0% by volume to about 60% by volume, about 0% by volume to about 40% by volume, and about 0% by volume to about 20% by volume. Typical temperatures and / or pressures include temperatures from about 0°C to about 300°C, preferably from about 20°C to about 200°C, preferably from about 35°C to about 150°C, preferably from about 40°C to about 120°C, preferably from about 45°C to about 80°C; and at a pressure of about 0.35MPa to about 10MPa, preferably from about 0.45MPa to about 6MPa, or preferably from about 0.5MPa to about 4MPa.

[0125] In any polymerization reaction disclosed herein, the polymerization reaction conditions may include a reaction temperature of about 30° C. to about 200° C., or about 50° C. to about 150° C., or about 80° C. to about 140° C., or about 90° C. to about 130° C. Alternatively, the polymerization reaction conditions may include a temperature of about 30° C. or higher, or about 50° C. or higher, or about 100° C. or higher up to the boiling point of the solvent used in the solution polymerization under the conditions present in the reactor.

[0126] The polymerization run time may be up to about 300 minutes, for example, in the range of about 5 minutes to about 250 minutes, including about 10 minutes to about 120 minutes. For continuous polymerization processes, the run time may correspond to the residence time in the reactor.

[0127] The processing of oligomers can be carried out after polymerization. Suitable processing operations may include, but are not limited to, blending or coextrusion with any other polymer. Non-limiting examples of other polymers include, but are not limited to, linear low density polyethylene, elastomers, plastomers, high pressure low density polyethylene, high density polyethylene, polypropylene and / or the like. The oligomers formed according to the present disclosure may also be blended with additives to form compositions that can then be used in articles. Suitable additives may include, but are not limited to, antioxidants, nucleating agents, acid scavengers, plasticizers, stabilizers, preservatives, foaming agents, ultraviolet light absorbers, quenchers, antistatic agents, slip agents, phosphites, phenolic resins, pigments, dyes and fillers and curing agents such as peroxides.

[0128] In various embodiments, hydrogen can be included in the polymerization reaction conditions to provide the activity of increase without significantly damaging the catalytic activity of metal-ligand complex. Catalyst activity (for example, calculated with g / mmol catalyst / hour) can be at least 20% higher than the same reaction without hydrogen, and it includes at least 50% and at least 100% higher. The activity of catalyst can be at least 50g / mmol / hour, at least about 500g / mmol / hour, at least about 5,000g / mmol / hour or at least about 50,000g / mmol / hour. Based on the weight of the olefin monomers of oligomer yield and entering reaction zone, the conversion rate of olefinic feed can be at least about 10%, at least about 20%, at least about 30%, at least about 50% or at least about 80%.

[0129] In a preferred embodiment, the polymerization is: 1) carried out at a temperature of 0°C to 300°C (preferably 25°C to 150°C, preferably 40°C to 120°C, preferably 45°C to 80°C); 2) carried out at a pressure of normal pressure to 10 MPa (preferably 0.35 MPa to 10 MPa, preferably 0.45 MPa to 6 MPa, preferably 0.5 MPa to 4 MPa); 3) carried out in an aliphatic hydrocarbon solvent (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof); 5) the polymerization is carried out in a method of preparing the polymerization product, wherein the polymerization product comprises alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; preferably wherein the aromatic compound is present in the solvent at less than 1 wt %, preferably less than 0.5 wt %, preferably 0 wt %, based on the weight of the solvent); 6) the polymerization is carried out in a method of preparing the polymerization product, wherein the polymerization product comprises alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; preferably wherein the aromatic compound is present in the solvent at less than 1 wt %, preferably less than 0.5 wt %, preferably 0 wt %, based on the weight of the solvent); 7) the polymerization is carried out in a method of preparing the polymerization product, wherein the polymerization product comprises alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; preferably wherein the aromatic compound is present in the solvent at less than 1 wt %, preferably less than 0.5 wt %, preferably 0 wt %, based on the weight of the solvent); 8) the polymerization is carried out in a method of preparing the polymerization product, wherein the polymerization product comprises alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; preferably wherein the aromatic compound is present in the solvent at less than 1 wt %, preferably less than 0.5 wt %, preferably 0 wt %, based on the weight of the solvent); 9) the polymerization is carried out in a method of preparing the polymerization product, wherein the polymerization product comprises alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; preferably wherein the aromatic compound is present in the solvent at less than 1 wt %, preferably less than 0.5 wt %, preferably 0 wt 5) the polymerization is preferably carried out in one reaction zone; 6) the productivity of the catalyst compound is 80,000 g / mmol / hr (preferably at least 150,000 g / mmol / hr, preferably at least 200,000 g / mmol / hr, preferably at least 250,000 g / mmol / hr, preferably at least 300,000 g / mmol / hr); 7) optionally, a scavenger (e.g., a trialkylaluminum compound) is absent (e.g., present at zero mol %, or The scavenger is present in a scavenger metal to transition metal molar ratio of less than 100:1, preferably less than 50:1, preferably less than 15:1, preferably less than 10:1); and 8) optionally, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345 kPa), preferably 0.01 psig to 25 psig (0.07 kPa to 172 kPa), more preferably 0.1 psig to 10 psig (0.7 kPa to 70 kPa). In a preferred embodiment, the catalyst system used in the polymerization comprises at most one catalyst compound. A "reaction zone", also called a "polymerization zone", is a container in which polymerization is carried out, such as a batch reactor. When multiple reactors are used in a series or parallel configuration, each reactor is considered to be a separate polymerization zone. For multi-stage polymerization in both batch reactors and continuous reactors, each polymerization stage is considered to be a separate polymerization zone. In a preferred embodiment, the polymerization is carried out in one reaction zone. Room temperature is 23°C, unless otherwise specified.

[0130] The polymerization of the olefinic feed stream can be carried out in a reaction zone within the reactor. The system may include multiple reactors and / or multiple reaction zones. The reactor may be a batch reactor, a semi-batch reactor or a continuous reactor. Examples of suitable continuous reactors include, but are not limited to: a continuous stirred tank (and its equipment group), a loop reactor, a fluidized bed reactor, a combination thereof and / or the like. Multiple reactors may be connected in series or in parallel. The reactor may include at least one reaction zone, the reaction zone comprising one or more metal-ligand complexes containing a ligand represented by Formula 1 as a polymerization catalyst. The reactor may also include at least one inlet and at least one outlet, the at least one inlet being configured and arranged to receive a feed stream, and the at least one outlet being configured and arranged to receive a product stream. In any embodiment of two or more different α-olefin reactions, the reactor may include an additional inlet for receiving a stream containing additional monomers. The reactor may further include one or more additional inlets for introducing one or more of a catalyst (e.g., one or more of the metal-ligand complexes described herein), a diluent or any other material (e.g., a hydrogen stream and / or a catalyst poison) into the reactor. The system may also include a conduit for transporting the spent catalyst to a catalyst regeneration system. The system comprising the reactor may also include equipment, processors and controllers for adjusting various reactor conditions (including but not limited to pressure, temperature and flow rate). The system comprising the reactor may also include equipment and pipelines for recycling unused monomers, process gases, hydrogen or any combination thereof back into the system. Those of ordinary skill in the art will be able to use reactors well known in the art and equipment to use catalyst systems disclosed herein to produce product streams comprising PAOs in high yields without excessive experimentation.

[0131] The PAOs prepared herein can be functionalized by reacting heteroatom-containing groups (e.g., amines, aldehydes, alcohols, acids, succinic acid, maleic acid, maleic anhydride) with the allyl groups of the polymer with or without a catalyst. Examples include, but are not limited to, catalytic hydrosilylation, hydroformylation, hydroboration, epoxidation, hydration, dihydroxylation, hydroamination, or maleation with or without an activator such as a free radical generator (e.g., peroxide). The functionalized PAOs can be used as oil additives and in many other applications, such as additives for lubricants and / or fuels.

[0132] Any olefinic feed can be polymerized using the catalyst systems disclosed herein. Suitable olefinic feeds may include any C 2 -C 40 α-olefins, preferably C 3 -C 32 α-olefins, optionally further combined with ethylene, which may be linear or branched, cyclic or acyclic, optionally containing heteroatom substitution. For example, the olefinic feed may comprise one or more of the following: C3 α-olefins, C 4 α-olefins, C 5 α-olefins, C 6 α-olefins, C 7 α-olefins, C 8 α-olefins, C 9 α-olefins, C 10 α-olefins, C 11 α-olefins, C 12 α-olefins, C 13 α-olefins, C 14 α-olefins, C 15 α-olefins, C 16 α-olefins, C 17 α-olefins, C 18 α-olefins, C 19 α-olefins, C 20 α-olefins, C 21 α-olefins, C 22 α-olefins, C 23 α-olefins, C 24 α-olefins, C 25 α-olefins, C 26 α-olefins, C 27 α-olefins, C 28 α-olefins, C 29 α-olefins, C 30 α-olefins, C 31 α-olefins, C 32 α-olefins, C 33 α-olefins, C 34 α-olefins, C 35 α-olefins, C 36 α-olefins, C 37 α-olefins, C 38 α-olefins, C 39 α-olefins and C 40 In a more specific embodiment, the olefinic feed may comprise C 2 -C 12 The alpha-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene or any combination thereof. For example, a combination of propylene and 1-decene may be used. Alternatively, 1-decene may be used without any comonomer. The olefinic feed may include any single alpha-olefin or any mixture of one or more of the above-mentioned alpha-olefins.

[0133] By contacting an olefinic feed with a metal-ligand complex as described herein, a variety of PAOs can be produced comprising monomer units derived from alpha-olefins in the olefinic feed.

[0134] For example, in any embodiment, the methods described herein can be used to produce a variety of vinyl terminated PAOs from a single α-olefin (PAO homopolymer). Examples of vinyl terminated PAO homopolymers that can be produced include C-containing 2 To C 40 α-olefins, more preferably C 3 -C 20 A homopolymer of an α-olefin, still more preferably an oligomer of 1-decene.

[0135] In any embodiment, the methods described herein can be used to generate a mixture of two, three, four or more C 2 -C 40 α-olefins (PAO copolymers) produce a variety of PAOs. In any embodiment, suitable C 2 To C 40 The α-olefin may include two or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene. Preferably, the PAO copolymer comprises propylene and 1-decene.

[0136] Thus, the polymerization methods described herein may include reacting the catalyst system of the present disclosure with a catalyst comprising C 2 -C 32 α-olefins, preferably C 2 To C 20 An olefinic feed of alpha-olefins or any combination thereof is contacted. In the present disclosure, ethylene is considered to be an alpha-olefin.

[0137] Oligomers (or polymers) produced using the metal-ligand complexes and polymerization reactions of the present disclosure can be characterized by a range of physical property measurements, as discussed below.

[0138] In any embodiment, the catalyst system of the present disclosure is capable of producing a plurality of PAOs having a density of about 0.86 g / cc to about 0.97 g / cc, about 0.90 g / cc to about 0.950 g / cc, about 0.905 g / cc to about 0.940 g / cc, or about 0.910 g / cc to about 0.930 g / cc as determined by ASTM D 1505-18.

[0139] In any embodiment, the catalyst system of the present disclosure is capable of producing 1A plurality of PAOs having a number average molecular weight (Mn) of at least about 500 g / mol as determined by H NMR, including about 500 g / mol to about 60,000 g / mol, about 500 g / mol to about 50,000 g / mol, about 500 g / mol to about 35,000 g / mol, about 500 g / mol to about 15,000 g / mol, about 500 g / mol to about 12,000 g / mol, or about 500 g / mol to about 10,000 g / mol.

[0140] In any embodiment, the catalyst system of the present disclosure is capable of producing 1 Various PAOs have a weight average molecular weight to number average molecular weight ratio (Mw / Mn) of from about 1.5 to about 10, from about 2.0 to about 10, from about 2.2 to about 8, from about 2.4 to about 7, or from about 2.5 to about 6 as determined by H NMR.

[0141] In any embodiment, the catalyst system of the present disclosure is capable of producing a catalyst having a pass rate of 10 or greater (including about 10 to about 50, about 12 to about 45, and about 15 to about 40). 1 The ratio of z-average molecular weight to number average molecular weight (Mz / Mn) of various PAOs was determined by H NMR.

[0142] In any embodiment, the catalyst system of the present disclosure is capable of producing a variety of PAOs having a melting point (Tm) of about 100°C to about 200°C, about 45°C to about 135°C, about 80°C to about 130°C, or about 115°C to about 135°C as determined by differential scanning calorimetry.

[0143] Unless otherwise specified, analytical testing of polymer samples was performed according to the following procedures. For analytical testing, polymer sample solutions were prepared in a shaker oven at 165°C by dissolving the polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity, obtained from Sigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%, obtained from Aldrich) for approximately 3 hours. Typical concentrations of polymer in solution were 0.1-0.9 mg / mL and BHT concentration was 1.25 mg BHT / mL TCB. Samples were cooled to 135°C for testing.

[0144] High temperature size exclusion chromatography was performed using an automated "Rapid GPC" system as described in US Pat. Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407 and 6,294,388, each of which is incorporated herein by reference. 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, are measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector (ELSD) and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) between 5,000 and 3,390,000 g / mol). Alternatively, the samples are measured using a Symyx Technology GPC equipped with a dual wavelength infrared detector and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) between 580 and 3,039,000). The samples were run using three Polymer Laboratories: PLgel 10 μm Mixed-B 300×7.5 mm columns in series at an eluent flow rate of 2.0 mL / min (135°C sample temperature, 165°C oven / column) (250 μl of polymer in TCB solution was injected into the system). Column normal time difference correction was not used. A 10 μm column column available from Symyx Technologies was used. Numerical analysis was performed using the Automation Studio software available from Freeslate or the Automation Studio software available from Freeslate. The molecular weights obtained were relative to linear polystyrene standards.

[0145] Differential Scanning Calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point of the polymer. The samples were pre-annealed at 220°C for 15 minutes and then allowed to cool to room temperature overnight. The samples were then heated to 220°C at a rate of 100°C / min and then cooled at a rate of 50°C / min. The melting point [Tm (°C)] was collected during the heating period.

[0146] The samples for infrared analysis were prepared by depositing the stabilized polymer solution onto a silanized wafer. By this method, approximately 0.12 mg to 0.24 mg of polymer was deposited on the wafer slots. The samples were then analyzed on a Bruker Equinox 55 FTIR spectrometer equipped with a Pikes specular reflectance sample accessory.-1 Resolution: 32 scans were collected to cover 5000 cm -1 Up to 500cm -1 For ethylene-1-octene copolymers, the spectral range of 1375 cm -1 The octene weight percent in the copolymer was determined by the methyl deformation band at ~4321 cm -1 The peak height of this band is normalized by combining and overtone bands at , which corrects for path length differences. The normalized peak height is compared with the peak height from 1 The various calibration curves for the H NMR data were correlated to predict the octene wt% content over a concentration range of 2 wt% to 35 wt% octene. Typically, an R of 0.98 or greater was achieved. 2 Relevance.

[0147] Polymers synthesized according to various embodiments described herein (e.g., polyethylene and / or polypropylene polymers) can be combined with one or more additional polymers prior to forming a film, molded part, or other article. 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, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetals, polyvinylidene fluoride, polyethylene glycol, and / or polyisobutylene.

[0148] In addition, one or more polymers synthesized according to the various embodiments described herein can be included in the polymer blend at 10 wt % to 99 wt %, preferably 20 wt % to 95 wt %, even more preferably at least 30 wt % to 90 wt %, even more preferably at least 40 wt % to 90 wt %, even more preferably at least 50 wt % to 90 wt %, even more preferably at least 60 wt % to 90 wt %, even more preferably at least 70 wt % to 90 wt %, based on the weight of the polymers in the blend.

[0149] The above blends can be prepared by mixing a polymer described herein (e.g., synthesized using one or more metal-ligand complexes described herein as a catalyst) with one or more polymers (as described above), by connecting reactors together in series to prepare reactor blends, or by using more than one catalyst in the same reactor to prepare multiple polymers. The polymers can be mixed together before being fed into the extruder or can be mixed in the extruder.

[0150] The blend can be formed using conventional equipment and methods, such as dry blending the components and then melt mixing in a mixer, or mixing the components directly together in a mixer such as a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin screw extruder, which can include a compounding extruder and a side arm extruder used directly downstream of the polymerization process, which can include blending powders or pellets of the resin at the hopper of a film extruder. In addition, additives can be included in the blend, in one or more components of the blend, and / or in a product formed from the blend, such as a film, as desired. Such additives are well known in the art and can include, for example: fillers; antioxidants (e.g., hindered phenolic compounds such as IRGANOX available from Ciba-Geigy); TM 1010 or IRGANOX TM 1076); phosphites (e.g., IRGAFOS available from Ciba-Geigy TM 168); anti-adhesive additives; tackifiers, such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates and hydrogenated rosin; UV stabilizers; heat stabilizers; anti-blocking agents; anti-adhesive agents; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; talc, etc.

[0151] In particular, any of the above polymers, such as the above polypropylene or its blend can be used for various end-use applications. These applications include, for example, single or multilayer blow molding, extrusion and / or shrink film. These films can be formed by many well-known extrusion or coextrusion techniques, such as blown film processing technology, wherein the composition can be extruded through an annular die in a molten state, then expanded to form a uniaxial or biaxially oriented melt, then cooled to form a tubular, blown film, and then axially cut and unfolded to form a flat film. The film can be subsequently non-oriented, uniaxially oriented, or biaxially oriented to the same or different extents. One or more of the film layers can be oriented to the same or different extents in the transverse and / or longitudinal directions. Uniaxial orientation can be carried out using typical cold stretching or hot stretching methods. Biaxial orientation can be carried out using a tentering machine device or a double bubble method and can be carried out before or after each layer is assembled. For example, a polyethylene layer can be extrusion coated or laminated to an oriented polypropylene layer or polyethylene and polypropylene can be coextruded into a film together, and then oriented. Similarly, oriented polypropylene can be laminated to an oriented polyethylene or oriented polyethylene can be coated on polypropylene, and then optionally, the combination can be even further oriented. Typically, the film is oriented in the machine direction (MD) by a ratio of up to 15, preferably 5 to 7, and in the transverse direction (TD) by a ratio of up to 15, preferably 7 to 9. However, in another embodiment, the film is oriented in both the MD and TD directions to the same extent.

[0152] The thickness of the film can vary depending on the intended application; however, films of a thickness of 1 μm to 50 μm are generally suitable. Films intended for packaging are generally 10 to 50 μm thick. The thickness of the sealant is typically 0.2 to 50 μm. The sealant may be present on both the inner and outer surfaces of the film or may be present only on the inner or outer surface.

[0153] In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment or microwaves.In a preferred embodiment, one or both of the surface layers are modified by corona treatment.

[0154] Embodiments disclosed herein include:

[0155] A. A metal-ligand complex comprising a transition metal atom or a lanthanide metal atom and a ligand having a structure represented by Formula 1: in: R 1 and R 2 are independently hydrogen or C 1 -C 14 Hydrocarbon; R 3 and R 4are independently hydrogen or C 1 -C 14 Hydrocarbyl, or R 3 and R 4 joined together to form an optionally substituted 6-membered aromatic ring; R 5 It is hydrogen, C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 30 aryl, heteroaryl or CN, provided that if the transition metal atom is Ti or Zr and R 3 and R 4 are connected together to form a 6-membered aromatic ring, then R 5 It is C 3 -C 10 Cycloalkyl, C 6 -C 30 Aryl, heteroaryl or CN; R 6 and R 7 are independently hydrogen or C 1 -C 14 a hydrocarbon group; and Z is a bridging atom.

[0156] B. A catalyst system comprising: at least one activator; and A metal-ligand complex including a transition metal atom or a lanthanide metal atom and a ligand having a structure represented by Formula 1. in: R 1 and R 2 are independently hydrogen or C 1 -C 14 Hydrocarbon; R 3 and R 4 are independently hydrogen or C 1 -C 14 Hydrocarbyl, or R 3 and R 4 joined together to form an optionally substituted 6-membered aromatic ring; R 5 It is hydrogen, C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 30 aryl, heteroaryl or CN, provided that if the transition metal atom is Ti or Zr and R 3and R 4 are connected together to form a 6-membered aromatic ring, then R 5 It is C 3 -C 10 Cycloalkyl, C 6 -C 30 Aryl, heteroaryl or CN; R 6 and R 7 are independently hydrogen or C 1 -C 14 a hydrocarbon group; and Z is a bridging atom.

[0157] C. A polymerization process comprising: providing an olefinic feed; and contacting the catalyst system of B with the olefinic feed under polymerization conditions.

[0158] Embodiments AC may have one or more of the following additional elements in any combination:

[0159] Element 1: wherein the metal-ligand complex has a structure represented by Formula 1A in: M is a transition metal atom or a lanthanide metal atom; X is independently a leaving group, or two X are linked and bonded to M to form a metal cyclize ring, a chelate ligand, a diene ligand, or an alkylidene group.

[0160] Element 2: where each X independently contains C 1 -C 20 A hydrocarbon group, a hydrogen group, an alkoxy group, a thiol group, a phosphorus group, a halide group, a diene group, an amine group, a phosphine group, an ether group or any combination thereof.

[0161] Element 3: wherein each X is dimethylamino or bis(dimethylsilylamino).

[0162] Element 4: wherein M is a Group 4 transition metal, a lanthanide element or chromium.

[0163] Element 5: wherein M is hafnium, chromium, neodymium or lanthanum.

[0164] Element 6: wherein the metal-ligand complex has a structure represented by one or more of Formulas 3-5,

[0165] Element 7: Where Z is CH 2 .

[0166] Element 8: wherein the metal-ligand complex further comprises a solvent or a Lewis base complexed with the transition metal atom or the lanthanide metal atom as a second ligand.

[0167] Factor 9: R 1 , R 2 , R 6 and R 7 are independently hydrogen, C 1 -C 10 Alkyl or C 6 -C 10 Aryl.

[0168] Factor 10: R 1 and R 2 is independently hydrogen, methyl or optionally substituted phenyl.

[0169] Factor 11: R 6 and R 7 All are H.

[0170] Factor 12: R 3 and R 4 are independently hydrogen, C 1 -C 10 Alkyl or C 6 -C 10 Aryl.

[0171] Factor 13: R 3 and R 4 is independently hydrogen, methyl or optionally substituted phenyl.

[0172] Element 14: R 3 and R 4 are not linked together to form an optionally substituted 6-membered aromatic ring.

[0173] Factor 15: R 3 and R 4 are joined together to form an optionally substituted 6-membered aromatic ring, and R 5 It is C 1 -C 10 Alkyl or C 6 -C 30 Aryl.

[0174] Factor 16: R 5 is tert-butyl or optionally substituted phenyl.

[0175] Element 17: wherein the at least one activator comprises an alumoxane, a non-coordinating anion, or any combination thereof.

[0176] As non-limiting examples, exemplary combinations suitable for A, B, and C include, but are not limited to: 1 and 2 or 3; 1, 2 or 3 and 4; 1 and 6; 1, 2 or 3 and 7; 1, 2 or 3 and 8; 1, 2 or 3 and 8; 1, 2 or 3, 5, and 8; 1 and 9; 1, 7 and 9; 1, 4, 7 and 9; 1, 4 and 10; 1, 7 and 11; 1, 4, 7 and 11; 1, 7 and 12; 1, 4, 7 and 12; 1, 7, 9 and 12 or 13; 1, 7 and 14; 1, 4, 7 and 14; 1, 7 and 15 or 16; 1, 4, 7 and 15 or 16; 2 or 3, and 4 or 5; 2 or 3 and 7; 2 or 3 and 8; 2 or 3 and 9; 2 or 3 and 4; 2 or 3, 4 and 10; 2 or 3 and 11; 2 or 3, 4 and 11; 2 or 3, and 12 or 13; 2 or 3, 4 and 12 or 13; 2 or 3 and 14; 2 or 3, 4 and 14; 2 or 3 and 15; 2 or 3, 4 and 15; 4 and 6; 4 and 7; 4 and 8; 4 and 9; 4 and 10; 4, 10 and 11; 4 and 11; 4 and 12 or 13; 4 and 14; 4 and 15; 7 and 9 or 10 ; 7, 9 or 10 and 11; 7 and 12 or 13; 7 and 9, 10 or 11 and 12 or 13; 7 and 14; 7 and 15; 9 and 10; 9 and 11; 9 and 12 or 13; 9, 11 and 12 or 13; 9 and 14; 9 and 15; 10 and 11; 10 and 12 or 13; 10, 11 and 12 or 13; 10 and 14; and 10 and 15. Any of the foregoing may further occur in combination with 16. As for B, any of the foregoing may further occur in combination with 17.

[0177] The present disclosure further relates to the following non-limiting clauses:

[0178] Item 1. A metal-ligand complex comprising a transition metal atom or a lanthanide metal atom and a ligand having a structure represented by Formula 1 in: R 1 and R 2 are independently hydrogen or C 1 -C 14 Hydrocarbon; R 3 and R 4 are independently hydrogen or C 1 -C 14 Hydrocarbyl, or R 3 and R 4 joined together to form an optionally substituted 6-membered aromatic ring; R 5 It is hydrogen, C 1 -C 10 Alkyl, C 3 -C 10Cycloalkyl, C 6 -C 30 aryl, heteroaryl or CN, provided that if the transition metal atom is Ti or Zr and R 3 and R 4 are connected together to form a 6-membered aromatic ring, then R 5 It is C 3 -C 10 Cycloalkyl, C 6 -C 30 Aryl, heteroaryl or CN; R 6 and R 7 are independently hydrogen or C 1 -C 14 a hydrocarbon group; and Z is a bridging atom.

[0179] Item 2. The metal-ligand complex of Item 1, wherein the metal-ligand complex has a structure represented by Formula 1A in: M is a transition metal atom or a lanthanide metal atom; and X is independently a leaving group, or two X are linked and bonded to M to form a metal cyclize ring, a chelate ligand, a diene ligand, or an alkylidene group.

[0180] Item 3. The metal-ligand complex of Item 2, wherein each X independently comprises C 1 -C 20 A hydrocarbon group, a hydrogen group, an alkoxy group, a thiol group, a phosphorus group, a halide group, a diene group, an amine group, a phosphine group, an ether group or any combination thereof.

[0181] Item 4. The metal-ligand complex of Item 2 or Item 3, wherein each X is a dimethylamino group or a bis(dimethylsilylamino group).

[0182] Item 5. The metal-ligand complex of any one of Items 2-4, wherein M is a Group 4 transition metal, a lanthanide element, or chromium.

[0183] Item 6. The metal-ligand complex of any one of Items 2-5, wherein M is hafnium, chromium, neodymium or lanthanum.

[0184] Item 7. The metal-ligand complex of any one of Items 2-6, wherein the metal-ligand complex has a structure represented by one or more of Formulas 3-5,

[0185] Item 8. The metal-ligand complex of any one of Items 1 to 7, wherein Z is CH 2 .

[0186] Item 9. The metal-ligand complex of Item 1, further comprising: A solvent or a Lewis base complexed with the transition metal atom or lanthanide metal atom as a second ligand.

[0187] Item 10. The metal-ligand complex of any one of Items 1 to 9, wherein R 1 , R 2 , R 6 and R 7 are independently hydrogen, C 1 -C 10 Alkyl or C 6 -C 10 Aryl.

[0188] Item 11. The metal-ligand complex of any one of Items 1 to 10, wherein R 1 and R 2 is independently hydrogen, methyl or optionally substituted phenyl.

[0189] Item 12. The metal-ligand complex of any one of Items 1 to 11, wherein R 6 and R 7 All are H.

[0190] Item 13. The metal-ligand complex of any one of Items 1 to 12, wherein R 3 and R 4 are independently hydrogen, C 1 -C 10 Alkyl or C 6 -C 10 Aryl.

[0191] Item 14. The metal-ligand complex of any one of Items 1 to 13, wherein R 3 and R 4 is independently hydrogen, methyl or optionally substituted phenyl.

[0192] Item 15. The metal-ligand complex of any one of Items 1 to 14, wherein R 3 and R 4 are not linked together to form an optionally substituted 6-membered aromatic ring.

[0193] Item 16. The metal-ligand complex of any one of Items 1 to 12, wherein R 3 and R 4 are joined together to form an optionally substituted 6-membered aromatic ring, and R 5 It is C 1 -C 10 Alkyl or C 6 -C 30 Aryl.

[0194] Item 17. The metal-ligand complex of any one of Items 1 to 16, wherein R 5 is tert-butyl or optionally substituted phenyl.

[0195] Item 18. A catalyst system comprising: at least one activating agent; and A metal-ligand complex comprising a transition metal atom or a lanthanide metal atom and a ligand having a structure represented by Formula 1: in: R 1 and R 2 are independently hydrogen or C 1 -C 14 Hydrocarbon; R 3 and R 4 are independently hydrogen or C 1 -C 14 Hydrocarbyl, or R 3 and R 4 joined together to form an optionally substituted 6-membered aromatic ring; R 5 It is hydrogen, C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 30 aryl, heteroaryl or CN, provided that if the transition metal atom is Ti or Zr and R 3 and R 4 are connected together to form a 6-membered aromatic ring, then R 5 It is C 3 -C 10 Cycloalkyl, C 6 -C 30 Aryl, heteroaryl or CN; R 6 and R 7 are independently hydrogen or C 1 -C 14 a hydrocarbon group; and Z is a bridging atom.

[0196] Item 19. The catalyst system of Item 18, wherein the metal-ligand complex has a structure represented by Formula 1A, in: M is a transition metal atom or a lanthanide metal atom; and X is independently a leaving group, or two X are linked and bonded to M to form a metal cyclize ring, a chelate ligand, a diene ligand, or an alkylidene group.

[0197] Item 20. The catalyst system of Item 19, wherein each X independently comprises C 1 -C 20 A hydrocarbon group, a hydrogen group, an alkoxy group, a thiol group, a phosphorus group, a halide group, a diene group, an amine group, a phosphine group, an ether group or any combination thereof.

[0198] Item 21. The catalyst system of Item 19 or Item 20, wherein each X is dimethylamino or bis(dimethylsilylamino).

[0199] Item 22. The catalyst system of any one of Items 19-21, wherein M is a Group 4 transition metal, a lanthanide, or chromium.

[0200] Item 23. The catalyst system of any one of Items 19-22, wherein M is hafnium, chromium, neodymium, or lanthanum.

[0201] Item 24. The catalyst system of any one of Items 18-23, wherein Z is CH 2 .

[0202] Item 25. The catalyst system of any one of Items 18-24, wherein R 1 , R 2 , R 5 and R 6 are independently hydrogen, C 1 -C 10 Alkyl or C 6 -C 10 Aryl.

[0203] Item 26. The catalyst system of any one of Items 18-25, wherein R 3 and R 4 are independently hydrogen, C 1 -C 10 Alkyl or C 6 -C 10 Aryl.

[0204] Item 27. The catalyst system of any one of Items 18-26, wherein R 3 and R 4 are not linked together to form an optionally substituted 6-membered aromatic ring.

[0205] Item 28. The catalyst system of any one of Items 18-25, wherein R 3 and R 4 are joined together to form an optionally substituted 6-membered aromatic ring, and R 5 It is C 1 -C10 Alkyl or C 6 -C 30 Aryl.

[0206] Item 29. The catalyst system of any of Items 18-28, wherein the at least one activator comprises an alumoxane, a non-coordinating anion, or any combination thereof.

[0207] Item 30. A method comprising: providing an olefinic feed; and The catalyst system of any one of items 18 to 28 is contacted with an olefinic feed under polymerization conditions.

[0208] In order to facilitate a better understanding of the embodiments described herein, the following examples of various representative embodiments are given. The following examples should not be construed in any way to limit, or define the scope of the present disclosure. Specific implementation plan Example

[0209] Representative syntheses of ligands and metal-ligand complexes are as follows.Polymerization reactions using metal-ligand complexes are described in further detail below. Ligand synthesis

[0210] Example 1: 2-(tert-butyl)-5-{(tetracyclic [11.4.0.0 2,6 .0 7,12 Synthesis of heptadecan-1,3,6,8,10,12,14,16-octaen-3-yl)methyl}pyrrole (Formula 3) 1H-cyclopenta[l]phenanthrene (2.535 g) and 5-tert-butyl-1H-pyrrole-2-carbaldehyde (3.626 g) were dissolved in 1% KOH-ethanol (60 mL) and the mixture was heated at reflux for two days. The color of the reaction deepened, ranging from orange to red. The solvent was reduced and the reaction mixture was cooled to room temperature. The mixture was taken up in dichloromethane and washed with water and brine. The organic matter was collected and washed with MgSO 4 The solvent was removed and the residue was used in the next step without further purification. The compound was dissolved in 25 mL of tetrahydrofuran and cooled to -20 °C. Powdered LiAlH 4 (1.909 g), and the reaction was stirred overnight. In addition, the reaction was cooled to 0 °C and quenched with ice water. The mixture was extracted with diethyl ether (3 × 50 mL), and the combined organics were washed with water and brine, and then concentrated in MgSO 4The mixture was dried over medium and filtered. The solution was subjected to TLC in 10% EtOAc / Hex and showed good separation with some stationary material. After column chromatography (5-20% EtOAc / Hex), 2.15 g (37%) of the title compound ligand was collected.

[0211] Example 2: 2-(9-anthryl)-5-{(tetracyclic [11.4.0.0 2,6 .0 7,12 Synthesis of heptadecan-1,3,6,8,10,12,14,16-octaen-3-yl)methyl}pyrrole (Formula 4) Pyrrolidine (281 mg) was added to a cold 5 mL methanol solution of 5-(anthracen-9-yl)-1H-pyrrole-2-carboxaldehyde (535 mg) and 1H-cyclopenta[l]phenanthrene (426 mg). The solution was warmed to room temperature and stirred for 2.5 hours while slowly turning orange. The solution was cooled on ice and acetic acid was added at 0°C, followed by cold 10 mL DCM and 1 mL water. The solid was stirred at room temperature for 15 minutes. The organics were separated by dichloromethane extraction. The organic layer was separated and heated to 40°C in MgSO 4 The mixture was stirred on ice and filtered through Celite. The solvent was then removed. The remaining solid was stirred and washed with a minimum amount of hexane and diethyl ether to isolate the fulvene intermediate as a red powder. The compound was washed once more with ether and hexane and dried to obtain 800 mg of the fulvene intermediate. Using LiAlH 4 and 237 mg of the fulvene intermediate, which was reduced as described above for Formula 3 to give the title compound (164 mg).

[0212] Example 3: Synthesis of 2-(9-anthryl)-5-[(1H-inden-3-yl)methyl]pyrrole (Formula 5) The title compound was obtained in a similar manner as described for Formula 4 in Example 2, except that indene was used instead of 1H-cyclopenta[1]phenanthrene.

[0213] Example 4: Synthesis of 2-methyl-5-((4,5,6,7-tetramethyl-1H-inden-1-yl)methyl)-1H-pyrrole (Formula 6)

[0214] Pyrrolidine (281 mg) and acetic acid (599 mg) were added to a cold 5 mL methanol solution of 5-methyl-1H-pyrrole-2-carbaldehyde (535 mg) and 4,5,6,7-tetramethyl-1H-indene (426 mg). The solution was warmed to room temperature and stirred for 2.5 hours, during which the reaction mixture slowly turned orange. The solution was cooled on ice and acetic acid was added at 0°C, followed by 10 mL of cold dichloromethane and 1 mL of water. The resulting solid was stirred at room temperature for 15 minutes. The organic matter was separated by dichloromethane extraction and the dichloromethane extract was concentrated in MgSO 4 The solvent was removed and the remaining solid was stirred and washed with minimal hexanes and diethyl ether to isolate the fulvene intermediate as a red powder which was used without further purification.

[0215] The fulvene intermediate was dissolved in 25 mL of tetrahydrofuran and cooled to -20 °C. LiAlH 4 (0.567 g) was added as a powder to the reaction mixture, which was then stirred overnight. The reaction mixture was then cooled to 0 °C and quenched with ice water. The mixture was extracted with diethyl ether (3 × 50 mL). The combined organics were washed with water and brine and concentrated in MgSO 4 After removal of the solvent in vacuo, the title compound (267 mg) was obtained as an orange solid.

[0216] Example 5: Synthesis of 2-((2,3-diphenylcyclopenta-2,4-dien-1-yl)methyl)-5-methyl-1H-pyrrole (Formula 7) The title compound (267 mg) was obtained in a similar manner to that described for Formula 6 in Example 4, except that 2,3-diphenylcyclopenta-1,3-diene was used instead of 4,5,6,7-tetramethyl-1H-indene.

[0217] Example 6: Synthesis of 2-((1H-cyclopenta[a]naphth-1-yl)methyl)-5-methyl-1H-pyrrole (Formula 8) The title compound (594 mg) was obtained in a similar manner to that described for Formula 6 in Example 4, except 3H-cyclopenta[a]naphthalene was used instead of 4,5,6,7-tetramethyl-1H-indene.

[0218] Example 7: Synthesis of 2-((6,6-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)methyl)-5-methyl-1H-pyrrole (Formula 9) The title compound (593 mg) was obtained in a similar manner to that described for Formula 6 in Example 4, except 2,2-dimethyl-3,5-dihydro-1H-s-indacene was used instead of 4,5,6,7-tetramethyl-1H-indene. Synthesis of Metal-Ligand Complexes

[0219] Example 8: Synthesis of Formula 3-Ti The ligand (180 mg) of Example 1 and Ti(NMe 2 ) 4 (115 mg) was combined in 2 mL of toluene and stirred at 60°C for 16 hours. The solvent was removed and the remaining solid was suspended in 2 mL of pentane and collected by filtration to give 150 mg of a brick red powder in 60% yield. X-ray crystallography and 1 The product was characterized by H NMR spectroscopy. 1 H NMR (400 MHz, benzene-d 6 )δ8.60-8.47(m,1H),8.23-8.13(m,2H),7.93-7.85(m,1H),7.37-7.18(m,5H),6.79(d,J=3.3Hz,1H),6.34(s,2 H), 6.14 (d, J = 3.3Hz, 1H), 4.66 (d, J = 16.0Hz, 1H), 4.20 (d, J = 16.1Hz, 1H), 3.01 (s, 6H), 1.41 (d, J = 37.6Hz, 15H). Figure 1 The X-ray crystal structure of the metal-ligand complex having the formula 3-Ti is shown. Other bridged metal complexes have similar X-ray crystal structures.

[0220] Example 9: Synthesis of Formula 3-Zr The ligand (50 mg) of Example 1 and Zr(NMe 2 ) 4 (38 mg) was combined in 2 mL of toluene and stirred at 60°C for 16 hours. The solvent was removed and the remaining solid was washed with pentane until the washings were colorless. A white powder was quantitatively isolated and characterized by X-ray crystallography and 1 H NMR spectroscopy characterization. 1H NMR (400MHz, chloroform-d) δ8.52(q,J=5.5,3.2Hz,3H),8.22-8.15(m,1H),7.66-7.46(m,4H),7.16(d,J=3.3Hz,1H),6.67(d,J=3.5Hz,1H),6.15( d,J=3.0Hz,1H),6.00(d,J=3.1Hz,1H),4.81(d,J=16.4Hz,1H),4.45(d,J=16.4Hz,1H),3.03(s,5H),3.00(s,1H),1.18(d,J=20.9Hz,15H).

[0221] Example 10: Synthesis of Formula 3-Hf. The ligand (192 mg) of Example 1 and Hf(NMe 2 ) 4 (194 mg) were combined in 2 mL of toluene and stirred at 60°C for 16 hours. The solvent was removed and the remaining solid was washed with pentane until the washings were colorless. A white powder was isolated in 83% yield and characterized by X-ray crystallography and 1 H NMR spectroscopy characterization. 1 H NMR (400 MHz, benzene-d 6 )δ8.58(dd,J=8.1,1.4Hz,1H),8.26-8.17(m,2H),7.92-7.84(m,1H),7.33 -7.24(m,3H),7.28-7.12(m,3H),6.74(d,J=3.3Hz,1H),6.40(dd,J=3.1,1 .3Hz,1H),6.32(d,J=3.1Hz,1H),6.23(d,J=3.3Hz,1H),4.69(d,J=16.2Hz ,1H),4.27(dd,J=16.3,1.5Hz,1H),2.92(s,6H),1.33(d,J=38.4Hz,16H).

[0222] Example 11: Synthesis of Formula 4-Ti The ligand (181 mg) of Example 2 and Ti(NMe 2 ) 4 (86 mg) was combined in 2 mL THF and stirred at 60°C for 16 hours. The solvent was removed and the remaining solid was washed with 2 mL diethyl ether and 2 mL pentane and dried in vacuo to give a red powder (198 mg). X-ray crystallography and 1 The product was characterized by H NMR spectroscopy.1 H NMR (500MHz, chloroform-d) δ8.56 (dt, J=8.0, 1.9Hz, 2H), 8.47 (dd, J=8.0, 1.5Hz, 1H), 8.19-8.10 (m, 2H), 7.99 (dd, J=7.7, 1.7Hz, 1H),7.86(d,J=8.4Hz,1H),7.76-7.63(m,3H),7.47(dtd,J=17.4,7.2,1.5Hz,2H),7.36(ddd,J=8.2,6.6,1.3Hz,1H),7.2 9(ddd,J=8.0,6.6,1.4Hz,1H),7.20-7.14(m,1H),7.08(ddd,J=8.2,6.6,1.2Hz,1H),6.65(d,J=3.2Hz,1H),6.54-6.45(m ,2H),6.44(d,J=3.2Hz,1H),6.23(d,J=2.9Hz,1H),4.91(d,J=16.6Hz,1H),4.59-4.51(m,1H),2.60(s,6H),0.73(s,5H).

[0223] Example 12: Synthesis of Formula 4-Zr The ligand (108 mg) of Example 2 and Zr(NMe 2 ) 4 (61 mg) was combined in 2 mL of toluene and stirred at 60°C for 16 hours. An orange powder precipitated and the solvent was removed. The remaining solid was washed with 2 mL of diethyl ether and 2 mL of pentane and dried in vacuo to give an orange powder (150 mg). The results were obtained by X-ray crystallography and 1 The product was characterized by H NMR spectroscopy. 1H NMR (500MHz, chloroform-d) δ8.61-8.50(m,2H),8.51-8.41(m,1H),8.22(s,1H),7.99-7.92(m,2H),7.87(d,J=8.4Hz,1H), 7.73(td,J=8.4,3.9Hz,2H),7.64(ddd,J=8.4,7.1,1.4Hz,1H),7.44(tt,J=7.1,5.4Hz,2H),7.36(dd,J=8.5,6.7H z,2H),7.32-7.25(m,1H),7.14(ddd,J=8.1,6.6,1.2Hz,1H),6.81(d,J=3.3Hz,1H),6.78-6.66(m,2H),6.52(d,J= 2.8Hz, 1H), 6.30 (d, J = 2.9Hz, 1H), 4.91 (d, J = 16.7Hz, 1H), 4.61 (dd, J = 16.7, 1.4Hz, 1H), 2.32 (s, 6H), 0.59 (s, 6H).

[0224] Example 13: Synthesis of Formula 4-Hf The ligand (102 mg) of Example 2 and Hf(NMe 2 ) 4 (77 mg) was combined in 2 mL of toluene and stirred at 60°C for 16 hours. The solvent was removed. The remaining solid was washed with 2 mL of diethyl ether and 2 mL of pentane and dried in vacuo to give an orange powder (112 mg). X-ray crystallography and 1 The product was characterized by H NMR spectroscopy. 1H NMR (500 MHz, chloroform-d) δ 8.38-8.30 (m, 2H), 8.28-8.22 (m, 1H), 8.03 (s, 1H), 7.80-7.74 (m, 1H), 7.73-7.64 (m, 2H), 7.56 (d, J = 8.5 Hz, 1H), 7.55-7.47 (m, 1H), 7.43 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), 7.31-7.19 (m, 3H), 7.16 (ddd, J = 8.2, 6.5, 1. 3Hz,1H),7.13-7.06(m,1H),6.95(ddd,J=8.2,6.6,1.2Hz,1H),6.60-6.52(m,2H),6.47(d,J=3.2Hz,1H),6.36(d,J =2.8Hz, 1H), 6.08 (d, J = 3.0Hz, 1H), 4.76 (d, J = 16.8Hz, 1H), 4.44 (dd, J = 16.8, 1.4Hz, 1H), 2.07 (s, 6H), 0.46 (s, 5H).

[0225] Example 14: Synthesis of Formula 5-Ti The ligand of Example 3 and Ti(NMe 2 ) 4 Combine in 2 mL of toluene and stir at 60°C for 16 hours. Remove the solvent and wash the remaining solid with 2 mL of diethyl ether and 2 mL of pentane and dry in vacuo. The product was used without further characterization.

[0226] Example 15: Synthesis of Formula 5-Zr The ligand of Example 3 and Zr(NMe 2 ) 4 Combine in 2 mL of toluene and stir at 60°C for 16 hours. Remove the solvent and wash the remaining solid with 2 mL of diethyl ether and 2 mL of pentane and dry in vacuo. The product was used without further characterization.

[0227] Example 16: Synthesis of Formula 5-Hf The ligand of Example 3 and Hf(NMe 2 ) 4 Combine in 2 mL of toluene and stir at 60°C for 16 hours. Remove the solvent and wash the remaining solid with 2 mL of diethyl ether and 2 mL of pentane and dry in vacuo. The product was used without further characterization.

[0228] Example 17: Synthesis of Formula 3'-Nd The ligand of Example 1 and Nd[N(SiHMe 2 ) 2 ] 3 (THF) 2 Combine in 4 mL of toluene and stir at 60 °C for 16 h. Remove the solvent and extract the solid into 4 mL of Et 2 O, filtered through celite and dried to give 40 mg of orange powder with a yield of 40%. The structure was confirmed by X-ray crystal diffraction. Figure 2A and 2B An alternative view of the X-ray crystal structure of a metal-ligand complex having the formula 3'-Nd is shown.

[0229] Example 18: Synthesis of Formula 10-La The ligand of Example 1 and La[N(SiHMe 2 ) 2 ] 3 (THF) 2 Combine in 6 mL of toluene and stir at 60°C for 16 hours. Remove solvent and wash solid with pentane and dry. Confirm structure by X-ray crystallography. Figure 3A and 3B An alternative view of the X-ray crystal structure of a metal-ligand complex having the formula 10-La is shown. Polymerization Example

[0230] Solvents, polymer grade toluene and / or isohexane, were supplied by ExxonMobil Chemical Company and purified by passing through a series of columns: two 500 cm 3 The OxyClear tandem column is then filled with dry Two 500 cm molecular sieves (8-12 mesh; Aldrich Chemical Company) 3 Columns in series, and packed with dry Two 500 cm molecular sieves (8-12 mesh; Aldrich Chemical Company) 3 Series columns.

[0231] 1-Octene (98%) (Aldrich Chemical Company) was dried by stirring over Na-K alloy overnight and then filtered through basic alumina (Aldrich Chemical Company, Brockman Basic 1). Tri(n-octyl)aluminum (TNOA) was purchased from Aldrich Chemical Company or Akzo Nobel and used as received.

[0232] Polymerization grade ethylene was further purified by passing through a series of columns: 500 cm 3 Oxyclear cylinders are then filled with dry Molecular sieve (8-12 mesh; Aldrich Chemical Company) 500 cm 3 Column, and filled with dry Molecular sieve (8-12 mesh; Aldrich Chemical Company) 500 cm 3 column.

[0233] Polymer grade propylene was further purified by passing through a series of columns: 2,250 cm 3 Oxyclear cylinders, then filled with Molecular sieves (8-12 mesh; Aldrich Chemical Company) 2,250 cm 3 Column, then filled with Two 500 cm molecular sieves (8-12 mesh; Aldrich Chemical Company) were connected in series. 3 Column, 500 cm packed with Selexsorb CD (BASF) 3 Column, finally filled with Selexsorb COS (BASF) 500cm 3 column.

[0234] Methylaluminoxane (MAO) was purchased from Albemarle Corporation as 10 wt % in toluene. N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate was purchased from Albemarle Corporation. All complexes and activators were added to the reactor as dilute solutions in toluene. The concentrations of the solutions of activators, scavengers, and complexes added to the reactor were selected so that 40 microliters to 200 microliters of solution were added to the reactor to ensure accurate delivery.

[0235] Unless otherwise stated, polymerization was carried out under an inert atmosphere (N 2 ) in a drying oven using an autoclave equipped with an external heater for temperature control, a glass insert (the internal volume of the reactor is about C 2 and C 2 / C 8 Run = 23.5 mL; for C 3 Run = 22.5 mL), septum inlet, regulated supply of nitrogen, ethylene and propylene, and equipped with a disposable polyetheretherketone mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110°C or 115°C for 5 hours, then at 25°C for 5 hours.

[0236] Polymer characterization was performed according to the procedure given above. Ethylene polymerization or ethylene / 1-octene copolymerization and polymer characterization

[0237] The reactor is prepared as described above and then purged with ethylene. Toluene (solvent, unless otherwise stated), optional 1-octene and MAO (500 equivalents plus optional TIBAL-20 equivalents, specified in the table below) are added via a syringe at room temperature and atmospheric pressure in the amount specified in the table below. The reactor is then brought to process temperature (specified in the table below) and ethylene is added to the process pressure (135psig) while stirring. Then an optional scavenger solution (e.g., TNOA in isohexane) is added to the reactor via a syringe under process conditions. A toluene solution of the metal-ligand complex is added to the reactor via a syringe under process conditions. Ethylene is allowed to enter (via a solenoid valve controlled by a computer) autoclave during polymerization to maintain the reactor gauge pressure (+ / -2psi). The reactor temperature is monitored and typically maintained within + / -1°C. The reactor is heated to room temperature by adding approximately 50psi. 2 / Ar(5mol%O 2 ) gas mixture into the autoclave and hold for about 30 seconds to stop the polymerization. The polymerization is quenched after a predetermined cumulative amount of ethylene has been added or a maximum polymerization time of 30 minutes has been maintained. The reactor is cooled and vented. The polymer is isolated after removing the solvent in vacuo.

[0238] Analytical testing of various polymer samples was performed according to the disclosure provided above.

[0239] The polymerization conditions and characterization data for high throughput polymerization are summarized in Tables 2-14 below. Table 2 Table 3 Table 4 Table 5 Table 6 Table 7 Table 8 Table 9 Table 10 Table 11 Table 12 Formula 3'-Nd,70° Vinyl only 200 μL 1-octene entry Mw(g / mol) Mn(g / mol) 1 1,877,919 1,112,479

[0240] Based on the polymerization data obtained, the catalyst represented by formula 3-Zr showed the highest ethylene polymerization activity. The Mw values ​​produced by the catalyst represented by formula 3-Zr were the highest at a polymerization temperature of 70°C and decreased at higher temperatures, but there was no significant loss in activity or comonomer incorporation ability. Under the screening conditions with MAO, the catalyst represented by formula 3-Hf produced higher Mw values ​​than the catalysts represented by formula 3-Ti and formula 3-Zr. When TIBAL pre-alkylation was performed, the catalyst represented by formula 3-Ti produced a higher Mw. Under these conditions, comonomer incorporation was also slightly higher compared to the other catalysts. Isoprene polymerization

[0241] At room temperature, triisobutylaluminum (185 mg) was added to a 1 mL toluene solution of the metal-ligand complex (65 mg). The solution was stirred for 3 minutes and triphenylcarbon tetrakis(pentafluorophenyl)borate was added all at once. (86 mg). After stirring at room temperature for 10 minutes, 2 g of isoprene was added and the solution was allowed to stand at room temperature for 16 hours. The solvent was removed from the viscous mixture, and the solid was then suspended in 10 mL of a mixture of diethyl ether and methanol (1:1) and stirred for 30 minutes. The liquid was then decanted from the precipitated polymer, and the polymer was dried in a vacuum oven for 2 hours. NMR analysis almost indicated that it was mainly cis-1,4 isoprene units. The monomer distribution in the polymer product is shown in Table 13 below. GPC analysis showed that Mw was 151,153 g / mol and Mn was 4,286 g / mol. Table 13 Monomer type Mole % cis-1,4-isoprene 65.8 trans-1,4-isoprene 4.6 1,2-Isoprene 8.6 3,4-Isoprene 21.1

[0242] All documents described herein, including any priority documents and / or test procedures, are incorporated herein by reference in all jurisdictions not inconsistent with this document. It is apparent from the above overview and specific embodiments that, although the form of the present disclosure has been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Therefore, it is not desired that the present disclosure be limited in this manner. For example, the compositions described herein may not contain any component, or composition, that is not specifically listed or disclosed herein. Any method may lack any step that is not listed or disclosed herein. Similarly, the term "comprising" is considered to be synonymous with the term "including". Whenever a method, composition, element, or group of elements is preceded by the transitional term "comprising", it should be understood that the same composition or group of elements in which the transitional phrase "essentially consisting of", "consisting of", "selected from" or "is" in front of the listed composition, element, or each element is also considered, and vice versa.

[0243] Unless otherwise indicated, all numerical values ​​used in the specification and appended claims to express quantities of ingredients, properties such as molecular weight, reaction conditions, and the like are to be understood in all instances as modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties sought to be achieved by one or more embodiments described herein. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0244] Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is explicitly disclosed. In particular, each range of values ​​disclosed herein (in the form of "from about a to about b" or equivalently "from approximately a to b" or equivalently "from approximately ab") should be understood to list each number and range covered in the wider range of numerical values. In addition, the terms in the claims have their ordinary normal meaning unless otherwise clearly and clearly defined by the patentee. In addition, the indefinite article "a" or "an" used in the claims is defined herein to represent one or more of the elements it introduces.

[0245] One or more illustrative embodiments are provided here. For the sake of clarity, all features of physical implementation are not described or shown in this application. It should be understood that in the development of the physical implementation scheme incorporating the present disclosure, many execution-specific decisions must be made to achieve the developer's goal, such as complying with system-related, business-related, government-related and other constraints, which depend on implementation and change from time to time. Although the efforts of the developers may be time-consuming, this effort remains a routine task for those of ordinary skill in the art, and benefits from the present disclosure.

[0246] Therefore, the present disclosure is well adapted to obtain the objects and advantages mentioned, as well as those inherent therein. The particular embodiments disclosed above are illustrative only, as the present disclosure may be modified and practiced in different but equivalent ways apparent to one of ordinary skill in the art having the benefit of the teachings herein. In addition, except as described in the claims below, there is no intention to limit the details of construction or design shown herein. Therefore, it is apparent that the particular illustrative embodiments disclosed above may be changed, combined or modified, and all such variations are considered to be within the scope and spirit of the present disclosure. The embodiments illustratively disclosed herein may be appropriately practiced in the absence of any elements not specifically disclosed herein and / or any optional elements disclosed herein.

Claims

1. A metal-ligand complex comprising a transition metal atom or a lanthanide metal atom and a ligand having a structure represented by Formula 1: in: R 1 and R 2 are independently hydrogen or C1-C 14 Hydrocarbon; R 3 and R 4 are independently hydrogen or C1-C 14 Hydrocarbyl, or R 3 and R 4 joined together to form an optionally substituted 6-membered aromatic ring; R 5 is hydrogen, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 30 aryl, heteroaryl or CN, provided that if the transition metal atom is Ti or Zr and R 3 and R 4 are connected together to form a 6-membered aromatic ring, then R 5 It is C3-C 10 Cycloalkyl, C6-C 30 aryl, heteroaryl or CN, or if the transition metal atom is Ti or Zr and R 1 -R 4 All are H, then R 5 It is C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 30 Aryl, heteroaryl or CN; R 6 and R 7 are independently hydrogen or C1-C 14 a hydrocarbon group; and Z is a bridging atom.

2. The metal-ligand complex of claim 1, wherein the metal-ligand complex has a structure represented by Formula 1A: in: M is a transition metal atom or a lanthanide metal atom; and X is independently a leaving group, or two X are linked and bonded to M to form a metal cyclize ring, a chelate ligand, a diene ligand, or an alkylidene group.

3. The metal-ligand complex of claim 2, wherein each X independently comprises C1-C 20 A hydrocarbon group, a hydrogen group, an alkoxy group, a thiol group, a phosphorus group, a halide group, a diene group, an amine group, a phosphine group, an ether group or any combination thereof.

4. The metal-ligand complex of claim 2, wherein each X is dimethylamino or bis(dimethylsilylamino).

5. The metal-ligand complex of claim 2, wherein M is a Group 4 transition metal, a lanthanide element, or chromium.

6. The metal-ligand complex of claim 2, wherein M is hafnium, chromium, neodymium or lanthanum.

7. The metal-ligand complex of claim 1, wherein the metal-ligand complex has a structure represented by one or more of Formulas 3-5:

8. The metal-ligand complex of claim 1, wherein Z is CH2.

9. The metal-ligand complex of claim 1, further comprising: A solvent or a Lewis base complexed with the transition metal atom or lanthanide metal atom as a second ligand.

10. The metal-ligand complex of claim 1, wherein R 1 , R 2 , R 6 and R 7 are independently hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl.

11. The metal-ligand complex of claim 1, wherein R 1 and R 2 is independently hydrogen, methyl or optionally substituted phenyl.

12. The metal-ligand complex of claim 1, wherein R 6 and R 7 All are H.

13. The metal-ligand complex of claim 1, wherein R 3 and R 4 are independently hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl.

14. The metal-ligand complex of claim 1, wherein R 3 and R 4 is independently hydrogen, methyl or optionally substituted phenyl.

15. The metal-ligand complex of claim 1, wherein R 3 and R 4 are not linked together to form an optionally substituted 6-membered aromatic ring.

16. The metal-ligand complex of claim 1, wherein R 3 and R 4 are joined together to form an optionally substituted 6-membered aromatic ring, and R 5 It is C1-C 10 Alkyl or C6-C 30 Aryl.

17. The metal-ligand complex of claim 1, wherein R 5 is tert-butyl or optionally substituted phenyl.

18. A catalyst system comprising: at least one activating agent; and A metal-ligand complex comprising a transition metal atom or a lanthanide metal atom and a ligand having a structure represented by Formula 1: in: R 1 and R 2 are independently hydrogen or C1-C 14 Hydrocarbon; R 3 and R 4 are independently hydrogen or C1-C 14 Hydrocarbyl, or R 3 and R 4 joined together to form an optionally substituted 6-membered aromatic ring; R 5 is hydrogen, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 30 aryl, heteroaryl or CN, provided that if the transition metal atom is Ti or Zr and R 3 and R 4 are connected together to form a 6-membered aromatic ring, then R 5 It is C3-C 10 Cycloalkyl, C6-C 30 aryl, heteroaryl or CN, or if the transition metal atom is Ti or Zr and R 1 -R 4 All are H, then R 5 It is C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 30 Aryl, heteroaryl or CN; R 6 and R 7 are independently hydrogen or C1-C 14 a hydrocarbon group; and Z is a bridging atom.

19. The catalyst system of claim 18, wherein the metal-ligand complex has a structure represented by Formula 1A: in: M is a transition metal atom or a lanthanide metal atom; and X is independently a leaving group, or two X are linked and bonded to M to form a metal cyclize ring, a chelate ligand, a diene ligand, or an alkylidene group.

20. The catalyst system of claim 19, wherein each X independently comprises C1-C 20 A hydrocarbon group, a hydrogen group, an alkoxy group, a thiol group, a phosphorus group, a halide group, a diene group, an amine group, a phosphine group, an ether group or any combination thereof.

21. The catalyst system of claim 19, wherein each X is dimethylamino or bis(dimethylsilylamino).

22. The catalyst system of claim 19, wherein M is a Group 4 transition metal, a lanthanide, or chromium.

23. The catalyst system of claim 19, wherein M is hafnium, chromium, neodymium or lanthanum.

24. The catalyst system of claim 18, wherein Z is CH2.

25. The catalyst system of claim 18, wherein R 1 , R 2 , R 6 and R 7 are independently hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl.

26. The catalyst system of claim 18, wherein R 3 and R 4 are independently hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl.

27. The catalyst system of claim 18, wherein R 3 and R 4 are not linked together to form an optionally substituted 6-membered aromatic ring.

28. The catalyst system of claim 18, wherein R 3 and R 4 are joined together to form an optionally substituted 6-membered aromatic ring, and R 5 It is C1-C 10 Alkyl or C6-C 30 Aryl.

29. The catalyst system of claim 18, wherein the at least one activator comprises an alumoxane, a non-coordinating anion, or any combination thereof.

30. A method comprising: providing an olefinic feed; and The catalyst system of claim 18 is contacted with the olefinic feed under polymerization conditions.

31. The method of claim 30, wherein the metal-ligand complex has a structure represented by Formula 1A: in: M is a transition metal atom or a lanthanide metal atom; and X is independently a leaving group, or two X are linked and bonded to M to form a metal cyclize ring, a chelate ligand, a diene ligand, or an alkylidene group.

Images