Process for recycling ethylene in an ethylene oligomerization reactor system

Abstract

A process for recycling ethylene from a reaction zone effluent stream from an oligomerization reaction zone, wherein the reaction zone effluent stream comprises an oligomer product effluent having at least 20 mass % octenes, comprising separating the reaction zone effluent stream into an effluent containing ethylene and less than 5 mass % C 4+ The first stream of olefins, containing butene and less than 10 mass % C 6+ The steps of preparing a second stream of olefins, a third stream containing at least 96% by mass of hexene and a fourth stream containing at least 96% by mass of octene. The first stream rich in ethylene is recycled to the oligomerization reaction zone, while the recycling of 1-butene and other butenes is significantly reduced.

Description

Technical Field

[0001] The present disclosure relates generally to ethylene oligomerization processes and downstream processes for recovering desired hexene and octene products, and more particularly to processes wherein the amount of ethylene in an ethylene recycle stream is increased while the amount of butenes, such as 1-butene, in the ethylene recycle stream is decreased. Background Art

[0002] Chromium-based catalyst systems are generally used for the continuous oligomerization of ethylene in the reaction zone to produce hexene and / or octene.Usually, it is desirable that unreacted ethylene is recycled to the reaction zone.However, if some oligomerization byproducts are recycled together with ethylene, the productivity and / or the purity of the 1-hexene and / or 1-octene product of required separation can be reduced.Therefore, in the ethylene oligomerization method that ethylene is recycled, the purity of 1-hexene and / or 1-octene product and / or the output of 1-hexene and / or 1-octene are improved, and the recycling of reducing some undesirable byproducts of reaction simultaneously will be useful.Therefore, the present invention is directed to this purpose in general. Summary of the invention

[0003] This summary is provided to introduce selected concepts that are further described below in the detailed description in a simplified form. This summary is not intended to identify required or essential features of the claimed subject matter. This summary is also not intended to be used to limit the scope of the claimed subject matter.

[0004] Disclosed herein are methods for recycling ethylene from a reaction zone effluent stream from an oligomerization reaction zone, wherein the reaction zone effluent stream contains an oligomer product effluent containing at least 20 mass % octene. A first method may include a) separating the reaction zone effluent stream into a stream containing ethylene and less than or equal to 5 mass % C 4+ A second method may include: a) separating the reaction zone effluent stream into a first stream of olefins, a second stream comprising butenes and hexenes, and a third stream comprising at least 96 mass % octene; and b) recycling the first stream to the oligomerization reaction zone. A second method may include: a) separating the reaction zone effluent stream into a stream comprising ethylene and less than or equal to 5 mass % C 4+ The first stream of olefins, comprising butene and less than or equal to 10 mass % C 6+ a) recycling the first stream to the oligomerization reaction zone; b) recycling the first stream to the oligomerization reaction zone; and b) recycling the first stream to the oligomerization reaction zone.

[0005] Typically, in the first method, the second stream mainly contains butenes and hexenes. Typically, in the second method, the third stream mainly contains 1-hexene, and the fourth stream mainly contains 1-octene. In the first method and the second method, the first stream recycled to the oligomerization reaction zone can be mainly ethylene and less than or equal to 2 mass % butenes. In general, the amount of 1-butene in the oligomerization reaction zone can be significantly less than 1 mass %, such as less than or equal to 0.5 mass % or less than or equal to 0.2 mass %.

[0006] Both the foregoing summary of the invention and the following detailed description provide examples and are illustrative only. Therefore, the foregoing summary of the invention and the following detailed description should not be considered restrictive. In addition, in addition to the features or variations listed herein, other features or variations may also be provided. For example, certain aspects may be directed to various feature combinations and sub-combinations described in the detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The accompanying drawings, which are incorporated in and constitute a part of this disclosure, illustrate various aspects of the present invention. In the drawings:

[0008] Figure 1 An ethylene oligomerization reaction system consistent with one aspect of the present invention is shown.

[0009] Figure 2 An ethylene oligomerization reaction system consistent with another aspect of the invention is shown.

[0010] definition

[0011] In order to more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to the present disclosure. If a term is used in the present disclosure but is not specifically defined in this article, the definition in the 2nd edition (1997) of IUPAC Compendium of Chemical Terminology can be applied, as long as the definition does not conflict with any other disclosure or definition used herein, or any claim applying the definition is unclear or invalid. If any definition or usage provided by any file incorporated herein by reference conflicts with the definition or usage provided herein, then the definition or usage provided herein shall prevail.

[0012] Herein, the features of the subject matter may be described so that in a particular aspect and / or statement, a combination of different features may be envisioned. For each aspect, and / or statement, and / or feature disclosed herein, all combinations that do not adversely affect the systems, compositions, processes, and / or methods described herein are contemplated with or without explicit description of a particular combination. In addition, unless otherwise expressly stated, any aspect, and / or statement, and / or feature disclosed herein may be combined to describe the inventive process and system consistent with the present disclosure.

[0013] Unless otherwise stated, the terms "a", "an" and "the" are intended to include multiple alternatives, such as at least one. For example, unless otherwise stated, disclosure of "a compression stage" is intended to cover one or more than one compression stage.

[0014] Generally, element groups are indicated using the numbering scheme indicated in the version of the periodic table published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, element groups may be indicated using the common name assigned to the group; for example, alkali metals indicate Group 1 elements, alkaline earth metals indicate Group 2 elements, transition metals indicate Groups 3-12 elements, and halogens or halide ions indicate Group 17 elements.

[0015] For any particular compound or group disclosed herein, unless otherwise indicated, any name or structure presented is intended to encompass all conformational isomers, positional isomers, stereoisomers, and mixtures thereof that may result from a particular set of substituents. Unless otherwise indicated, the name or structure also encompasses all enantiomers, diastereomers, and other optical isomers, if any, in both enantiomeric and racemic forms, as well as mixtures of stereoisomers, as known to those skilled in the art. For example, a general reference to pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane; and a general reference to butyl includes n-butyl, sec-butyl, isobutyl, and tert-butyl.

[0016] Likewise, a general reference to hexene includes all straight or branched, acyclic or cyclic hydrocarbon compounds having six carbon atoms and one carbon-carbon double bond. Thus, hexene encompasses, for example, 1-hexene, 2-hexene, 3-hexene, neohexene, and cyclohexene. When it is indicated that a stream contains a certain amount of hexene, the amount represents the total amount of hexene present, whether just a single compound (e.g., 1-hexene) or a mixture of different compounds in any relative proportions. Similar explanations apply to butene and octene.

[0017] Chemical "groups" are described according to how the group is formally derived from a reference or "parent" compound, such as by the number of hydrogen atoms formally removed from the parent compound to produce the group, even if the group is not literally synthesized in this way. For example, an "alkyl" can be formally derived by removing one hydrogen atom from an alkane, while an "alkylene" can be formally derived by removing two hydrogen atoms from an alkane. In addition, more general terms can be used to cover various groups formally derived by removing any number ("one or more") of hydrogen atoms from a parent compound, which in this example can be described as an "alkane group", and it covers "alkyl", "alkylene", and the material has three or more hydrogen atoms removed from the alkane as the case may be. Throughout this article, the disclosure that a substituent, ligand or other chemical moiety can constitute a specific "group" means that when the group is used as described, the well-known chemical structure and bonding rules are followed. When a group is described as "derived from," "derived from," "formed from," or "formed from," these terms are used in a formal sense and are not intended to reflect any particular synthetic method or procedure, unless otherwise indicated or the context requires otherwise.

[0018] The term "organic alkyl" is used herein according to the definition specified by IUPAC: an organic substituent with one free valence on a carbon atom, regardless of the functional type. Similarly, "organoalkylene" refers to an organic alkyl derived by removing two hydrogen atoms from an organic compound, regardless of the functional type, the two hydrogen atoms coming from one carbon atom, or one hydrogen atom coming from each of two different carbon atoms. "Organic group" refers to a generalized group formed by removing one or more hydrogen atoms from a carbon atom of an organic compound. Therefore, "organic alkyl", "organoalkylene" and "organic group" can contain organic functional groups and / or atoms other than carbon and hydrogen, i.e., the organic group can also contain functional groups and / or atoms other than carbon and hydrogen. "Organic alkyl", "organoalkylene" or "organic group" can be aliphatic (including cyclic or acyclic, or straight or branched) or can be aromatic.

[0019] For the purposes of this application, the term "organoalkyl consisting of inert functional groups" or variants thereof refers to an organic alkyl group, wherein the organic functional groups and / or atoms other than carbon and hydrogen present in the functional group are limited to those functional groups and / or atoms other than carbon and hydrogen that are not complexed with metal compounds and / or inert under the process conditions defined herein. Therefore, the term "organoalkyl consisting of inert functional groups" or variants thereof further defines the specific organic alkyl groups that may be present in the organic alkyl group consisting of inert functional groups. In addition, the term "organoalkyl consisting of inert functional groups" may refer to the presence of one or more inert functional groups in the organic alkyl group. Similarly, "organoalkylene consisting of inert functional groups" refers to an organic group formed by removing two hydrogen atoms from one or two carbon atoms of an organic compound consisting of inert functional groups, while "organic group consisting of inert functional groups" refers to a generalized organic group consisting of inert functional groups formed by removing one or more hydrogen atoms from one or more carbon atoms of an organic compound consisting of inert functional groups.

[0020] For the purposes of this application, an "inert functional group" is a group that does not substantially interfere with the processes described herein, wherein the material having the inert functional group participates in and / or does not complex with the metal compound of the metal complex. The term "not complexing with the metal compound" can include groups that can complex with the metal compound, but in particular, the molecules described herein may not complex with the metal compound due to their positional relationship within the ligand. For example, although an ether group can complex with a metal compound, an ether group located in the para position of a substituted phenylphosphinyl group may be an inert functional group because a single metal compound cannot complex with the para ether group and N-terminal ether groups of the same metal complex molecule. 2 -phosphinyl amidino complex. Therefore, the inertness of a particular functional group is not only related to the inherent inability of the functional group to complex metal compounds, but also to the position of the functional group within the metal complex. Non-limiting examples of inert functional groups that do not substantially interfere with the processes described herein may include halogens (fluorine, chlorine, bromine and iodine), nitro, alkoxy groups (e.g., alkoxy and / or aryloxy, etc.), and / or sulfide groups, etc.

[0021] Whenever used in this specification and claims, the term "hydrocarbon" refers to a compound containing only carbon and hydrogen. Other identifiers can be used to indicate the presence of a specific group in a hydrocarbon (for example, a halogenated hydrocarbon indicates that one or more halogen atoms replace an equal number of hydrogen atoms in the hydrocarbon). The term "hydrocarbon group" is used herein according to the definition specified by IUPAC: a monovalent group formed by removing one hydrogen atom from a hydrocarbon. Similarly, "alkylene" refers to a group formed by removing two hydrogen atoms from a hydrocarbon (two hydrogen atoms from one carbon atom or one hydrogen atom from one of two different carbon atoms). Therefore, according to the terms used herein, "hydrocarbon" refers to a generalized group formed by removing one or more hydrogen atoms (necessary for a specific group) from a hydrocarbon. "Hydrocarbon group", "alkylene" and "hydrocarbon" can be acyclic or cyclic groups, and / or can be straight or branched. "Hydrocarbon group", "alkylene" and "hydrocarbon" can include rings, ring systems, aromatic rings and aromatic ring systems containing only carbon and hydrogen. "Alkyl group," "alkylene group," and "alkyl" include as members groups such as aryl, arylene, arene, alkyl, alkylene, alkane, cycloalkyl, cycloalkylene, cycloalkane, aralkyl, aralkylene, and aralkane groups.

[0022] Whenever used in this specification and claims, the term "alkane" refers to a saturated hydrocarbon compound. Other identifiers can be used to indicate the presence of a specific group in an alkane (e.g., a halogenated alkane indicates that one or more halogen atoms replace an equal number of hydrogen atoms in the alkane). The term "alkyl group" is used herein according to the definition specified by IUPAC: a monovalent group formed by removing one hydrogen atom from an alkane. Similarly, "alkylene" refers to a group formed by removing two hydrogen atoms (two hydrogen atoms from one carbon atom or one hydrogen atom from two different carbon atoms) from an alkane. "Alkane group" is a general term, which refers to a group formed by removing one or more hydrogen atoms (according to the needs of a specific group) from an alkane. Unless otherwise indicated, "alkyl group", "alkylene" and "alkane group" may be acyclic or cyclic groups, and / or may be linear or branched. Primary alkyl, secondary alkyl and tertiary alkyl are derived by removing hydrogen atoms from primary carbon atoms, secondary carbon atoms or tertiary carbon atoms of an alkane, respectively. A normal alkyl group can be derived by removing hydrogen atoms from the terminal carbon atoms of a linear alkane.

[0023] The term "substituted" when used to describe a compound or group, for example, when referring to a substituted analog of a particular compound or group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in the group, and is intended to be non-limiting. A group or groups may also be referred to herein as "unsubstituted," or referred to by equivalent terms such as "non-substituted," which refers to the original group in which a non-hydrogen moiety does not replace a hydrogen in the group. "Substituted" is intended to be non-limiting and includes inorganic or organic substituents.

[0024] Whenever used in this specification and claims, the term "olefin" refers to a hydrocarbon having at least one carbon-carbon double bond that is not part of an aromatic ring or aromatic ring system. Unless otherwise specifically provided, the term "olefin" includes aliphatic and aromatic, cyclic and acyclic and / or straight and branched hydrocarbons having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. Olefins having only one, only two, only three, etc. carbon-carbon double bonds can be identified by using the terms "single", "two", "three", etc. in the name of the olefin. Olefins can be further identified by the position of the carbon-carbon double bonds.

[0025] The term "reaction zone effluent" and its derivatives (e.g., oligomerization reaction zone effluent, trimerization reaction zone effluent, tetramerization reaction zone effluent, or trimerization and tetramerization reaction zone effluent) generally refers to all materials that leave the reaction zone through the reaction zone outlet / discharge port from which the reaction mixture is discharged, and may include reaction zone feed (e.g., olefins, catalyst system or catalyst system components, and / or solvent), and / or reaction products (e.g., oligomer products including oligomers and non-oligomers, trimer products including trimers and non-trimers, tetramer products including tetramers and non-tetramers, or trimer and tetramer products including trimers and tetramers and non-trimers and tetramers). The term "reaction zone effluent" and its derivatives may be limited to refer to certain portions by using additional limiting terms. For example, reaction zone effluent refers to all materials that leave the reaction zone through the reaction zone outlet / discharge port, while reaction zone oligomer product effluent refers only to the oligomer products within the reaction zone effluent.

[0026] Features provided as minimum values ​​within the present disclosure may alternatively be expressed as "at least" or "greater than or equal to" any recited minimum value of features disclosed herein. Features provided as maximum values ​​within the present disclosure may alternatively be expressed as "less than or equal to" or "lower than" any recited maximum value of features disclosed herein.

[0027] In the present disclosure, the general rules of organic nomenclature shall prevail. For example, when referring to a substituted compound or group, the reference to the substitution pattern is used to indicate that the indicated group is located at the indicated position and all other unindicated positions are hydrogen. For example, the reference to the phenyl substituted by 4- indicates that the non-hydrogen substituent is located at the 4th position and hydrogen is located at the 2nd, 3rd, 5th and 6th positions. The reference to the compound or group having a substitution in the position other than the indicated position can be referred to using some other alternative language. For example, the reference to the phenyl group containing a substituent at the 4th position refers to a group having a non-hydrogen substituent at the 4th position and having hydrogen or any non-hydrogen substituent at the 2nd, 3rd, 5th and 6th positions.

[0028] The terms "catalyst composition", "catalyst mixture", "catalyst system", etc. do not depend on the actual products or compositions produced by the contact or reaction of the initial components of the disclosed or claimed catalyst composition / mixture / system, the nature of the active catalytic sites, or the fate of the organoaluminum compound and the heteroatom ligand transition metal compound complex after combining these components. Thus, the terms "catalyst composition", "catalyst mixture", "catalyst system", etc. encompass the initial starting components of the composition as well as any products that may be produced by contacting these initial starting components. The terms "catalyst composition", "catalyst mixture", "catalyst system", etc. may be used interchangeably throughout this disclosure.

[0029] The term oligomer refers to products containing 2 to 20 monomer units. The terms "oligomer product" and "oligomer product effluent" include all oligomer products prepared by the "oligomerization" process, but do not include other non-oligomer components of the reaction zone effluent stream, such as unreacted monomer (ethylene), organic reaction medium and hydrogen, and other components.

[0030] The term "oligomerization" and its derivatives refer to a process that produces an oligomer product containing at least 20%, 35%, 50%, or 60% by weight of products containing 2 to 20 monomer units. In one example, an "oligomerization" process using ethylene as a monomer produces a product mixture containing at least 20%, 35%, 50%, or 60% by weight of oligomers having 4 to 40 carbon atoms.

[0031] The term "trimerization" and its derivatives refer to a method for producing a product mixture comprising at least 20 wt %, 35 wt %, 50 wt % or 60 wt % of a product comprising three and only three monomeric units. A "trimer" is a product comprising three and only three monomeric units. A "trimer product" includes all products prepared by a trimerization process, including trimers and products that are not trimers (e.g., dimers or tetramers, solid polymers). In an example, a "trimerization" process using ethylene as a monomer produces a product mixture comprising at least 20 wt %, 35 wt %, 50 wt % or 60 wt % hexene.

[0032] The term "tetramerization" and its derivatives refer to a method for producing a product mixture comprising at least 20 wt%, 35 wt%, 50 wt% or 60 wt% of a product comprising four and only four monomeric units. A "tetramer" is a product comprising four and only four monomeric units. A "tetramer product" includes all products prepared by a tetramerization process, including tetramers and products that are not tetramers (e.g., dimers or trimers, solid polymers). In an example, a "tetramerization" process using ethylene as a monomer produces a product mixture comprising at least 20 wt%, 35 wt%, 50 wt% or 60 wt% octenes.

[0033] The term "trimerization and tetramerization" and its derivatives refer to a process that produces a product mixture containing at least 20%, 35%, 50%, or 60% by weight of a product containing three and / or four and only three and / or four monomer units. "Trimerization and tetramerization products" include all products prepared by the "trimerization and tetramerization" process, including trimers, tetramers, and products that are not trimers and tetramers (e.g., dimers, solid polymers). In an example, the "trimerization and tetramerization" process using ethylene as a monomer produces a product mixture containing at least 20%, 35%, 50%, or 60% by weight of hexene and octene.

[0034] In this specification, the word "reactor" refers to a single piece of equipment, such as a container, in which a reaction occurs, but does not include any associated equipment outside the container, such as piping, pumps, etc. Examples of reactors include stirred tank reactors (e.g., continuous stirred tank reactors), plug flow reactors, or any other type of reactor. The term "reactor" can be qualified by using additional qualifying terms to refer to a more specific "reactor." For example, the use of the term "oligomerization reactor" indicates that the desired reaction within the reactor is an oligomerization reaction.

[0035] In this specification, the term "reaction zone" refers to a part of a reaction system in which all necessary reaction components and reaction conditions are present so that the reaction can occur at a desired rate. That is, the reaction zone begins at a place where necessary reaction components and reaction conditions are present to maintain the reaction within 25% of the average reaction rate, and the reaction system ends at a place where the conditions cannot maintain the reaction rate within 25% of the average reaction rate (based on the volume average of the reaction rate of the reaction zone). For example, with respect to an ethylene oligomerization process, the reaction zone begins at a point where there are enough ethylene and active catalyst systems to maintain the production of oligomer products at a desired rate under sufficient reaction conditions (e.g., temperature and / or pressure, etc.), and the reaction zone ends at a point where the catalyst system is deactivated, there is not enough ethylene to maintain the production of oligomer products or other reaction conditions (e.g., temperature and / or pressure, etc.) that are not sufficient to maintain the production of oligomer products or the desired oligomer product production rate. In this specification, a "reaction zone" may include one or more reactors. The term "reaction zone" may be defined by using additional limiting terms to refer to a more specific "reaction zone". For example, use of the term "oligomerization reaction zone" indicates that the desired reaction within the "reaction zone" is an oligomerization reaction.

[0036] The term "reaction system" refers to all equipment for producing a product. The term "reaction system" includes reactors, reaction zones, and all associated equipment, associated process lines, and control equipment that can bring necessary components into and out of the reaction system and control the reaction. In this specification, a "reaction system" may include one or more reaction zones, one or more reactors, and associated equipment for producing a product. The term "reaction system" may be qualified by using additional qualifying terms to refer to a more specific "reaction system." For example, the use of the term "oligomerization reaction system" indicates that the "reaction system" involves an oligomerization reaction.

[0037] Catalyst system productivity is defined herein as kilograms of normal alpha olefin product produced per gram of transition metal (or chromium) of heteroatom ligand transition metal compound complex (or chromium compound) used in the catalyst system per hour - kg NAO / g transition metal / hour (or kg NAO / g Cr / hr).

[0038] Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, typical methods and materials are described herein.

[0039] All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which might be used in connection with the presently described invention. DETAILED DESCRIPTION

[0040] Disclosed herein are processes for recycling ethylene from a reaction zone effluent stream from an oligomerization reaction zone, wherein the effluent stream comprises an oligomer product effluent containing at least 20 mass %, and typically at least 40 mass % octenes. In these processes, in addition to the octenes product stream, a hexene product stream may be separated and an ethylene-rich stream formed and subsequently recycled to the oligomerization reaction zone.

[0041] Advantageously, the disclosed process increases the amount of ethylene in the ethylene recycle stream while reducing the amount of butenes such as 1-butene recycled to the oligomerization reaction zone. The presence of 1-butene and other butenes in the oligomerization reaction zone may result in a large amount of by-product octenes (such as branched octenes) instead of the desired 1-octene product, thereby greatly reducing the purity of 1-octene in the octene product stream.

[0042] Recycling ethylene in oligomerization reactor systems

[0043] Aspects of the invention relate to methods for recovering and recycling ethylene in an oligomerization reactor system. In some aspects, these methods for recovering and recycling ethylene in an oligomerization reaction system are performed to reduce C 4+ A first representative method for recycling ethylene from a reaction zone effluent stream from an oligomerization reaction zone, wherein the reaction zone effluent stream contains an oligomer product effluent comprising at least 20 mass % octene, can include a) separating the reaction zone effluent stream into a stream comprising ethylene and less than or equal to 5 mass % C 4+ a) recycling the first stream to the oligomerization reaction zone. Typically, the characteristics of the first process for recovering ethylene (e.g., the amount of octenes in the oligomer product effluent, the amount of ethylene and C in the first stream) are as follows: 4+ The present invention relates to a method for recycling ethylene from a reaction zone effluent stream from an oligomerization reaction zone, wherein the reaction zone effluent stream contains an oligomer product effluent containing at least 20 mass % octene, and a method for separating the effluent stream into respective streams, and the like) are described independently herein, and these features may be combined without limitation and in any combination to further describe the disclosed method for recycling ethylene. A second representative method for recycling ethylene from a reaction zone effluent stream from an oligomerization reaction zone, wherein the reaction zone effluent stream contains an oligomer product effluent containing at least 20 mass % octene, can include a) separating the reaction zone effluent stream into a stream containing ethylene and less than or equal to 5 mass % C 4+ The first stream of olefins, comprising butene and less than or equal to 10 mass % C 6+a) recycling the first stream to the oligomerization reaction zone. Typically, the characteristics of the second process for recovering ethylene (e.g., the amount of octenes in the oligomer product effluent, the amount of ethylene and C in the first stream) are as follows: 4+ The amount of olefins, butenes and C 6+ The amount of olefins, the amount of hexene in the third stream, the amount of octene in the fourth stream, and the technology for separating the effluent stream into corresponding streams, etc.) are described independently in this article, and these features can be combined without restriction and in any combination to further describe the disclosed method for recycling ethylene. In addition, unless otherwise indicated, additional processing steps can be carried out before, during and / or after the step of these methods, and can be used without restriction and in any combination to further describe the method for reclaiming ethylene. In addition, and advantageously, the method for reclaiming ethylene can be carried out continuously.

[0044] In the disclosed method, the amount of octenes in the oligomer product effluent can generally fall within the range of 20 to 99 mass % based on the total amount of oligomers in the oligomer product effluent. On the one hand, the minimum amount of octenes in the oligomer product effluent can be 20,30 or 40 mass %. On the other hand, the maximum amount of octenes in the oligomer product effluent can be 99,95,92.5,90,87.5 or 85 mass %. Typically, the amount of octenes in the oligomer product effluent can be in the range of any minimum amount of octenes in the oligomer product effluent described herein to any maximum amount of octenes in the oligomer product effluent. For example, the amount of octene can be 20 to 99 mass%, 30 to 95 mass%, 40 to 95 mass%, 40 to 90 mass%, 20 to 90 mass%, 30 to 87.5 mass%, 30 to 85 mass%, 40 to 87.5 mass%, 40 to 85 mass%, 20 to 60 mass%, 30 to 55 mass%, or 40 to 55 mass% octene based on the total mass of oligomers in the oligomer product effluent. Other suitable amounts of octene in the oligomer product effluent will be apparent from this disclosure.

[0045] In addition to octenes, the oligomer product effluent can also include any suitable amount of hexene.On the one hand, the minimum amount of hexene in the oligomer product effluent can be 5,10,15,20,25,30 or 35 mass %.On the other hand, the maximum amount of hexene in the oligomer product effluent can be 75,65,60,55 or 50 mass %.Usually, the amount of hexene in the oligomer product effluent can be in the scope of any maximum amount of hexene in any minimum amount of hexene in the oligomer product effluent as described herein to the oligomer product effluent.For example, the amount of hexene can be 5 to 75 mass %, 10 to 75 mass %, 15 to 75 mass %, 20 to 60 mass %, 25 to 55 mass %, 30 to 50 mass %, 35 to 65 mass % or 35 to 50 mass % hexene based on the total mass of oligomers in the oligomer product effluent.Other suitable amounts of hexene in the oligomer product effluent are apparent from the disclosure.

[0046] In addition to the oligomer product effluent (which contains octenes and / or hexenes), the reaction zone effluent stream may also contain the catalyst system, unreacted ethylene, other oligomer product olefins (e.g., butenes and / or C 10+ Olefins), hydrogen and organic reaction medium. In some aspects, the catalyst system can be deactivated in any typical manner, such as by contacting the reaction zone effluent stream with a suitable catalyst system deactivator. When the catalyst system is deactivated, the catalyst system can be deactivated at any point in the reaction zone effluent stream processing and / or product recovery processing, which is conducive to deactivating the catalyst system. As used herein, the reaction zone effluent stream (or reaction zone effluent) refers to a general reaction effluent stream, regardless of whether the reaction zone effluent or its subsequent stream has been processed to deactivate the catalyst system.

[0047] In step a) of the first method for recovering ethylene, the reaction zone effluent stream (which contains an oligomer product effluent containing at least 20 mass % octene) can be separated into a first stream, a second stream, and a third stream. In step a) of the second method for recovering ethylene, the reaction zone effluent stream (which contains an oligomer product effluent containing at least 20 mass % octene) can be separated into a first stream, a second stream, a third stream, and a fourth stream. Now referring to the first stream of the first method and the second method, the first stream can contain ethylene and less than or equal to 5 mass % C 4+Olefins.Because the first stream is recycled in the oligomerization reaction zone in step b), the overwhelming majority of the first stream is ethylene, and the amount of ethylene usually exceeds 85% by mass of the first stream. In some aspects, the first stream can include at least 85, at least 86, at least 87, at least 88, at least 89 or at least 90% by mass ethylene, and usually at most 99, 97, 95 or 92.5% by mass ethylene. The amount of ethylene in the first stream can be in the range of any minimum ethylene content as described herein to any maximum ethylene content. The illustrative and non-limiting range of the amount of ethylene in the first stream can include 85 to 99% by mass, 85 to 95% by mass, 87 to 97% by mass, 88 to 92.5% by mass, 90 to 99% by mass, 90 to 97% by mass or 90 to 95% by mass ethylene. Other suitable amounts of ethylene in the first stream are apparent from the present disclosure.

[0048] The first stream of the first and second methods may also contain up to 5 mass % C 4+ Olefins, including C4 olefins, C6 olefins, C8 olefins, etc. In the disclosed method for recycling ethylene, any C 4+ The amount of olefins is reduced, and therefore, the C 4+ The total amount of olefins may generally be less than or equal to 4 mass %; alternatively, less than or equal to 3 mass %; alternatively, less than or equal to 2 mass %; or alternatively, less than or equal to 1 mass %C 4+ Olefins.

[0049] In addition to reducing the C 4+ In addition to the amount of olefins, the amount of butenes is also particularly reduced. The presence of butenes (e.g., 1-butene) in the reaction zone may result in the undesirable reaction of C8 producing except 1-octene. Therefore, consistent with the present invention, on the one hand, the amount of butenes in the first stream can be less than or equal to 2 mass % or less than or equal to 1.5 mass %, and on the other hand, the amount of butenes in the first stream can be less than or equal to 1 mass % or less than or equal to 0.75 mass %, and on the other hand, the amount of butenes in the first stream can be less than or equal to 0.5 mass %, less than or equal to 0.35 mass % or less than or equal to 0.2 mass %.

[0050] In other words, the increase in ethylene and the reduction in 1-butene and other butenes in the first stream can be characterized by a mass ratio of ethylene:butene of at least 100:1, 150:1, 200:1, 300:1, or 350:1, and typically up to a maximum mass ratio of 5000:1, 1500:1, 1000:1, or 500:1. Illustrative and non-limiting ranges of the mass ratio of ethylene:butene in the first stream (and recycled to the oligomerization reaction zone) can include 100:1 to 5000:1, 100:1 to 500:1, 150:1 to 1500:1, 200:1 to 500:1, 300:1 to 1500:1, 350:1 to 5000:1, 350:1 to 1000:1, or 350:1 to 500:1. Other suitable mass ratios of ethylene:butene in the first stream will be apparent from this disclosure.

[0051] In addition or alternatively, reducing butenes while increasing the ethylene recycled to the oligomerization reaction zone can cause the level of butenes in the reaction zone to be very low. On the one hand, the minimum amount of butenes in the reaction zone can be 0.01, 0.02, 0.035, 0.05 or 0.1 mass %. On the other hand, the maximum amount of butenes in the reaction zone can be 1, 0.75, 0.5, 0.35, 0.25 or 0.2 mass %. Usually, the amount of butenes in the reaction zone can be in the range of any minimum amount of butenes as described herein to any maximum amount of butenes. For example, the amount of butenes in the reaction zone can be 0.01 to 0.75 mass %, 0.02 to 0.5 mass %, 0.05 to 0.35 mass % or 0.1 to 0.2 mass % butenes. Other suitable amounts of butenes in the oligomerization reaction zone are apparent from the disclosure.

[0052] Certain light compounds can be separated from the reaction zone effluent stream and eventually become part of the first stream. Non-limiting examples of these light compounds can include hydrogen (H2) and methane. Although not limited thereto, the first stream can contain less than or equal to 5, 4, 3, 2 or 1 mass % hydrogen; additionally or alternatively, less than or equal to 5, 4, 3, 2 or 1 mass % methane. In some aspects, the first stream can contain (total) less than or equal to 5, 4, 3, 2 or 1 mass % hydrogen and methane.

[0053] Referring now to the second stream of the first process separated from the reaction zone effluent stream, the second stream of the first process may comprise butenes and hexenes and less than or equal to 10 mass % C 8+ Olefins (including C8 olefins, C 10Olefins, etc.). In aspects of the present invention, the second stream of the first method can be a non-product stream, for example, the second stream of the first method can be a heavy purge stream in which effluent butenes and hexenes (particularly butenes) are accumulated so that they are not recycled to the oligomerization reaction zone together with ethylene. This is illustrated by the second stream of the first method, which contains more butenes than the butenes present in the first stream of the first method by mass. In some aspects, by mass, the butenes that the second stream of the first method can contain are at least twice (2x) of the butenes in the first stream of the first method, or at least three times (3x) of the butenes in the first stream of the first method, and generally the butene amount that the second stream of the first method can contain is 5 times or 10 times of the butene amount present in the first stream of the first method.

[0054] Since some C 8+ Olefin products such as 1-octene are desired, so any C 8+ Amount of olefins. Up to 10 mass % C in the second stream of the first process 8+ Olefins are standard. In one aspect, any C 8+ The amount of olefin may be less than or equal to 8, 6, 5, 4, 3 or 2 mass %.

[0055] In the second stream of the first method, the amount of butene and hexene can generally fall within the range of 1 to 50 mass %, but is not limited thereto. On the one hand, the minimum amount of butene and hexene can be 1,2,3,4 or 5 mass % in the second stream of the first method. On the other hand, the maximum amount of butene and hexene can be 50,40,35,30,25,20,18,15 or 12 mass % in the second stream of the first method. Usually, the amount of butene and hexene (based on the total mass of the second stream) in the second stream of the first method can be in the range of any minimum amount of butene and hexene as described herein to any maximum amount of butene and hexene. For example, the amount of butene and hexene can be 1 to 50 mass %, 1 to 40 mass %, 2 to 35 mass %, 2 to 30 mass % or 3 to 25 mass % butene and hexene in the second stream of the first method. Other suitable amounts of butene (for example, 1-butene) in the second stream of the first method are apparent from the present disclosure. The second stream of the first process may also contain ethylene and ethane in addition to butene and hexene, and / or C 8+ In the second stream of the first method, the amount of ethylene and ethane can be in the range of 40 to 90 mass %, 50 to 87.5 mass % or 60 to 85 mass %. In the second stream of the first method, C 8+ The amount of olefin may be less than or equal to 10, 8, 7, 6, 5, 4, or 3 mass %.

[0056] Referring now to the second stream of the second process separated from the reaction zone effluent stream, the second stream of the second process may comprise butenes and less than or equal to 10 mass % C 6+ Olefins (including C6 olefins, C8 olefins, C 10 Olefins, etc.). In aspects of the present invention, the second stream of the second method can be a non-product stream, for example, the second stream of the second method can be a purge stream of effluent 1-butene and other butene heavy gases, so that they are not recycled to the oligomerization reaction zone together with ethylene. This is illustrated by the second stream of the second method, and the second stream contains more butenes than the butenes present in the first stream of the second method by mass. In some aspects, the butenes that the second stream of the second method can contain are at least twice (2x) of the butenes in the first stream of the second method by mass, or at least three times (3x) of the butenes in the first stream of the second method, and usually the second stream of the second method can contain the butene amount of at most 5x or 10x present in the first stream of the second method.

[0057] Since some C 6+ Olefin products such as 1-hexene and 1-octene are desired in the second process, so any C 6+ Amount of olefins. Up to 10 mass % C in the second stream of the second process 6+ Olefins are standard, but more often any C 6+ The amount of olefins can be less than or equal to 8 mass % in one aspect, less than or equal to 7 mass % in another aspect, less than or equal to 6 mass % in yet another aspect, or less than or equal to 5 mass % in another aspect. 6+ Olefins.

[0058] In the second stream of the second method, the amount of butene can generally fall within the range of 1 to 25 mass %, but is not limited thereto. On the one hand, the minimum amount of butene in the second stream of the second method can be 1, 2, 3, 4 or 5 mass %. On the other hand, the maximum amount of butene in the second stream of the second method can be 25, 20, 18, 15 or 12 mass %. Typically, the amount of butene in the second stream (based on the total mass of the second stream of the second method) can be within the range of any minimum amount of butene as described herein to any maximum amount of butene. For example, the amount of butene in the second stream of the second method can be 1 to 25 mass %, 1 to 12 mass %, 2 to 20 mass %, 2 to 18 mass %, 3 to 25 mass %, 4 to 15 mass % or 5 to 12 mass % butene. Other suitable amounts of butene in the second stream of the second method are apparent from the present disclosure. The second stream of the second method, in addition to butene and C 6+In addition to olefins, ethylene and / or ethane may also be included. In the second stream of the second method, the total amount of ethylene and ethane may be in the range of 60 to 90 mass %, 70 to 87.5 mass % or 70 to 85 mass %. In the second stream of the second method, C 6+ The amount of olefin may be less than or equal to 8, 7, 6, 5, 4 or 3 mass %.

[0059] The amount of 1-butene in the second stream of the first method and the second method is usually very similar to the amount of butene in the second stream of the corresponding first method and the second method. On the one hand, for example, the second stream of the first method and the second method can contain at least 80 mass % or at least 85 mass % 1-butene, and on the other hand, the second stream of the first method and the second method can contain at least 90 mass % or at least 95 mass % 1-butene, and on the other hand, the second stream of the first method and the second method can contain at least 98 mass % or at least 99 mass % 1-butene based on the total mass of butene in the second stream of the first method and the second method. These representative levels of 1-butene in butene in the second stream of the first method and the second method are also applicable to any other stream containing butene described herein, and can be used without limitation to describe the amount of 1-butene in butene of these other streams containing butene.

[0060] Now refer to the third stream of the second method separated from the reaction zone effluent stream, the third stream of the second method can include at least 96% by mass hexene. Some hexenes (such as 1-hexene) are desired oligomer products, so the amount of hexene in the third stream is generally maximized. Therefore, in other aspects, the third stream of the second method can include at least 97% by mass hexene; alternatively, at least 98% by mass hexene; or alternatively, at least 99% by mass hexene. In other aspects, the third stream of the second method separated from the reaction zone effluent stream can include less than 4, 3, 2, 1, 0.75 or 0.5% by mass C4-olefins (including C4 olefins, C2 olefins, etc.). In yet another aspect, the third stream of the second method separated from the reaction zone effluent stream can include less than 2, 1, 0.75 or 0.5% by mass C 8+ Olefins (including C8 olefins, C 10 olefins, etc.).

[0061] The purity of 1-hexene in the third stream of the second method can be at least 90% by mass of 1-hexene based on the total mass of hexene in the third stream. On the one hand, for example, the third stream of the second method can contain at least 92.5% by mass or at least 95% by mass 1-hexene, and on the other hand, the third stream of the second method can contain at least 97.5% by mass or at least 98% by mass 1-hexene, and on the other hand, the third stream of the second method can contain at least 98.5% by mass or at least 99% by mass 1-hexene based on the total mass of hexene in the third stream of the second method. In other aspects, the third stream of the first method separated from the reaction zone effluent stream or the fourth stream of the second method can contain less than 4, 3, 2, 1, 0.75 or 0.5% by mass C6-olefins (including C6 olefins, C4 olefins, C2 olefins, etc.). In other aspects, the third stream of the first method separated from the reaction zone effluent stream or the fourth stream of the second method can contain less than 2, 1, 0.75 or 0.5% by mass C6-olefins. 10+ Olefins (including C 10 Olefins, C 12 olefins, etc.).

[0062] Now with reference to the third stream of the first method and the fourth stream of the second method separated from the reaction zone effluent stream, the third stream of the first method and the fourth stream of the second method can contain at least 96% by mass octenes. Certain octenes (such as 1-octene) are desired oligomer products. Therefore, in other aspects, the third stream of the first method and the fourth stream of the second method can contain at least 97% by mass octenes; alternatively, at least 98% by mass octenes; or alternatively, at least 99% by mass octenes.

[0063] The purity of 1-octene in the third stream of the first process and the fourth stream of the second process can also be maximized, so that the third stream of the first process and the fourth stream of the second process can contain at least 95 mass % 1-octene based on the total mass of octene. In one aspect, for example, the third stream of the first process and the fourth stream of the second process can contain at least 96.5 mass % or at least 97 mass % 1-octene, while in another aspect, the third stream of the first process and the fourth stream of the second process can contain at least 97.5 mass % or at least 98 mass % 1-octene, and in yet another aspect, can contain at least 98.5 mass % or at least 99 mass % 1-octene based on the total mass of octene.

[0064] The total ethylene recycling rate in the disclosed method is usually very high. The amount of ethylene recycled (in mass %) is determined by dividing the amount of ethylene in the first stream (which is recycled to the oligomerization reaction zone) by the amount of ethylene in the reaction zone effluent stream. On the one hand, the minimum amount of the recycled ethylene can be at least 86, 88, 89, 90 or 91 mass %. On the other hand, the maximum amount of the recycled ethylene can be 99, 97, 96, 95 or 94 mass %. Usually, the amount of the recycled ethylene can be in the range of any minimum amount of recycled ethylene as described herein to any maximum amount of recycled ethylene. For example, the amount of recycled ethylene can be 86 to 99 mass %, 88 to 97 mass %, 89 to 96 mass %, 90 to 95 mass % or 91 to 94 mass %. Other suitable ethylene recycling rates are apparent from the present disclosure.

[0065] High-level ethylene recycling is very important because ethylene conversion is usually no more than 90% in the oligomerization reaction zone. Based on the total amount of the ethylene entering reaction zone (fresh and recycled) and the amount of unreacted ethylene in the reaction zone effluent stream, determine that the minimum ethylene conversion can be at least 20,30,35,40,45 or 50 mass %, and the maximum ethylene conversion can be 99,95,90,80,75,70 or 65 mass %. Usually, the ethylene conversion in the reaction zone can be in the range of any minimum conversion as described herein to any maximum conversion. For example, ethylene conversion can be 20 to 100 mass %, 35 to 99 mass %, 30 to 90 mass %, 40 to 80 mass %, 50 to 70 mass % or 55 to 65 mass %. Other suitable ethylene conversions are apparent from the disclosure.

[0066] The disclosed method for recycling ethylene includes separating the reaction zone effluent stream into the first stream, the second stream and the third stream of the first method, or the first stream, the second stream, the third stream and the fourth stream of the second method. Although not limited to this, the step of separating the reaction zone effluent stream into the first stream of the first method and the second method can include at least two separation stages, or at least two compression stages, or at least two separation stages and at least two compression stages. Any suitable separation technology can be used, such as flash, heating, evaporation, cooling / quenching, distillation, etc., and a combination of more than one separation technology. The compression stage can be carried out with a compressor, but is not limited to this. It should be noted that although the disclosed method for separating the reaction zone effluent stream into the first stream can include at least two separation stages, or at least two compression stages, or at least two separation stages and at least two compression stages, according to the actual design, not all ethylene, butene or other components of the first stream of the first method and the second method can pass through at least two separation stages, or at least two compression stages, or at least two separation stages and at least two compression stages.

[0067] In one aspect, separating the reaction zone effluent stream into a first stream for a first method and a second method may include (a) separating the reaction zone effluent stream into a first vapor stream and a first liquid stream, (b) separating the first liquid stream into a second vapor stream and a second liquid stream, (c) separating the second vapor stream into a light fraction and a first oligomer fraction, and (d) combining the first vapor stream with the light fraction and forming a first stream and a light gas purge stream. The light gas purge stream may contain lights, such as hydrogen (H2) and / or methane, and in this regard, the light gas purge stream may contain (in mass %) more hydrogen than in the first stream and / or more methane than in the first stream.

[0068] Although not limited thereto, the light gas purge stream may contain less than or equal to 5, 4, 3, 2 or 1 mass % hydrogen; additionally or alternatively, less than or equal to 5, 4, 3, 2 or 1 mass % methane. In some aspects, the light gas purge stream may contain (total) less than or equal to 5, 4, 3, 2 or 1 mass % hydrogen and methane. Typically, the total amount of the light gas purge stream is significantly less than the total amount of the second stream (heavy gas purge stream, which contains a large amount of butene). In addition, although not limited thereto, the mass ratio of the light gas purge stream to the second stream (heavy gas purge stream) may be 1:5 to 1:20; alternatively, 1:6 to 1:15; or alternatively, 1:7 to 1:12. On the other hand, the light gas purge stream may contain at least 80, 85, 90, 92, 94 or 96 mass % ethylene.

[0069] In another aspect of the first method, the second liquid stream can be separated into an overhead stream, a second stream, and a third stream. Any suitable number of separation stages can be used to form the overhead stream, the second stream, and the third stream of the first method, and any suitable separation techniques can be used, such as flashing, evaporation, cooling / quenching, distillation, etc., and combinations of more than one separation techniques. In another aspect of the second method, the second liquid stream can be separated into an overhead stream, the second stream, the third stream, and a fourth stream. Any suitable number of separation stages can be used to form the overhead stream, the second stream, the third stream, and the fourth stream, and any suitable separation techniques can be used, such as flashing, evaporation, cooling / quenching, distillation, etc., and combinations of more than one separation techniques.

[0070] Consistent with aspects of the present invention, the methods for recycling ethylene described herein may also include the steps of: introducing (1) ethylene, (2) a catalyst system or catalyst system components, (3) an optional organic reaction medium, and (4) optional hydrogen into an oligomerization reaction zone; forming an oligomer product effluent; and discharging an oligomerization reaction zone effluent stream from the oligomerization reaction zone. Ethylene, the catalyst system or catalyst system components, the organic reaction medium, and hydrogen are independently described herein, and these independent descriptions may be used without limitation and in any combination to further describe the methods for recycling ethylene described herein.

[0071] Ethylene, catalyst system or catalyst system components, organic reaction medium and hydrogen can be combined in any order or sequence and introduced into the oligomerization reaction zone alone or in any combination. For example, hydrogen and ethylene can be combined with the catalyst system or catalyst system components alone and fed into the reaction zone. The present invention is not limited by the manner in which the corresponding feed streams are introduced into the reaction zone.

[0072] When used, any suitable organic reaction medium may be used in the disclosed methods, such as hydrocarbons. Illustrative hydrocarbons may include, for example, aliphatic hydrocarbons, aromatic hydrocarbons, petroleum distillates, or combinations thereof; alternatively, aliphatic hydrocarbons; or alternatively, aromatic hydrocarbons. Aliphatic hydrocarbons that may be used as the first organic reaction medium include C3 to C 20 aliphatic hydrocarbons; alternatively, C4 to C 15 Aliphatic hydrocarbons; or alternatively, C5 to C 10Aliphatic hydrocarbons. Unless otherwise specified, aliphatic hydrocarbons may be cyclic or acyclic and / or may be straight or branched. In some aspects, aliphatic hydrocarbons useful as the first organic reaction medium may be hydrocarbon olefins (straight or branched, or terminal or internal). Non-limiting examples of suitable acyclic aliphatic hydrocarbon reaction media that may be used alone or in any combination include propane, isobutane, n-butane, butane (n-butane or a mixture of straight and branched C4 acyclic aliphatic hydrocarbons), pentane (n-pentane or a mixture of straight and branched C5 acyclic aliphatic hydrocarbons), hexane (n-hexane or a mixture of straight and branched C6 acyclic aliphatic hydrocarbons), heptane (n-heptane or a mixture of straight and branched C7 acyclic aliphatic hydrocarbons), octane (n-octane or a mixture of straight and branched C8 acyclic aliphatic hydrocarbons), pentane (n-pentane or a mixture of straight and branched C9 acyclic aliphatic hydrocarbons), heptane (n-heptane or a mixture of straight and branched C10 acyclic aliphatic hydrocarbons), octane (n-octane or a mixture of straight and branched C11 acyclic aliphatic hydrocarbons), octane (n-octane or a mixture of straight and branched C12 acyclic aliphatic hydrocarbons), octane (n-octane or a mixture of straight and branched C13 acyclic aliphatic hydrocarbons), octane (n-octane or a mixture of straight and branched C14 acyclic aliphatic hydrocarbons), octane (n-octane or a mixture of straight and branched C13 ... a mixture of linear and branched C8 acyclic aliphatic hydrocarbons), or a combination thereof; alternatively, isobutane, n-butane, butane (n-butane or a mixture of linear and branched C4 acyclic aliphatic hydrocarbons), pentane (n-pentane or a mixture of linear and branched C5 acyclic aliphatic hydrocarbons), hexane (n-hexane or a mixture of linear and branched C6 acyclic aliphatic hydrocarbons), heptane (n-heptane or a mixture of linear and branched C7 acyclic aliphatic hydrocarbons), octane (n-octane or a mixture of linear and branched C8 acyclic aliphatic hydrocarbons), a mixture of straight-chain and branched C4 acyclic aliphatic hydrocarbons), or a combination thereof; alternatively, isobutane, n-butane, butane (n-butane or a mixture of straight-chain and branched C4 acyclic aliphatic hydrocarbons), pentane (n-pentane or a mixture of straight-chain and branched C5 acyclic aliphatic hydrocarbons), heptane (n-heptane or a mixture of straight-chain and branched C7 acyclic aliphatic hydrocarbons), octane (n-octane or a mixture of straight-chain and branched C8 acyclic aliphatic hydrocarbons), or a combination thereof; alternatively, propane; alternatively, isobutane; alternatively, n-butane Alternatively, butane (n-butane or a mixture of straight-chain and branched C4 acyclic aliphatic hydrocarbons); Alternatively, pentane (n-pentane or a mixture of straight-chain and branched C5 acyclic aliphatic hydrocarbons); Alternatively, hexane (n-hexane or a mixture of straight-chain and branched C6 acyclic aliphatic hydrocarbons); Alternatively, heptane (n-heptane or a mixture of straight-chain and branched C7 acyclic aliphatic hydrocarbons); Or alternatively, octane (n-octane or a mixture of straight-chain and branched C8 acyclic aliphatic hydrocarbons). In other aspects, the acyclic aliphatic reaction medium can be the product of an oligomerization reaction (e.g., 1-hexene and / or 1-octene). Non-limiting examples of suitable cyclic aliphatic hydrocarbon reaction media include cyclohexane and methylcyclohexane; Alternatively, cyclohexane; Or alternatively, methylcyclohexane. Aromatic hydrocarbons that can be used as organic reaction media include C6 to C 20 Aromatic hydrocarbons, or alternatively, C6 to C 10Aromatic hydrocarbons. Non-limiting examples of suitable aromatic hydrocarbons that can be used alone or in any combination include benzene, toluene, xylene (including o-xylene, m-xylene, p-xylene or mixtures thereof), and ethylbenzene or combinations thereof; alternatively, benzene; alternatively, toluene; alternatively, xylene (including o-xylene, m-xylene, p-xylene or mixtures thereof); alternatively, ethylbenzene. In a particular aspect of the invention, the organic reaction medium may comprise, consist essentially of, or consist of cyclohexane.

[0073] The catalyst system or catalyst system components may comprise (i) a heteroatom ligand transition metal compound complex (or a heteroatom ligand chromium compound complex) and an organoaluminum compound, or (ii) a heteroatom ligand, a transition metal compound (or a chromium compound) and an organoaluminum compound. The catalyst system and catalyst system components are disclosed in more detail herein.

[0074] The formation of the oligomer product effluent in the oligomerization reaction zone can be carried out at any suitable oligomerization temperature and pressure. Typically, the oligomer product can be formed at a minimum temperature of 0°C, 20°C, 30°C, 40°C, 45°C, or 50°C; additionally or alternatively, at a maximum temperature of 165°C, 160°C, 150°C, 140°C, 130°C, 115°C, 100°C, or 90°C. Typically, the oligomerization temperature for forming the oligomer product can range from any minimum temperature disclosed herein to any maximum temperature disclosed herein. Thus, suitable non-limiting ranges may include the following: 0° C. to 165° C., 20° C. to 160° C., 20° C. to 115° C., 40° C. to 160° C., 40° C. to 140° C., 50° C. to 150° C., 50° C. to 140° C., 50° C. to 130° C., 50° C. to 100° C., 60° C. to 115° C., 70° C. to 100° C., or 75° C. to 95° C. Other suitable oligomerization temperatures and temperature ranges will be apparent from this disclosure.

[0075] The oligomer product can be formed at a minimum pressure (or ethylene partial pressure) of 50 psig (344 kPa), 100 psig (689 kPa), 200 psig (1.4 MPa), or 250 psig (1.5 MPa); additionally or alternatively, at a maximum pressure (or ethylene partial pressure) of 4,000 psig (27.6 MPa), 3,000 psig (20.9 MPa), 2,000 psig (13.8 MPa), or 1,500 psig (10.3 MPa). Generally, the oligomerization pressure (or ethylene partial pressure) at which the oligomer product is formed can be within the range of any minimum pressure disclosed herein to any maximum pressure disclosed herein. Thus, suitable non-limiting ranges may include the following: 50 psig (344 kPa) to 4,000 psig (27.6 MPa), 100 psig (689 kPa) to 3,000 psig (20.9 MPa), 100 psig (689 kPa) to 2,000 psig (13.8 MPa), 200 psig (1.4 MPa) to 2,000 psig (13.8 MPa), 200 psig (1.4 MPa) to 1,500 psig (10.3 MPa), or 250 psig (1.5 MPa) to 1,500 psig (10.3 MPa). Other suitable oligomerization pressures (or ethylene partial pressures) will be apparent from this disclosure.

[0076] When used, hydrogen can be fed directly to the reaction zone, or the hydrogen can be combined with the ethylene feed prior to the reaction zone. In the reaction zone, the hydrogen partial pressure can be at least 1 psig (6.9 kPa), 5 psig (34 kPa), 10 psig (69 kPa), 25 psig (172 kPa), or 50 psig (345 kPa); additionally or alternatively, the maximum hydrogen partial pressure is 2000 psig (13.8 MPa), 1750 psig (12.1 MPa), 1500 psig (10.3 MPa), 1250 psig (8.6 MPa), 1000 psig (6.9 MPa), 750 psig (5.2 MPa), 500 psig (3.4 MPa), or 400 psig (2.8 MPa). Generally, the hydrogen partial pressure can be within the range of any minimum hydrogen partial pressure disclosed herein to any maximum hydrogen partial pressure disclosed herein. Thus, suitable non-limiting ranges for hydrogen partial pressures may include the following ranges: 1 psig (6.9 kPa) to 2000 psig (13.8 MPa), 1 psig (6.9 kPa) to 1750 psig (12.1 MPa), 5 psig (34 kPa) to 1500 psig (10.3 MPa), 5 psig (34 kPa) to 1250 psig (8.6 MPa), 10 psig (69 kPa) to 1000 psig (6.9 MPa), 1 psig (69 kPa) to 750 psig (5.2 MPa), 10 psig (69 kPa) to 500 psig (3.5 MPa), 25 psig (172 kPa) to 750 psig (5.2 MPa), 25 psig (172 kPa) to 500 psig (3.4 MPa), 25 psig (172 kPa) to 400 psig (2.8 MPa), or 50 psig (345 kPa) to 500 psig (3.4 MPa). Other suitable hydrogen partial pressures in the reaction zone for forming the oligomer product will be apparent from this disclosure.

[0077] The oligomerization reaction zone for forming the oligomer product may include any suitable reactor. Non-limiting examples of reactor types may include stirred tank reactors, plug flow reactors, or any combination thereof; alternatively, fixed bed reactors, continuous stirred tank reactors, loop slurry reactors, solution reactors, tubular reactors, circulation reactors, or any combination thereof. In one aspect, the reaction zone may have more than one reactor in series or in parallel, and include any combination of reactor types and arrangements. In addition, the oligomerization process for forming the oligomer product may be a continuous process or a batch process, or any reactor or container in the oligomerization reaction system may be operated continuously or in batches.

[0078] Figure 1An ethylene oligomerization reaction system 10 consistent with one aspect of the present invention is shown. The system 10 can include an oligomerization reaction zone 20 and a separation system 60. The feed stream 15 (representing one or more feed streams) entering the oligomerization reaction zone can include, for example, a catalyst system feed stream, an organic reaction medium feed stream, an ethylene feed stream, and a hydrogen feed stream (if hydrogen is used), and these feed streams can be fed directly into the oligomerization reaction zone 20, or any of these feed streams can be combined prior to the oligomerization reaction zone 20 and the resulting mixture fed into the oligomerization reaction zone 20. It should be understood that there are many different options for where the feed components can be introduced into the oligomerization reaction zone 20, and the present invention is not limited by the specific configuration of the feed stream 15 entering the oligomerization reaction zone. In addition, it should be noted that although Figure 1 It is shown that the feed stream 15 is introduced directly into the oligomerization reaction zone 20, but it is further contemplated that some of the oligomerization reaction zone 20 feed can be introduced into the ethylene recycle stream, i.e., the first stream 95, before entering the oligomerization reaction zone 20. For example, all or a portion of the ethylene, all or a portion of the organic reaction medium, or a combination thereof can be introduced into the ethylene recycle stream before the ethylene recycle stream enters the oligomerization reaction zone. U.S. Patent Publication 2017 / 0342000 describes potential methods for introducing a feed stream into the oligomerization reaction zone, as well as other methods that can be used to introduce the feed stream 15 into the oligomerization reaction zone 20.

[0079] Ethylene oligomerization occurs in oligomerization reaction zone 20, and leaving the reaction zone is reaction zone effluent stream 25, which enters separation system 60 for separation of desired oligomer products, such as 1-hexene and 1-octene, and recovery of ethylene. Separation system 60 may also be configured for catalyst deactivation. The main streams leaving separation system 60 are first stream 95, second stream 63, third stream 65, and fourth stream 67. First stream 95 contains primarily ethylene and less than 5 mass % C 4+ The first stream is recycled to the reaction zone 20. The second stream 63 contains butenes such as 1-butene and less than 10 mass % of C 6+ The oligomers (also referred to as heavy gas purge stream) may contain any other second stream having the compositional properties of the second method disclosed herein. The third stream 65 contains at least 96 mass % hexene, most of which is 1-hexene, and may contain any other third stream having the compositional properties of the second method disclosed herein. The fourth stream 67 contains at least 96 mass % octene, most of which is 1-octene, and may contain any other fourth stream having the compositional properties of the second method disclosed herein.

[0080] Reference now Figure 2, which shows another ethylene oligomerization reaction system 100 consistent with one aspect of the present invention. System 100 may include an oligomerization reaction zone 120, a first stage separator 130, a second stage separator 140, a separation tank 150, a liquid oligomer separation system 160, a first stage compressor 170, a separation tank 180, and a second stage compressor 190. Figure 2 The feed stream 115 (representing one or more feed streams), the oligomerization reaction zone 120, the reaction zone effluent stream 125, the second stream 163 (butene and less than 10 mass % C 6+ oligomers), third stream 165 (at least 96 mass % hexene), fourth stream 167 (at least 96 mass % octene), and first stream 195 (ethylene and less than 5 mass % C 4+ Oligomers) are usually Figure 1 Similar numbered components are the same as described in . Figure 1 The separation system 60 in has been significantly expanded to provide Figure 2 of separation schemes, which have additional but not all potential separation scheme details.

[0081] Figure 2 The reaction zone effluent stream 125 in the reaction zone enters the first stage separator 130, and the first liquid stream 132 and the first vapor stream 138 leave the first stage separator 130. The first liquid stream enters the second stage separator 140, and the second liquid stream 142 and the second vapor stream 148 leave the second stage separator 140. The second liquid stream 142 is fed to the liquid oligomer separation system 160.

[0082] The second vapor stream 148 is fed to a knockout drum 150 where a first oligomer fraction 155 exits and is fed to a liquid oligomer separation system 160, while a vapor stream 158 exits and is fed to a first stage compressor 170. The light fraction 173 from the compressor 170 is combined with the first vapor stream 138 to form a combined light stream 178 that enters a knockout drum 180. Exiting the knockout drum 180 is a liquid stream 183 that is fed to the liquid oligomer separation system 160, a light gas purge stream 185, and a low pressure ethylene stream 188 that enters a second stage compressor 190 to form a first stream 195 that is recycled to the reaction zone 120.

[0083] exist Figure 2 In the liquid oligomer separation system 160, the main oligomer product streams are formed and separated: the third stream 165 (at least 96 mass % hexene) and the fourth stream 167 (at least 96 mass % octene). 6+ A heavy gas purge stream of oligomers (second stream 163 ) and an overhead lights stream 161 also exit the liquid oligomer separation system 160 .

[0084] In one aspect, the octene stream produced by the methods described herein (the third stream of the first method and the fourth stream of the second method) can contain at least 95 mass%, 96 mass%, 96.5 mass%, 97 mass%, 97.5 mass%, 98.5 mass%, or 99 mass% of 1-octene based on the total octenes in the third stream of the first method and the fourth stream of the second method. In other aspects, the octene stream produced by the methods described herein (the third stream of the first method and the fourth stream of the second method) can contain 95 mass% to 99.9 mass%, 96 mass% to 99.9 mass%, 96.5 mass% to 99.9 mass%, 97 mass% to 99.9 mass%, 97.5 mass% to 99.9 mass%, 98 mass% to 99.9 mass%, or 98.5 mass% to 99.9 mass% of 1-octene based on the total octenes in the third stream of the first method and the fourth stream of the second method.

[0085] In one aspect, the hexene stream (the third stream of the second process) produced by the process described herein can contain at least 90 mass%, 92.5 mass%, 95 mass%, 97 mass%, 98 mass%, 98.5 mass% or 99 mass% of 1-hexene based on the total hexene in the third stream of the second process. In other aspects, the hexene stream (the third stream of the second process) can contain 90 mass% to 99.9 mass%, 92.5 mass% to 99.9 mass%, 95 mass% to 99.9 mass%, 97 mass% to 99.9 mass%, 98 mass% to 99.9 mass%, 98.5 mass% to 99.9 mass% or 99 mass% to 99.9 mass% of 1-hexene based on the total hexene in the third stream of the second process.

[0086] Catalyst system

[0087] The method disclosed herein can utilize a catalyst system (or catalyst system mixture) comprising i) a heteroatom ligand transition metal compound complex and an organoaluminum compound, or ii) a heteroatom ligand, a transition metal compound and an organoaluminum compound; alternatively, a heteroatom ligand transition metal compound complex and an organoaluminum compound; or alternatively, a heteroatom ligand, a transition metal compound and an organoaluminum compound. In one aspect, the catalyst system (or catalyst system mixture) may further comprise (optionally) a catalyst system organic medium. In some aspects, a catalyst system (or catalyst system mixture) comprising i) a heteroatom ligand transition metal compound complex and an organoaluminum compound or ii) a heteroatom ligand, a transition metal compound and an organoaluminum compound) can be introduced into the reaction mixture in the reaction zone. In other aspects, at least one of i) a heteroatom ligand transition metal compound complex and an organoaluminum compound or ii) a heteroatom ligand, a transition metal compound and an organoaluminum compound can be introduced into the reaction mixture in the reaction zone separately from the other components of the catalyst system (or catalyst system mixture). Heteroatom ligands, transition metal compounds, heteroatom ligand transition metal compound complexes, heteroatom ligands of heteroatom ligand transition metal compound complexes, transition metal compounds of heteroatom ligand transition metal compounds, organoaluminum compounds, and optional catalyst system organic media are independent elements of the methods and reaction systems described herein and are independently described herein. These independently described catalyst system (or catalyst system mixture) elements can be used in any combination, and without limitation, to further describe the methods and reaction systems provided herein.

[0088] In one aspect, the heteroatom ligand transition metal compound complex or transition metal compound MX pThe transition metal atom of can be any transition metal atom. In one embodiment, the transition metal atom of the transition metal compound can include or consist essentially of: a transition metal of Group 3-12, Group 4-10, Group 6-9, or Group 7-8. In some embodiments, the transition metal atom of the transition metal compound can include or consist essentially of: a transition metal of Group 4; alternatively, a transition metal of Group 5; alternatively, a transition metal of Group 6; alternatively, a transition metal of Group 7; alternatively, a transition metal of Group 8; alternatively, a transition metal of Group 9; or alternatively, a transition metal of Group 10. In an embodiment, the transition metal atom of the transition metal compound may include or consist essentially of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium, platinum, copper or zinc; alternatively, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, iron, cobalt, nickel, palladium or platinum; alternatively, chromium, iron, cobalt or nickel; alternatively, titanium, zirconium or hafnium; alternatively, vanadium or niobium; alternatively, chromium, molybdenum or tungsten; alternatively, iron or cobalt; or alternatively, nickel, palladium, platinum, copper or zinc. In other embodiments, the metal salt may comprise titanium; alternatively, zirconium; alternatively, hafnium; alternatively, vanadium; alternatively, niobium; alternatively, tantalum; alternatively, chromium; alternatively, molybdenum; alternatively, tungsten; alternatively, manganese; alternatively, iron; alternatively, cobalt; alternatively, nickel; alternatively, palladium; alternatively, platinum; alternatively, copper; or alternatively, zinc. Typically, the heteroatom ligand transition metal compound complex or transition metal compound MX p The transition metal atom of can have any positive oxidation state that a transition metal atom can obtain. In one embodiment, the transition metal atom can have an oxidation state of +2 to +6; alternatively, +2 to +4; or alternatively, +2 to +3. In some embodiments, the transition metal compound MX p The transition metal atom can have an oxidation state of +1; alternatively, +2; alternatively, +3; or alternatively, +4.

[0089] The methods disclosed herein may utilize a catalyst system (or catalyst system mixture) comprising i) a heteroatom ligand chromium compound complex and an organoaluminum compound, or ii) a heteroatom ligand, a chromium compound, and an organoaluminum compound; alternatively, a heteroatom ligand chromium compound complex and an organoaluminum compound; or alternatively, a heteroatom ligand, a chromium compound, and an organoaluminum compound. In one aspect, the catalyst system (or catalyst system mixture) may further comprise (optionally) a catalyst system organic medium. In some aspects, a catalyst system (or catalyst system mixture) comprising i) a heteroatom ligand chromium compound complex and an organoaluminum compound or ii) a heteroatom ligand, a chromium compound, and an organoaluminum compound) may be introduced into the reaction mixture in the reaction zone. In other aspects, at least one of i) a heteroatom ligand chromium compound complex and an organoaluminum compound or ii) a heteroatom ligand, a chromium compound, and an organoaluminum compound may be introduced into the reaction mixture in the reaction zone separately from the other components of the catalyst system (or catalyst system mixture). The heteroatom ligand, chromium compound, heteroatom ligand chromium compound complex, heteroatom ligand of the heteroatom ligand chromium compound complex, chromium compound of the heteroatom ligand chromium compound, organoaluminum compound, and optional catalyst system organic medium are independent elements of the methods and reaction systems described herein and are independently described herein. These independently described catalyst system (or catalyst system mixture) elements can be used in any combination, without limitation, to further describe the methods and reaction systems provided herein.

[0090] Non-limiting examples of suitable catalyst system organic media include hydrocarbons, such as aromatic hydrocarbons. Aromatic hydrocarbons that can be used alone or in any combination include benzene, toluene, xylenes (including o-xylene, m-xylene, p-xylene, or mixtures thereof), ethylbenzene, or combinations thereof; alternatively, benzene; alternatively, toluene; alternatively, xylenes (including o-xylene, m-xylene, p-xylene, or mixtures thereof); alternatively, ethylbenzene. In a particular aspect of the invention, the catalyst system organic medium can comprise, consist essentially of, or consist of ethylbenzene.

[0091] In general, the heteroatom ligand or heteroatom ligand of the heteroatom ligand chromium compound complex can be any heteroatom ligand that can form an oligomer product in the reaction zone when used in the catalyst system (or catalyst system mixture) described herein for the method and / or reaction system described herein. In one aspect, the heteroatom ligand or heteroatom ligand of the heteroatom ligand chromium compound complex can be a neutral heteroatom ligand or an anionic heteroatom ligand; alternatively, a neutral heteroatom ligand; or alternatively, an anionic heteroatom ligand. In one aspect, the neutral heteroatom ligand can contain one or more heteroatom complexing moieties; alternatively, two heteroatom complexing moieties; or alternatively, three heteroatom complexing moieties. In one aspect, the anionic heteroatom ligand can also contain one or more neutral heteroatom complexing moieties; alternatively, two heteroatom complexing moieties; or alternatively, three heteroatom complexing moieties. In one aspect, each neutral heteroatom complexing moiety of the neutral ligand or anionic ligand comprising a neutral heteroatom complexing moiety can independently be an ether group, a sulfide group, an amine group, an imine group, a phosphine group, a phosphite group, or a phosphite group; alternatively, an ether group, a sulfide group, an amine group, an imine group, or a phosphine group; alternatively, an ether group; alternatively, a sulfide group; alternatively, an amine group; alternatively, an imine group; or alternatively, a phosphine group. In one aspect, the anionic atom of the anionic heteroatom ligand (which forms a covalent bond or an ionic bond with the chromium of the chromium compound) can be an anionic carbon atom, an anionic oxygen atom, or an anionic nitrogen atom; alternatively, an anionic carbon atom; alternatively, an anionic oxygen atom; or alternatively, an anionic nitrogen atom.

[0092] In any aspect, the heteroatom ligand or the heteroatom ligand of the heteroatom ligand chromium compound complex may comprise, consist of, or may be: N 2 -phosphinylformamidine, N 2 -phosphinyl amidine, N 2 -phosphinylguanidine, heterocyclic 2-[(phosphinyl)amino]imine, or any combination thereof; alternatively, N 2 -phosphinylformamidine; alternatively, N 2 -phosphinyl amidine; alternatively, N 2 -phosphinylguanidine; or alternatively, heterocyclic 2-[(phosphinyl)amino]imine. Typically, N 2 -phosphinylformamidine may have the structure NPF1, N 2 The -phosphinyl amidine may have the structure NPA1, N 2 The -phosphinylguanidine can have structure Gu1, structure Gu2, structure Gu3, structure Gu4, or structure Gu5, and the heterocyclic 2-[(phosphinyl)amino]imine can have structure HCPA1. In some aspects, N 2The -phosphinylguanidine has structure Gu2, structure Gu3 or structure Gu4; alternatively, structure Gu1; alternatively, structure Gu2; alternatively, structure Gu3; alternatively, structure Gu4; alternatively, structure Gu5.

[0093]

[0094] In any aspect, the heteroatom ligand chromium compound complex may comprise, may consist essentially of, or may be: N 2 -phosphinylformamidinium chromium compound complex, N 2 -phosphinyl amidine chromium compound complex, N 2 -phosphinylguanidine chromium compound complex, heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex or any combination thereof; alternatively, N 2 -phosphinylformamidinium chromium compound complex; alternatively, N 2 -phosphinyl amidine chromium compound complex; alternatively, N 2 -phosphinylguanidine chromium compound complex; alternatively, N 2 -phosphinylguanidine chromium compound complex; or alternatively, a heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex. Typically, N 2 The phosphinylformamidinium chromium compound complex may have the structure NPFCr1, N 2 The phosphinyl amidine chromium compound complex may have the structure NPACr1, N 2 The -phosphinylguanidine chromium compound complex can have the structure GuCr1, structure GuCr2, structure GuCr3, structure GuCr4, or structure GuCr5, and the heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex can have the structure HCPACr1. In some aspects, N 2 The -phosphinylguanidine chromium compound complex has the structure GuCr2, the structure GuCr3 or the structure GuCr4; alternatively, the structure GuCr1; alternatively, the structure GuCr2; alternatively, the structure GuCr3; alternatively, the structure GuCr4; or alternatively, the structure GuCr5.

[0095]

[0096] In N 2 -phosphinylformamidine, N 2 -phosphinylformamidinium chromium compound complex, N 2 -phosphinyl amidine, N 2 In the complex of chromium-phosphinyl amidine compound and heterocyclic 2-[(phosphinyl)amino]imine compound, the nitrogen forming a double bond with the central carbon atom is called N 1 Nitrogen that forms a single bond with the central carbon atom is called N2 Nitrogen. Similarly, in N 2 -phosphinylguanidine and N 2 -In the phosphinylguanidine chromium complex, the nitrogen that forms a double bond with the central carbon atom of the guanidine nucleus is called N 1 The nitrogen atom that forms a single bond with the central carbon atom of the guanidine nucleus and with the phosphorus atom of the phosphine group is called N 2 The remaining nitrogen atoms that form single bonds with the central carbon atom of the guanidine nucleus are called N 3 Nitrogen. It should be noted that N 2 -phosphinylguanidine and N 2 The guanidine group of the guanidine in the phosphinylguanidine chromium complex can be part of a larger group that does not contain guanidine in the name. For example, although the compound 7-dimethylphosphinylimidazo[1,2-a]imidazole can be classified as a compound having an imidazo[1,2-a]imidazole core (or a compound having a phosphinylimidazo[1,2-a]imidazole group), 7-dimethylphosphinylimidazo[1,2-a]imidazole will still be classified as a compound having a guanidine core (or a compound having a guanidine group) because it contains the defined general structure of a guanidine compound.

[0097] N 2 -phosphinylformamidine structure and N 2 -R in the structure of the phosphinylformamidine chromium compound complex 1 , R 3 , R 4 and R 5 , N 2 -phosphinyl amidine structure and N 2 -R in the structure of the phosphine amidine chromium compound complex 1 , R 2 , R 3 , R 4 and R 5 , N 2 -phosphinylguanidine structure and N 2 -R in the structure of the phosphinylguanidine chromium compound complex 1 , R 2a , R 2b , R 3 , R 4 , R 5 , L 12 , L 22 and L 23 , and L in the heterocyclic 2-[(phosphinyl)amino]imine structure and the heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex structure 12 , T, R 3 , R 4 and R 5 Can be used in any combination and without limitation to further describe the N disclosed herein2 -phosphinylformamidine structure, N 2 -phosphinylformamidinium chromium compound complex structure, N 2 -phosphinyl amidine structure, N 2 -phosphinyl amidine chromium compound complex structure, N 2 -phosphinylguanidine structure, N 2 -phosphinylguanidine chromium compound complex structure, heterocyclic 2-[(phosphinyl)amino]imine structure and heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex structure. 2 -phosphinylformamidinium chromium compound complex structure, N 2 -phosphinyl amidine chromium compound complex structure, N 2 -phosphinylguanidine chromium compound complex structure and heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex structure X p , Q and q are independently described herein and may be used in any combination without limitation to further describe the N disclosed herein. 2 -phosphinylformamidinium chromium compound complex structure, N 2 -phosphinyl amidine chromium compound complex structure, N 2 -phosphinylguanidine chromium compound complex structure and heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex structure. p The independent descriptions of Q and q can be combined with the independent descriptions of R without restriction. 1 , R 2 , R 2a , R 2b , R 3 , R 4 , R 5 , L 12 , L 22 and L 23 Combined to further describe the appropriate N considered herein 2 -phosphinylformamidinium chromium compound complex structure, N 2 -phosphinyl amidine chromium compound complex structure, N 2 -phosphinylguanidine chromium compound complex structure and heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex structure.

[0098] Usually, with R 1 N 2 -phosphinylformamidine, N 2 -phosphinylformamidinium chromium compound complex, N 2 -phosphinyl amidine, N 2 -phosphinyl amidine chromium compound complex, N 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium compound complex R 1can be an organic alkyl group; alternatively, an organic alkyl group consisting of inert functional groups; or alternatively, a hydrocarbon group. In one aspect, R 1 The organic alkyl group may be C1 to C 20 , C1 to C 15 , C1 to C 10 or C1 to C5 organic alkyl. In one aspect, R consisting of an inert functional group 1 The organic alkyl group can be a C1 to C 20 , C1 to C 15 , C1 to C 10 or a C1 to C5 organic alkyl group. 1 The hydrocarbon group may be C1 to C 20 , C1 to C 15 , C1 to C 10 or a C1 to C5 hydrocarbon group.

[0099] On the one hand, having R 1 N 2 -phosphinylformamidine, N 2 -phosphinylformamidinium chromium compound complex, N 2 -phosphinyl amidine, N 2 -phosphinyl amidine chromium compound complex, N 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium compound complex R 1 can be alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, aralkyl, or substituted aralkyl; alternatively, alkyl or substituted alkyl; alternatively, cycloalkyl or substituted cycloalkyl; alternatively, aryl or substituted aryl; alternatively, aralkyl or substituted aralkyl; alternatively, alkyl, cycloalkyl, aryl, or aralkyl; alternatively, alkyl; alternatively, substituted alkyl, alternatively, cycloalkyl; alternatively, substituted cycloalkyl; alternatively, aryl; alternatively, substituted aryl; alternatively, aralkyl; or alternatively, substituted aralkyl. In any aspect disclosed herein, R 1 The alkyl group can be C1 to C 20 , C1 to C 10 or C1 to C5 alkyl. In any aspect disclosed herein, the substituted R 1 The alkyl group may be substituted with C1 to C 20 , C1 to C 10 or C1 to C5 alkyl. In any aspect disclosed herein, R 1 The cycloalkyl group may be C4 to C 20 , C4 to C 15 or C4 to C 10In any aspect disclosed herein, substituted R 1 The cycloalkyl group may be substituted C4 to C 20 , C4 to C 15 or C4 to C 10 In any aspect disclosed herein, R 1 The aryl group can be C6 to C 20 , C6 to C 15 or C6 to C 10 In any aspect disclosed herein, substituted R 1 The aryl group may be a substituted C6 to C 20 , C6 to C 15 or C6 to C 10 In any aspect disclosed herein, R 1 The aralkyl group may be C7 to C 20 , C7 to C 15 or C7 to C 10 In any aspect disclosed herein, the substituted R 1 The aralkyl group may be a substituted C7 to C 20 , C7 to C 15 or C7 to C 10 Aralkyl. Each substituent of substituted alkyl (general or specific), substituted cycloalkyl (general or specific), substituted aryl (general or specific) and / or substituted aralkyl (general or specific) can be halogen, hydrocarbyl or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific) and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents and hydrocarbyloxy substituents can be used without limitation to further describe substituted R 1 Group.

[0100] On the one hand, R 1 Can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl; Or alternatively, methyl, ethyl, n-propyl (1-propyl), isopropyl (2-propyl), tert-butyl (2-methyl-2-propyl) or neopentyl (2,2-dimethyl-1-propyl). In some aspects, can be used as R 1 The alkyl group may be substituted. Each substituent of the substituted alkyl group (general or specific) may independently be halogen or hydrocarbyloxy; alternatively, halogen; or alternatively, hydrocarbyloxy. Halogen substituents and hydrocarbyl substituents (general and specific) are independently disclosed herein. These halogen substituents and hydrocarbyloxy substituents may be used without limitation to further describe the substituents that may be used as R1 of a substituted alkyl group.

[0101] On the one hand, R 1 Can be cyclopentyl, substituted cyclopentyl, cyclohexyl or substituted cyclohexyl; alternatively, cyclopentyl or substituted cyclopentyl; or alternatively, cyclohexyl or substituted cyclohexyl. In one aspect, can be used as R 1 The substituted cycloalkyl group may be 2-substituted cyclohexyl, 2,6-disubstituted cyclohexyl, 2-substituted cyclopentyl, or 2,5-disubstituted cyclopentyl; alternatively, 2-substituted cyclohexyl or 2,6-disubstituted cyclohexyl; alternatively, 2-substituted cyclopentyl or 2,5-disubstituted cyclopentyl; alternatively, 2-substituted cyclohexyl or 2-substituted cyclopentyl; or alternatively, 2,6-disubstituted cyclohexyl or 2,5-disubstituted cyclopentyl. In one aspect, the cycloalkyl group used as R 1 The one or more substituents of a polysubstituted cycloalkyl group may be the same or different; alternatively, all substituents of the polysubstituted cycloalkyl group may be the same; or alternatively, all substituents of the polysubstituted cycloalkyl group may be different. Each substituent of a substituted cycloalkyl group having a specified number of ring carbon atoms may independently be a halogen, a hydrocarbyl group, or a hydrocarbyloxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarbyloxy group; alternatively, a hydrocarbyl group or a hydrocarbyloxy group; alternatively, a halogen; alternatively, a hydrocarbyl group; or alternatively, a hydrocarbyloxy group. Halogen substituents, hydrocarbyl substituents (general and specific), and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents, and hydrocarbyloxy substituents may be used without limitation to further describe the groups that may be used as R 1 of substituted cycloalkyl (general and specific).

[0102] In one non-limiting aspect, R 1 It can be cyclohexyl, 2-alkylcyclohexyl or 2,6-dialkylcyclohexyl; or alternatively, cyclopentyl, 2-alkylcyclopentyl or 2,5-dialkylcyclopentyl. Alkyl substituents (general and specific) are described independently herein, and these alkyl substituents can be used without limitation to further describe the alkyl groups that can be used as R. 1 alkylcyclohexyl (general and specific), dialkylcyclohexyl (general and specific), alkylcyclopentyl (general or specific) and / or dialkylcyclopentyl (general and specific). Typically, the alkyl substituents of the dialkylcyclohexyl or dialkylcyclopentyl may be the same; or alternatively, the alkyl substituents of the dialkylcyclohexyl or dialkylcyclopentyl may be different. In some non-limiting aspects, R 1It can be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, 2-tert-butylcyclohexyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl or 2,6-di-tert-butylcyclohexyl. In other non-limiting aspects, R 1 It may be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl or 2-tert-butylcyclohexyl; or alternatively, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl or 2,6-di-tert-butylcyclohexyl.

[0103] On the one hand, R 1 can be phenyl, substituted phenyl; alternatively, phenyl; or alternatively, substituted phenyl. In one aspect, it can be used as R 1 The substituted phenyl group may be 2-substituted phenyl, 3-substituted phenyl, 4-substituted phenyl, 2,4-disubstituted phenyl, 2,6-disubstituted phenyl, 3,5-disubstituted phenyl, or 2,4,6-trisubstituted phenyl; alternatively, 2-substituted phenyl, 4-substituted phenyl, 2,4-disubstituted phenyl, or 2,6-disubstituted phenyl; alternatively, 3-substituted phenyl or 3,5-disubstituted phenyl; alternatively, 2-substituted phenyl or 4-substituted phenyl; alternatively, 2,4-disubstituted phenyl or 2,6-disubstituted phenyl; or alternatively, 2,4,6-trisubstituted phenyl. In one aspect, the substituted phenyl group used as R 1 The one or more substituents of the polysubstituted phenyl may be the same or different; alternatively, all substituents of the polysubstituted cycloalkyl may be the same; or alternatively, all substituents of the polysubstituted cycloalkyl are different. Each substituent of the substituted phenyl (general or specific) may independently be halogen, hydrocarbyl, or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific), and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents, and hydrocarbyloxy substituents may be used without limitation to further describe the radicals that may be used as R 1 Substituted phenyl (general and specific).

[0104] In one non-limiting aspect, R 1It can be phenyl, 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl, 3,5-dialkylphenyl or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl or 4-alkylphenyl; alternatively, 2,4-dialkylphenyl or 2,6-dialkylphenyl; alternatively, 3-alkylphenyl or 3,5-dialkylphenyl; alternatively, 2-alkylphenyl or 2,6-dialkylphenyl; or alternatively, 2,4,6-trialkylphenyl. Alkyl substituents (general and specific) are described independently herein and these alkyl substituents can be used without limitation to further describe the alkyl substituents that can be used as R 1 Typically, the alkyl substituents of the dialkylphenyl (general or specific) or trialkylphenyl (general or specific) may be the same; or alternatively, the alkyl substituents of the dialkylphenyl or trialkylphenyl may be different. In some non-limiting aspects, R 1 The radical may independently be phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl or 2,4,6-trimethylphenyl; alternatively, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl or 2-tert-butylphenyl; alternatively, phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl or 2,4,6-trimethylphenyl.

[0105] On the one hand, R 1 can be benzyl or substituted benzyl; alternatively, benzyl; or alternatively, substituted benzyl. Each substituent of the substituted benzyl can independently be halogen, hydrocarbyl, or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific), and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents, and hydrocarbyloxy substituents can be used without limitation to further describe the substituents that can be used as R 1 Substituted benzyl (general and specific).

[0106] Usually, N 2 -phosphinyl amidine and / or N 2-phosphinyl amidine chromium compound complex R 2 can be an organic alkyl group; alternatively, an organic alkyl group consisting of inert functional groups; or alternatively, a hydrocarbon group. In one aspect, R 2 The organic alkyl group may be C1 to C 20 , C1 to C 15 , C1 to C 10 or C1 to C5 organic alkyl. In one aspect, R consisting of an inert functional group 2 The organic alkyl group can be a C1 to C 20 , C1 to C 15 , C1 to C 10 or a C1 to C5 organic alkyl group. 2 The hydrocarbon group may be C1 to C 20 , C1 to C 15 , C1 to C 10 or a C1 to C5 hydrocarbon group.

[0107] On the one hand, N 2 -phosphinoamidine and / or N 2 -phosphinoamidine chromium compound complex R 2 It can be acyl or substituted acyl; acyl; or alternatively, substituted acyl. In one aspect, the acyl group can be C1 to C 20 , C1 to C 15 , C1 to C 10 In one aspect, the substituted acyl group can be a substituted C1 to C5 acyl group. 20 , C1 to C 15 , C1 to C 10 or C1 to C5 acyl. In some aspects, N 2 -phosphinyl amidine and / or N 2 -phosphinyl amidine chromium compound complex R 2 can be alkanoyl, substituted alkanoyl, benzoyl or substituted benzoyl; alternatively, alkanoyl or substituted alkanoyl; alternatively, benzoyl or substituted benzoyl; alternatively, alkanoyl; alternatively, substituted alkanoyl; alternatively, benzoyl; or alternatively, substituted benzoyl. In any aspect disclosed herein, R 2 The alkanoyl group can be C1 to C 20 , C1 to C 10 , or C1 to C5 alkanoyl. In any aspect disclosed herein, the substituted R 2 The alkanoyl group may be substituted with C1 to C 20 , C1 to C 10 or C1 to C5 R 2 In any aspect disclosed herein, R2 The benzoyl group can be C7 to C 20 , C7 to C 15 or C7 to C 10 In any aspect disclosed herein, the substituted R 2 The benzoyl group may be substituted with C7 to C 20 , C1 to C 15 or C1 to C 10 R 2 Benzoyl. Each substituent of the substituted alkanoyl (general or specific) and / or substituted benzoyl (general or specific) can be halogen, hydrocarbyl or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific) and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents and hydrocarbyloxy substituents can be used without limitation to further describe the substituents that can be used as R 2 substituted alkanoyl and / or substituted benzoyl.

[0108] On the one hand, N 2 -phosphinyl amidine and / or N 2 -phosphinyl amidine chromium compound complex R 2 can be alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, aralkyl, or substituted aralkyl; alternatively, alkyl or substituted alkyl; alternatively, cycloalkyl or substituted cycloalkyl; alternatively, aryl or substituted aryl; alternatively, aralkyl or substituted aralkyl; or alternatively, alkyl, cycloalkyl, aryl, or aralkyl. In other aspects, N 2 -phosphinyl amidine and / or N 2 -phosphinyl amidine chromium compound complex R 2 can be alkyl; alternatively, substituted alkyl; alternatively, cycloalkyl; alternatively, substituted cycloalkyl; alternatively, aryl; alternatively, substituted aryl; alternatively, aralkyl; or alternatively, substituted aralkyl. In any aspect disclosed herein, R 2 The alkyl group can be C1 to C 20 , C1 to C 10 or C1 to C5 alkyl. In any aspect disclosed herein, the substituted R 2 The alkyl group may be substituted with C1 to C 20 , C1 to C 10 or C1 to C5 alkyl. In any aspect disclosed herein, R 2 The cycloalkyl group may be C4 to C 20, C4 to C 15 or C4 to C 10 In any aspect disclosed herein, substituted R 2 The cycloalkyl group may be substituted C4 to C 20 , C4 to C 15 or C4 to C 10 In any aspect disclosed herein, R 2 The aryl group can be C6 to C 20 , C6 to C 15 or C6 to C 10 In any aspect disclosed herein, substituted R 2 The aryl group may be a substituted C6 to C 20 , C6 to C 15 or C6 to C 10 In any aspect disclosed herein, R 2 The aralkyl group may be C7 to C 20 , C7 to C 15 or C7 to C 10 In any aspect disclosed herein, the substituted R 2 The aryl group may be substituted C7 to C 20 , C7 to C 15 or C7 to C 10 Aralkyl. Each substituent of substituted alkyl (general or specific), substituted cycloalkyl (general or specific), substituted aryl (general or specific) and / or substituted aralkyl (general or specific) can be halogen, hydrocarbyl or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific) and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents and hydrocarbyloxy substituents can be used without limitation to further describe R 2 .

[0109] On the one hand, R 2 Can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl; Or alternatively, methyl, ethyl, n-propyl (1-propyl), isopropyl (2-propyl), tert-butyl (2-methyl-2-propyl) or neopentyl (2,2-dimethyl-1-propyl). In some aspects, can be used as R 2The alkyl group may be substituted. Each substituent of the substituted alkyl group may independently be a halogen or a hydrocarbyl group; alternatively, a halogen; or alternatively, a hydrocarbyl group. Halogen substituents and hydrocarbyl substituents (general and specific) are independently disclosed herein. These halogen substituents and hydrocarbyl substituents may be used without limitation to further describe the moieties that may be used as R 2 Substituted alkyl (general and specific).

[0110] On the one hand, R 2 Can be cyclopentyl, substituted cyclopentyl, cyclohexyl or substituted cyclohexyl; alternatively, cyclopentyl or substituted cyclopentyl; or alternatively, cyclohexyl or substituted cyclohexyl. In one aspect, can be used as R 2 The substituted cycloalkyl group may be 2-substituted cyclohexyl, 2,6-disubstituted cyclohexyl, 2-substituted cyclopentyl, or 2,5-disubstituted cyclopentyl; alternatively, 2-substituted cyclohexyl or 2,6-disubstituted cyclohexyl; alternatively, 2-substituted cyclopentyl or 2,5-disubstituted cyclopentyl; alternatively, 2-substituted cyclohexyl or 2-substituted cyclopentyl; or alternatively, 2,6-disubstituted cyclohexyl or 2,5-disubstituted cyclopentyl. In one aspect, the cycloalkyl group used as R 2 The one or more substituents of a polysubstituted cycloalkyl group may be the same or different; alternatively, all substituents of the polysubstituted cycloalkyl group may be the same; or alternatively, all substituents of the polysubstituted cycloalkyl group may be different. Each substituent of a cycloalkyl group having a specified number of ring carbon atoms may independently be a halogen, a hydrocarbyl group, or a hydrocarbyloxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarbyloxy group; alternatively, a hydrocarbyl group or a hydrocarbyloxy group; alternatively, a halogen; alternatively, a hydrocarbyl group; or alternatively, a hydrocarbyloxy group. Halogen substituents, hydrocarbyl substituents (general and specific), and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents, and hydrocarbyloxy substituents may be used without limitation to further describe the groups that may be used as R 2 of substituted cycloalkyl (general and specific).

[0111] In one non-limiting aspect, R 2 It can be cyclohexyl, 2-alkylcyclohexyl or 2,6-dialkylcyclohexyl; or alternatively, cyclopentyl, 2-alkylcyclopentyl or 2,5-dialkylcyclopentyl. Alkyl substituents (general and specific) are described independently herein, and these alkyl substituents can be used without limitation to further describe the alkyl groups that can be used as R. 2alkylcyclohexyl (general or specific), dialkylcyclohexyl (general or specific), alkylcyclopentyl (general or specific) and / or dialkylcyclopentyl (general or specific). Typically, the alkyl substituents of the disubstituted cyclohexyl or cyclopentyl may be the same; or alternatively, the alkyl substituents of the dialkylcyclohexyl or cyclopentyl may be different. In some non-limiting aspects, R 2 It can be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, 2-tert-butylcyclohexyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl or 2,6-di-tert-butylcyclohexyl. In other non-limiting aspects, R 2 It may be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl or 2-tert-butylcyclohexyl; or alternatively, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl or 2,6-di-tert-butylcyclohexyl.

[0112] On the one hand, R 2 can be phenyl, substituted phenyl; alternatively, phenyl; or alternatively, substituted phenyl. In one aspect, can be used as R 2 The substituted phenyl group may be 2-substituted phenyl, 3-substituted phenyl, 4-substituted phenyl, 2,4-disubstituted phenyl, 2,6-disubstituted phenyl, 3,5-disubstituted phenyl, or 2,4,6-trisubstituted phenyl; alternatively, 2-substituted phenyl, 4-substituted phenyl, 2,4-disubstituted phenyl, or 2,6-disubstituted phenyl; alternatively, 3-substituted phenyl or 3,5-disubstituted phenyl; alternatively, 2-substituted phenyl or 4-substituted phenyl; alternatively, 2,4-disubstituted phenyl or 2,6-disubstituted phenyl; or alternatively, 2,4,6-trisubstituted phenyl. In one aspect, the substituted phenyl group used as R 2 The one or more substituents of the polysubstituted phenyl may be the same or different; alternatively, all substituents of the polysubstituted cycloalkyl may be the same; or alternatively, all substituents of the polysubstituted cycloalkyl may be different. Each substituent of the substituted phenyl (general or specific) may independently be halogen, hydrocarbyl, or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific), and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents, and hydrocarbyloxy substituents may be used without limitation to further describe the radicals that may be used as R 2 Substituted phenyl (general and specific).

[0113] In one non-limiting aspect, R2 It can be phenyl, 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl, 3,5-dialkylphenyl or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl or 4-alkylphenyl; alternatively, 2,4-dialkylphenyl or 2,6-dialkylphenyl; alternatively, 3-alkylphenyl or 3,5-dialkylphenyl; alternatively, 2-alkylphenyl or 2,6-dialkylphenyl; or alternatively, 2,4,6-trialkylphenyl. Alkyl substituents (general and specific) are described independently herein and these alkyl substituents can be used without limitation to further describe the alkyl substituents that can be used as R 2 Typically, the alkyl substituents of the dialkylphenyl (general or specific) or trialkylphenyl (general or specific) may be the same; or alternatively, the alkyl substituents of the dialkylphenyl or trialkylphenyl may be different. In some non-limiting aspects, R 2 The radical may independently be phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl or 2,4,6-trimethylphenyl; alternatively, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl or 2-tert-butylphenyl; alternatively, phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl or 2,4,6-trimethylphenyl.

[0114] In one non-limiting aspect, R 2 Can be phenyl, 2-alkoxyphenyl or 4-alkoxyphenyl. In some non-limiting aspects, R 2 can be phenyl, 2-methoxyphenyl, 2-ethoxyphenyl, 2-isopropoxyphenyl, 2-tert-butoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-isopropoxyphenyl or 4-tert-butoxyphenyl; alternatively, 2-methoxyphenyl, 2-ethoxyphenyl, 2-isopropoxyphenyl or 2-tert-butoxyphenyl; or alternatively, 4-methoxyphenyl, 4-ethoxyphenyl, 4-isopropoxyphenyl or 4-tert-butoxyphenyl. In another non-limiting aspect, R 2Can be phenyl, 2-halophenyl, 4-halophenyl or 2,6-dihalophenyl. Typically, the halides of the dihalophenyl can be the same; or alternatively, the halides of the dihalophenyl can be different. In some aspects, R 2 It may be phenyl, 2-fluorophenyl, 4-fluorophenyl or 2,6-difluorophenyl.

[0115] On the one hand, R 2 can be benzyl or substituted benzyl; alternatively, benzyl; or alternatively, substituted benzyl. Each substituent of the substituted benzyl can independently be halogen, hydrocarbyl, or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific), and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents, and hydrocarbyloxy substituents can be used without limitation to further describe the substituents that can be used as R 2 of a substituted benzyl group.

[0116] In other respects, R 1 and R 2 Can be connected to form N 2 -phosphinyl amidine and / or N 2 -A ring or ring system having a carbon-nitrogen double bond of the phosphinyl amidine chromium compound complex. 1 and R 2 The connection can be specified as L 12r and can be an organoalkylene group; alternatively, an organoalkylene group consisting of inert functional groups; alternatively, an alkylene group; or alternatively, an alkylene group. In one aspect, L 12r The organoalkylene group, when present, can be C3 to C 30 , C3 to C 20 , C3 to C 15 or C3 to C 10 In some aspects, L consisting of an inert functional group 12r The organoalkylene group, when present, may be a C3 to C 30 , C3 to C 20 , C3 to C 15 or C3 to C 10 In other aspects, L 12r The hydrocarbon group, when present, may independently be C3 to C 30 , C3 to C 20 , C3 to C 15 or C3 to C 10 In yet another aspect, L 12rAlkylene, when present, may independently be C3 to C 30 , C3 to C 20 , C3 to C 15 or C3 to C 10 In one aspect, L 12r It may be 1,3-propylene, 1,3-butylene, 3-methyl-1,3-butylene (-CH2CH2C(CH3)2-), 1,4-butylene, or 1,4-1,4-pentylene.

[0117] Typically, T of the heterocyclic 2-[(phosphinyl)amino]imine and / or heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex can be oxygen or sulfur. In one aspect, T of the heterocyclic 2-[(phosphinyl)amino]imine and / or heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex can be oxygen; or alternatively, sulfur.

[0118] Usually, with R 2a and / or R 2b N 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium compound complex R 2a and / or R 2b , can be independently hydrogen or organic alkyl; alternatively, hydrogen or organic alkyl consisting of inert functional groups; alternatively, hydrogen or hydrocarbon group; alternatively, hydrogen; alternatively, organic alkyl; alternatively, organic alkyl consisting of inert functional groups; or alternatively, hydrocarbon group. In one aspect, R 2a and / or R 2b The organic alkyl group can be independently C1 to C 20 , C1 to C 15 , C1 to C 10 or C1 to C5 organic alkyl. In some aspects, R consisting of an inert functional group 2a and / or R 2b The organic alkyl group may be independently a C1 to C 20 , C1 to C 15 , C1 to C 10 or C1 to C5 organic alkyl. In other aspects, R 2a and / or R 2b The hydrocarbon groups can independently be C1 to C 20 , C1 to C 15 , C1 to C 10 or a C1 to C5 hydrocarbon group.

[0119] On the one hand, having R 2a and / or R 2b N of organic alkyl 2 -phosphinylguanidine and / or N2 -phosphinylguanidine chromium compound complex R 2a and R 2b R may independently be alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, aralkyl, or substituted aralkyl; alternatively, alkyl or substituted alkyl; alternatively, cycloalkyl or substituted cycloalkyl; alternatively, aryl or substituted aryl; alternatively, aralkyl or substituted aralkyl; alternatively, alkyl, cycloalkyl, aryl, or aralkyl; alternatively, alkyl; alternatively, substituted alkyl; alternatively, cycloalkyl; alternatively, substituted cycloalkyl; alternatively, aryl; alternatively, substituted aryl; alternatively, aralkyl; or alternatively, substituted aralkyl. In any aspect disclosed herein, R 2a and / or R 2b The alkyl group can be independently C1 to C 20 , C1 to C 10 or C1 to C5 alkyl. In any aspect disclosed herein, R 2a and / or R 2b The cycloalkyl groups can be independently C4 to C 20 , C4 to C 15 or C4 to C 10 In any aspect disclosed herein, substituted R 2a and / or R 2b The cycloalkyl groups may be independently substituted C4 to C 20 , C4 to C 15 or C4 to C 10 In any aspect disclosed herein, R 2a and / or R 2b The aryl groups can independently be C6 to C 20 , C6 to C 15 or C6 to C 10 In any aspect disclosed herein, substituted R 2a and / or R 2b The aryl groups may be independently substituted C6 to C 20 , C6 to C 15 or C6 to C 10 Aryl. Each substituent of the substituted cycloalkyl (general or specific) / or substituted aryl (general or specific) can be halogen, hydrocarbyl or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific) and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents and hydrocarbyloxy substituents can be used without limitation to further describe R2a and / or R 2b .

[0120] On the one hand, N 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium compound complex R 1 and R 2a Can be linked to form group L 12 , where L 12 、N 1 Nitrogen atoms and N 3 The nitrogen atoms form a ring or ring system. 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium compound complex R 3 and R 2b Can be linked to form group L 23 , where L 23 、N 2 Nitrogen atoms and N 3 The nitrogen atom forms a ring or ring system. 12 Group and / or L 23 N 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium complex L 12 and / or L 23 L may independently be an organoalkylene group; alternatively, an organoalkylene group consisting of inert functional groups; or alternatively, an alkylene group. 12 and / or L 23 The organoalkylene group can independently be C2 to C 20 , C2 to C 15 , C2 to C 10 or C2 to C5 organoalkylene. L consisting of inert functional groups 12 and / or L 23 The organoalkylene group may be independently a C2 to C 20 , C2 to C 15 , C2 to C 10 Or C2 to C5 organoalkylene. 12 and / or L 23 The alkylene groups can independently be C2 to C 20 , C2 to C 15 , C2 to C 10 or a C2 to C5 alkylene group.

[0121] In one aspect, having L 12 N 2 -Phosphinylguanidine, N 2-phosphinylguanidine chromium compound complex, heterocyclic 2-[(phosphinyl)amino]imine and / or heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex 12 And with L 23 N 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium complex L 23 Can have any structure provided in Table 1. In some aspects, L 12 and / or L 23 It can have structure 1L, structure 2L, structure 3L, structure 4L or structure 5L. In some aspects, L 12 and / or L 23 It can have structure 2L or structure 3L; alternatively, structure 4L or structure 5L. In other aspects, L 12 and / or L 23 may have structure 1L; alternatively, structure 2L; alternatively, structure 3L; alternatively, structure 4L; or alternatively, structure 5L. In some N 2 -phosphinylguanidine and N 2 -phosphinylguanidine chromium compound complex, L 12 and / or L 23 It can have structure 6L. It should be noted that when L 12 or L 23 With structure 6L, the corresponding R 2b or R 2a Due to N 2 -phosphinylguanidine and / or N 2 -Oxyphosphinylguanidine chromium compounds 3 The double bonds of the nitrogen atoms are connected and empty.

[0122] Table 1 - Linking group L 12 and / or L 23 structure.

[0123]

[0124] In the structure of Table 1, L 12 and / or L 23 The unspecified valence indicates L 12 and / or L 23 Attach to N when present 2 -phosphinylguanidine and N 2 -phosphinylguanidine chromium compound complex. In addition, for the structure of Table 1, L 12 The unspecified valence indicates L 12The point of attachment to T and the corresponding nitrogen atom of the heterocyclic 2-[(phosphinyl)amino]imine and / or the heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex. Typically, m can be an integer ranging from 2 to 5. In other aspects, m can be 2 or 3; alternatively, m can be 2; or alternatively, m can be 3. R of the linking group having structure 1L L1 and R L2 , R having a linker group of structure 2L L3 , R L4 , R L5 and R L6 , R having a linker group of structure 3L L3 , R L4 , R L5 , R L6 , R L7 and R L8 , R having a linker group of structure 4L L11 and R L12 , R having a linker group of structure 5L L23 , R L24 , R L25 and R L26 , R having a linker group of structure 6L L27 , R L28 and R L29 can be independently hydrogen or a non-hydrogen substituent; or alternatively, hydrogen. Non-hydrogen substituents (general and specific) are independently disclosed herein and can be used without limitation to further describe linking groups having Structure 1L, Structure 2L, Structure 3L, Structure 4L, Structure 5L, and / or Structure 6L. In one aspect, L 12 and / or L 23 L may independently be 1,2-vinyl (—CH2CH2—), 1,2-vinylene (—CH═CH—), 1,3-propenyl (—CH2CH2CH2—), 1-methyl-1,2-vinylene (—C(CH3)═CH—), 1,3-butenyl (—CH2CH2CH(CH3)—), 3-methyl-1,3-butenyl (—CH2CH2C(CH3)2—), or 1,2-phenylene. In some non-limiting aspects, L 12 and / or L 23It is 1,2-vinyl (-CH2CH2-), 1,3-propenyl (-CH2CH2CH2-), 1-methyl-1,2-vinyl (-C(CH3)=CH-), 1,3-butenyl (-CH2CH2CH(CH3)-) or 3-methyl-1,3-butenyl (-CH2CH2C(CH3)2-); alternatively, 1,2-vinyl (-CH2CH2-), 1,2-vinylene (-CH=CH-), 1,3-propenyl (-CH2CH2CH2-) or 1,2-phenylene; alternatively, 1,2-vinyl (-CH2CH2-) or 1,3-propenyl (-CH2CH2CH2-); alternatively, 1,2-vinylene (-CH=CH-) or 1,2-phenylene.

[0125] On the one hand, L 12 It may have a structure that includes at least one 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium complex N 1 A substituent on a carbon atom of a nitrogen atom; alternatively, it may contain only one 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium complex N 1 A substituent on a carbon atom of a nitrogen atom; or alternatively, two substituents may be present on a carbon atom attached to the nitrogen atom; 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium complex N 1 In another aspect, L 12 It may have a structure that may be located attached to N 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium complex N 1 or alternatively, may consist of a substituent on a carbon atom attached to the nitrogen atom; 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium complex N 1 It consists of two substituents on the carbon atom of the nitrogen atom.

[0126] On the one hand, N 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium compound complex R 2a and R 2b can be linked to form the group L 22 , where R 2a , R 2b and N 3Nitrogen atom (or L 22 and N 3 In one aspect, L 22 N 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium complex L 22 L may be an organoalkylene group; alternatively, an organoalkylene group consisting of inert functional groups; or alternatively, an alkylene group. 22 The organoalkylene group can be C3 to C 20 , C3 to C 15 or C3 to C 10 Organoalkylene. L composed of inert functional groups 22 The organoalkylene group can be a C3 to C 20 , C3 to C 15 or C3 to C 10 Organoalkylene. 22 The alkylene group can be C4 to C 20 , C4 to C 15 or C4 to C 10 Alkylene.

[0127] On the one hand, L 22 Can have any structure provided in Table 2. In some aspects, L 22 It may have structure 11L, structure 12L, structure 13L, structure 14L, structure 15L or structure 16L. In other aspects, L 22 There may be structure 11L; alternatively, structure 12L; alternatively, structure 13L; alternatively, structure 14L; or alternatively, structure 15L.

[0128] Table 2 - Linking group L 22 structure.

[0129]

[0130] In the structures in Table 2, unspecified valences represent N 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium complex L 22 Attach to N when present 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium complex N 3 The site of the nitrogen atom. Generally, n can be an integer ranging from 4 to 7. In other aspects, n can be 4 or 5; alternatively, n can be 4; or alternatively, n can be 5. The R of the linking group having structure 11L L31 and R L32, R having a linker group of structure 12L L41 , R L42 , R L43 , R L44 , R L45 , R L46 , R L47 and R L48 , R having a linker group of structure 13L L41 , R L42 , R L43 , R L44 , R L45 , R L46 , R L47 , R L48 , R L49 and R L50 , R having a linker group of structure 14L L41 , R L42 , R L43 , R L44 , R L45 , R L46 , R L47 and R L48 , and R having a linker group of structure 15L L41 , R L42 , R L43 , R L44 , R L45 , R L46 , R L47 and R L48 can be independently hydrogen or a non-hydrogen substituent; alternatively, hydrogen. Non-hydrogen substituents are independently disclosed herein and can be used without limitation to further describe a linking group having Structure 11L, Structure 12L, Structure 13L, Structure 14L, and / or Structure 15L. In one aspect, L 22 It may be 1,4-butenyl, 1,4-pentenyl, 1,5-pentenyl, 2,5-hexenyl, 1,5-hexenyl, 2,5-heptenyl, 1,3-butadien-1,4-ylidene or bis(eth-2-yl)ether; or alternatively, 1,4-butenyl, 1,5-pentenyl or bis(eth-2-yl)ether.

[0131] Usually, with R 3 N 2 -phosphinylformamidine, N 2 -phosphinylformamidinium chromium compound complex, N 2 -phosphinyl amidine, N 2 -phosphinyl amidine chromium compound complex, N 2 -Phosphinylguanidine, N 2-phosphinylguanidine chromium compound complex, heterocyclic 2-[(phosphinyl)amino]imine and / or heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex 3 can be hydrogen or organoalkyl; hydrogen or organoalkyl consisting of inert functional groups; alternatively, hydrogen or hydrocarbon; alternatively, hydrogen; alternatively, organoalkyl; alternatively, organoalkyl consisting of inert functional groups; or alternatively, hydrocarbon. In one aspect, R 3 The organic alkyl group may be C1 to C 20 , C1 to C 15 , C1 to C 10 or C1 to C5 organic alkyl. In one aspect, R consisting of an inert functional group 3 The organic alkyl group can be a C1 to C 20 , C1 to C 15 , C1 to C 10 or a C1 to C5 organic alkyl group. 3 The hydrocarbon group may be C1 to C 20 , C1 to C 15 , C1 to C 10 or a C1 to C5 hydrocarbon group. In other aspects, R 3 N 2 -phosphinylformamidine, N 2 -phosphinylformamidinium chromium compound complex, N 2 -phosphinyl amidine, N 2 -phosphinyl amidine chromium compound complex, N 2 -Phosphinylguanidine, N 2 -phosphinylguanidine chromium compound complex, heterocyclic 2-[(phosphinyl)amino]imine and / or heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex 3 Can be C1 to C 30 , C1 to C 20 , C1 to C 15 , C1 to C 10 or C1 to C5 alkyl. In other aspects, N 2 -phosphinylformamidine, N 2 -phosphinylformamidinium chromium compound complex, N 2 -phosphinyl amidine, N 2 -phosphinyl amidine chromium compound complex, N 2 -Phosphinylguanidine, N 2 -phosphinylguanidine chromium compound complex, heterocyclic 2-[(phosphinyl)amino]imine and / or heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex 3 It can be phenyl or substituted C6 to C 20 Phenyl; alternatively, phenyl or substituted C6 to C15 Phenyl; or alternatively, phenyl or substituted C6 to C 10 Phenyl. Substituents (general and specific) are provided herein, and these substituents can be used to further describe the substituents that can be used as having non-hydrogen R 3 N 2 -phosphinylformamidine, N 2 -phosphinylformamidinium chromium compound complex, N 2 -phosphinyl amidine, N 2 -phosphinyl amidine chromium compound complex, N 2 -phosphinylguanidine and / or N 2 -phosphinylguanidine chromium compound complex R 3 of a substituted phenyl group.

[0132] Usually, N 2 -phosphinylformamidine, N 2 -phosphinylformamidinium chromium compound complex, N 2 -phosphinyl amidine, N 2 -phosphinyl amidine chromium compound complex, N 2 -Phosphinylguanidine, N 2 -phosphinylguanidine chromium compound complex, heterocyclic 2-[(phosphinyl)amino]imine and / or heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex 4 and / or R 5 can be independently an organic alkyl group; alternatively, an organic alkyl group consisting of inert functional groups; or alternatively, a hydrocarbon group. In one aspect, R 4 and / or R 5 The organic alkyl group may be C1 to C 20 , C1 to C 15 , C1 to C 10 or C1 to C5 organic alkyl. In one aspect, R consisting of an inert functional group 4 and / or R 5 The organic alkyl group can be a C1 to C 20 , C1 to C 15 , C1 to C 10 or a C1 to C5 organic alkyl group. 4 and / or R 5 The hydrocarbon group may be C1 to C 20 , C1 to C 15 , C1 to C 10 or a C1 to C5 hydrocarbon group. 2 -phosphinylformamidine, N 2 -phosphinylformamidinium chromium compound complex, N 2 -phosphinyl amidine, N 2 -phosphinyl amidine chromium compound complex, N2 -Phosphinylguanidine, N 2 -phosphinylguanidine chromium compound complex, heterocyclic 2-[(phosphinyl)amino]imine and / or heterocyclic 2-[(phosphinyl)amino]imine chromium compound complex 4 and / or R 5 and may independently be alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, aralkyl or substituted aralkyl; alternatively, alkyl or substituted alkyl; alternatively, cycloalkyl or substituted cycloalkyl; alternatively, aryl or substituted aryl; alternatively, aralkyl or substituted aralkyl; alternatively, alkyl, cycloalkyl, aryl or aralkyl; alternatively, alkyl; alternatively, substituted alkyl, alternatively, cycloalkyl; alternatively, substituted cycloalkyl; alternatively, aryl; alternatively, substituted aryl; alternatively, aralkyl; or alternatively, substituted aralkyl.

[0133] In any aspect disclosed herein, R 4 and / or R 5 The alkyl group can be independently C1 to C 20 , C1 to C 10 or C1 to C5 alkyl. In any aspect disclosed herein, the substituted R 4 and / or R 5 The alkyl group may be independently substituted C1 to C 20 , C1 to C 10 or C1 to C5 alkyl. In any aspect disclosed herein, R 4 and / or R 5 The cycloalkyl groups can be independently C4 to C 20 , C4 to C 15 or C4 to C 10 In any aspect disclosed herein, substituted R 4 and / or R 5 The cycloalkyl groups may be independently substituted C4 to C 20 , C4 to C 15 or C4 to C 10 In any aspect disclosed herein, R 4 and / or R 5 The aryl groups can independently be C6 to C 20 , C6 to C 15 or C6 to C 10 In any aspect disclosed herein, substituted R 4 and / or R 5 The aryl groups may be independently substituted C6 to C 20 , C6 to C 15 or C6 to C 10In any aspect disclosed herein, R 4 and / or R 5 The aralkyl groups can independently be C7 to C 20 , C7 to C 15 or C7 to C 10 In any aspect disclosed herein, the substituted R 4 and / or R 5 The aryl groups may be independently substituted C7 to C 20 , C7 to C 15 or C7 to C 10 Aralkyl. Each substituent of substituted alkyl (general or specific), substituted cycloalkyl (general or specific), substituted aryl (general or specific) and / or substituted aralkyl (general or specific) can be halogen, hydrocarbyl or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific) and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents and hydrocarbyloxy substituents can be used without limitation to further describe R 4 and / or R 5 .

[0134] On the one hand, R 4 and R 5 Can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl independently; Or alternatively, methyl, ethyl, n-propyl (1-propyl), isopropyl (2-propyl), 2-methyl-1-propyl, tert-butyl (2-methyl-2-propyl) or neopentyl (2,2-dimethyl-1-propyl). In some aspects, can be used as R 4 and / or R 5 The alkyl group may be substituted. Each substituent of the substituted alkyl group may independently be a halogen or a hydrocarbyl group; alternatively, a halogen; or alternatively, a hydrocarbyl group. Halogen substituents and hydrocarbyl substituents (general and specific) are independently disclosed herein. These halogen substituents and hydrocarbyl substituents may be used without limitation to further describe the moieties that may be used as R 4 and / or R 5 of a substituted alkyl group.

[0135] On the one hand, R 4 and R 5 Can be independently cyclopentyl, substituted cyclopentyl, cyclohexyl or substituted cyclohexyl; alternatively, cyclopentyl or substituted cyclopentyl; or alternatively, cyclohexyl or substituted cyclohexyl. In one aspect, can be used for R 4 and / or R5 The substituted cycloalkyl can be 2-substituted cyclohexyl, 2,6-disubstituted cyclohexyl, 2-substituted cyclopentyl or 2,5-disubstituted cyclopentyl; alternatively, 2-substituted cyclohexyl or 2,6-disubstituted cyclohexyl; alternatively, 2-substituted cyclopentyl or 2,5-disubstituted cyclopentyl; alternatively, 2-substituted cyclohexyl or 2-substituted cyclopentyl; or alternatively, 2,6-disubstituted cyclohexyl or 2,5-disubstituted cyclopentyl. In the aspect that the substituted cycloalkyl (generally or specifically) has more than one substituent, the substituents can be the same or different; alternatively, the same; or alternatively, different. Each substituent of a cycloalkyl group (general or specific) having a specified number of ring carbon atoms may independently be halogen, hydrocarbyl, or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific), and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents, and hydrocarbyloxy substituents may be used without limitation to further describe the substituents that may be used as R. 4 and / or R 5 of substituted cycloalkyl (general and specific).

[0136] In one non-limiting aspect, R 4 and R 5 R is independently cyclohexyl, 2-alkylcyclohexyl or 2,6-dialkylcyclohexyl; or alternatively, cyclopentyl, 2-alkylcyclopentyl or 2,5-dialkylcyclopentyl. Alkyl substituents (general and specific) are described independently herein, and these alkyl substituents can be used without limitation to further describe the alkyl groups that can be used as R. 4 and / or R 5 alkylcyclohexyl (general or specific), dialkylcyclohexyl (general or specific), alkylcyclopentyl (general or specific) and / or dialkylcyclopentyl (general or specific). Typically, the alkyl substituents of the disubstituted cyclohexyl or cyclopentyl may be the same; or alternatively, the alkyl substituents of the dialkylcyclohexyl or cyclopentyl may be different. In some non-limiting aspects, R 4 and R 5 R may independently be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, 2-tert-butylcyclohexyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl or 2,6-di-tert-butylcyclohexyl. 4 and R 5may independently be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl or 2-tert-butylcyclohexyl; or alternatively, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl or 2,6-di-tert-butylcyclohexyl.

[0137] On the one hand, R 4 and R 5 can be independently phenyl, substituted phenyl; alternatively, phenyl; or alternatively, substituted phenyl. In one aspect, it can be used for R 4 and / or R 5 The substituted phenyl group may be 2-substituted phenyl, 3-substituted phenyl, 4-substituted phenyl, 2,4-disubstituted phenyl, 2,6-disubstituted phenyl, 3,5-disubstituted phenyl, or 2,4,6-trisubstituted phenyl; alternatively, 2-substituted phenyl, 4-substituted phenyl, 2,4-disubstituted phenyl, or 2,6-disubstituted phenyl; alternatively, 3-substituted phenyl or 3,5-disubstituted phenyl; alternatively, 2-substituted phenyl or 4-substituted phenyl; alternatively, 2,4-disubstituted phenyl or 2,6-disubstituted phenyl; or alternatively, 2,4,6-trisubstituted phenyl. In one aspect, the substituted phenyl group used as R 4 and / or R 5 The one or more substituents of the polysubstituted phenyl may be the same or different; alternatively, all substituents of the polysubstituted cycloalkyl may be the same; or alternatively, all substituents of the polysubstituted cycloalkyl are different. Each substituent of the substituted phenyl (general or specific) may independently be halogen, hydrocarbyl, or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific), and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents, and hydrocarbyloxy substituents may be used without limitation to further describe the radicals that may be used as R 4 and / or R 5 Substituted phenyl (general and specific).

[0138] In one non-limiting aspect, R 4 and R 5R is independently phenyl, 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl, 3,5-dialkylphenyl or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl or 4-alkylphenyl; alternatively, 2,4-dialkylphenyl or 2,6-dialkylphenyl; alternatively, 3-alkylphenyl or 3,5-dialkylphenyl; alternatively, 2-alkylphenyl or 2,6-dialkylphenyl; or alternatively, 2,4,6-trialkylphenyl. Alkyl substituents (general and specific) are described independently herein and these alkyl substituents can be used without limitation to further describe the alkyl substituents that can be used as R. 4 and / or R 5 In some non-limiting aspects, R 4 and R 5 The radical may independently be phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl or 2,4,6-trimethylphenyl; alternatively, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl or 2-tert-butylphenyl; alternatively, phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl or 2,4,6-trimethylphenyl.

[0139] In one non-limiting aspect, R 4 and R 5 Can be phenyl, 2-alkoxyphenyl or 4-alkoxyphenyl. In some non-limiting aspects, R 4 and / or R 5 Can be phenyl, 2-methoxyphenyl, 2-ethoxyphenyl, 2-isopropoxyphenyl, 2-tert-butoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-isopropoxyphenyl or 4-tert-butoxyphenyl; alternatively, 2-methoxyphenyl, 2-ethoxyphenyl, 2-isopropoxyphenyl or 2-tert-butoxyphenyl; or alternatively, 4-methoxyphenyl, 4-ethoxyphenyl, 4-isopropoxyphenyl or 4-tert-butoxyphenyl. In one non-limiting aspect, R4 and R 5 R may independently be phenyl, 2-halophenyl, 4-halophenyl or 2,6-dihalophenyl. Typically, the halides of the dihalophenyl may be the same; or alternatively, the halides of the dihalophenyl may be different. In some aspects, R 4 and R 5 and phenyl and 2-fluorophenyl groups may independently be phenyl, 2-fluorophenyl, 4-fluorophenyl or 2,6-difluorophenyl groups.

[0140] On the one hand, R 4 and R 5 R is independently benzyl or substituted benzyl; alternatively, benzyl; or alternatively, substituted benzyl. Each substituent of the substituted benzyl group can independently be halogen, hydrocarbyl, or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific), and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents, and hydrocarbyloxy substituents can be used without limitation to further describe the substituents that can be used as R 4 and / or R 5 of a substituted benzyl group.

[0141] In other respects, R 4 and R 5 They may be linked to form a ring or ring system containing a phosphorus atom. 4 and R 5 The connection can be specified as L 45 and may be an organoalkylene group; alternatively, an organoalkylene group consisting of inert functional groups; alternatively, an alkylene group; or alternatively, an alkylene group. In one aspect, L 45 The organoalkylene group, when present, can be C4 to C 30 , C4 to C 20 , C4 to C 15 or C4 to C 10 In one aspect, L consisting of an inert functional group 45 The organoalkylene group, when present, may be a C4 to C 30 , C4 to C 20 , C4 to C 15 or C4 to C 10 In one aspect, L 45 The hydrocarbon group, when present, may independently be C4 to C 30 , C4 to C 20 , C4 to C 15 or C4 to C 10In yet another aspect, L 45 Alkylene, when present, may independently be C4 to C 30 , C4 to C 20 , C4 to C 15 or C4 to C 10 In one aspect, L 45 It may be 1,4-butenyl, 1,4-diphenyl-1,4-butenyl, 1,4-di(2-methylphenyl)-1,4-butenyl, 1,4-di(4-methylphenyl)-1,4-butenyl, 1,4-di(4-tert-butylphenyl)-1,4-butenyl, 1,4-di(3,5-dimethylphenyl)-1,4-butenyl, 1,4-pentenyl, 1-phenyl-1,4-pentenyl, 4-phenyl-1,4-pentenyl, 2,5-hexenyl, 2,2'-biphenylene, 2,2'-(methanediyl)diphenylene or 2,2'-(1,2-ethanediyl)diphenylene.

[0142] In one aspect, the heteroatom ligand or the heteroatom ligand of the heteroatom ligand chromium compound complex can have the formula (R 1s ) m X 1s (L 1s )X 2s (R 2s ) n , while the heteroatom ligand chromium compound complex may have the formula:

[0143]

[0144] In some aspects, the heteroatom ligand or the heteroatom ligand of the heteroatom ligand chromium compound complex can have a structure that can be represented by the formula (R 1s ) m X 1s (L 1s )X 2s (R 2s ) n The heteroatom ligand may have a structure that can be represented by the formula (R 1s ) m X 1s (L 1s )X 2s (R 2s ) n In the case of two groups described, the two L 1s The groups are connected and the heteroatom ligand and the heteroatom ligand chromium compound complex may have the formula:

[0145] They are

[0146] In the case of (R 1s )m X 1s (L 1s )X 2s (R 2s ) n or with two connected (R 1s ) m X 1s (L 1s )X 2s (R 2s ) n In the heteroatom ligand of the group or the heteroatom ligand of the chromium compound complex, each X 1s and each X 2s may be independently selected from N, P, O and S; each L 1s Can be the corresponding X 1s s and X 2s s; each m and each n can independently be 1 or 2; and each R 1s and each R 2s R is independently hydrogen, organic alkyl (or alternatively, organic alkyl consisting of inert functional groups; or alternatively, hydrocarbon) or heterohydrocarbon, wherein when there are two or more R 1s and / or two R 2s When each R 1s may be the same or different (alternatively, the same; or alternatively, different) and / or each R 2s may be the same or different (alternatively, the same; or alternatively, different). L 1s , X 1s , X 2s , R 1s , R 2s , m and n are L 1s , X 1s , X 2s , R 1s , R 2s Any heteroatom ligand of m, m and / or n or any heteroatom ligand of a heteroatom ligand chromium compound complex is an independent element and is described independently herein. 1s , X 1s , X 2s , R 1s , R 2s These independent descriptions of m and n can be used without limitation and in any combination to further describe the structure of L 1s , X 1s , X 2s , R 1s , R 2s Any heteroatom ligand of m and / or n or any heteroatom ligand of a heteroatom ligand chromium compound complex.p are independent elements of the heteroatom ligand chromium compound complex and are described independently herein and may be used without limitation and in combination with the heteroatom ligand L 1s , X 1s , X 2s , R 1s , R 2s , m, and n in any combination are used to further describe the heteroatom ligand chromium compound complexes contemplated herein.

[0147] In one aspect, the present invention has X 1s and / or X 2s Any heteroatom ligand or any heteroatom ligand of the chromium compound complex of any heteroatom ligand X 1s and each X 2s can be independently selected from N, P, O, and S; alternatively, independently selected from N and P; or alternatively, independently selected from O and S. In some aspects, each X 1s and each X 2s can be N; alternatively, P; alternatively, O; or alternatively, S. Each m and each n of any heteroatom ligand of any heteroatom ligand chromium compound complex having m and / or n described herein can be independently selected from 1 or 2; alternatively, 1; or alternatively, 2. In some specific aspects, when X 1s and / or X 2s When X is O or S, respectively; alternatively, O; or alternatively, S, each m and / or each n may be 1. In some other specific aspects, when X 1s and / or X 2s When it is N or P respectively, alternatively, it is N; or alternatively, when it is P, each m and / or each n can be 2.

[0148] In one non-limiting aspect, the heteroatom ligand can have the formula R 1s S(L 1s )SR 2s , (R 1s )2P(L 1s )P(R 2s )2 or (R 1s )2N(L 1s )N(R 2s )2; Alternatively, R 1s S(L 1s )SR 2s ; Alternatively, (R 1s )2P(L 1s )P(R 2s )2; or alternatively, (R 1s )2N(L 1s)N(R 2s )2, and the heteroatom ligand chromium compound complex may have any of the following formulae:

[0149] and / or

[0150] In non-limiting aspects where the heteroatom ligand or heteroatom ligand of the heteroatom ligand chromium compound complex has two linked heteroatom groups, the heteroatom ligand may have a formula selected from one or more of the following:

[0151] and / or

[0152] The heteroatom ligand chromium compound complex may have any of the following formulae:

[0153] and / or

[0154] In one aspect, each L of any heteroatom ligand or any heteroatom ligand of a heteroatom ligand chromium compound complex described herein 1s can independently be capable of connecting group X 1s and X 2s Any group (and when there are more than one L 1s When it is a heteroatom ligand or other L of a heteroatom ligand of a heteroatom ligand chromium compound complex 1s In some aspects, each L 1s and L may be independently an organoalkylene, an amine-diyl or a phosphine-diyl; alternatively, an organoalkylene, an amine-diyl or a phosphine-diyl consisting of inert functional groups; alternatively, a hydrocarbylene, an amine-diyl or a phosphine-diyl; alternatively, an amine-diyl or a phosphine-diyl; alternatively, an organoalkylene; alternatively, an organoalkylene consisting of inert functional groups; alternatively, a hydrocarbylene; alternatively, an amine-diyl; or alternatively, a phosphine-diyl. When more than one L is present in the heteroatom ligand or the heteroatom ligand chromium compound complex 1s When each L 1s can be independently an organic group, an amine group or a phosphine group; alternatively, an organic group, an amine group or a phosphine group consisting of inert functional groups; alternatively, a hydrocarbon group, an amine group or a phosphine group; alternatively, an amine group or a phosphine group; alternatively, an organic group; alternatively, an organic group consisting of inert functional groups; alternatively, a hydrocarbon group; alternatively, an amine group; or alternatively, a phosphine group. In one aspect, L 1s The organoalkylene or organic group can be C1 to C 20 , C1 to C 15 , C1 to C 10or C1 to C5 organoalkylene or organic groups. In one aspect, L consisting of inert functional groups 1s The organoalkylene group can be a C1 to C 20 , C1 to C 15 , C1 to C 10 or a C1 to C5 organoalkylene group or an organic group. 1s The alkylene group can be C1 to C 20 , C1 to C 15 , C1 to C 10 or C1 to C5 alkylene or alkyl. In one aspect, the amine-diyl or amine group can be C1 to C5 30 , C1 to C 20 , C1 to C 15 or C1 to C 10 In one aspect, the phosphine-diyl or phosphine group can be C1 to C 30 , C1 to C 20 , C1 to C 15 or C1 to C 10 Phosphine-diyl or phosphino.

[0155] On the one hand, each L 1s The organoalkylene group or the organic group may have the formula -(L 3s )NR 5s (L 4s )-or-(L 3s )PR 5s (L 4s )-; alternatively, -(L 3s )NR 5s (L 4s )-; or alternatively, -(L 3s )PR 5s (L 4s In one aspect, each amine-diyl group can have the formula -N(R 5s In one aspect, each phosphine-diyl group can have the formula -P(R 5s )-. In these L 1s In the formula of the group, the dash represents the heteroatom ligand X of the heteroatom ligand or heteroatom ligand chromium compound complex described herein. 1s and X 2s When there are more than one L in the heteroatom ligand or the heteroatom ligand chromium compound complex 1s When each L 1s R 5s Can be combined to indicate L 2sIn some non-limiting aspects, the heteroatom ligand can have the structure PNP1, structure PNP2, structure NRN, structure PRP, structure SRN, structure PRN, and structure NRP; alternatively, structure PNP1 or structure PNP2; alternatively, structure PRP, structure SRN, or structure PRN; alternatively, structure PNP1; alternatively, structure PNP2; alternatively, structure NRN; alternatively, structure PRP; alternatively, structure SRN; alternatively, structure PRN; or; alternatively, structure NRP. In some non-limiting aspects, the heteroatom ligand (R) that can be used in the catalyst system described herein is 1s ) m X 1s (L 1s )X 2s (R 2s ) n The heteroatom ligand chromium compound complex may have structure PNCr1, structure PNPCr2, structure NRNCr, structure PRPCr, structure SRNCr, structure PRNCr and structure NRPCr; alternatively, structure PNPCr1 or structure PNPCr2; alternatively, structure PRPCr, structure SRNCr or structure PRNCr; alternatively, structure PNPCr1; alternatively, structure PNPCr2; alternatively, structure NRNCr; alternatively, structure PRPCr; alternatively, structure SRNCr; alternatively, structure PRNCr; or alternatively, structure NRPCr.

[0156]

[0157] R 5s , L 2s , L 3s , L 4s , R 11s , R 12s , R 13s and R 14s Each is a heteroatom ligand having the structure PNP1, structure PNP2, structure NRN, structure PRP, structure SRN, structure PRN or structure NRP, and / or an independent element of a heteroatom ligand chromium compound complex having the structure PNPCr1, structure PNPCr2, structure NRNCr, structure PRPCr, structure SRNCr, structure PRNCr and structure NRPCr (where they appear and are described independently). 5s , L 2s , L 3s , L 4s , R 11s , R 12s , R 13s and R14s The independent descriptions of X and p can be used in any combination without limitation to further describe the heteroatom ligand structures and / or heteroatom ligand chromium compound complex structures in which they appear. Similarly, X and p are independent elements of the heteroatom ligand chromium compound complex having the structures PNCr1, PNPCr2, NRNCr, PRPCr, SRNCr, PRNCr, and NRPCr and are independently described herein. The independent descriptions of X and p can be used in any combination without limitation to further describe the heteroatom ligand structures and / or heteroatom ligand chromium compound complex structures in which they appear. Similarly, X and p are independent elements of the heteroatom ligand chromium compound complex having the structures PNCr1, PNPCr2, NRNCr, PRPCr, SRNCr, PRNCr, and NRPCr and are independently described herein. 5s , L 2s , L 3s , L 4s , R 11s , R 12s , R 13s and R 14s Used in any combination to further describe any heteroatom ligand chromium compound complex having structure PNPCr1, structure PNPCr2, structure NRNCr, structure PRPCr, structure SRNCr, structure PRNCr and / or structure NRPCr.

[0158] Usually, with R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s The group R of any heteroatom ligand structure depicted herein and / or any heteroatom ligand chromium compound complex depicted herein 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s can be independently an organic alkyl group; alternatively, an organic alkyl group consisting of inert functional groups; or alternatively, a hydrocarbon group. In one aspect, it can be used as R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s The organic alkyl radicals may independently be C1 to C 20 , C1 to C 15 , C1 to C 10 Or C1 to C5 organic alkyl. In one aspect, it can be used as R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s The organic alkyl group consisting of inert functional groups can be C1 to C20 , C1 to C 15 , C1 to C 10 Or C1 to C5 organic alkyl. In one aspect, it can be used as R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s The hydrocarbon groups can independently be C1 to C 20 , C1 to C 15 , C1 to C 10 or a C1 to C5 hydrocarbon group.

[0159] On the one hand, having R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s The group R of any heteroatom ligand structure depicted herein and / or any heteroatom ligand chromium compound complex depicted herein 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s can be independently alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, aralkyl, or substituted aralkyl; alternatively, alkyl or substituted alkyl; alternatively, cycloalkyl or substituted cycloalkyl; alternatively, aryl or substituted aryl; alternatively, aralkyl or substituted aralkyl; or alternatively, alkyl, cycloalkyl, aryl, or aralkyl. In other aspects, R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s Each R of any heteroatom ligand structure depicted herein and / or any heteroatom ligand chromium compound complex depicted herein 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s and R is independently alkyl; alternatively, substituted alkyl; alternatively, cycloalkyl; alternatively, substituted cycloalkyl; alternatively, aryl; alternatively, substituted aryl; alternatively, aralkyl; or alternatively, substituted aralkyl.

[0160] In any aspect disclosed herein, each R 1s , R2s , R 11s , R 12s , R 13s and / or R 14s The alkyl group can be independently C1 to C 20 , C1 to C 10 or C1 to C5 alkyl. In any aspect disclosed herein, each substituted R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s The alkyl group may be independently substituted C1 to C 20 , C1 to C 10 or C1 to C5 alkyl. In any aspect disclosed herein, each R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s The cycloalkyl groups can be independently C4 to C 20 , C4 to C 15 or C4 to C 10 In any aspect disclosed herein, each substituted R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s The cycloalkyl groups may be independently substituted C4 to C 20 , C4 to C 15 or C4 to C 10 In any aspect disclosed herein, each R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s The aryl groups can independently be C6 to C 20 , C6 to C 15 or C6 to C 10 In any aspect disclosed herein, each substituted R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s The aryl groups may be independently substituted C6 to C 20 , C6 to C 15 or C6 to C 10 In any aspect disclosed herein, each R1s , R 2s , R 11s , R 12s , R 13s and / or R 14s The aralkyl groups can independently be C7 to C 20 , C7 to C 15 or C7 to C 10 In any aspect disclosed herein, each substituted R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s The aralkyl group may be independently substituted C7 to C 20 , C7 to C 15 or C7 to C 10 Aralkyl. Each substituent of substituted alkyl (general or specific), substituted cycloalkyl (general or specific), substituted aryl (general or specific) and / or substituted aralkyl (general or specific) can be halogen, hydrocarbyl or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific) and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyloxy substituents and hydrocarbyloxy substituents can be used without limitation to further describe the substituents that can be used as R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s substituted groups (general or specific).

[0161] On the one hand, each R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s Can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl independently; Or alternatively, methyl, ethyl, isopropyl (2-propyl), tert-butyl (2-methyl-2-propyl) or neopentyl (2,2-dimethyl-1-propyl). In some aspects, can be used as each R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14sThe alkyl radicals of R may be independently substituted. Each substituent of the substituted alkyl radical may independently be a halogen or a hydrocarbyloxy radical; alternatively, a halogen radical; or alternatively, a hydrocarbyloxy radical. Halogen substituents and hydrocarbyl substituents (generally and specifically) are independently disclosed herein. These halogen substituents and hydrocarbyloxy substituents may be used without limitation to further describe the radicals that may be used as R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s substituted alkyl (general or specific).

[0162] On the one hand, each R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s can be independently cyclopentyl, substituted cyclopentyl, cyclohexyl or substituted cyclohexyl; alternatively, cyclopentyl or substituted cyclopentyl; alternatively, cyclohexyl or substituted cyclohexyl; alternatively, cyclopentyl; alternatively, substituted cyclopentyl; alternatively, cyclohexyl; or alternatively, substituted cyclohexyl. In one aspect, when present in any heteroatom ligand described herein, any heteroatom ligand of the heteroatom ligand chromium compound complex described herein, any heteroatom ligand formula or structure provided herein, and / or any heteroatom ligand chromium compound complex structure provided herein, can be used for R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s The substituted cycloalkyl of any one of the above may be independently 2-substituted cyclohexyl, 2,6-disubstituted cyclohexyl, 2-substituted cyclopentyl or 2,5-disubstituted cyclopentyl; alternatively, 2-substituted cyclohexyl or 2,6-disubstituted cyclohexyl; alternatively, 2-substituted cyclopentyl or 2,5-disubstituted cyclopentyl; alternatively, 2-substituted cyclohexyl or 2-substituted cyclopentyl; or alternatively, 2,6-disubstituted cyclohexyl or 2,5-disubstituted cyclopentyl. In one aspect, R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14sThe one or more substituents of a polysubstituted cycloalkyl may be the same or different; alternatively, all substituents of a polysubstituted cycloalkyl may be the same; or alternatively, all substituents of a polysubstituted cycloalkyl may be different. Each substituent of a substituted cycloalkyl (general or specific) having a specified number of ring carbon atoms may independently be halogen, hydrocarbyl, or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific), and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents, and hydrocarbyloxy substituents may be used without limitation to further describe the radicals that may be used as R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s of a substituted cycloalkyl group (general or specific).

[0163] In one non-limiting aspect, each R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s R is independently cyclohexyl, 2-alkylcyclohexyl or 2,6-dialkylcyclohexyl; or alternatively, cyclopentyl, 2-alkylcyclopentyl or 2,5-dialkylcyclopentyl. Alkyl substituents (general and specific) are described independently herein, and these alkyl substituents can be used without limitation to further describe the alkyl groups that can be used as R. 1s , R 2s , R 11s , R 12s , R 13s and / or R 14 alkylcyclohexyl (general or specific), dialkylcyclohexyl (general or specific), alkylcyclopentyl (general or specific) and / or dialkylcyclopentyl (general or specific). Typically, the alkyl substituents of the disubstituted cyclohexyl or cyclopentyl may be the same; or alternatively, the alkyl substituents may be different. In some non-limiting aspects, each R, when present in any heteroatom ligand described herein, any heteroatom ligand of the heteroatom ligand chromium compound complex described herein, any heteroatom ligand formula or structure provided herein, and / or any heteroatom ligand chromium compound complex structure provided herein, 1s , R 2s , R 11s , R 12s , R 13s and R 14s, may independently be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, 2-tert-butylcyclohexyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl or 2,6-di-tert-butylcyclohexyl; alternatively, 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl or 2-tert-butylcyclohexyl; or alternatively, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl or 2,6-di-tert-butylcyclohexyl.

[0164] On the one hand, each R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s can be independently phenyl or substituted phenyl; alternatively, phenyl; or alternatively, substituted phenyl. In one aspect, when present in any heteroatom ligand described herein, any heteroatom ligand of a heteroatom ligand chromium compound complex described herein, any heteroatom ligand formula or structure provided herein, and / or any heteroatom ligand chromium compound complex structure provided herein, each R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s The substituted phenyl groups may be independently 2-substituted phenyl, 3-substituted phenyl, 4-substituted phenyl, 2,4-disubstituted phenyl, 2,6-disubstituted phenyl, 3,5-disubstituted phenyl or 2,4,6-trisubstituted phenyl; alternatively, 2-substituted phenyl, 4-substituted phenyl, 2,4-disubstituted phenyl or 2,6-disubstituted phenyl; alternatively, 3-substituted phenyl or 3,5-disubstituted phenyl; alternatively, 2-substituted phenyl or 4-substituted phenyl; alternatively, 2,4-disubstituted phenyl or 2,6-disubstituted phenyl; alternatively, 2-substituted phenyl; alternatively, 3-substituted phenyl; alternatively, 4-substituted phenyl; alternatively, 2,4-disubstituted phenyl; alternatively, 2,6-disubstituted phenyl; alternatively, 3,5-disubstituted phenyl; or alternatively, 2,4,6-trisubstituted phenyl. In one aspect, R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14sThe one or more substituents of the polysubstituted phenyl may be the same or different; alternatively, all substituents may be the same; or alternatively, all substituents may be different. Each substituent of the substituted phenyl (general or specific) may independently be halogen, hydrocarbyl, or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific), and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents, and hydrocarbyloxy substituents may be used without limitation to further describe the groups that may be used as R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s of substituted phenyl (general or specific).

[0165] In one non-limiting aspect, R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s R is independently phenyl, 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl, 3,5-dialkylphenyl or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl or 4-alkylphenyl; alternatively, 2,4-dialkylphenyl or 2,6-dialkylphenyl; alternatively, 3-alkylphenyl or 3,5-dialkylphenyl; alternatively, 2-alkylphenyl or 2,6-dialkylphenyl; or alternatively, 2,4,6-trialkylphenyl. Alkyl substituents (general and specific) are described independently herein and these alkyl substituents can be used without limitation to further describe the alkyl substituents that can be used as R. 1s , R 2s , R 11s , R 12s , R 13s and / or R 14sIn some non-limiting aspects, when present in any heteroatom ligand described herein, any heteroatom ligand of the heteroatom ligand chromium compound complex described herein, any heteroatom ligand formula or structure provided herein, and / or any heteroatom ligand chromium compound complex structure provided herein, each R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s , may independently be phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl or 2,4,6-trimethylphenyl; alternatively, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl or 2-tert-butylphenyl; or alternatively, phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl or 2,4,6-trimethylphenyl.

[0166] In one non-limiting aspect, each R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s R , when present in any heteroatom ligand described herein, any heteroatom ligand of a heteroatom ligand chromium compound complex described herein, any heteroatom ligand formula or structure provided herein, and / or any heteroatom ligand chromium compound complex structure provided herein, each R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s, can be independently phenyl, 2-methoxyphenyl, 2-ethoxyphenyl, 2-isopropoxyphenyl, 2-tert-butoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-isopropoxyphenyl or 4-tert-butoxyphenyl; alternatively, 2-methoxyphenyl, 2-ethoxyphenyl, 2-isopropoxyphenyl or 2-tert-butoxyphenyl; or alternatively, 4-methoxyphenyl, 4-ethoxyphenyl, 4-isopropoxyphenyl or 4-tert-butoxyphenyl. In one non-limiting aspect, each R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s R may be independently phenyl, 2-halophenyl, 4-halophenyl or 2,6-dihalophenyl. Typically, the halides of the dihalophenyl may be the same, or alternatively, the halides may be different. In some aspects, each R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s and phenyl and 2-fluorophenyl groups may independently be phenyl, 2-fluorophenyl, 4-fluorophenyl or 2,6-difluorophenyl groups.

[0167] On the one hand, each R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s R is independently benzyl or substituted benzyl; alternatively, benzyl; or alternatively, substituted benzyl. Each substituent of the substituted benzyl (general or specific) can independently be halogen, hydrocarbyl or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific) and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents and hydrocarbyloxy substituents can be used without limitation to further describe the substituents that can be used as R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s substituted benzyl (general or specific).

[0168] In another aspect, attached to a single X 1s The two R's 1s , attached to a single X 2s The two R's2s , R 11s and R 12s and / or R 13s and R 14s may independently link to form a ring or ring system containing the heteroatom to which they are attached. 1s The two R's 1s The connection can be specified as L 11s . Attached to a single X 2s The two R's 2s The connection can be specified as L 22s . R 11s and R 12s The connection can be specified as L 12s . R 13s and R 14s The connection can be specified as L 34s In one aspect, L 11s , L 22s , L 12s and / or L 34s can be independently an organoalkylene group; alternatively, an organoalkylene group consisting of inert functional groups; alternatively, an alkylene group; or alternatively, an alkylene group. In one aspect, L 11s , L 22s , L 12s and / or L 34s The organoalkylene group, when present, may independently be C4 to C 30 , C4 to C 20 , C4 to C 15 or C4 to C 10 In some aspects, L consisting of an inert functional group 11s , L 22s , L 12s and / or L 34s The organoalkylene group, when present, may independently be a C4 to C 30 , C4 to C 20 , C4 to C 15 or C4 to C 10 In other aspects, L 11s , L 22s , L 12s and / or L 34s The hydrocarbon group, when present, may independently be C4 to C 30 , C4 to C 20 , C4 to C 15 or C4 to C 10 In yet another aspect, L 11s , L 22s , L 12s and / or L 34sAlkylene, when present, may independently be C4 to C 30 , C4 to C 20 , C4 to C 15 or C4 to C 10 In one aspect, L 12s and / or L 34s , when present, may independently be 1,4-butenyl, 1,4-diphenyl-1,4-butenyl, 1,4-di(2-methylphenyl)-1,4-butenyl, 1,4-di(4-methylphenyl)-1,4-butenyl, 1,4-di(4-tert-butylphenyl)-1,4-butenyl, 1,4-di(3,5-dimethylphenyl)-1,4-butenyl, 1,4-pentenyl, 1-phenyl-1,4-pentenyl, 4-phenyl-1,4-pentenyl, 2,5-hexenyl, 2,2'-biphenylene, 2,2'-(methanediyl)diphenylene or 2,2'-(1,2-ethanediyl)diphenylene.

[0169] Usually, with R 5s The R of any heteroatom ligand structure depicted herein and any heteroatom ligand chromium compound complex depicted herein 5s can be an organic group; alternatively, an organic alkyl group consisting of inert functional groups; or alternatively, a hydrocarbon group. In one aspect, R 5s The organic alkyl group may be C1 to C 20 , C1 to C 15 , C1 to C 10 or C1 to C5 organic alkyl. In one aspect, R consisting of an inert functional group 5s The organic alkyl group can be a C1 to C 20 , C1 to C 15 , C1 to C 10 or a C1 to C5 organic alkyl group. 5s The hydrocarbon group may be C1 to C 20 , C1 to C 15 , C1 to C 10 or a C1 to C5 hydrocarbon group.

[0170] On the one hand, having R 5s The R of any heteroatom ligand structure depicted herein and any heteroatom ligand chromium compound complex depicted herein 5s can be alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, aralkyl, or substituted aralkyl; can be alkyl or substituted alkyl; alternatively, cycloalkyl or substituted cycloalkyl; alternatively, aryl or substituted aryl; alternatively, aralkyl or substituted aralkyl; or alternatively, alkyl, cycloalkyl, aryl, or aralkyl. In other aspects, R5s The R of any heteroatom ligand structure depicted herein and any heteroatom ligand chromium compound complex depicted herein 5s can be alkyl; alternatively, substituted alkyl; alternatively, cycloalkyl; alternatively, substituted cycloalkyl; alternatively, aryl; alternatively, substituted aryl; alternatively, aralkyl; or alternatively, substituted aralkyl. In any aspect disclosed herein, R 5s The alkyl group can be C1 to C 20 , C1 to C 15 or C1 to C 10 In any aspect disclosed herein, the substituted R 5s The alkyl group may be substituted with C1 to C 20 , C1 to C 15 or C1 to C 10 In any aspect disclosed herein, R 5s The cycloalkyl group may be C4 to C 20 , C4 to C 15 or C4 to C 10 In any aspect disclosed herein, substituted R 5s The cycloalkyl group may be substituted C4 to C 20 , C4 or C4 to C 10 In any aspect disclosed herein, R 5s The aryl group can be C6 to C 20 , C6 to C 15 or C6 to C 10 In any aspect disclosed herein, substituted R 5s The aryl group may be a substituted C6 to C 20 , C6 to C 15 or C6 to C 10 In any aspect disclosed herein, R 5s The aralkyl group may be C7 to C 20 , C7 to C 15 or C7 to C 10 In any aspect disclosed herein, the substituted R 5s The aralkyl group may be a substituted C7 to C 20 , C7 to C 15 or C7 to C 10Aralkyl. Each substituent of substituted alkyl (general or specific), substituted cycloalkyl (general or specific), substituted aryl (general or specific) and / or substituted aralkyl (general or specific) can be halogen, hydrocarbyl or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl (general and specific) and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents and hydrocarbyloxy substituents can be used without limitation to further describe the substituents that can be used as R 5s Substituted groups (general and specific).

[0171] On the one hand, R 5s R may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl; alternatively, methyl, ethyl, n-propyl (1-propyl), isopropyl (2-propyl), n-butyl (1-butyl), sec-butyl (2-butyl), isobutyl (2-methyl-1-propyl), tert-butyl (2-methyl-2-propyl), n-pentyl (1-pentyl), 2-pentyl, 3-pentyl, 2-methyl-1-butyl, tert-pentyl (2-methyl-2-butyl), 3-methyl-1-butyl, 3-methyl-2-butyl or neopentyl (2,2-dimethyl-1-propyl); or alternatively, methyl, ethyl, isopropyl (2-propyl), tert-butyl (2-methyl-2-propyl) or neopentyl (2,2-dimethyl-1-propyl). In some aspects, R 5s The alkyl group may be substituted. 5s Each substituent of the alkyl group may independently be a halogen or a hydrocarbyloxy group; alternatively, a halogen group; or alternatively, a hydrocarbyloxy group. Halogen substituents and hydrocarbyloxy substituents (generally and specifically) are described independently herein and these substituents may be used without limitation to further describe substituents that may be used as R. 5s substituted alkyl (general or specific).

[0172] On the one hand, R 5s Can be cyclopentyl, substituted cyclopentyl, cyclohexyl, substituted cyclohexyl; alternatively, cyclopentyl or substituted cyclopentyl; or alternatively, cyclohexyl or substituted cyclohexyl. In other aspects, R 5sCan be 2-substituted cyclohexyl, 2,6-disubstituted cyclohexyl, 2-substituted cyclopentyl or 2,5-disubstituted cyclopentyl; alternatively, 2-substituted cyclohexyl or 2,6-disubstituted cyclohexyl; alternatively, 2-substituted cyclohexyl or 2,6-disubstituted cyclohexyl; alternatively, 2-substituted cyclopentyl or 2,5-disubstituted cyclopentyl; alternatively, 2-substituted cyclohexyl or 2-substituted cyclopentyl; or alternatively, 2,6-disubstituted cyclohexyl or 2,5-disubstituted cyclopentyl. In one aspect, used as R 5s The one or more substituents of a polysubstituted cycloalkyl group may be the same or different; alternatively, all substituents of a polysubstituted cycloalkyl group may be the same; or alternatively, all substituents of a polysubstituted cycloalkyl group may be different. Each substituent of a cycloalkyl group (general or specific) having a specified number of ring carbon atoms may independently be halogen, hydrocarbyl, or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific), and hydrocarbyloxy substituents (general and specific) are described independently herein and these substituents may be used without limitation to further describe substituents that may be used as R. 5s of a substituted cycloalkyl group (general or specific).

[0173] In one non-limiting aspect, R 5s It can be cyclohexyl, 2-alkylcyclohexyl or 2,6-dialkylcyclohexyl; or alternatively, cyclopentyl, 2-alkylcyclopentyl or 2,5-dialkylcyclopentyl. Alkyl substituents (general and specific) are described independently herein, and these alkyl substituents can be used without limitation to further describe the alkyl groups that can be used as R. 5s alkylcyclohexyl (general or specific), dialkylcyclohexyl (general or specific), alkylcyclopentyl (general or specific) and / or dialkylcyclopentyl (general or specific). Typically, the alkyl substituents of the disubstituted cyclohexyl or cyclopentyl may be the same; or alternatively, the alkyl substituents may be different. In some non-limiting aspects, the heteroatom ligand structures provided herein and / or any heteroatom ligand chromium compound complex structures provided herein are R 5s It can be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, 2-tert-butylcyclohexyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl or 2,6-di-tert-butylcyclohexyl. In other non-limiting aspects, R 5sCan be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl or 2-tert-butylcyclohexyl; Or alternatively, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl or 2,6-di-tert-butylcyclohexyl. In one aspect, R of the heteroatom ligand structure provided herein and / or any heteroatom ligand chromium compound complex structure provided herein 5s It may be cyclopentyl, 2-methylcyclopentyl, cyclohexyl or 2-methylcyclohexyl; alternatively, cyclopentyl or cyclohexyl; or alternatively, 2-methylcyclopentyl or 2-methylcyclohexyl.

[0174] On the one hand, R 5s can be phenyl or substituted phenyl; alternatively, phenyl; or alternatively, substituted phenyl. In some aspects, R 5s can be 2-substituted phenyl, 4-substituted phenyl, 2,4-disubstituted phenyl, 2,6-disubstituted phenyl or 2,4,6-trisubstituted phenyl; alternatively, 2-substituted phenyl or 4-substituted phenyl; alternatively, 2,4-disubstituted phenyl, 2,6-disubstituted phenyl or 2,4,6-trisubstituted phenyl; alternatively, 2,4-disubstituted phenyl or 2,6-disubstituted phenyl; alternatively, 2-substituted phenyl; alternatively, 4-substituted phenyl; alternatively, 2,4-disubstituted phenyl; alternatively, 2,6-disubstituted phenyl; or alternatively, 2,4,6-trisubstituted phenyl. In one aspect, used as R 5s The one or more substituents of the polysubstituted phenyl may be the same or different; alternatively, all substituents may be the same, or alternatively, all substituents may be different. Each substituent of the substituted phenyl (general or specific) may independently be halogen, hydrocarbyl, or hydrocarbyloxy; alternatively, halogen or hydrocarbyl; alternatively, halogen or hydrocarbyloxy; alternatively, hydrocarbyl or hydrocarbyloxy; alternatively, halogen; alternatively, hydrocarbyl; or alternatively, hydrocarbyloxy. Halogen substituents, hydrocarbyl substituents (general and specific), and hydrocarbyloxy substituents (general and specific) are described independently herein and these substituents may be used without limitation to further describe the substituents that may be used as R. 5s of substituted phenyl (general or specific).

[0175] In one non-limiting aspect, R 5s It can be phenyl, 2-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl or 2,4,6-trialkylphenyl. Alkyl substituents (general and specific) are described independently herein and these alkyl substituents can be used without limitation to further describe the alkyl groups that can be used as R.5s In some non-limiting aspects, R 5s It may be phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl or 2,4,6-trimethylphenyl; alternatively, phenyl, 2-methylphenyl, 2,6-dimethylphenyl or 2,4,6-trimethylphenyl.

[0176] Usually, with L 2s Any heteroatom ligand of the group and / or any heteroatom ligand chromium compound complex L 2s can be an organoalkylene group; alternatively, an organoalkylene group consisting of inert functional groups; alternatively, a hydrocarbylene group; or alternatively, an alkylene group. In one aspect, L 2s The organoalkylene group can be C1 to C 20 , C1 to C 15 or C1 to C 10 In one aspect, L consisting of an inert functional group 2s The organoalkylene group can be a C1 to C 20 , C1 to C 15 or C1 to C 10 In one aspect, L 2s The alkylene group can be C1 to C 20 , C1 to C 15 or C1 to C 10 Alkylene.

[0177] In one aspect, having L 2s Any heteroatom ligand of the group and / or any heteroatom ligand chromium compound complex L 2s Can be -(CR P R P’ ) m -, where each R P and R P’ L may independently be hydrogen, methyl, ethyl, propyl, isopropyl or butyl and m may be an integer from 1 to 12. 2s Any heteroatom ligand of the group and / or any heteroatom ligand chromium compound complex L 2sIt may be a methylene (-CH2-), 1,2-ethylidene (-CH2CH2-), 1,3-propylene (-CH2CH2CH2-), 1,2-propylene (-CH(CH3)CH2-), 2,2-propylene (-C(CH3)2-), 1,4-butylidene (-CH2CH2CH2CH2-) or 2-methylpropylene-1,3-yl (-CH2CH(CH3)CH2-); or alternatively, a methylene (-CH2-), 1,2-ethylene (-CH2CH2-) or 1,2-propylene (-CH(CH3)CH2-).

[0178] In one aspect, having L 2s Any heteroatom ligand of the group and / or any heteroatom ligand chromium compound complex L 2s The cyclohexylene radical may be 1,2-cyclohexylene, substituted 1,2-cyclohexylene, 1,3-cyclohexylene, substituted 1,3-cyclohexylene, 1,4-cyclohexylene, substituted 1,4-cyclohexylene, 3,3'-bicyclohexylene, substituted 3,3'-bicyclohexylene, 4,4'-bicyclohexylene, substituted 4,4'-bicyclohexylene, bis(3-cyclohexylene)methane, substituted bis(3-cyclohexylene)methane, bis(4-cyclohexylene)methane, substituted bis(4-cyclohexylene)methane, 1,2-bis(3-cyclohexylene)ethane, substituted In some aspects, the compound has L 2s Any heteroatom ligand of the group and / or any heteroatom ligand chromium compound complex L 2s It can be substituted 1,2-cyclohexylene, substituted 1,3-cyclohexylene, substituted 1,4-cyclohexylene, substituted 3,3'-bicyclohexylene, substituted 4,4'-bicyclohexylene, substituted bis(3-cyclohexylene)methane, substituted bis(4-cyclohexylene)methane, substituted 1,2-bis(3-cyclohexylene)ethane, substituted 1,2-bis(4-cyclohexylene)ethane, substituted 1,2-bis(3-cyclohexylene)propane, substituted 1,2-bis(4-cyclohexylene)propane, substituted 2,2-bis(3-cyclohexylene)propane or substituted 2,2-bis(4-cyclohexylene)propane. In one aspect, it can be used as L2s Each substituent of the substituted cyclohexylene, substituted bis(cyclohexylene)methane, substituted bis(cyclohexylene)ethane, or substituted 1,2-bis(3-cyclohexylene)propane may be a hydrocarbon group. The substituents (general and specific) are independently disclosed herein and may be used without limitation to further describe the moieties that may be used as L. 2s substituted cyclohexylene (general or specific), substituted bis(cyclohexylene)methane (general or specific), substituted bis(cyclohexylene)ethane (general or specific) or substituted 1,2-bis(3-cyclohexylene)propane (general or specific).

[0179] In one aspect, having L 2s Any heteroatom ligand of the group and / or any heteroatom ligand chromium compound complex L 2s The 1,2-phenylene, substituted 1,2-phenylene, 1,3-phenylene, substituted 1,3-phenylene, 1,4-phenylene, substituted 1,4-phenylene, 3,3'-biphenylene, substituted 3,3'-biphenylene, 4,4'-biphenylene, substituted 4,4'-biphenylene, bis(3-phenylene)methane, substituted bis(3-phenylene)methane, bis(4-phenylene)methane, substituted bis(4-phenylene)methane, 1,2-bis(3-phenylene)ethane, substituted 1 ,2-bis(3-phenylene)ethane, 1,2-bis(4-phenylene)ethane, substituted 1,2-bis(4-phenylene)ethane, 1,2-bis(3-phenylene)propane, substituted 1,2-bis(3-phenylene)propane, 1,2-bis(4-phenylene)propane, substituted 1,2-bis(4-phenylene)propane, 2,2-bis(3-phenylene)propane, substituted 2,2-bis(3-phenylene)propane, 2,2-bis(4-phenylene)propane or substituted 2,2-bis(4-phenylene)propane. In some aspects, L 2s Any heteroatom ligand of the group and / or any heteroatom ligand chromium compound complex L 2s It can be substituted 1,2-phenylene, substituted 1,3-phenylene, substituted 1,4-phenylene, substituted 3,3'-biphenylene, substituted 4,4'-biphenylene, substituted bis(3-phenylene)methane, substituted bis(4-phenylene)methane, substituted 1,2-bis(3-phenylene)ethane, substituted 1,2-bis(4-phenylene)ethane, substituted 1,2-bis(3-phenylene)propane, substituted 1,2-bis(4-phenylene)propane, substituted 2,2-bis(3-phenylene)propane or substituted 2,2-bis(4-phenylene)propane. In one aspect, it can be used as L 2sEach substituent of the substituted phenylene (general or specific), substituted biphenylene (general or specific), substituted bis(phenylene)methane (general or specific), substituted bis(phenylene)ethane (general or specific), and / or substituted bis(phenylene)propane (general or specific) can be a hydrocarbyl group. The hydrocarbyl substituents (general and specific) are independently disclosed herein and can be used without limitation to further describe the moieties that can be used as L. 2s substituted phenylene (general or specific), substituted biphenylene, substituted bis(phenylene)methane (general or specific), substituted bis(phenylene)ethane (general or specific) and / or substituted bis(phenylene)propane (general or specific).

[0180] Usually, with L 3s and / or L 4s Any heteroatom ligand of the group and / or any heteroatom ligand chromium compound complex L 3s and / or L 4s can be independently an organoalkylene group; alternatively, an organoalkylene group consisting of inert functional groups; alternatively, an alkylene group; alternatively, an alkylene group. In one aspect, L 3s and / or L 4s The organoalkylene group can independently be C1 to C 20 , C1 to C 15 or C1 to C 10 In one aspect, L consisting of an inert functional group 3s and / or L 4s The organoalkylene group can be independently C1 to C1 20 , C1 to C 15 or C1 to C 10 In one aspect, L 3s and / or L 4s The alkylene groups can independently be C1 to C 20 , C1 to C 15 or C1 to C 10 In one aspect, L 3s and / or L 4s The alkylene group can be independently C1 to C 20 , C1 to C 15 or C1 to C 10 Alkylene.

[0181] In one aspect, having L 3s and / or L 4s L of any heteroatom ligand structure and / or any heteroatom ligand chromium compound complex 3s and / or L 4s Can be -(CRP R P’ ) m -, where each R P and R P’ L may independently be hydrogen, methyl, ethyl, propyl, isopropyl or butyl and m may be an integer from 1 to 12. 3s and / or L 4s L of any heteroatom ligand structure and / or any heteroatom ligand chromium compound complex 3s and / or L 4s The 1,2-propenyl group may be independently selected from the group consisting of methylene (—CH2—), 1,2-vinyl (—CH2CH2—), 1,2-vinylene (—CH═CH—), 1,3-propenyl (—CH2CH2CH2—), 1,2-propenyl (—CH(CH3)CH2—), 2,2-propenyl (—C(CH3)2—), 1-methyl-1,2-vinylene (—C(CH3)═CH—), 1,4-butenyl (—CH2CH2CH2—), CH2-), 1,3-butenyl (-CH2CH2CH(CH3)-), 2,3-butenyl (-CH(CH3)CH(CH3)-), 2-2,3-butenylene (-C(CH3)C(CH3)-), 3-methyl-1,3-butenyl (-CH2CH2C(CH3)2-), 1,2-cyclopentylene, 1,2-cyclohexylene or 1,2-phenylene; alternatively, methylene (-CH2-), 1,2- Vinyl (-CH2CH2-), 1,3-propenyl (-CH2CH2CH2-), 1,2-propenyl (-CH(CH3)CH2-), 2,2-propenyl (-C(CH3)2-), 1,4-butenyl (-CH2CH2CH2-CH2-), 1,3-butenyl (-CH2CH2CH(CH3)-), 2,3-butenyl (–CH(CH3)CH(CH3)-), 1,2-cyclopentylene, 1,2-cyclohexylene or 1,2-phenylene; or alternatively, 1,2-vinyl (-CH2CH2-), 1,3-propenyl (-CH2CH2CH2-), 1,2-propenyl (-CH(CH3)CH2-), 1,3-butenyl (-CH2CH2CH(CH3)-), 2,3-butenyl (-CH(CH3)CH(CH3)-), 1,2-cyclopentylene, 1,2-cyclohexylene or 1,2-phenylene.

[0182] Various aspects described herein relate to non-hydrogen substituents, such as halogen (or halide, halide), hydrocarbyl, hydrocarbyloxy, alkyl and / or alkoxy substituents. In one embodiment, each non-hydrogen substituent of any aspect requiring a substituent can be a halogen, hydrocarbyl, or hydrocarbyloxy; alternatively, a halogen or hydrocarbyl; alternatively, a halogen or hydrocarbyloxy; alternatively, a hydrocarbyl or hydrocarbyloxy; alternatively, a halogen; alternatively, a hydrocarbyl; or alternatively, a hydrocarbyloxy. Each hydrocarbyl substituent can independently be C1 to C 10 or, alternatively, a C1 to C5 hydrocarbon group. Each hydrocarbonoxy substituent may independently be a C1 to C 10 or alternatively, a C1 to C5 alkoxy group. Each halide substituent may independently be a fluoride, chloride, bromide or iodide; alternatively, a fluoride or chloride; alternatively, a fluoride; alternatively, a chloride; alternatively, a bromide; or alternatively, an iodide.

[0183] In one aspect, any hydrocarbyl substituent can be independently alkyl, aryl or aralkyl; alternatively, alkyl; alternatively, aryl; or alternatively, aralkyl. In one aspect, any alkyl substituent can be independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, tert-pentyl, 3-methyl-1-butyl, 3-methyl-2-butyl or neopentyl; alternatively, methyl, ethyl, isopropyl, tert-butyl or neopentyl; alternatively, methyl; alternatively, ethyl; alternatively, isopropyl; alternatively, tert-butyl; or alternatively, neopentyl. In one aspect, any aryl substituent can be independently phenyl, tolyl, xylyl or 2,4,6-trimethylphenyl; alternatively, phenyl; alternatively, tolyl; alternatively, xylyl; or alternatively, 2,4,6-trimethylphenyl. In one aspect, any aralkyl substituent can be independently be benzyl or ethylphenyl (2-phenylethyl-1-yl or 1-phenylethyl-1-yl); alternatively, benzyl; alternatively, ethylphenyl; alternatively, 2-phenylethyl-1-yl; or alternatively, 1-phenylethyl-1-yl.

[0184] In one aspect, any hydrocarbyloxy substituent can be independently alkoxy, aryloxy or aralkoxy; alternatively, alkoxy; alternatively, aryloxy or aralkoxy. In one aspect, any alkoxy substituent can be independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, tert-pentoxy, 3-methyl-1-butoxy, 3-methyl-2-butoxy or neopentoxy; alternatively, methoxy, ethoxy, isopropoxy, tert-butoxy or neopentoxy; alternatively, methoxy; alternatively, ethoxy; alternatively, isopropoxy; alternatively, tert-butoxy; or alternatively, neopentoxy. In one aspect, any aryloxy substituent can independently be phenoxy, tolyloxy, xylyloxy, or 2,4,6-methylphenoxy; alternatively, phenoxy; alternatively, tolyloxy; alternatively, xylyloxy; or alternatively, 2,4,6-trimethylphenoxy. In one aspect, any aralkyloxy substituent can independently be phenoxy.

[0185] Typically, the chromium compound or the chromium compound of the heteroatom ligand chromium compound complex described herein may have the formula CrX p , wherein X represents a monoanionic ligand, and p represents the number of monoanionic ligands (and the oxidation state of the chromium in the chromium compound. The monoanionic ligand (X) and p are independent elements of the chromium compound or the chromium compound of the heteroatom ligand chromium compound complex described herein and are independently described herein. The independent descriptions of the monoanionic ligand (X) and p can be used in any combination without limitation to further describe the chromium compound or the chromium compound of the heteroatom ligand chromium compound complex described herein.

[0186] Typically, chromium compounds (CrX p ) can have any positive oxidation state that a chromium atom can obtain. In one aspect, the chromium atom can have an oxidation state of +2 to +6; alternatively, +2 to +4; or alternatively, +2 to +3. In some aspects, the chromium compound (CrX p )'s chromium atom may have an oxidation state of +1; alternatively, +2; alternatively, +3; or alternatively, +4.

[0187] The monoanion (X) of the chromium compound can be any monoanion. In one aspect, the monoanion (X) can be a halide, a carboxylate, a β-diketonate, a hydroxyl, a nitrate or a chlorate. In some aspects, the monoanion (X) can be a halide, a carboxylate, a β-diketonate or a hydroxyl. In any aspect, the hydroxyl can be an alkoxy, an aryloxy or an arylalkoxy. Typically, the hydroxyl (and the branch of the hydroxyl) is an anionic analog of the alkoxy. In other aspects, the monoanion (X) can be a halide, a carboxylate, a β-diketonate or an alkoxy; or alternatively, a halide or a β-diketonate. In other aspects, the monoanion (X) can be a halide; alternatively, a carboxylate; alternatively, a β-diketonate; alternatively, a hydroxyl; alternatively, an alkoxy; or alternatively, an aryloxy. Typically, when the heteroatom ligand of the heteroatom ligand chromium compound complex is a neutral heteroatom ligand, the number of monoanions (p) can be equal to the oxidation state of the chromium atom. When the heteroatom ligand of the heteroatom ligand chromium compound complex is an anionic heteroatom ligand, the number of monoanions (p) can be equal to one less than the oxidation state of the chromium atom. In one aspect, the number of monoanions can be 2 to 6; alternatively, 2 to 4; alternatively, 2 to 3; alternatively, 1; alternatively, 2; alternatively, 3; or alternatively, 4.

[0188] Typically, each halide of the chromium compound can independently be fluorine, chlorine, bromine or iodine; or alternatively, chlorine, bromine or iodine. In one aspect, each halide monoanion of the chromium compound can be chlorine; alternatively, bromine; or alternatively, iodine.

[0189] Typically, each carboxylate group of the chromium compound may independently be C1 to C 20 carboxylate; or alternatively, C1 to C 10In one aspect, each carboxylate of the chromium compound can independently be acetate, propionate, butyrate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, or dodecanoate; or alternatively, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, or dodecanoate. In some aspects, each carboxylate of the chromium compound can independently be acetate, propionate, n-butyrate, valerate (n-valerate), neopentanoate, hexanoate (n-hexanoate), n-heptanoate, octanoate (n-octanoate), 2-ethylhexanoate, n-nonanoate, decanoate (n-decanoate), n-undecanoate, or laurate (n-dodecanoate); alternatively, valerate (n-valerate), neopentanoate, hexanoate (n-hexanoate), n-heptanoate, octanoate (n-octanoate), 2-ethylhexanoate, n-nonanoate, decanoate (n-decanoate), n-undecanoate, or laurate (n-dodecanoate); alternatively, hexanoate (n-hexanoate); alternatively, n-heptanoate; alternatively, octanoate (n-octanoate); or alternatively, 2-ethylhexanoate. In some aspects, the carboxylate of the chromium compound can be triflate (trifluoroacetate).

[0190] Generally, each β-diketonate of the chromium compound can independently be any C1 to C 20 β-diketonate; or alternatively, any C1 to C 10 In one aspect, each β-diketonate of the chromium compound can independently be acetylacetonate (i.e., 2,4-pentanedione), hexafluoroacetylacetonate (i.e., 1,1,1,5,5,5-hexafluoro-2,4-pentanedione) or benzoyl acetonate); alternatively, acetylacetonate; alternatively, hexafluoroacetylacetonate; or alternatively, benzoyl acetonate.

[0191] Generally, each oxyhydroxide of the chromium compound may independently be any C1 to C 20 or, alternatively, any C1 to C 10 In one aspect, each alkoxide of the chromium compound can independently be C1 to C 20 Alkoxy; Alternatively, C1 to C 10 Alkoxy; Alternatively, C6 to C 20 or, alternatively, C6 to C 10 Aryloxide. In one aspect, each alkoxide of the chromium compound can independently be methoxide, ethoxide, propoxide, or butoxide; alternatively, methoxide, ethoxide, isopropoxide, or tert-butoxide; alternatively, methoxide; alternatively, ethoxide; alternatively, isopropoxide; or alternatively, tert-butoxide. In one aspect, the aryloxide can be a phenoxide.

[0192] In some non-limiting aspects, the chromium compound and / or the chromium compound of the heteroatom ligand chromium compound complex may include, consist essentially of, or consist of a chromium (II) halide, a chromium (II) carboxylate, or a chromium (II) beta-diketonate; or alternatively, a chromium (III) halide, a chromium (III) carboxylate, or a chromium (III) beta-diketonate. In other non-limiting aspects, the chromium compound and / or the chromium compound of the heteroatom ligand chromium compound complex may include, consist essentially of, or consist of a chromium (II) halide; alternatively, a chromium (III) halide; alternatively, a chromium (II) carboxylate; alternatively, a chromium (III) carboxylate; alternatively, a chromium (II) beta-diketonate; or alternatively, a chromium (III) beta-diketonate. Halides, carboxylates, beta-diketonates are described independently herein and these halides, carboxylates, beta-diketonates and these independently described halides, carboxylates, beta-diketonates can be used in any combination without limitation to further describe the chromium compound and / or the chromium compound of the heteroatom ligand chromium compound complex. In other non-limiting aspects, the chromium compound and / or the chromium compound of the heteroatom ligand chromium compound complex can include, can consist essentially of, or consist of chromium (II) chloride, chromium (III) chloride, chromium (II) fluoride, chromium (III) fluoride, chromium (II) bromide, chromium (III) bromide, chromium (II) iodide, chromium (III) iodide, chromium (II) acetate, chromium (III) acetate, chromium (II) 2-ethylhexanoate, chromium (III) 2-ethylhexanoate, chromium (II) trifluoromethanesulfonate, chromium (III) trifluoromethanesulfonate, chromium (II) nitrate, chromium (III) nitrate, chromium (II) acetylacetonate, chromium (III) acetylacetonate, chromium (II) hexafluoroacetylacetonate ), chromium (III) hexafluoroacetylacetonate, chromium (III) benzoyl acetonate or chromium (III) benzoyl acetonate; alternatively, chromium (III) chloride, chromium (III) fluoride, chromium (III) bromide, chromium (III) iodide, chromium (III) chloride (THF) complex, chromium (III) acetate, chromium (III) 2-ethylhexanoate, chromium (III) trifluoromethanesulfonate, chromium (III) nitrate, chromium (III) acetylacetonate, chromium (III) hexafluoroacetylacetonate or chromium (III) benzoyl acetonate; alternatively, chromium (III) chloride or chromium (III) acetylacetonate; alternatively, chromium (III) chloride; or alternatively, chromium (III) acetylacetonate.

[0193] In one non-limiting aspect, the heteroatom ligand chromium compound complex can be selected from any one or more of the heteroatom ligand chromium compound complexes having the following structure: i) NPFCr1, wherein R 1 is 2,6-dimethylphenyl, R 3 For H, R4 and R 5 is isopropyl, and X is chlorine; R 1 is 2,6-dimethylphenyl, R 3 For H, R 4 and R 5 is phenyl, and X is chlorine; R 1 is 2,6-dimethylphenyl, R 3 For H, R 4 and R 5 is 4-methoxyphenyl, and X is chlorine; R 1 is 2,4,6-trimethylphenyl, R 3 For H, R 4 and R 5 is isopropyl, and X is chlorine; R 1 is 2,4,6-trimethylphenyl, R 3 For H, R 4 and R 5 is phenyl, and X is chlorine; and R 1 is 2,4,6-trimethylphenyl, R 3 For H, R 4 and R 5 is 4-methoxyphenyl, and X is chlorine; ii) structure NPACr1, wherein R 1 is 2,6-dimethylphenyl, R 2 is phenyl, R 3 For H, R 4 and R 5 is isopropyl, and X is chlorine; R 1 is 2,4,6-trimethylphenyl, R 2 is phenyl, R 3 For H, R 4 and R 5 is isopropyl, and X is chlorine; R 1 is 2,6-dimethylphenyl, R 2 is phenyl, R 3 For H, R 4 and R 5 is phenyl, and X is chlorine; R 1 is 2,4,6-trimethylphenyl, R 2 is phenyl, R 3 For H, R 4 and R 5 is phenyl, and X is chlorine; R 1 is 2,6-dimethylphenyl, R 2 is 4-methylbenzyl, R 3 For H, R 4 and R 5 is phenyl, and X is chlorine; R 1is 2,6-dimethylphenyl, R 2 is phenyl, R 3 For H, R 4 and R 5 is 4-methoxyphenyl, and X is chlorine; R 1 is 2,6-dimethylphenyl, R 2 is 4-tert-butylphenyl, R 3 For H, R 4 and R 5 is methyl, and X is chlorine; R 1 is 2,4,6-trimethylphenyl, R 2 is 4-tert-butylphenyl, R 3 For H, R 4 and R 5 is methyl, and X is chlorine; R 1 is 2,4,6-trimethylphenyl, R 2 is 4-methylbenzyl, R 3 For H, R 4 and R 5 is isopropyl, and X is chlorine; R 1 is 2,4,6-trimethylphenyl, R 2 is 4-methylbenzyl, R 3 For H, R 4 and R 5 is phenyl, and X is chlorine; R 1 is 3,5-dimethylphenyl, R 2 is phenyl, R 3 For H, R 4 and R 5 is isopropyl, and X is chlorine; R 1 is 2,4,6-trimethylphenyl, R 2 is 4-methylbenzyl, R 3 For H, R 4 and R 5 is 4-methoxyphenyl, and X is chlorine; R 1 is 2,4,6-trimethylphenyl, R 2 is 4-methylbenzyl, R 3 For H, R 4 is tert-butyl, R 5 is phenyl, and X is chlorine; R 1 is 2,4,6-trimethylphenyl, R 2 is 4-methylbenzyl, R 3 For H, R 4 is methyl, R 5 is phenyl, and X is chlorine; R 1 and R 2 Connected to form 1,3-propenyl, R 3 For H, R4 and R 5 is isopropyl, and X is chlorine; R 1 and R 2 Connected to form 1,4-butenyl, R 3 For H, R 4 and R 5 is isopropyl, and X is chlorine; R 1 is 2,4,6-trimethylphenyl, R 2 is 4-methylbenzyl, R 3 For H, R 4 and R 5 connect to form 1,4-butenyl, and X is chlorine; R 1 is 2,4,6-trimethylphenyl, R 2 is 4-methylbenzyl, R 3 For H, R 4 and R 5 connect to form 2,2'-dimethylbiphenylene, and X is chlorine; iii) structure GUCr1, wherein R 1 is 2-methylphenyl, R 2a is 2-methylphenyl, R 2b For H, R 3 For H, R 4 and R 5 is isopropyl, and X is chlorine; R 1 is 2,6-dimethylphenyl, R 2a is phenyl, R 2b For H, R 3 For H, R 4 and R 5 is isopropyl, and X is chlorine; R 1 is 2,6-dimethylphenyl, R 2a is phenyl, R 2b For H, R 3 For H, R 4 and R 5 is phenyl, and X is chlorine; R 1 is 2,6-dimethylphenyl, R 2a and R 2b is phenyl, R 3 For H, R 4 and R 5 is isopropyl, and X is chlorine; iv) structure GUCr4, wherein L 12 is 1,3-propenyl, L 23 is 1,3-propenyl, R 4 and R 5 is isopropyl, and X is chlorine; L 12 is 1,3-propenyl, L 23 is 1,3-propenyl, R4 and R 5 is cyclopentyl, and X is chlorine; L 12 is 1,3-propenyl, L 23 is 1,3-propenyl, R 4 and R 5 is cyclohexyl, and X is chlorine; L 12 is 1,3-propenyl, L 23 is 1,3-propenyl, R 4 and R 5 is phenyl, and X is chlorine; L 12 is 1,3-butenyl, L 23 is 1,3-propenyl, R 4 and R 5 is isopropyl, and X is chlorine; L 12 is 1,3-butenyl, L 23 is 1,3-propenyl, R 4 and R 5 is cyclopentyl, and X is chlorine; L 12 is 1,3-butenyl, L 23 is 1,3-butenyl, R 4 and R 5 is isopropyl, and X is chlorine; L 12 is 1,3-butenyl, L 23 is 1,3-butenyl, R 4 and R 5 is phenyl, and X is chlorine; L 12 is 1,2-vinylene, L 23 is 1,3-propenyl, R 4 and R 5 is isopropyl, and X is chlorine; L 12 is 1,2-vinylene, L 23 is 1,3-propenyl, R 4 and R 5 is cyclopentyl, and X is chlorine; L 12 is 1,2-vinylene, L 23 is 1,3-propenyl, R 4 and R 5 is cyclohexyl, and X is chlorine; L 12 is 1,2-phenylene, L 23 For 1,2-vinyl, R 4 and R 5 isopropyl, and X is chlorine; and v) structure HCPACr2, wherein T is sulfur, L 12 is 1,2-vinylene, R 3 For H, R 4 and R 5is isopropyl, and X is chlorine; and T is sulfur, L 12 is 1,2-phenylene, R 3 For H, R 4 and R 5 is isopropyl, and X is chlorine.

[0194] In one non-limiting aspect, the heteroatom ligand can be any one or more of HL 1, HL 2, HL 3, HL 4, HL 5, HL 6, HL 7, HL 7, and HL 9. In some non-limiting aspects, the diphosphamide chromium compound complex can be a chromium compound complex of any one or more of HLCr 1, HLCr 2, HLCr 3, HLCr 4, HLCr 5, HLCr 6, HLCr 7, HLCr 8, and HLCr 9. In other non-limiting aspects, the diphosphamide chromium compound complex can be a chromium (III) chloride or chromium (III) acetylacetonate complex of any one or more of HLCr 1, HLCr 2, HLCr 3, HLCr 4, HLCr 5, HLCr 6, HLCr 7, HLCr 8, and HLCr 9.

[0195]

[0196]

[0197] Although not shown in all chromium compound names and formulas and / or heteroatom ligand chromium compound complex formulas and structures provided herein, one of ordinary skill in the art will recognize that neutral ligands Q can be associated with chromium compounds and / or heteroatom ligand chromium compound complexes described / depicted herein that do not explicitly disclose / depict neutral ligands. In addition, it should be understood that although some of the chromium compounds and / or heteroatom ligand chromium compound complexes described / depicted / provided herein do not formally show the presence of neutral ligands, chromium compounds and / or heteroatom ligand chromium compound complexes with neutral ligands (e.g., nitriles and ethers, etc.) are implicitly and fully considered as potential chromium compounds and / or heteroatom ligand chromium compound complexes that can be used in the catalyst systems used in aspects of the invention described herein.

[0198] In general, the neutral ligands of any chromium compound and / or heteroatom ligand chromium compound complex, when present, can independently be any neutral ligand that forms a separable compound with the chromium compound and / or heteroatom ligand chromium compound complex. In one aspect, each neutral ligand can independently be a nitrile or an ether; alternatively, a nitrile; or alternatively, an ether. The number of neutral ligands q can be any number that forms a separable compound with the chromium compound and / or heteroatom ligand chromium compound complex. In one aspect, the number of neutral ligands can be 0 to 6; alternatively, 0 to 3; alternatively, 0; alternatively, 1; alternatively, 2; alternatively, 3; or alternatively, 4.

[0199] Typically, each nitrile ligand can independently be C2 to C 20 Nitrile; or alternatively, C2 to C 10 In one aspect, each nitrile ligand can independently be C2 to C 20 Aliphatic nitrile, C7 to C 20 Aromatic nitriles, C8 to C 20 Aranenitrile or any combination thereof; Alternatively, C2 to C 20 aliphatic nitrile; alternatively, C7 to C 20 Aromatic nitrile; or alternatively, C8 to C 20 In some aspects, each nitrile ligand can independently be C2 to C 10 Aliphatic nitrile, C7 to C 10 Aromatic nitriles, C8 to C 10 Aranenitrile or any combination thereof; Alternatively, C1 to C 10 aliphatic nitrile; alternatively, C7 to C 10 Aromatic nitrile; or alternatively, C8 to C 10 Aranenitrile. In one aspect, each aliphatic nitrile can independently be acetonitrile, propionitrile, butyronitrile, benzonitrile, or any combination thereof; alternatively, acetonitrile; alternatively, propionitrile; alternatively, butyronitrile; or alternatively, benzonitrile.

[0200] Typically, each ether ligand can be independently C2 to C 40 ether; alternatively, C2 to C 30 ether; or alternatively, C2 to C 20 In one aspect, each ether ligand can independently be C2 to C 40 Aliphatic ethers, C3 to C 40 Aliphatic cyclic ethers, C4 to C 40 Aromatic cyclic ether; alternatively, C2 to C 40 Aliphatic acyclic ether or C3 to C 40 aliphatic cyclic ether; alternatively, C2 to C 40 aliphatic acyclic ether; alternatively, C3 to C 40aliphatic cyclic ether; or alternatively, C4 to C 40 In some aspects, each ether ligand can independently be C2 to C 30 Aliphatic ethers, C3 to C 30 Aliphatic cyclic ethers, C4 to C 30 Aromatic cyclic ether; alternatively, C2 to C 30 Aliphatic acyclic ether or C3 to C 30 aliphatic cyclic ether; alternatively, C2 to C 30 aliphatic acyclic ether; alternatively, C3 to C 30 aliphatic cyclic ether; or alternatively, C4 to C 30 In other aspects, each ether ligand can independently be C2 to C 20 Aliphatic ethers, C3 to C 20 Aliphatic cyclic ethers, C4 to C 20 Aromatic cyclic ether; alternatively, C2 to C 20 Aliphatic acyclic ether or C3 to C 20 aliphatic cyclic ether; alternatively, C2 to C 20 aliphatic acyclic ether; alternatively, C3 to C 20 aliphatic cyclic ether; or alternatively, C4 to C 20 Aromatic cyclic ethers. In some aspects, each ether ligand can independently be methyl ether, ethyl ether, propyl ether, butyl ether, methyl ethyl ether, methyl propyl ether, methyl butyl ether, tetrahydrofuran, dihydrofuran, 1,3-dioxolane, tetrahydropyran, dihydropyran, pyran, dioxane, furan, benzofuran, isobenzofuran, dibenzofuran, diphenyl ether, ditoluene ether, or any combination thereof; alternatively, methyl ether, ethyl ether, propyl ether, butyl ether, methyl ethyl ether, methyl propyl ether, methyl butyl ether, or any combination thereof; tetrahydrofuran, dihydrofuran, 1,3-dioxolane, tetrahydropyran, dihydropyran, pyran, dioxane, or any combination thereof; furan, benzofuran, isobenzofuran, dibenzofuran, or any combination thereof; diphenyl ether, ditolyl ether, or any combination thereof; alternatively, methyl ether; alternatively, ethyl ether; alternatively, propyl ether; alternatively, butyl ether; alternatively, methyl ethyl ether; alternatively, methyl propyl ether; alternatively, methyl butyl ether; alternatively, tetrahydrofuran; alternatively, dihydrofuran; alternatively, 1,3-dioxolane; alternatively, tetrahydropyran; alternatively, dihydropyran; alternatively, pyran; alternatively, dioxane; alternatively, furan; alternatively, benzofuran; alternatively, isobenzofuran; alternatively, dibenzofuran; alternatively, diphenyl ether; alternatively, ditolyl ether.

[0201] In general, the organoaluminum compound used in the catalyst systems disclosed herein can be any organoaluminum compound that can catalyze the formation of oligomer products together with the heteroatom ligand chromium compound complex (or chromium compound and heteroatom ligand). In one aspect, the organoaluminum compound can be an aluminoxane, an alkylaluminum compound, or any combination thereof; alternatively, an aluminoxane; or alternatively, an alkylaluminum compound. In one aspect, the alkylaluminum compound can be a trialkylaluminum, an alkylaluminum halide, an alkylaluminum alkoxide, or any combination thereof. In some aspects, the alkylaluminum compound can be a trialkylaluminum, an alkylaluminum halide, or any combination thereof; alternatively, a trialkylaluminum, an alkylaluminum alkoxide, or any combination thereof; or alternatively, a trialkylaluminum. In other aspects, the alkylaluminum compound can be a trialkylaluminum; alternatively, an alkylaluminum halide; or alternatively, an alkylaluminum alkoxide. In one aspect, the aluminoxane utilized in the catalyst system utilized in the process and system can be any aluminoxane that can catalyze the formation of oligomer products together with the heteroatom ligand chromium compound complex (or chromium compound and heteroatom ligand). In one non-limiting aspect, the aluminoxane can have repeating units characterized by Formula I:

[0202]

[0203] wherein R' is a linear or branched alkyl group. The alkyl groups of the aluminoxanes and alkylaluminum compounds are described independently herein and can be used without limitation to further describe the aluminoxanes and / or alkylaluminum compounds of Formula I. Typically, n of Formula I can be greater than 1; or alternatively, greater than 2. In one aspect, n can range from 2 to 15; or alternatively, range from 3 to 10.

[0204] In one aspect, each halide of any alkylaluminum halide disclosed herein can independently be a fluoride, chloride, bromide, or iodide; or alternatively, a chloride, bromide, or iodide. In one aspect, each halide of any alkylaluminum halide disclosed herein can be a fluoride; alternatively, a chloride; alternatively, a bromide; or alternatively, an iodide.

[0205] In one aspect, each alkyl group of the aluminoxane and / or alkylaluminum compound can independently be C1 to C 20 Alkyl; alternatively, C1 to C 10In one aspect, each alkyl group of the aluminoxane and / or alkylaluminum compound is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl; alternatively, methyl, ethyl, butyl, hexyl or octyl. In some aspects, each alkyl group of the aluminoxane and / or alkylaluminum compound can be methyl, ethyl, n-propyl, n-butyl, isobutyl, n-hexyl or n-octyl; alternatively, methyl, ethyl, n-butyl or isobutyl; alternatively, methyl; alternatively, ethyl; alternatively, n-propyl; alternatively, n-butyl; alternatively, isobutyl; alternatively, n-hexyl; or alternatively, n-octyl.

[0206] In one aspect, each alkoxy group of any alkylaluminum alkoxide disclosed herein can independently be C1 to C 20 Alkoxy, C1 to C 10 Alkoxy or C1 to C6 alkoxy. In one embodiment, each alkoxy group of any alkylaluminum alkoxide disclosed herein may independently be methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy or octyloxy; alternatively, methoxy, ethoxy, butoxy, hexyloxy or octyloxy. In some embodiments, each alkoxy group of any alkylaluminum alkoxide disclosed herein may independently be methoxy, ethoxy, n-propoxy, n-butoxy, isobutoxy, n-hexyloxy or n-octyloxy; alternatively, methoxy, ethoxy, n-butoxy or isobutoxy; alternatively, methoxy; alternatively, ethoxy; alternatively, n-propoxy; alternatively, n-butoxy; alternatively, isobutoxy; alternatively, n-hexyloxy; or alternatively, n-octyloxy.

[0207] In one non-limiting aspect, useful trialkylaluminum compounds may include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, or mixtures thereof. In some non-limiting embodiments, useful trialkylaluminum compounds may include trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof; alternatively, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof; alternatively, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof. In other non-limiting embodiments, useful trialkylaluminum compounds may include trimethylaluminum; alternatively, triethylaluminum; alternatively, tripropylaluminum; alternatively, tri-n-butylaluminum; alternatively, triisobutylaluminum; alternatively, trihexylaluminum; or alternatively, tri-n-octylaluminum.

[0208] In one non-limiting embodiment, useful alkylaluminum halides may include diethylaluminum chloride, diethylaluminum bromide, ethylaluminum dichloride, ethylaluminum sesquichloride, and mixtures thereof. In some non-limiting embodiments, useful alkylaluminum halides may include diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, and mixtures thereof. In other non-limiting embodiments, useful alkylaluminum halides may include diethylaluminum chloride; alternatively, diethylaluminum bromide; alternatively, ethylaluminum dichloride; or alternatively, ethylaluminum sesquichloride.

[0209] In one non-limiting aspect, the aluminoxane can be, include, or consist essentially of methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, tert-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, or a mixture thereof. In some non-limiting aspects, the aluminoxane can be, include, or consist essentially of methylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutylaluminoxane, tert-butylaluminoxane, or a mixture thereof. In other non-limiting aspects, the aluminoxane can be, comprise, or consist essentially of methylaluminoxane (MAO); alternatively, ethylaluminoxane; alternatively, modified methylaluminoxane (MMAO); alternatively, n-propylaluminoxane; alternatively, isopropylaluminoxane; alternatively, n-butylaluminoxane; alternatively, sec-butylaluminoxane; alternatively, isobutylaluminoxane; alternatively, tert-butylaluminoxane; alternatively, 1-pentylaluminoxane; alternatively, 2-pentylaluminoxane; alternatively, 3-pentylaluminoxane; alternatively, isopentylaluminoxane; or alternatively, neopentylaluminoxane.

[0210] The components of the catalyst system can be combined in any order, in any manner and in any time length (e.g., aging) to prepare the catalyst system. Before the catalyst system mixture is introduced into the reaction zone, the catalyst system mixture can be aged in the absence of ethylene in any suitable time period (e.g., 5 seconds to 48 hours, 10 seconds to 36 hours, 30 seconds to 24 hours, 1 minute to 18 hours, 5 minutes to 6 hours, 10 minutes to 4 hours or 20 minutes to 2 hours). In this article, the absence of ethylene refers to the total weight of the catalyst system mixture, and the catalyst system mixture contains less than 1 weight % ethylene. In some cases, before the reaction zone, less than 0.5 weight %, less than 0.1 weight % or less than 0.05 weight % ethylene is present in the catalyst system mixture.

[0211] Although not limited thereto, the catalyst system can be formed at a temperature in the range of 0° C. to 100° C., 10° C. to 75° C., 15° C. to 60° C., or 20° C. to 40° C. In these and other aspects, these temperature ranges are also meant to encompass situations where the catalyst system is formed at a range of different temperatures rather than at a single fixed temperature within the corresponding range.

[0212] The Al to Cr molar ratio of the catalyst system (or the oligomer product formed therein) can range from 10: 1 to 5,000: 1, 50: 1 to 3,000: 1, 50: 1 to 3,000: 1, 75: 1 to 2,000: 1, 100: 1 to 2,000: 1, 100: 1 to 1,000: 1. If more than one complex and / or more than one organoaluminum is used, the Al to Cr ratio is based on the total moles of chromium and / or aluminum.

[0213] Example

[0214] The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the present invention in any way. Various other aspects, modifications and equivalents thereof may be contemplated by those of ordinary skill in the art after reading the description herein without departing from the spirit of the present invention or the scope of the appended claims.

[0215] for Figure 2 A computer simulation was performed to determine the mass flow rate and corresponding composition of each stream under a specific set of pressure and temperature conditions for the ethylene oligomerization reaction system 100. The results are summarized in Table A. Note that Figure 2 Not every piece of equipment and flow is shown in , and only some of the main components of each flow are summarized in Table A.

[0216] Figure 2 The reaction zone effluent stream 125 ( Figure 1 The majority of the stream 25 in the reactor is organic reaction medium (cyclohexane), but based on the total oligomer product alone, octene represents about 50 mass % and hexene represents about 40 mass %. The reaction zone effluent stream 125, which can be heated before the first stage separator 130 (e.g., flash chamber), is separated into a first liquid stream 132 of 81 mass % (which is mainly cyclohexane and oligomer products) and a first vapor stream 138 of 19 mass % (which is mainly ethylene). The liquid: vapor split of about 4:25:1 can be varied as desired.

[0217] The first liquid stream 132, which may be heated prior to the second stage separator 140, is separated into a 90 mass % second liquid stream 142 (which is primarily cyclohexane and oligomer products) and a 10 mass % second vapor stream 148 (which is primarily ethylene and cyclohexane). The approximately 9:1 liquid: vapor split may be varied as desired.

[0218] The second vapor stream 148, which may be cooled prior to the knockout drum 150, is separated into a first oligomer fraction 155, which is primarily cyclohexane and oligomer products, and a vapor stream 158, which is primarily ethylene. The vapor stream 158 enters a first stage compressor 170, and the light fraction 173 exiting the compressor 170 is combined with the first vapor stream 138 to form a combined light stream 178, which may then be cooled. The combined light stream 178 has a higher percentage of ethylene than the first vapor stream 138 due to the addition of the ethylene-rich light fraction 173.

[0219] The combined light stream 178 enters a knockout drum 180. Leaving the knockout drum 180 are a liquid stream 183 (which has significant cyclohexane and oligomer product content and is fed to the liquid oligomer separation system 160), a low pressure ethylene stream 188 (which contains approximately 91 mass % ethylene and less than 0.25 mass % butenes), and a light gas purge stream 185 (which may have approximately the same composition as the ethylene stream 188).

[0220] Figure 2 The liquid oligomer separation system 160 in FIG. 1 does not show all influent and effluent streams. As can be readily appreciated, the C exiting the separation system 160 is not shown. 10+ oligomer stream. In addition, separation system 160 may include more than one separation device to separate and purify the desired hexene and octene products. For example, separation system 160 may include two distillation columns. Thus, in Table A, Figure 2 The final stream in FIG. 1 shows some of the precursor stream compositions previously. In separation system 160, the precursor stream (pre-167) contains primarily octenes, but also has significant amounts of C 10+ oligomers and cyclohexane, but after further separation, containing more than 97 mass % octenes Figure 2 The fourth stream in 167 ( Figure 1 Stream 67 in the fourth stream) exits separation system 160. For the catalyst systems disclosed herein, the amount of 1-octene in the octene stream is described independently herein and can be used without limitation to describe the amount of 1-octene in the octene stream (based on the total octenes in the fourth stream).

[0221] Likewise, the precursor stream (pre-165) is primarily cyclohexane but is additionally enriched in hexene and, after further separation, contains more than 99 mass % hexene. Figure 2 The third stream in 165 ( Figure 1 Stream 65 in the third stream) exits separation system 160. For the catalyst systems disclosed herein, the amount of 1-hexene in the hexene stream is described independently herein and can be used without limitation to describe the amount of 1-hexene in the hexene stream (based on the total hexene in the third stream).

[0222] Another precursor stream (pre-163) contains a large amount of ethylene, desired hexene and undesired butene. After further separation to recover the desired hexene, it contains 8-9 mass % butene and less than 5 mass % C 6+ Oligomer Figure 2 The second stream 163 (heavy gas purge stream) in Figure 1 Stream 63) leaves the separation system 160.

[0223] An overhead light stream 161, which is primarily ethylene, also leaves the liquid oligomer separation system 160. Optionally, and Figure 2 1, some ethylene may be further concentrated from light stream 161 (to over 90 mass % ethylene), and this ethylene-rich stream may be combined with low pressure ethylene stream 188 at second stage compressor 190 to form a recycle stream to reaction zone 120. Figure 2 The first-rate 195 ( Figure 1 The first stream 195 (ethylene recycle stream) contains about 91 mass % ethylene, less than 1 mass % C 4+ olefins and less than 0.25 mass % butene (the mass ratio of ethylene:butene is 380:1). The first stream 195 also contains only small amounts of hydrogen (0.01 mass %) and methane (1.5 mass %). Since very little butene is recycled, the amount of butene in the reaction zone 120 is significantly reduced: the reaction zone effluent stream 125 surprisingly contains only 0.16 mass % butene. It is also advantageous that the second stream 163 contains more than three times as much butene by mass as the butene in the first stream 195.

[0224] Recycled ethylene from first stream 195 is combined with feed stream 115 in oligomerization reaction zone 115. The feed streams may include, for example, a catalyst system feed stream, an organic reaction medium feed stream, an ethylene feed stream, and a hydrogen feed stream (if hydrogen is used). In some cases, a (fresh) ethylene feed stream may be combined with first stream 195 (ethylene recycle stream) and fed to the reaction zone separately from other feed streams (e.g., catalyst system feed stream).

[0225] According to Table A and Figure 2 , the following additional results are apparent. The total ethylene recycle rate is unexpectedly high, at 91-92 mass %, and is determined by dividing the amount of ethylene in the first stream 195 by the amount of ethylene in the effluent stream 125. This high level of recycle is very important because the ethylene conversion in the reaction zone 120 is about 60 mass %, which is determined based on the total amount of ethylene entering the reaction zone (about 116,400 lb / hr, not shown in Table A) and the amount of unreacted ethylene in the reaction zone effluent stream 125.

[0226] In terms of mass %, the light gas purge stream 185 contains more hydrogen and more methane than the first stream 195. The light gas purge stream 185 contains 0.015 mass % hydrogen and 1.67 mass % methane. In addition, the mass ratio of the light gas purge stream 185 to the second stream 163 (heavy gas purge stream) (ratio of light purge stream: heavy purge stream) is about 1:9.

[0227] As shown in Table A and Figure 1-Figure 2 As shown in , the processes disclosed herein demonstrate that the amount of ethylene recycled to the oligomerization reaction zone can be significantly increased while significantly reducing the amount of butene recycled to the oligomerization reaction zone.

[0228]

[0229]

[0230] The present invention has been described above by reference to multiple aspects and specific embodiments. Those skilled in the art will appreciate many variations based on the foregoing specific embodiments. All such obvious variations are within the full intended scope of the appended claims. Other statements of the present invention may include, but are not limited to, the following (each statement is described as "comprising / including...", but alternatively, may be "consisting essentially of..." or "consisting of..."):

[0231] Statement 1. A process for recycling ethylene from a reaction zone effluent stream from an oligomerization reaction zone, the reaction zone effluent stream containing an oligomer product effluent comprising at least 20 mass % octene, the process comprising:

[0232] a) separating the reaction zone effluent stream into

[0233] i) a first stream comprising ethylene and less than or equal to 5 mass % C 4+ Olefins,

[0234] ii) a second stream comprising butene and less than or equal to 10 mass % C 6+ Olefins,

[0235] iii) a third stream comprising any amount of hexene disclosed herein, such as at least 96, 97, 98 or 99 mass % hexene, and

[0236] iv) a fourth stream comprising any amount of octenes disclosed herein, such as at least 96, 97, 98, or 99 mass % octenes; and

[0237] b) recycling the first stream into the oligomerization reaction zone.

[0238] Statement 2. A process as defined in statement 1, wherein the oligomer product effluent comprises any amount of octenes disclosed herein, e.g., at least 20, 30, or 40 mass %; up to 99, 95, 92.5, 90, 87.5, or 85 mass %; or from 20 to 99 mass %, 30 to 95 mass %, 40 to 95 mass %, 40 to 90 mass %, 20 to 90 mass %, 30 to 87.5 mass %, 30 to 85 mass %, 40 to 87.5 mass %, 40 to 85 mass %, 20 to 60 mass %, 30 to 55 mass % or 40 to 55 mass % octenes, based on the total amount of oligomers in the oligomer product effluent.

[0239] Statement 3. A process as defined in statement 1 or 2, wherein the fourth stream comprises any amount of 1-octene disclosed herein, e.g., at least 95, 96, 96.5, 97, 97.5, 98, or 98.5 mass % 1-octene (as well as other amounts disclosed herein), based on the total mass of the octenes.

[0240] Statement 4. A process as defined in any of the preceding statements, wherein the third stream comprises any amount of 1-hexene disclosed herein, e.g., at least 90, 92.5, 95, 97.5, 98, 98.5, or 99 mass % 1-hexene (as well as other amounts disclosed herein), based on the total mass of the hexenes.

[0241] Statement 5. A method as defined in any of the preceding statements, wherein the second stream comprises any amount of C disclosed herein. 6+ Olefins, for example less than or equal to 8, 7, 6, 5, 4 or 3 mass % C 6+ Olefins.

[0242] Statement 6. A method as defined in any of the preceding statements, wherein the second stream contains more butenes by mass than the butenes in the first stream, or at least twice as much butene as the first stream, or at least three times as much butene as the first stream.

[0243] Statement 7. A method as defined in any of the preceding statements, wherein the first stream comprises any amount of C disclosed herein. 4+ Olefins, such as less than or equal to 4, 3, 2 or 1 mass % C 4+ Olefins.

[0244] Statement 8. A process as defined in any of the preceding statements, wherein the first stream comprises any amount of butene disclosed herein, such as less than or equal to 2, 1.5, 1, 0.75, 0.5, 0.35, or 0.2 mass % butene (as well as other amounts disclosed herein).

[0245] Statement 9. A process as defined in any of the preceding statements, wherein the first stream comprises any amount of ethylene disclosed herein, such as at least 85, 86, 87, 88, or 90 mass % ethylene (as well as other amounts disclosed herein).

[0246] Statement 10. A method as defined in any of the preceding statements, wherein the first stream further comprises any amount of hydrogen and / or methane disclosed herein, such as less than or equal to 5, 4, 3, 2, or 1 mass % hydrogen and / or methane.

[0247] Statement 11. A process as defined in any of the preceding statements, wherein the first stream is characterized by any mass ratio of ethylene:butene disclosed herein, e.g., at least 100:1, 150:1, 200:1, 300:1, or 350:1 (as well as other amounts disclosed herein).

[0248] Statement 12. A process as defined in any of the preceding statements, wherein any amount of ethylene in the reaction zone effluent stream disclosed herein is recycled to the oligomerization reaction zone, e.g., at least 86, 88, 89, 90, or 91 mass %; up to 99, 97, 96, 95, or 94 mass %; or from 86 to 99 mass %, 88 to 97 mass %, 89 to 96 mass %, 90 to 95 mass % or 91 to 94 mass % (as well as other amounts disclosed herein).

[0249] Statement 13. A method as defined in any of the preceding statements, wherein the oligomer product effluent further comprises any amount of hexene disclosed herein, such as at least 15, 20, 25, 30, or 35 mass %; up to 75, 65, 60, 55, or 50 mass %; or from 20 to 60 mass %, from 25 to 55 mass % or from 30 to 50 mass % hexene (as well as other amounts disclosed herein).

[0250] Statement 14. A process as defined in any one of the preceding statements wherein separating the reaction zone effluent stream into the first stream comprises at least two separation stages.

[0251] Statement 15. A method as defined in any one of the preceding statements, wherein separating the reaction zone effluent stream into the first stream comprises at least two compression stages.

[0252] Statement 16. The method as defined in any one of the preceding statements, wherein separating the reaction zone effluent stream into the first stream comprises:

[0253] (a) separating the reaction zone effluent stream into a first vapor stream and a first liquid stream;

[0254] (b) separating the first liquid stream into a second vapor stream and a second liquid stream;

[0255] (c) separating the second vapor stream into a light fraction and a first oligomer fraction; and

[0256] (d) combining the first vapor stream with the light fraction and forming the first stream and a light gas purge stream.

[0257] Statement 17. The method as defined in statement 16, wherein the light gas purge stream contains more hydrogen on a mass % basis than the first stream.

[0258] Statement 18. The method of statement 16 or 17, wherein the light gas purge stream contains more methane on a mass % basis than the first stream.

[0259] Statement 19. A method as defined in any of Statements 16-18, wherein the light gas purge stream comprises an amount of hydrogen and / or methane within any range disclosed herein, for example, less than or equal to 5, 4, 3, 2 or 1 mass % hydrogen and / or methane (as well as other amounts disclosed herein), based on the total mass of the light gas purge stream.

[0260] Statement 20. The method as defined in any one of statements 16-19, further comprising separating the second liquid stream into an overhead stream, the second stream, the third stream, and the fourth stream.

[0261] Statement 21. A process as defined in any of the preceding statements, wherein the oligomerization reaction zone has any ethylene conversion disclosed herein, e.g., at least 20, 30, 35, 40, 45, or 50 mass %; at most 99, 95, 90, 80, 75, 70, or 65 mass %; or a conversion of 20 to 100 mass %, 30 to 90 mass %, 40 to 80 mass %, 50 to 70 mass % or 55 to 65 mass % (as well as other conversions disclosed herein), based on the amount of ethylene entering the reaction zone and the amount of ethylene in the reaction zone effluent stream.

[0262] Statement 22. A method as defined in any of the preceding statements, wherein the oligomerization reaction zone has any amount of butene disclosed herein, such as at least 0.01, 0.02, 0.035, 0.05, or 0.1 mass %; at most 1, 0.75, 0.5, 0.35, 0.25, or 0.2 mass %; or 0.02 to 0.5 mass %, 0.05 to 0.35 mass % or 0.1 to 0.2 mass % butene (as well as other amounts disclosed herein).

[0263] Statement 23. A method as defined in any of the preceding statements, wherein the second stream comprises an amount of butenes in any range disclosed herein, based on the total mass of the second stream, such as at least 1, 2, 3, 4, or 5 mass %; up to 25, 20, 18, 15, or 12 mass %; or from 3 to 25 mass %, from 4 to 15 mass % or from 5 to 12 mass % butenes (as well as other amounts disclosed herein).

[0264] Statement 24. The method as defined in any of statements 16-23, wherein the mass ratio of the light gas purge stream to the second stream is within any range disclosed herein, such as 1:5 to 1:20, 1:6 to 1:15, or 1:7 to 1:12.

[0265] Statement 25. The process of any of the preceding statements wherein the amount of 1-butene in any butene-containing stream is any amount disclosed herein, e.g., at least 80, 85, 90, 95, or 98 mass % 1-butene, based on the total mass of the butenes.

[0266] Statement 26. A method as described in any of the preceding statements, further comprising the steps of:

[0267] introducing into the oligomerization reaction zone (1) ethylene, (2) a catalyst system or catalyst system components, (3) optionally an organic reaction medium, and (4) optionally hydrogen;

[0268] forming the oligomer product effluent; and

[0269] The oligomerization reaction zone effluent stream is withdrawn from the oligomerization reaction zone.

[0270] Statement 27. The method of statement 26 wherein the catalyst system or catalyst system components comprises (i) a heteroatom ligand transition metal compound complex and an organoaluminum compound, or (ii) a heteroatom ligand, a transition metal compound, and an organoaluminum compound.

[0271] Statement 28. The method of any of the preceding statements wherein the method is performed continuously.

Claims

1. A process for recycling ethylene from a reaction zone effluent stream from an oligomerization reaction zone, the reaction zone effluent stream containing an oligomer product effluent comprising at least 20 mass % octene, the process comprising: a) separating the reaction zone effluent into i) a first stream comprising ethylene and less than or equal to 5 mass % C 4+ Olefins, ii) a second stream comprising butene and less than or equal to 10 mass % C 6+ Olefins, iii) a third stream comprising at least 96 mass % hexene, and iv) a fourth stream comprising at least 96 mass % octene; and b) recycling the first stream into the oligomerization reaction zone.

2. The process of claim 1 wherein at least 88 mass % of the ethylene is recycled to the oligomerization reaction zone.

3. The method of claim 1, wherein the first stream comprises: Less than or equal to 3 mass% C 4+ Olefins; Less than or equal to 1 mass % butene; and At least 88 mass % ethylene.

4. The process of claim 1 wherein the first stream is characterized by an ethylene:butene mass ratio of at least 200:

1.

5. The method of claim 1 wherein separating the reaction zone effluent stream into the first stream comprises at least two separation stages.

6. The method of claim 5, wherein separating the reaction zone effluent stream into the first stream comprises at least two compression stages.

7. The process of claim 1, wherein the ethylene conversion of the oligomerization reaction zone is in the range of 30 to 90 mass %.

8. The process of claim 1 wherein the oligomerization reaction zone contains less than or equal to 0.5 mass % butene.

9. The method of claim 1, wherein: The third stream comprises at least 98 mass % hexene; and The fourth stream comprises at least 97 mass % octene.

10. The process of claim 9, wherein the fourth stream comprises at least 97 mass % 1-octene based on the total mass of the octenes.

11. The process of claim 1 wherein the oligomer product effluent comprises at least 30 mass % octenes and at least 30 mass % hexenes based on the total amount of oligomers in the oligomer product effluent.

12. The method of claim 1, wherein: The second stream comprises 3 to 25 mass % butene and less than or equal to 7 mass % C 6+ Olefins; and The second stream contains at least twice as much butene by mass as the first stream.

13. The method of claim 1, wherein separating the reaction zone effluent stream into the first stream comprises: (a) separating the reaction zone effluent stream into a first vapor stream and a first liquid stream; (b) separating the first liquid stream into a second vapor stream and a second liquid stream; (c) separating the second vapor stream into a light fraction and a first oligomer fraction; as well as (d) combining the first vapor stream with the light fraction and forming the first stream and a light gas purge stream.

14. The method of claim 13, further comprising separating the second liquid stream into an overhead stream, the second stream, the third stream, and the fourth stream.

15. The method of claim 14, wherein a mass ratio of the light gas purge flow to the second flow is in the range of 1:5 to 1:

20.

16. A method comprising: A) introducing ethylene, a catalyst system or catalyst system components, optionally an organic reaction medium, and optionally hydrogen into an oligomerization reaction zone; B) forming an oligomer product effluent in the oligomerization reaction zone, the oligomer product effluent comprising at least 20 mass % octene; C) discharging a reaction zone effluent stream from the oligomerization reaction zone, the reaction zone effluent stream comprising the oligomer product effluent stream; D) separating the reaction zone effluent into i) a first stream comprising ethylene and less than or equal to 5 mass % C 4+ Olefins, ii) a second stream comprising butene and less than or equal to 10 mass % C 6+ Olefins, iii) a third stream comprising at least 96 mass % hexene, and iv) a fourth stream comprising at least 96 mass % octene; and E) recycling the first stream to the oligomerization reaction zone.

17. The process of claim 16, wherein the catalyst system or catalyst system components comprise (i) a heteroatom ligand transition metal compound complex and an organoaluminum compound, or (ii) a heteroatom ligand, a transition metal compound, and an organoaluminum compound.

18. The method of claim 16, wherein the first stream comprises: Less than or equal to 4 mass% C 4+ Olefins; Less than or equal to 0.75 mass % butene; and At least 87 mass % ethylene.

19. The method of claim 18, wherein the first stream is further characterized by a mass ratio of ethylene:butene of at least 150:

1.

20. The process of claim 19, wherein the oligomerization reaction zone contains less than or equal to 0.35 mass % butene.

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