Ethylene oligomerization process

Abstract

The present disclosure relates to an ethylene oligomerization process. A process for producing an alpha-olefin comprising contacting ethylene, a zirconium-based catalyst system comprising a hydrocarbyl metal compound, a chain transfer agent, and optionally an organic reaction medium. Utible chain transfer agents include: a) hydrogen; b) a compound containing hydrogen-silicon bonds; a compound having a hydrogen-sulfur bond; a compound having a hydrogen-phosphorus bond; or c) a transition metal compound chain transfer agent.

Description

[0001] This application is a divisional application. The filing date of the original application is May 3, 2022, the application number is 202280036284.2, and the invention title is "Process for the oligomerization of ethylene", which is hereby incorporated by reference in its entirety. Technical Field

[0002] The present disclosure relates to processes for producing linear alpha-olefins. More specifically, the present disclosure relates to improved processes for the oligomerization of ethylene to linear alpha-olefins. Background Art

[0003] Alpha-olefins are important commercial products. Many of their applications include use as intermediates in detergent manufacture, as precursors for more environmentally friendly refined oils, as monomers, and as precursors for many other types of products. One way to manufacture alpha-olefins is by the oligomerization of ethylene in a catalytic reaction involving various types of catalysts and / or catalyst systems. Some ethylene oligomerization catalyst systems produce large amounts of polymer, which can shorten the run time of the reaction system before the reactor needs to be cleaned, reduce the reliability of the reaction system, and / or complicate product separation. The applications and demand for linear alpha-olefins are increasing, and the competition to supply them is accordingly intensifying. Therefore, new and improved processes for the oligomerization of ethylene are desirable. Summary of the Invention

[0004] This application relates to a process that includes: a) contacting: i) ethylene, ii) a catalyst system that comprises 1) a zirconium compound having the formula ZrX 1 m Y 1 q wherein each X 1 is independently a halogen group, and each Y 1Each is independently a hydrocarboxide, dihydrocarbyl azanide, hydrocarbyl carboxylate, hydrocarbyl sulfonate or β-diketonate, m ranges from 0 to 4, q ranges from 0 to 4, and m + q is an integer from 2 to 4, and 2) a hydrocarbyl metal compound; iii) a chain transfer agent; and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone; and wherein the Schulz-Flory K value of the oligomer product is from 0.4 to 0.8. In one aspect, the chain transfer agent can be i) a compound containing a hydrosilyl bond, a compound having a hydrosulfide bond, a compound having a hydrophosphide bond or any combination thereof; ii) hydrogen gas; or 3) a transition metal compound. In some aspects, the method can produce an oligomer product that contains (a) less than 1 wt% of a polymer, (b) less than 1 wt.% of a compound having a weight average molecular weight greater than 1000 g / mol, or (c) any combination thereof, wherein the wt.% is based on the total weight of the oligomer product. In another aspect, relative to the same method without using a chain transfer agent that contains a compound having a hydrosilyl bond, a compound having a hydrosulfide bond, a compound having a hydrophosphide bond or any combination thereof, the method can produce an oligomer product that contains: (a) a polymer having a lower Mw, (b) a polymer having a lower Mw maximum peak, (c) a reduced percentage of polymer, (d) a polymer having a reduced percentage of polymer with an Mw greater than 100,000, or (e) any combination thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0005] The subject matter of the present application can be understood with reference to the following description in conjunction with the accompanying drawings, in which like reference numerals refer to like elements, and in which:

[0006] Figure 1 An example of an ethylene oligomerization unit is illustrated.

[0007] While the subject matter of the present application is susceptible to various modifications and alternative forms, the drawings illustrate specific embodiments herein described in detail by way of example. However, it should be understood that the description of specific embodiments herein is not intended to limit the claimed subject matter to the particular forms disclosed, but on the contrary, the invention will cover all modifications, equivalents, and alternative forms falling within the spirit and scope of the invention as defined by the appended claims.

[0008] DEFINITIONS

[0009] 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 not specifically defined herein, the definitions in the 2nd Edition of the IUPAC Compendium of Chemical Terminology (1997) may be applied, provided that the definitions do not conflict with any other disclosure or definition applied herein, or render any claim to which the definitions are applied unclear or invalid. If any definition or usage provided in any document incorporated herein by reference conflicts with the definitions or usage provided herein, then the definitions or usage provided herein shall prevail.

[0010] In this document, the features of the subject matter may be described such that in a particular aspect and / or claim, combinations of different features may be contemplated. For each aspect, and / or claim, and / or feature disclosed herein, all combinations that do not adversely affect the systems, compositions, processes, and / or methods described herein are considered, whether or not a particular combination is explicitly described. In addition, unless otherwise explicitly stated, any aspect, and / or claim, and / or feature disclosed herein may be combined to describe methods and systems of the invention consistent with the present disclosure.

[0011] Unless otherwise explicitly indicated, the terms "a", "an", and "the" are intended to include a plurality of alternatives, such as at least one alternative, or one or more alternatives. For example, unless otherwise stated, the disclosure of "trialkylaluminum compound" is intended to cover one trialkylaluminum compound, or a mixture or combination of more than one trialkylaluminum compound.

[0012] The numbering scheme found in the version of the periodic table published in Chemical and Engineering News, 63(5), 27, 1985 is used to indicate the groups of the periodic table. In some cases, a group of elements 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 indicate Group 17 elements, and so on.

[0013] For any specific compound disclosed herein, unless otherwise indicated, the general structure or name presented also is intended to cover all structural isomers, conformational isomers, and stereoisomers that can be generated by a particular set of substituents. Accordingly, unless otherwise clearly indicated, a general reference to a compound includes all structural isomers; for example, a general reference to a C6 hydrocarbon refers to all hydrocarbons having six carbon atoms, a general reference to pentane includes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, and a general reference to butyl includes n-butyl, sec-butyl, isobutyl, and tert-butyl. Additionally, when the context permits or requires, a reference to a general structure or name covers all enantiomers, diastereomers, and other optical isomers (whether in enantiomeric or racemic form), as well as mixtures of stereoisomers. For any specific formula or name provided, any general formula or name provided also covers all conformational isomers, regioisomers, and stereoisomers that can be generated by a particular set of substituents.

[0014] Chemical "groups" are described in terms of how the group is formally derived from a reference or "parent" compound, e.g., by the number of hydrogen atoms formally removed from the parent compound to generate the group, even if the group is not literally synthesized in this manner. By way of example, an "alkyl" group can be formally derived by removing one hydrogen atom from an alkane, and an "alkylene" group can be formally derived by removing two hydrogen atoms from an alkane. Additionally, 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 instance can be described as "alkane groups" and which cover "alkyl", "alkylene", and materials having three or more hydrogen atoms removed from the alkane as required by the circumstances. Throughout this document, the disclosure that a substituent, ligand, or other chemical moiety can constitute a particular "group" means that when the group is used as described, well-known chemical structure and bonding rules are followed. When a group is described as "derived from", "formed from", "derived by", or "formed by", these terms are used in a formal sense and are not intended to reflect any particular synthetic method or procedure, unless otherwise specified or the context otherwise requires.

[0015] Whenever used in this specification and the claims, the term "hydrocarbon" refers to a compound containing only carbon and hydrogen. Other identifiers may be used to indicate the presence of specific groups in the hydrocarbon (e.g., halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equal number of hydrogen atoms in the hydrocarbon). The term "hydrocarbyl" is used herein according to the IUPAC-defined definition: a monovalent group formed by removing one hydrogen atom from a hydrocarbon. Similarly, "hydrocarbylene" refers to a group formed by removing two hydrogen atoms from a hydrocarbon (removing two hydrogen atoms from one carbon atom or one hydrogen atom from each of two different carbon atoms). Thus, according to the terms used herein, "hydrocarbyl" refers to a general group formed by removing one or more hydrogen atoms (as required for a particular group) from a hydrocarbon. "Hydrocarbyl", "hydrocarbylene", and "hydrocarbyl group" can be acyclic or cyclic groups, and / or can be straight-chain or branched-chain. "Hydrocarbyl", "hydrocarbylene", and "hydrocarbyl group" can contain rings, ring systems, aromatic rings, and aromatic ring systems containing only carbon and hydrogen. By way of example, "hydrocarbyl", "hydrocarbylene", and "hydrocarbyl group" include other groups such as aryl, arylene, aromatic hydrocarbon, alkyl, alkylene, alkane, cycloalkyl, cycloalkylene, cycloalkane, aralkyl, aralkylene, and aralkane groups as members.

[0016] Whenever used in this specification and the claims, the term "alkane" refers to a saturated hydrocarbon compound. Other identifiers may be used to indicate the presence of specific groups in the alkane (e.g., halogenated alkane indicates the presence of one or more halogen atoms replacing an equal number of hydrogen atoms in the alkane). The term "alkyl" is used herein according to the IUPAC-defined definition: a monovalent group formed by removing a hydrogen atom from an alkane. Similarly, "alkylene" refers to a group formed by removing two hydrogen atoms from an alkane (removing two hydrogen atoms from one carbon atom or one hydrogen atom from each of two different carbon atoms). "Alkane group" is a general term referring to a group formed by removing one or more hydrogen atoms (as required for a particular group) from an alkane. Unless otherwise specified, "alkyl", "alkylene", and "alkane group" can be acyclic or cyclic groups, and / or can be straight-chain or branched-chain. Primary, secondary, and tertiary alkyls are obtained by removing a hydrogen atom from a primary, secondary, or tertiary carbon atom of an alkane, respectively. A normal alkyl can be obtained by removing a hydrogen atom from a terminal carbon atom of a straight-chain alkane.

[0017] As used herein, the term "substituted" when used to describe a compound or a group, e.g., when referring to a substituted analogue 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 by an equivalent term such as "non-substituted", which refers to the original group in which no non-hydrogen moiety replaces a hydrogen in the group. "Substituted" is intended to be non-limiting and includes inorganic or organic substituents.

[0018] 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 stated, the term "olefin" includes aliphatic and aromatic, cyclic and acyclic and / or straight-chain and branched-chain 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 may be identified by using the terms "mono", "di", "tri", etc. in the name of the olefin. Olefins may be further identified by the position of one or more carbon-carbon double bonds.

[0019] The term "α-olefin" as used in this specification and claims refers to an olefin having a carbon-carbon double bond between the first and second carbon atoms of the longest continuous carbon atom chain. Unless otherwise expressly stated, the term "α-olefin" includes straight-chain and branched α-olefins. In the case of a branched α-olefin, the branch may be at the 2-position (vinylidene) and / or at the 3-position or higher relative to the olefin double bond. Whenever used in this specification and claims, the term "vinylidene" refers to an α-olefin having a branch at the 2-position relative to the olefin double bond. Unless expressly indicated, the term "α-olefin" by itself does not indicate the presence or absence of other carbon-carbon double bonds. As used herein, the term "straight-chain α-olefin" refers to an unbranched α-olefin having a carbon-carbon double bond between the first and second carbon atoms.

[0020] Whenever used in this specification and claims, the term "normal α-olefin" refers to a straight-chain aliphatic monoolefin having a carbon-carbon double bond between the first and second carbon atoms. It should be noted that "normal α-olefin" and "straight-chain α-olefin" are not synonyms, since the term "straight-chain α-olefin" may include straight-chain olefin compounds having a double bond between the first and second carbon atoms and additional double bonds.

[0021] "Cycloalkane" is a saturated cyclic hydrocarbon with or without side chains, such as cyclobutane. Unsaturated cyclic hydrocarbons with one or more internal double bonds or one triple bond are called cycloalkenes and cycloalkynes, respectively. Cycloalkenes and cycloalkynes with only one, only two, only three, etc. internal double bonds or triple bonds can be identified by using the terms "mono-", "di-", "tri-", etc. in the name of the cycloalkene or cycloalkyne, respectively. The position of the internal double bond or triple bond in cycloalkenes and cycloalkynes can be further identified.

[0022] "Cycloalkyl" is a monovalent group obtained by removing one hydrogen atom from a ring carbon atom of a cycloalkane. Similarly, "cycloalkylidene" refers to a group obtained by removing two hydrogen atoms from a cycloalkane, at least one of which is a ring carbon. Thus, "cycloalkylidene" includes: groups obtained from cycloalkanes in which two hydrogen atoms are formally removed from the same ring carbon; groups obtained from cycloalkanes in which two hydrogen atoms are formally removed from two different ring carbons; and groups obtained from cycloalkanes in which the first hydrogen atom is formally removed from a ring carbon and the second hydrogen atom is formally removed from a carbon atom that is not a ring carbon. "Cycloalkane group" refers to a general group formed by removing one or more hydrogen atoms (required for a particular group and at least one of which is a ring carbon) from a cycloalkane. It should be noted that, according to the definitions provided herein, general cycloalkane groups (including cycloalkyl and cycloalkylidene) include cycloalkane groups having zero, one, or more than one hydrocarbyl substituents attached to the cycloalkane ring carbon atoms (e.g., methylcyclopropyl), and are members of the group of hydrocarbyl groups. However, when referring to cycloalkane groups having a specified number of cycloalkane ring carbon atoms (e.g., cyclopentyl group or cyclohexyl group, etc.), the basic name of the cycloalkane group having a defined number of cycloalkane ring carbon atoms refers to an unsubstituted cycloalkane group (including those without hydrocarbyl groups located on the cycloalkane group ring carbon atoms). Thus, a substituted cycloalkane group having a specified number of carbon atoms (e.g., a substituted cyclopentane or a substituted cyclohexane, etc.) refers to the corresponding group having one or more substituents (including other substituents such as halogen, hydrocarbyl, or hydrocarbyloxy) attached to the cycloalkane group ring carbon atoms. When a substituted cycloalkane group having a defined number of cycloalkane ring carbon atoms is a member of the group of hydrocarbyl groups (or a member of the general group of cycloalkane groups), each substituent in the substituted cycloalkane group having a defined number of cycloalkane ring carbon atoms is limited to a hydrocarbyl substituent. One can easily distinguish and select general groups, specific groups, and / or one or more monosubstituted cycloalkane groups having a particular number of carbon atoms, which can be used as members of the group of hydrocarbyl groups (or members of the general group of cycloalkane groups).

[0023] An aliphatic compound is a non-cyclic or cyclic, saturated or unsaturated carbon compound other than an aromatic compound. An "aliphatic group" is a broad group formed by removing one or more hydrogen atoms (necessary for a particular group) from the carbon atoms of an aliphatic compound. Thus, aliphatic compounds and aliphatic groups can contain one or more organic functional groups and / or one or more atoms other than carbon and hydrogen.

[0024] An "aromatic" compound is a compound containing a cyclic conjugated double bond system that follows the Hückel (4n + 2) rule and contains (4n + 2) π electrons, where n is an integer from 1 to 5. Aromatic compounds include "aromatic hydrocarbons" (hydrocarbon aromatic compounds) and "heteroaromatic hydrocarbons" (also referred to as "hetarenes") (heteroaromatic compounds formally derived from aromatic hydrocarbons by replacing one or more methylene (-C=) carbon atoms in the cyclic conjugated double bond system with trivalent or divalent heteroatoms, in such a way as to maintain the characteristic of the continuous π electron system of the aromatic system and the number of out-of-plane π electrons corresponding to the Hückel rule (4n + 2)). Although aromatic hydrocarbon compounds and heteroaromatic hydrocarbon compounds are mutually exclusive members of the group of aromatic compounds, compounds having both an aromatic hydrocarbon group and a heteroaromatic hydrocarbon group are generally regarded as heteroaromatic hydrocarbon compounds. Unless otherwise specified, aromatic compounds, aromatic hydrocarbons, and heteroaromatic hydrocarbons can be monocyclic (e.g., benzene, toluene, furan, pyridine, picoline) or polycyclic. Unless otherwise specified, polycyclic aromatic compounds, aromatic hydrocarbons, and heteroaromatic hydrocarbons include compounds in which the aromatic rings can be fused (e.g., naphthalene, benzofuran, and indole), compounds in which the aromatic groups can be separated and linked by a bond (e.g., biphenyl or 4-phenylpyridine), or compounds in which the aromatic groups are linked by a group containing a linking atom (e.g., the carbon of the methylene in diphenylmethane; the oxygen of diphenyl ether; the nitrogen of triphenylamine; and other linking groups). As disclosed herein, the term "substituted" can be used to describe an aromatic group, aromatic hydrocarbon, or heteroaromatic hydrocarbon in which a non-hydrogen moiety formally replaces a hydrogen in the compound, and is intended to be non-limiting.

[0025] "Aromatic group" refers to a general group formed by removing one or more hydrogen atoms (as required for a particular group and where at least one is a carbon atom of an aromatic ring) from an aromatic compound. For a monovalent "aromatic group", the hydrogen atom removed must be from an aromatic ring carbon. For an "aromatic group" formed by removing more than one hydrogen atom from an aromatic compound, at least one hydrogen atom must be from an aromatic hydrocarbon ring carbon. Additionally, an "aromatic group" can have hydrogen atoms removed from the same ring of an aromatic ring or ring system (e.g., benzene-1,4-diyl, pyridine-2,3-diyl, naphthalene-1,2-diyl, and benzofuran-2,3-diyl), hydrogen atoms removed from two different rings of a ring system (e.g., naphthalene-1,8-diyl and benzofuran-2,7-diyl), or hydrogen atoms removed from two separate aromatic rings or ring systems (e.g., bis(benzene-4-yl)methane).

[0026] An aromatic hydrocarbon is an aromatic hydrocarbon with or without side chains (e.g., benzene, toluene, or xylene, etc.). "Aryl" refers to a group obtained by formally removing a hydrogen atom from an aromatic ring carbon of an aromatic hydrocarbon. It should be noted that an aromatic hydrocarbon can contain a single aromatic hydrocarbon ring (e.g., benzene or toluene), contain fused aromatic rings (e.g., naphthalene or anthracene), and contain one or more separate aromatic rings covalently linked via a bond (e.g., biphenyl) or one or more non-aromatic hydrocarbon groups (e.g., diphenylmethane). Similarly, "arylene" refers to a group formed by removing two hydrogen atoms from an aromatic hydrocarbon (where at least one hydrogen atom is from an aromatic ring carbon). "Aromatic hydrocarbon group" refers to a general group formed by removing one or more hydrogen atoms (as required for a particular group and where at least one is a carbon atom of an aromatic ring) from an aromatic hydrocarbon. It should be noted that according to the definitions provided herein, general aromatic hydrocarbon groups (including aryl and arylene) include those having zero, one, or more than one hydrocarbon group substituents located on the carbon atoms of an aromatic hydrocarbon ring or ring system (e.g., tolyl group or xylyl group, etc.) and are members of the group of hydrocarbon groups. However, phenyl (or phenylene) and / or naphthyl (or naphthylene) refer to specific unsubstituted aromatic hydrocarbon groups (excluding hydrocarbon groups located on the carbon atoms of an aromatic hydrocarbon ring or ring system). Thus, a substituted phenyl or a substituted naphthyl refers to the corresponding aromatic hydrocarbon group having one or more substituents (including halogen, hydrocarbon group, or alkoxy group, etc.) located on the carbon atoms of an aromatic hydrocarbon ring or ring system. When a substituted phenyl and / or a substituted naphthyl is a member of the group of hydrocarbon groups (or a general group of aromatic hydrocarbon groups), each substituent is limited to a hydrocarbon group substituent. One of ordinary skill in the art can readily distinguish and select general phenyl and / or naphthyl, specific phenyl and / or naphthyl, and / or each substituted phenyl or substituted naphthyl that can be used as a member of the group of hydrocarbon groups (or a general group of aromatic hydrocarbon groups).

[0027] "Arylalkyl" refers to an alkyl group substituted with an aryl group having a free valence on a non-aromatic carbon atom (e.g., benzyl, or 2-phenyleth-1-yl, etc.). Similarly, "arylenealkyl" refers to an alkylene group substituted with an aryl group having two free valences on a single non-aromatic carbon atom or free valences on two non-aromatic carbon atoms, and "arylalkane group" refers to an alkane group substituted with a generalized aryl group having one or more free valences on one or more non-aromatic carbon atoms. It should be noted that according to the definitions provided herein, general arylalkane groups include those having zero, one, or more than one hydrocarbyl substituents located on the carbon atoms of the arylalkane aromatic hydrocarbon ring or ring system and are members of the group of hydrocarbyl groups. However, a specific arylalkane group designating a specific aryl (e.g., the phenyl group in benzyl or 2-phenylethyl, etc.) refers to a specific unsubstituted arylalkane group (excluding hydrocarbyl groups located on the carbon atoms of the arylalkane aromatic hydrocarbon ring or ring system). Thus, a substituted arylalkane group designating a specific aryl refers to the corresponding arylalkane group having one or more substituents (including halogen, hydrocarbyl, or hydrocarbyloxy, etc.). When a substituted arylalkane group designating a specific aryl is a member of the group of hydrocarbyl groups (or a member of the general group of arylalkane groups), each substituent is limited to a hydrocarbyl substituent. One can easily distinguish and select a substituted arylalkane group designating a specific aryl, which can be used as a member of the group of hydrocarbyl groups (or a member of the general group of arylalkane groups).

[0028] As used herein, the term "hydrocarbyl metal compound" refers to a compound having at least one metal-carbon bond, wherein the carbon atom participating in the metal-carbon bond is part of a hydrocarbyl group. A "hydrocarbyl compound" may contain other non-hydrocarbyl groups, such as halogen, hydrocarbyloxy, alkoxy, carboxylate, and amino groups, and other non-hydrocarbyl groups, as long as the compound contains at least one metal-carbon bond (wherein the carbon atom participating in the metal-carbon bond is part of a hydrocarbyl group). Similarly, any specific "hydrocarbyl metal compound" (a compound designating the metal of the hydrocarbyl metal compound) refers to a compound having at least one specific metal-carbon bond, wherein the carbon atom participating in the metal-carbon bond is part of a hydrocarbyl group.

[0029] "Halogen group" has its usual meaning; thus, examples of halogen groups include fluorine, chlorine, bromine, and iodine.

[0030] The term "substituted", when used to describe a group (e.g., when referring to a substituted analogue of a specific group), is intended to describe any non-hydrogen moiety that formally replaces the hydrogen in the group and is intended to be non-limiting. A group or groups may also be referred to herein as "unsubstituted", or by an equivalent term such as "non-substituted", which refers to the original group in which the non-hydrogen moiety does not replace the hydrogen in the group. "Substituted" is intended to be non-limiting and includes inorganic substituents or organic substituents.

[0031] The terms "room temperature" or "ambient temperature" are used herein to describe any temperature from 15 °C to 35 °C where no external heat source or cooling source is directly applied. Thus, the terms "room temperature" and "ambient temperature" encompass each temperature and any and all ranges, sub-ranges, and combinations of sub-ranges of temperatures from 15 °C to 35 °C where no external heating or cooling source is directly applied. The term "atmospheric pressure" is used herein to describe the air pressure of the Earth without using an external pressure regulating device. Generally, unless implemented at extreme Earth altitudes, "atmospheric pressure" is approximately 1 atmosphere of pressure (alternatively, approximately 14.7 psi or approximately 101 kPa). References to gaseous, liquid, and / or solid materials refer to the physical state of the material at 25 °C and atmospheric pressure.

[0032] Features provided as minimum values within this disclosure may alternatively be phrased as "at least" or "greater than or equal to" any recited minimum value of a feature disclosed herein. Features provided as maximum values within this disclosure may alternatively be phrased as "less than or equal to" the maximum value of a feature disclosed herein.

[0033] Within this disclosure, general rules of organic nomenclature apply. 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, a reference to a 4-substituted phenyl indicates that the non-hydrogen substituent is at the 4-position and hydrogen is at the 2-, 3-, 5-, and 6-positions. References to compounds or groups having substitution at positions other than the indicated position may be made using including or some other alternative language. For example, a reference to a phenyl containing a substituent at the 4-position refers to a group having a non-hydrogen substituent at the 4-position and hydrogen or any non-hydrogen substituent at the 2-, 3-, 5-, and 6-positions.

[0034] The term "reaction zone effluent" and its derivatives (e.g., oligomerization reaction zone effluent) generally refer to all materials leaving the reaction zone. The term "reaction zone effluent" and its derivatives may also be prefaced with other descriptors that limit the portion of the reaction zone effluent being referred to. For example, the term "reaction zone effluent" refers to all materials leaving the reaction zone (e.g., product and solvent or diluent, etc.), while the term "olefin reaction zone effluent" refers only to olefins within the reaction zone effluent and the term "oligomer product reaction zone effluent" refers to oligomer products within the reaction zone effluent.

[0035] The term oligomer refers to a product containing from 2 to 20 monomer units. The terms "oligomer product" and "oligomer product effluent" include all oligomer products made by an "oligomerization" process, but do not include other non-oligomer components of the reaction zone effluent stream, such as unreacted monomers (ethylene), organic reaction medium, and hydrogen and other components. The term "oligomerization" and its derivatives refer to a process for producing an oligomer product that produces a product containing at least 20 wt.%, 35 wt.%, 50 wt.%, or 60 wt.% 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 wt.%, 35 wt.%, 50 wt.%, or 60 wt.% of oligomers having 4 to 40 carbon atoms.

[0036] The Schulz-Flory K value (sometimes referred to as the Schulz-Flory chain growth factor, K value) can be defined by the equation: K = X q+1 / X q , where X q +1 is the number of moles of oligomer product produced having q + 1 monomer (e.g., ethylene) units, and X q is the number of moles of oligomer product produced having q monomer (e.g., ethylene) units. Generally, the Schulz-Flory K value can be determined using any two oligomers of oligomer products that differ by one in the number of monomer units. However, it is understood that product separation and analysis can lead to inaccuracies in the determined oligomer product distribution using specific oligomers (e.g., incomplete recovery of gaseous and / or solid products during product separation). Those of ordinary skill in the art will recognize such problems and can select appropriate oligomers as a basis for determining the Schulz-Flory K value.

[0037] The catalyst system productivity is defined as the number of grams of product produced per gram (or mole) of zirconium in the catalyst system used in the oligomerization reaction. The catalyst system activity is defined as the number of grams of product produced per gram (or mole) of zirconium per unit time (e.g., hour) of the oligomerization reaction. The productivity and / or activity of the catalyst system can be expressed in terms of various products of the oligomerization reaction and / or components of the catalyst system. For example, in an ethylene oligomerization process using a catalyst system containing a zirconium compound, available catalyst system productivities include (g oligomer product) / (g Zr) and other productivities.

[0038] Unless otherwise specified, the terms "contact" and "combine" and their derivatives can refer to any addition order, sequence, or concentration used to bring two or more components of the disclosed embodiments into contact or combination. The combination or contact of the oligomeric components can occur in one or more reaction zones under suitable contact conditions such as temperature, pressure, contact time, flow rate, etc.

[0039] The terms "catalyst system", "catalyst composition", "catalyst mixture", etc. do not depend on the actual product or composition 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 heteroatom ligand transition metal compound complex after combining these components. Thus, the terms "catalyst system", "catalyst composition", "catalyst mixture", etc. encompass the initial starting components of the composition and any product that can be produced by bringing these initial starting components into contact. The terms "catalyst system", "catalyst composition", "catalyst mixture", etc. can be used interchangeably throughout this disclosure.

[0040] In this disclosure, a method can have multiple steps or can include features having many different elements (e.g., components in a catalyst system or components and other features in an olefin oligomerization method). These steps and / or elements can be designated as needed using terms such as first, second, and third, series a), b), c), etc., i), ii), iii), etc., (a), (b), (c), etc., and / or (i), (ii), (iii), etc. (and other designated series) to provide a designation for each method step and / or element. It should be understood that unless otherwise explicitly stated or required by other method steps, elements, and / or element features, the numerical or alphabetical ordering within a designated series does not imply a specific order or preference for the method steps in the methods described herein, one or more features described herein, and / or one or more elements of the features. Additionally, these designated series are provided to distinguish different method steps and / or elements in the features and can be utilized as necessary without regard to the specific series used for the steps, elements, or features utilized in this specification, as long as the designated series always distinguishes different features, different method steps, and / or different elements of the features.

[0041] When referring to a contacting method, the terms "simultaneously", "simultaneous contacting", "contacting simultaneously" and their derivatives refer to a contacting method in which the two or more recited compounds, mixtures, substances and / or compositions are contacted by flowing into a common junction, tank, vessel or reactor, etc. at the same time. When referring to a contacting method, the terms "substantially simultaneously", "substantially simultaneous contacting", "contacting substantially simultaneously" and their derivatives refer to a contacting method in which, during the contacting of the two or more recited compounds, mixtures, streams and / or compositions, the two or more recited compounds, mixtures, streams and / or compositions are contacted such that, for a period of time during the contacting process, the two or more recited compounds, mixtures, streams and / or compositions flow into a common junction, tank, vessel or reactor at the same time. It should be noted that the terms "substantially simultaneously", "substantially simultaneous contacting", "contacting substantially simultaneously" and their derivatives do not mean that the two or more recited compounds, mixtures, streams and / or compositions are contacted simultaneously during the entire addition process of each of the two or more recited compounds, mixtures, streams and / or compositions. The terms "substantially simultaneously", "substantially simultaneous contacting", "contacting substantially simultaneously" and their derivatives include the following situations: where one (or less than all) of the recited compounds, mixtures, streams and / or compositions may enter the common junction, tank, vessel or reactor before one (or less than all) of the other recited compounds, mixtures, streams and / or compositions and before the flow of one (or less than all) of the other substances and / or recited compounds, mixtures, streams and / or compositions into the common junction, tank, vessel or reactor can be completed, stopped or interrupted. In any aspect and / or embodiment described herein, the terms "simultaneously", "simultaneous contacting", "contacting simultaneously" and their derivatives may be modified by incorporating terms that provide the amounts of each of the recited compounds, mixtures, streams and / or compositions that can be contacted simultaneously, indicating different degrees of "substantially simultaneously", "substantially simultaneous contacting", "contacting substantially simultaneously" and their derivatives. For example, at least 20%, 30%, 40%, 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95% of each of the recited compounds, mixtures, streams and / or compositions may be "contacted simultaneously" or "contacted simultaneously". Generally, the percentage of the recited compounds, mixtures, streams and / or compositions that can be "contacted simultaneously" or "contacted simultaneously" may be by weight (wt.%), volume (volume %) or mole (mole %).Unless otherwise specified, the recited compounds, mixtures, streams, and / or compositions and their derivatives of "substantially simultaneously", "substantially simultaneous contacting", and "substantially simultaneously contacting" shall mean that at least 50% of each of the recited compounds, mixtures, streams, and / or compositions can be "contacted simultaneously" or "contacted substantially simultaneously".

[0042] It should be further noted that when referring to a contacting method or process, "simultaneously", "simultaneous contacting", "simultaneously contacting", "substantially simultaneous contacting", "substantially simultaneously contacting", and their derivatives are different from such methods or processes in which one or more first materials (e.g., compounds, mixtures, streams, and / or compositions) are already present in a tank, vessel, or reactor and one or more other compounds, mixtures, streams, and / or compositions are added to the tank, vessel, or reactor. In such cases, the first materials in the tank, container, or reactor do not flow into the tank, container, or reactor simultaneously with the other compounds, mixtures, streams, and / or compositions and the materials in the tank. Therefore, the first materials and the other compounds, mixtures, streams, and / or compositions cannot be said to be "contacted simultaneously" or "substantially simultaneously contacted" with one or more other components.

[0043] Unless otherwise specified, the term "contacting" is used herein to describe systems, compositions, processes, and methods in which components are contacted or combined together in any order, in any manner, and for any length of time. For example, the components can be combined by blending or mixing using any suitable technique. Here, contacting two or more components can result in a reaction product mixture or a reaction mixture.

[0044] In this specification, the word "reactor" refers to a single piece of equipment in which a reaction occurs, such as a vessel, but does not include any associated equipment outside the vessel, such as pipes, pumps, etc. Examples of reactors include stirred tank reactors (e.g., continuous stirred tank reactors), plug flow reactors, or any other type of reactor. In this specification, a "reactor system" refers to any part of the equipment in which the desired reaction occurs, including but not limited to reactors, associated pipes, associated pumps, and any other associated equipment. It should be noted that in some cases, a "reactor" can also be a "reactor system". For example, in some cases, a polyethylene loop reactor can be regarded as a reactor system. The terms "reactor" and "reactor system" can be qualified by using additional qualifying terms to refer to more specific "reactors" and "reactor systems". For example, the use of the terms "oligomerization reactor" and "oligomerization reactor system" indicates that the desired reaction within the reactor and / or reactor system is an oligomerization reaction.

[0045] In this specification, the term "reaction zone" refers to a part of a reaction system where all the necessary reaction components and reaction conditions are present such that the reaction can occur at a desired rate. That is, the reaction zone begins where the necessary reaction components and conditions exist to maintain the reaction within 25% of the average reaction rate, and the reaction system ends where the conditions cannot maintain the reaction rate within 25% of the average reaction rate (based on the volume average of the reaction rate in the reaction zone). For example, in the case of an ethylene oligomerization process, the reaction zone begins at the point where there is sufficient ethylene and an active catalyst system under sufficient reaction conditions (e.g., temperature and / or pressure, etc.) to maintain the production of oligomer products at a desired rate, and the reaction zone ends at the point where the catalyst system is deactivated, there is not sufficient ethylene to maintain the production of oligomer products, or other reaction conditions (e.g., temperature and / or pressure, etc.) are not sufficient to maintain the production of oligomer products or the desired oligomer product production rate. In this specification, the "reaction zone" may include one or more reactors. The term "reaction zone" may be qualified by using additional qualifying terms to refer to a more specific "reaction zone". For example, the use of the term "oligomerization reaction zone" indicates that the required reaction within the "reaction zone" is an oligomerization reaction.

[0046] The term "reaction system" refers to all the 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 the necessary components into and out of the reaction system and control the reaction. In this specification, the "reaction system" may include one or more reactor 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.

[0047] All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructs and methods described in the publications, which may be used in conjunction with the presently described invention. Detailed Description

[0048] The present disclosure relates to methods that include a) contacting: i) ethylene; ii) a catalyst system that includes 1) a zirconium compound and 2) a hydrocarbyl metal compound; iii) a chain transfer agent that includes a silyl hydride compound, a compound having a hydrogen-sulfur bond, a compound having a hydrogen-phosphorus bond, or any combination thereof; and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone. The present disclosure also relates to methods that include a) contacting: i) ethylene; ii) a catalyst system that includes 1) a zirconium compound and 2) a hydrocarbyl metal compound; iii) hydrogen; and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone. The present disclosure further relates to methods that include a) contacting: i) ethylene; ii) a catalyst system that includes 1) a zirconium compound and 2) a hydrocarbyl metal compound; iii) a transition metal compound chain transfer agent; and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone. The present disclosure also relates to methods that include a) introducing into a reaction zone: i) ethylene; ii) a catalyst system or catalyst system components that include 1) a zirconium compound and 2) a hydrocarbyl metal compound; iii) a chain transfer agent that includes a silyl hydride compound, a compound having a hydrogen-sulfur bond, a compound having a hydrogen-phosphorus bond, or any combination thereof; and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone. The present disclosure also relates to methods that include a) introducing into a reaction zone: i) ethylene; ii) a catalyst system or catalyst system components that include 1) a zirconium compound and 2) a hydrocarbyl metal compound; iii) hydrogen; and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone. The present disclosure further relates to methods that include a) introducing into a reaction zone: i) ethylene; ii) a catalyst system or catalyst system components that include 1) a zirconium compound and 2) a hydrocarbyl metal compound; iii) a transition metal compound chain transfer agent; and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone.

[0049] In one aspect, the oligomer product can be formed under conditions capable of forming the oligomer product, the reaction zone can have conditions capable of forming the oligomer product, or the reaction zone can be operated under conditions capable of forming the oligomer product. Generally, the catalyst system, elements of the catalyst system (e.g., zirconium compounds, hydrocarbyl metal compounds, and any other catalyst system elements described herein), chain transfer agents, hydrogen, transition metal compound chain transfer agents, optional organic reaction media, oligomer products, conditions for forming oligomer products, conditions that the reaction zone can have, conditions under which the reaction can be run, and / or any other catalyst systems and / or method elements described herein are independent elements of the methods described herein and are described independently herein. These independently described elements can be used, in any combination and without limitation, to further describe the methods provided herein.

[0050] In one aspect, the zirconium compound of the catalyst system can have the formula ZrX 1 m Y 1 q 、ZrX 1 m 、ZrY 1 q or any combination thereof; alternatively, ZrX 1 m Y 1 q ; alternatively, ZrX 1 m ; or alternatively, ZrY 1 q . The X 1 m Y 1 q 、ZrX 1 m or ZrY 1 q of the zirconium compound having the formula are independent elements of the zirconium compound and are described independently herein. The independent descriptions of X 1 、Y 1 、m and q can be used, in any combination and without limitation, to further describe the zirconium compound. In one embodiment, each X 1 can independently be a halogen group. In an embodiment, each Y 1 、m and q are independent elements of the zirconium compound and are described independently herein. The independent descriptions of X 1 、Y 1Each may independently be a hydrocarbyloxy group, a dihydrocarbylamino group, a hydrocarbyl carboxylate group, a hydrocarbyl sulfonate group or a β-diketonate group; alternatively, a hydrocarbyloxy group, a hydrocarbyl carboxylate group, a hydrocarbyl sulfonate group or a β-diketonate group; alternatively, a hydrocarbyloxy group, a hydrocarbyl carboxylate group or a hydrocarbyl sulfonate group; alternatively, a hydrocarbyl carboxylate group or a hydrocarbyl sulfonate group; alternatively, a hydrocarbyloxy group; alternatively, a dihydrocarbylamino group; alternatively, a hydrocarbyl carboxylate group; alternatively, a hydrocarbyl sulfonate group; or alternatively, a β-diketonate group. In one embodiment, m may range from 0 to 4; alternatively from 2 to 4; alternatively be 2; alternatively be 3; or alternatively be 4. In one embodiment, q may range from 0 to 4; alternatively from 2 to 4; alternatively be 2; alternatively be 3; or alternatively be 4. Wherein m + q is an integer from 2 to 4; alternatively be 2; alternatively be 3; or alternatively be 4.

[0051] X which can be used as a zirconium compound 1 Each halogen group of may independently be fluorine, chlorine, bromine or iodine; alternatively, chlorine, bromine or iodine; alternatively, chlorine; alternatively, bromine; or alternatively, iodine.

[0052] Y which can be used as a zirconium compound 1 The hydrocarbyloxy group of may be C1 to C 20 、C1 to C 10 or a C1 to C5 hydrocarbyloxy group. The hydrocarbyloxy group Y 1 may have the formula - OR 2 . Having the formula - OR 2 For the hydrocarbyloxy group, R 2 may be C1 to C 20 、C1 to C 10 or a C1 to C5 hydrocarbyl group. Having the formula - OR 2 The hydrocarbyl group may be an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group; alternatively, an alkyl group or an aryl group; alternatively, an alkyl group; alternatively, a cycloalkyl group; alternatively, an aryl group; or alternatively, an aralkyl group. R 2 The alkyl group may be C1 to C 20 、C1 to C 10 or a C1 to C5 alkyl group. R 2 The cycloalkyl group may be C4 to C 20 、C5 to C 15 or a C5 to C 10 cycloalkyl group. R 2 The aryl group may be C6 to C 20 、C6 to C 15 or a C6 to C 10 aryl group. R 2 The aralkyl group may be C7 to C20 , C7 to C 15 or C7 to C 10 aralkyl. In one aspect, the R - OR 2 group of the hydrocarbyloxy having the formula 2 can be methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, benzyl or ethylphenyl; alternatively, methyl, ethyl, propyl, butyl or pentyl; alternatively, cyclopentyl or cyclohexyl; alternatively, phenyl, tolyl or xylyl; or alternatively, benzyl or ethylphenyl. In one aspect, each hydrocarbyloxy Y 1 of the zirconium compound can be methoxy, ethoxy, propoxy, butoxy, pentyloxy, cyclopentyloxy, cyclohexyloxy, phenoxy, tolyloxy, xylyloxy, benzyloxy or ethylphenoxy; alternatively, methoxy, ethoxy, propoxy, butoxy or pentyloxy; alternatively, cyclopentyloxy or cyclohexyloxy; alternatively, phenoxy, tolyloxy or xylyloxy; or alternatively, benzyloxy or ethylphenoxy.

[0053] The hydrocarbyl carboxylate that can be used as Y 1 of the zirconium compound can be C1 to C 20 hydrocarbyl carboxylate, C1 to C 15 hydrocarbyl carboxylate, C1 to C 10 hydrocarbyl carboxylate or C1 to C5 hydrocarbyl carboxylate. The hydrocarbyl carboxylate that can be used as Y 1 of the zirconium compound can have the formula -OC (=O)R 3 . The hydrocarbyl sulfonate that can be used as Y 1 of the zirconium compound can be C1 to C 20 hydrocarbyl sulfonate, C1 to C 10 hydrocarbyl sulfonate or C1 to C5 hydrocarbyl sulfonate. The hydrocarbyl sulfonate that can be used as Y 1 of the zirconium compound can have the formula - OS(=O)2R 3 . The hydrocarbyl carboxylate having the formula - OC(=O)R 3 and / or the R - of the hydrocarbyl sulfonate having the formula 3 OS(=O)2R 3 can be C1 to C 20 , C1 to C 15 , C1 to C 10 or C1 to C5 hydrocarbyl. The hydrocarbyl carboxylate having the formula - OC(=O)R 3 and / or the R - of the hydrocarbyl sulfonate having the formula 3The R of the hydrocarbyl sulfonate 3 The hydrocarbyl can be alkyl, cycloalkyl, aryl or aralkyl; alternatively, alkyl or aryl; alternatively, alkyl; alternatively, cycloalkyl; alternatively, aryl; or alternatively, aralkyl. R 3 The alkyl can be C1 to C 20 alkyl, C1 to C 10 alkyl or C1 to C5 alkyl. R 3 The cycloalkyl can be C4 to C 20 cycloalkyl, C5 to C 15 cycloalkyl or C5 to C 10 cycloalkyl. R 3 The aryl can be C6 to C 20 aryl, C6 to C 15 aryl or C6 to C 10 aryl. R 3 The aralkyl can be C7 to C 20 aralkyl, C7 to C 15 aralkyl or C7 to C 10 aralkyl. Having the formula - OC(=O)R 3 of the hydrocarboxylate and / or having the formula - OS(=O)2R 3 The R of the hydrocarbyl sulfonate 3 group can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, benzyl or ethylphenyl; alternatively, methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl; alternatively, cyclopentyl or cyclohexyl; alternatively, phenyl, tolyl or xylyl; or alternatively, benzyl or ethylphenyl. Can be used as the zirconium compound Y 1 Each hydrocarboxylate of can be acetate, propionate, butyrate, valerate, hexanoate, heptanoate, octanoate, cyclopentylacetate, cyclohexylacetate, benzoate, methylbenzoate, dimethylbenzoate, phenylacetate or phenylpropionate; alternatively, acetate, propionate, butyrate, valerate, hexanoate, heptanoate or octanoate; alternatively, cyclopentylacetate or cyclohexylacetate; alternatively, benzoate, methylbenzoate or dimethylbenzoate; or alternatively, phenylacetate or phenylpropionate. Can be used as the Y of the zirconium compound 1Each hydrocarbylsulfonate group can be methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, pentylsulfonate, hexylsulfonate, heptylsulfonate, cyclopentylsulfonate, cyclohexylsulfonate, phenylsulfonate, tolylsulfonate, xylylsulfonate, benzylsulfonate or ethylphenylsulfonate; alternatively, methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, pentylsulfonate, hexylsulfonate or heptylsulfonate; alternatively, cyclopentylsulfonate or cyclohexylsulfonate; alternatively, phenylsulfonate, tolylsulfonate or xylylsulfonate.

[0054] Y that can be used as a zirconium compound 1 The dihydrocarbylamino group of can be C2 to C 30 Dihydrocarbylamino group, C2 to C 20 Dihydrocarbylamino group or C2 to C 15 Dihydrocarbylamino group. Y that can be used as a zirconium compound 1 The dihydrocarbylamino group of can have the formula - N(R 4 )2. In some embodiments, each R of the dihydrocarbylamino group having the formula - N(R 4 )2 4 hydrocarbyl group can independently be alkyl, cycloalkyl, aryl or aralkyl; alternatively, alkyl or aryl; alternatively, alkyl; alternatively, cycloalkyl; alternatively, aryl; or alternatively, aralkyl. Each R 4 alkyl group can independently be C1 to C 15 alkyl group, C1 to C 10 alkyl group or C1 to C5 alkyl group. Each R 4 cycloalkyl group can independently be C4 to C 15 cycloalkyl group or C5 to C 15 cycloalkyl group. Each R 4 aryl group can independently be C6 to C 20 aryl group, C6 to C 15 aryl group or C6 to C 10 aryl group. Each R 4 aralkyl group can independently be C7 to C 20 aralkyl group, C7 to C 15 aralkyl group or C7 to C 10 aralkyl group. Having the formula - N(R 4 )2 4The hydrocarbyl groups can each independently be methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, benzyl or ethylphenyl; alternatively, methyl, ethyl, propyl, butyl or pentyl; alternatively, cyclopentyl or cyclohexyl; alternatively, phenyl, tolyl or xylyl; or alternatively, benzyl or ethylphenyl. In one aspect, the two R 4 groups of the dihydrocarbylamino radical can be linked to form a hydrocarbylene group L 1 . In such an aspect, the linked R 4 groups, i.e., L 1 , form a ring or ring system containing the amino radical nitrogen atom. In some aspects, the L 1 hydrocarbylene group can be a C2 to C 30 hydrocarbylene group, a C2 to C 20 hydrocarbylene group or a C2 to C 10 hydrocarbylene group; or alternatively, L 1 can be a C2 to C 30 alkylene group, a C2 to C 20 alkylene group or a C2 to C 10 alkylene group. In one aspect, L 1 can be propylene, butylene, hexylene or heptylene. In one aspect, each dihydrocarbylamino radical of Y 1 usable in the zirconium compound can be a dimethylamino radical, a diethylamino radical, a dipropylamino radical, a pyrrolidino radical, a piperidino radical, a diphenylamino radical, a xylylamino radical, a bis-xylylamino radical or a dibenzylamino radical; alternatively, a dimethylamino radical, a diethylamino radical or a dipropylamino radical; alternatively, a pyrrolidino radical or a piperidino radical; alternatively, a diphenylamino radical, a xylylamino radical, a bis-xylylamino radical; or alternatively, a dibenzylamino radical.

[0055] The β-diketonate radical of Y 1 usable in the zirconium compound can be a C5 to C 20 β-diketonate radical, a C5 to C 15 β-diketonate radical or a C5 to C 10 β-diketonate radical. In one embodiment aspect, each β-diketonate radical can independently be an acetylacetonate radical (i.e., 2,4-pentanedionate radical) or a benzoylacetonate radical; alternatively, an acetylacetonate radical; or alternatively, a benzoylacetonate radical.

[0056] In one embodiment, the zirconium compound of the catalyst system can be at least partially hydrolyzed zirconium compound obtained by contacting the zirconium compound with water (referred to herein as partially hydrolyzed zirconium compound). In some embodiments, the partially hydrolyzed zirconium compound comprises, consists essentially of, or consists of the zirconium compound contacted with water (any described herein). In some embodiments, the zirconium compound of the partially hydrolyzed zirconium compound can have the formula ZrX 1 m Y 1 q , where each X 1 can independently be a halogen group (any disclosed herein), Y 1 can have the formula - OR 2 (where R 2 can be any R 2 hydrocarbon group (general or specific) described herein) or - OC(=O)R 3 (where R 3 can be any R 3 hydrocarbon group (general or specific) described herein), m can range from 0 to 4, q can range from 0 to 4, and m + q can be 4. In some embodiments, m can range from 0 to 3. In one embodiment, the molar ratio of water to zirconium of the zirconium compound can range from 0.01:1 to 3:1, 0.1: to 2:1, 0.25:1 to 1.75:1.

[0057] In a non-limiting aspect, the zirconium compound of the catalyst system can have the formula ZrX 1 m Y 1 q , where each X 1 can independently be a halogen group (any disclosed herein), Y 1 can have the formula - OC(=O)R 3 or - OS(=O)2R 3 , where R 3 can be any R 3 hydrocarbon group (general or specific), m can range from 0 to 4, q can range from 0 to 4, and m + q can be 4. In another non-limiting aspect, the zirconium compound of the catalyst system can have the formula ZrX 1 m , where each X 1Each can independently be a halogen group (any disclosed herein) and m can be an integer from 2 to 4, alternatively 2; or alternatively 4. In yet another non-limiting aspect, the zirconium compound can have the formula ZrY 1 q , where each Y 1 is independently - OR 2 , where R 2 is C1 to C 10 alkyl or -OC(=O)R 3 , where R 3 is C1 to C 10 alkyl, and q is an integer from 2 to 4, alternatively 2; alternatively 4. In another non-limiting aspect, the zirconium compound of the catalyst system can have the formula ZrX 1 m Y 1 q , where each X 1 can independently be a halogen group (any described herein), Y 1 can have the formula -OR 2 , where R 2 can be any R 2 hydrocarbyl described herein, or can have the formula -OC (=O)R 3 , where R 3 can be any R 3 hydrocarbyl (general or specific) described herein, m can range from 0 to 4, q can range from 0 to 4, and m + q can be 4. In a further non-limiting embodiment, the zirconium compound of the catalyst system can be a partially hydrolyzed zirconium compound, where the zirconium compound can have the formula ZrX 1 m Y 1 q , where each X 1 can independently be a halogen group (any described herein), Y 1 can have the formula - OR 2 , where R 2 can be any R 2 hydrocarbyl described herein, or can have the formula -OC (=O)R 3 , where R 3 can be any R 3 hydrocarbyl (general or specific) described herein, m can range from 0 to 4, q can range from 0 to 4, m + q can be 4, and the molar ratio of water to zirconium of the zirconium compound can range from 0.1: to 2:1.

[0058] Non-limiting exemplary zirconium compounds in the catalyst system that can be used in the methods described herein can include the following, can consist essentially of the following, or can be the following: ZrCl4, ZrBr4, ZrI4, ZrBr2Cl2, ZrBrCl3, Zr(OC2H5)4, Zr(OC2H5)3Cl, Zr(OC2H5)2Cl2, Zr(OC3H7)4, Zr(OC3H7)3Cl, Zr(OC3H7)2Cl2, Zr(OC4H9)4, Zr(OC4H9)3Cl, Zr(OC4H9)2Cl2, Zr(OC6H5)4, Zr(OC6H5)3Cl, Zr(OC6H5)2Cl2, Zr(OCOCH3)4, Zr(OCOCH3)3Cl, Zr(OCOCH3)2Cl2, Zr(OCOC2H5)4, Zr(OCOC2H5)3Cl, Zr(OCOC2H5)2Cl2, Zr(OCOC3H7)4, Zr(OCOC3H7)3Cl, Zr(OCOC3H7)2Cl2, Zr(OCOC4H9)4, Zr(OCOC4H9)3Cl, Zr(OCOC4H9)2Cl2, Zr(OCOC6H5)4, Zr(OCOC6H5)3Cl, Zr(OCOC6H5)2Cl2, Zr(OSO3CH3)4, Zr(OSO3C2H5)4, Zr(OSO3C3H7)4, Zr(OSO3C4H9)4, Zr(OSO3C6H5)4, Zr(H3CCOCHCOCH3)4, ZrCl2(H3CCOCHCOCH3)2, Zr((H5C6)COCHCO(C5F5))4, ZrCl2((H5C6)COCHCO(C5F5))2, Zr((CH3)2N)4, Zr((C2H5)2N)4, Zr((C3H7)2N)4 or Zr(C4H9)2N)4. In some aspects, the zirconium compound can include the following, can consist essentially of the following, or can be the following: ZrCl4, ZrBr4, ZrI4, ZrBr2Cl2 or ZrBrCl3; alternatively, Zr(OC2H5)4, Zr(OC2H5)3Cl, Zr(OC2H5)2Cl2, Zr(OC3H7)4, Zr(OC3H7)3Cl, Zr(OC3H7)2Cl2, Zr(OC4H9)4, Zr(OC4H9)3Cl, Zr(OC4H9)2Cl2, Zr(OC6H5)4, Zr(OC6H5)3Cl or Zr(OC6H5)2Cl2; alternatively, Zr(OC2H5)4, Zr(OC3H7)4, Zr(OC4H9)4 or Zr(OC6H5)4;Alternatively, Zr(OC2H5)3Cl, Zr(OC2H5)2Cl2, Zr(OC3H7)3Cl, Zr(OC3H7)2Cl2, Zr(OC4H9)3Cl, Zr(OC4H9)2Cl2, Zr(OC6H5)3Cl or Zr(OC6H5)2Cl2; alternatively, Zr(OCOCH3)4, Zr(OCOCH3)3Cl, Zr(OCOCH3)2Cl2, Zr(OCOC2H5)4, Zr(OCOC2H5)3Cl, Zr(OCOC2H5)2Cl2, Zr(OCOC3H7)4, Zr(OCOC3H7)3Cl, Zr(OCOC3H7)2Cl2, Zr(OCOC4H9)4, Zr(OCOC4H9)3Cl, Zr(OCOC4H9)2Cl2, Zr(OCOC6H5)4, Zr(OCOC6H5)3Cl or Zr(OCOC6H5)2Cl2; alternatively, Zr(OCOCH3)4, Zr(OCOC2H5)4, Zr(OCOC3H7)4, Zr(OCOC4H9)4 or Zr(OCOC6H5)4; alternatively, Zr(OCOCH3)3Cl, Zr(OCOCH3)2Cl2, Zr(OCOC2H5)3Cl, Zr(OCOC2H5)2Cl2, Zr(OCOC3H7)3Cl, Zr(OCOC3H7)2Cl2, Zr(OCOC4H9)3Cl, Zr(OCOC4H9)2Cl2, Zr(OCOC6H5)3Cl or Zr(OCOC6H5)2Cl2; alternatively, Zr(OSO3CH3)4, Zr(OSO3C2H5)4, Zr(OSO3C3H7)4, Zr(OSO3C4H9)4 or Zr(OSO3C6H5)4; alternatively, Zr(H3CCOCHCOCH3)4, ZrCl2(H3CCOCHCOCH3)2, Zr((H5C6)COCHCO(C5H5))4 or ZrCl2((H5C6)COCHCO(C5H5))2; alternatively, Zr(H3CCOCHCOCH3)4 or Zr((H5C6)COCHCO(C5H5))4; alternatively, ZrCl2(H3CCOCHCOCH3)2 or ZrCl2((H5C6)COCHCO(C5H5))2; or alternatively, Zr((CH3)2N)4, Zr((C2H5)2N)4 or Zr((C3H7)2N)4, Zr(C4H9)2N)4. In other respects, the zirconium compound can comprise the following, can consist essentially of the following, or can be the following: ZrCl4; alternatively, Zr(OC2H5)4; alternatively, Zr(OC3H7)4; alternatively, Zr(OC4H9)4; alternatively, Zr(OC6H5)4;Alternatively, Zr(OCOCH3)4; alternatively, Zr(OCOC2H5)4; alternatively, Zr(OCOC3H7)4; alternatively, Zr(OCOC4H9)4; alternatively, Zr(OCOC6H5)4; alternatively, Zr(OSO3CH3)4; alternatively, Zr(OSO3C2H5)4; alternatively, Zr(OSO3C3H7)4; alternatively, Zr(OSO3C4H9)4; or alternatively, or Zr(OSO3C6H5)4.;

[0059] Generally, the hydrocarbyl metal compound can be any hydrocarbyl metal compound that can form an oligomer product in combination with the zirconium compound upon contact with ethylene. The hydrocarbyl metal compound of the catalyst system can comprise any heteroleptic or homoleptic hydrocarbyl metal compound, can consist essentially of any heteroleptic or homoleptic hydrocarbyl metal compound, or can be any heteroleptic or homoleptic hydrocarbyl metal compound. In one aspect, the hydrocarbyl metal can have the formula (R 1 ) a M(X 2 ) b , where R 1 is a hydrocarbyl group, X 2 is a halogen group or a hydrocarbyloxy group, M is a metal, a is in the range of 1 to 4, b is in the range of 0 to 3, and a + b is equal to the oxidation state of the metal M. In one aspect, the metal of the hydrocarbyl metal compound can include the following, can consist essentially of the following, or can be composed of the following: Group 1, Group 2, Group 11, Group 12, Group 13, or Group 14 metals; alternatively, Group 1 or Group 2 metals; alternatively, Group 12, Group 13, or Group 14 metals; or alternatively, Group 12 or Group 13 metals; alternatively, Group 1 metal; alternatively, Group 2 metal; alternatively, Group 12 metal; or alternatively, Group 13 metal. In some aspects, the metal of the hydrocarbyl metal compound can comprise the following, can consist essentially of the following, or can be the following: lithium, sodium, potassium, magnesium, copper, zinc, aluminum, or tin; alternatively, lithium, sodium, potassium, or magnesium; alternatively, zinc, aluminum, or tin; alternatively, lithium; alternatively, sodium; alternatively, potassium; alternatively, magnesium; alternatively, zinc; alternatively, aluminum; or alternatively, tin.

[0060] The hydrocarbyl group of the hydrocarbyl metal compound can be a C1 to C 20 hydrocarbyl group, a C1 to C 10 hydrocarbyl group, or a C1 to C6 hydrocarbyl group. In one aspect, the hydrocarbyl group of the hydrocarbyl metal compound can be an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; alternatively, an alkyl group; alternatively, a cycloalkyl group; alternatively, an aryl group; or alternatively, an aralkyl group. The alkyl group of the hydrocarbyl metal compound can be a C1 to C 20 alkyl group, a C1 to C10 Alkyl or C1 to C6 alkyl. The cycloalkyl group of the organometallic compound can be C4 to C 20 Cycloalkyl, C4 to C 15 Cycloalkyl or C4 to C 10 Cycloalkyl. The aryl group of the organometallic compound can be C6 to C 20 Aryl, C6 to C 15 Aryl or C6 to C 10 Aryl. The aralkyl group of the organometallic compound can be C7 to C 20 Aralkyl, C7 to C 15 Aralkyl or C7 to C 10 Aralkyl.

[0061] In any aspect disclosed herein, the organometallic compound of the catalyst system can be an alkylmetal compound (i.e., an organometallic compound in which R 1 is alkyl). In one embodiment, the alkylmetal compound of the catalyst system can comprise the following, can consist essentially of the following, or can be the following: alkyllithium (R 1 Li), alkylsodium (R 1 Na), alkylpotassium (R 1 K), alkylmagnesium compounds (R 1 2Mg or R 1 MgX 2 ), alkylcopper compounds (R 1 2Cu or R 1 CuX 2 ), alkylzinc compounds (R 1 2Zn or R 1 ZnX 2 ), alkyltin compounds (R 1 4Sn, R 1 2Sn, R 1 3SnX 2 , R 1 2SnX 2 2, R 1 2SnX 2 3, R 1 2Sn or R 1 SnX 2 ), or alkylaluminum compounds (AlX 2 2R 1 , AlX 2 R 1 2, AlR 1 3, Al2X 2 5R 1 , Al2X 2 3(R 1 )3 or Al2X 2 R 15); Alternatively, alkyllithium (R 1 Li), alkylsodium (R 1 Na), alkylpotassium (R 1 K), alkylmagnesium compound (R 1 2Mg or R 1 MgX 2 ), alkylzinc compound (R 1 2Zn or R 1 ZnX 2 ), or alkylaluminum compound (AlX 2 2R 1 , AlX 2 R 1 2, AlR 1 3, Al2X 2 5R 1 , Al2X 2 3 R1 3 or Al2X 2 R 1 5); Alternatively, alkyllithium (R 1 Li), alkylsodium (R 1 Na) or alkylpotassium (R 1 K); Alternatively, alkyllithium (R 1 Li); Alternatively, alkylsodium (R 1 Na); Alternatively, alkylmagnesium compound (R 1 2Mg or R 1 MgX 2 ); Alternatively, alkylzinc compound (R 1 2Zn or R 1 ZnX 2 ); Alternatively, alkyltin compound (R 1 4Sn, R 1 2Sn, R 1 3SnX 2 , R 1 2SnX 2 2, R 1 2SnX 2 3, R 1 2Sn or R 1 SnX 2 ); Or alternatively, alkylaluminum compound (AlX 2 2R 1 , AlX 2 R 1 2, AlR 1 3, Al2X 2 5R 1 , Al2X 2 3R 1 3 or Al2X 2 R1 5). In some aspects, the organometallic compound of the catalyst system may comprise the following, may consist essentially of the following, or may be the following: alkyllithium (R 1 Li), sodium alkyl (R 1 Na), potassium alkyl (R 1 K), alkylmagnesium halide (R 1 MgX 2 ), dialkylmagnesium (R 1 2Mg), alkylcopper halide (R 1 CuX 2 ), dialkylcopper (R 1 2Cu), alkylzinc halide (R 1 ZnX 2 ), dialkylzinc (R 1 2Zn), alkyltin halide (R 1 3SnX 2 , R 1 2SnX 2 , R 1 2SnX 2 , R 1 2Sn or R 1 SnX 2 ), dialkyltin (R 1 2Sn), tetraalkyltin (R 1 4Sn), alkylaluminum dihalide (AlX 2 2R 1 ), dialkylaluminum halide (AlX 2 R 1 2), trialkylaluminum (AlR 1 3), alkylaluminum sesquihalide (Al2X 2 3R 1 3), alkylaluminum dialkoxide (AlX 2 2R 1 ), dialkylaluminum alkoxide (AlX 2 R 1 2) or aluminoxane; alternatively, alkyllithium (R 1 Li), sodium alkyl (R 1 Na), potassium alkyl (R 1 K), dialkylmagnesium (R 1 2Mg), dialkylzinc (R 1 2Zn), alkylaluminum dihalide (AlX 2 2R 1 ), dialkylaluminum halide (AlX 2 R 1 2), trialkylaluminum (AlR 1 3) or alkylaluminum sesquihalide (Al2X 2 3R1 3); Alternatively, alkyllithium (R 1 Li), sodium alkyl (R 1 Na), potassium alkyl (R 1 K); Alternatively, alkylmagnesium halide (R 1 MgX 2 ) or dialkylmagnesium (R 1 2Mg); Alternatively, dialkyltin (R 1 2Sn), tetraalkyltin (R 1 4Sn); Alternatively, alkylzinc compound (R 1 2Zn or R 1 ZnX 2 ) and alkylaluminum compound (AlX 2 2R 1 , AlX 2 R 1 2, AlR 1 3, Al2X 2 5R 1 , Al2X 2 3R 1 3 or Al2X 2 R 1 5); Alternatively, alkylaluminum dihalide (AlX 2 2R 1 ), dialkylaluminum halide (AlX 2 R 1 2), alkylaluminum sesquihalide (Al2X 2 3R 1 3), trialkylaluminum (AlR 1 3) or aluminoxane; Alternatively, alkyllithium (R 1 Li); Alternatively, sodium alkyl (R 1 Na); Alternatively, potassium alkyl (R 1 K); Alternatively, alkylmagnesium halide (R 1 MgX 2 ); Alternatively, dialkylmagnesium (R 1 2Mg); Alternatively, alkylzinc halide (R 1 ZnX 2 ); Alternatively, dialkylzinc (R 1 2Zn); Alternatively, alkylaluminum dihalide (AlX 2 2R 1 ); Alternatively, dialkylaluminum halide (AlX 2 R 1 2); Alternatively, alkylaluminum sesquihalide (Al2X 2 3R 13); Alternatively, an alkylaluminum dialkoxide (AlX 2 2R 1 ); Alternatively, a dialkylaluminum alkoxide (AlX 2 R 1 2); Alternatively, a trialkylaluminum (AlR 1 3); or alternatively, an aluminoxane.

[0062] Generally, each halogen group of any organometallic halide (or alkylmetal halide) can be any halogen group. Each halogen group of any alkylmetal halide disclosed herein can independently be fluorine, chlorine, bromine, or iodine; alternatively, chlorine, bromine, or iodine; alternatively, fluorine; alternatively, chlorine; alternatively, bromine; or alternatively, iodine.

[0063] Each alkyl group of any alkylmetal compound disclosed herein can independently be a C1 to C 20 alkyl group, a C1 to C 10 alkyl group, or a C1 to C6 alkyl group. In one aspect, each alkyl group of any alkylmetal compound disclosed herein can independently be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; alternatively, methyl, ethyl, butyl, hexyl, or octyl. In some aspects, each one or more alkyl groups of any alkylmetal compound disclosed herein can independently 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.

[0064] Each alkoxide group of any alkylmetal alkoxide disclosed herein can independently be a C1 to C 20 alkoxide group, a C1 to C 10 alkoxide group, or a C1 to C6 alkoxide group. In one aspect, each alkoxide group of any alkylmetal alkoxide disclosed herein can independently be methoxide, ethoxide, propoxide, butoxide, pentoxide, hexoxide, heptoxide, or octoxide; alternatively, methoxide, ethoxide, butoxide, hexoxide, or octoxide. In some aspects, each alkoxide group of any alkylmetal alkoxide disclosed herein can independently be methoxide, ethoxide, n-propoxide, n-butoxide, isobutoxide, n-hexoxide, or n-octoxide; alternatively, methoxide, ethoxide, n-butoxide, or isobutoxide; alternatively, methoxide; alternatively, ethoxide; alternatively, n-propoxide; alternatively, n-butoxide; alternatively, isobutoxide; alternatively, n-hexoxide; or alternatively, n-octoxide.

[0065] The organolithium compounds (or alkyllithium compounds) that can be used as organometallic compounds can include the following, can consist essentially of the following, or can be the following: methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium; alternatively, methyllithium; alternatively, n-butyllithium; alternatively, sec-butyllithium; or alternatively, tert-butyllithium. The organosodium compounds (or alkylsodium compounds) that can be used as organometallic compounds can include the following, can consist essentially of the following, or can be the following: sodium methylate, sodium n-butoxide, sodium sec-butoxide, sodium tert-butoxide; alternatively, sodium methylate; alternatively, sodium n-butoxide; alternatively, sodium sec-butoxide; or alternatively, sodium tert-butoxide. The organopotassium compounds (or alkylpotassium compounds) that can be used as organometallic compounds can include the following, can consist essentially of the following, or can be the following: potassium methylate, potassium n-butoxide, potassium sec-butoxide, potassium tert-butoxide; alternatively, potassium methylate; alternatively, potassium n-butoxide; alternatively, potassium sec-butoxide; or alternatively, potassium tert-butoxide.

[0066] The Grignard reagents (or alkylmagnesium halides) that can be used as organometallic compounds can include the following, can consist essentially of the following, or can be the following: methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide or butylmagnesium halide; alternatively, methylmagnesium halide; alternatively, ethylmagnesium halide; alternatively, propylmagnesium halide; alternatively, butylmagnesium halide. The dialkylmagnesiums (or dialkylmagnesiums) that can be used as organometallic compounds can include the following, can consist essentially of the following, or can be the following: dimethylmagnesium, diethylmagnesium, dipropylmagnesium or dibutylmagnesium; alternatively, dimethylmagnesium; alternatively, diethylmagnesium; alternatively, dipropylmagnesium; or alternatively, dibutylmagnesium.

[0067] The zinc hydrocarbyl halides that can be used as hydrocarbyl metal compounds can include the following, can consist essentially of the following, or can be the following: zinc methyl halide, zinc ethyl halide, zinc propyl halide, zinc butyl halide, zinc pentyl halide, zinc hexyl halide, zinc cyclopentyl halide, zinc cyclohexyl halide, zinc phenyl halide, zinc tolyl halide, zinc xylyl halide, or zinc benzyl halide; alternatively, zinc methyl halide, zinc ethyl halide, zinc propyl halide, zinc butyl halide, zinc pentyl halide, or zinc hexyl halide, alternatively, zinc cyclopentyl halide or zinc cyclohexyl halide; alternatively, zinc phenyl halide, zinc tolyl halide, or zinc xylyl halide; alternatively, zinc methyl halide; alternatively, zinc ethyl halide; alternatively, zinc propyl halide; alternatively, zinc butyl halide; alternatively, zinc pentyl halide; alternatively, zinc hexyl halide; alternatively, zinc cyclopentyl halide; alternatively, zinc cyclohexyl halide; alternatively, zinc phenyl halide; alternatively, zinc tolyl halide; alternatively, zinc xylene halide; or alternatively, zinc benzyl halide. The dialkylzincs that can be used as hydrocarbyl metal compounds can include the following, can consist essentially of the following, or can be the following: dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, dipentylzinc, dihexylzinc, dicyclopentylzinc, dicyclohexylzinc, diphenylzinc, dimethylphenylzinc, bis(dimethylphenyl)zinc, or dibenzylzinc; alternatively, dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, dipentylzinc, or dihexylzinc; alternatively, dicyclopentylzinc or dicyclohexylzinc; alternatively, diphenylzinc, dimethylphenylzinc, bis(dimethylphenyl)zinc; alternatively, or dibenzylzinc; alternatively, dimethylzinc; alternatively, diethylzinc; alternatively, dipropylzinc; alternatively, dibutylzinc; alternatively, dipentylzinc; alternatively, dihexylzinc; alternatively, dicyclopentylzinc; alternatively, dicyclohexylzinc; alternatively, diphenylzinc; alternatively, dimethylphenylzinc; alternatively, bis(dimethylphenyl)zinc; or alternatively, dibenzylzinc.

[0068] In one aspect, the hydrocarbyl metal compound in the catalyst system can be an alkylaluminum compound. Generally, the hydrocarbyl aluminum compounds that can be used as hydrocarbyl metal compounds in the catalyst system can have the formula AlX 2 3-n R 1 n 、Al2X 2 6-q R 1 q or any combination thereof; alternatively, AlX 2 n R 1 3-n ; or alternatively, Al2X 2 q R 1 6-q . The formula AlX2 3-n R 1 n and Al2X 2 6-q R 1 q for X of 2 、R 1 、n and q are independent elements of the hydrocarbyl aluminum compound having the formula AlX 2 3-n R 1 n and Al2X 2 6-q R 1 q and are independently described herein. X 2 、R 1 、n and q's independent descriptions can be used, non - restrictively and in any combination, to describe the hydrocarbyl aluminum compound having the formula AlX 2 3-n R 1 n or Al2X 2 6-q R 1 q In the formula AlX 2 3-n R 1 n and Al2X 2 6-q R 1 q each R 1 can independently be a C1 to C 20 hydrocarbyl, C1 to C 10 hydrocarbyl or C1 to C6 hydrocarbyl; or alternatively, a C1 to C 20 alkyl, C1 to C 10 alkyl or C1 to C6 alkyl (in which case the hydrocarbyl aluminum compound can be called an alkyl aluminum compound). In one aspect, each R 1 can independently be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl; alternatively, methyl, ethyl, butyl, hexyl, octyl; alternatively, 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. In the formula AlX 2 3-n R 1 n and Al2X 26-q R 1 q in which each X 2 can independently be fluorine, chlorine, bromine or iodine; alternatively, chlorine, bromine or iodine; alternatively, chlorine; alternatively, bromine; or alternatively iodine. In the formula AlX 2 3-n R 1 n and Al2X 2 6-q R 1 q n can range from 1 to 3; alternatively, from 1 to 2; alternatively be 1; alternatively be 2, or alternatively be 3. In the formula AlX 2 3-n R 1 n and Al2X 2 6-q R 1 q q can be 1, 3 or 5; alternatively be 1, alternatively be 3; or alternatively be 5. In one aspect, having the formula AlX 2 3-n R 1 n or Al2X 2 6-q R 1 qThe hydrocarbyl aluminum (or alkyl aluminum) compound can include the following, can consist essentially of the following, or can be the following: trialkyl aluminum, alkyl aluminum halide, or any combination thereof; alternatively, trialkyl aluminum; or alternatively, alkyl aluminum halide. The trialkyl aluminum compound can include the following, can consist essentially of the following, or can be the following: trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, trihexyl aluminum, trioctyl aluminum, or any combination thereof; alternatively, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, trihexyl aluminum, tri-n-octyl aluminum, or a mixture thereof; alternatively, triethyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, trihexyl aluminum, tri-n-octyl aluminum, or any combination thereof; alternatively, triethyl aluminum, tri-n-butyl aluminum, trihexyl aluminum, tri-n-octyl aluminum, or any combination thereof; alternatively, trimethyl aluminum; alternatively, triethyl aluminum; alternatively, tripropyl aluminum; alternatively, tri-n-butyl aluminum; alternatively, triisobutyl aluminum; alternatively, trihexyl aluminum; or alternatively, tri-n-octyl aluminum. The alkyl aluminum halide can include the following, can consist essentially of the following, or can be the following: diethyl aluminum chloride, diethyl aluminum bromide, ethyl aluminum dichloride, ethyl aluminum sesquichloride, or any combination thereof; alternatively, diethyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, or any combination thereof; alternatively, diethyl aluminum chloride; alternatively, diethyl aluminum bromide; alternatively, ethyl aluminum dichloride; or alternatively, ethyl aluminum sesquichloride.

[0069] In some aspects, the hydrocarbyl aluminum (or alkyl aluminum) compound that can be used as the hydrocarbyl metal compound in the catalyst system can have the formula AlX 2 3-n R 1 n 、Al2X 2 6-q R 1 q or any combination thereof (alternatively AlX 2 n R 1 3-n ; or alternatively Al2X 2 q R 1 6-q ), where at least a part (or all) of X 2 can be alkoxide, carboxylate, dihydrocarbylamino, or carboxamide anion; alternatively, alkoxide; alternatively, carboxylate; alternatively, dihydrocarbylamino; or alternatively, carboxamide anion. The formula AlX 2 3 -n R 1 n and Al2X 26-q R 1 q R of 1 、n and q are described herein as elements of hydrocarbylaluminum (or alkylaluminum) compounds, and these independent descriptions of R 1 、n and q can be used, without limitation and in any combination, to describe hydrocarbylaluminum compounds having the formula AlX 2 3-n R 1 n or Al2X 2 6-q R 1 q (where at least a part (or all) of X 2 is an alkoxide, carboxylate, dihydrocarbylamino, and / or carboxamido anion). When only a part (or all) of X 2 is an alkoxide, carboxylate, dihydrocarbylamino, and / or carboxamido anion, the remaining part of X 2 can be a halogen; alternatively, fluorine, chlorine, bromine, or iodine; alternatively, chlorine, bromine, or iodine; alternatively, chlorine; alternatively, bromine; or alternatively, iodine. The specific alkoxides of the hydrocarbylaluminum (or alkylaluminum) compounds having the formula AlX 2 3-n R 1 n and / or Al2X 2 6- q R 1 q (where at least a part (or all) of X 2 can be an alkoxide) can be C1 to C 20 alkoxide, C1 to C 10 alkoxide, or C1 to C6 alkoxide; alternatively, methoxide, ethoxide, propoxide, butoxide, pentoxide, hexoxide, heptoxide, or octoxide; alternatively, methoxide, ethoxide, butoxide, hexoxide, or octoxide; alternatively, methoxide, ethoxide, n-propoxide, n-butoxide, isobutoxide, n-hexoxide, or n-octoxide; alternatively, methoxide, ethoxide, n-butoxide, or isobutoxide; alternatively, methoxide; alternatively, ethoxide; alternatively, n-propoxide; alternatively, n-butoxide; alternatively, isobutoxide; alternatively, n-hexoxide; or alternatively, n-octoxide. The hydrocarbylaluminum (or alkylaluminum) compounds having the formula AlX 2 3-n R 1 n and / or Al2X 2 6-q R 1q( wherein at least a part (or all) of X 2 in the hydrocarbyl aluminum (or alkyl aluminum) compound which may be a carboxylate group can be a C2 - C20 carboxylate group, a C2 - C10 carboxylate group, a C2 - C6 carboxylate group; alternatively, acetate, propionate, butyrate, valerate, hexanoate, heptanoate, octanoate, benzoate, methylbenzoate, dimethylbenzoate or phenyl lactate; alternatively, acetate, propionate, butyrate, valerate, hexanoate, heptanoate or octanoate; alternatively, benzoate, methylbenzoate or dimethylbenzoate; or alternatively, phenylacetate. The hydrocarbyl aluminum (or alkyl aluminum) compound having the formula AlX 2 3-n R 1 n and / or Al2X 2 6-q R 1 q (wherein at least a part or all of X 2 in which may be a dialkylamino group) of the specific dialkylamino group in the hydrocarbyl aluminum (or alkyl aluminum) compound can be a C2 - C 20 , a C2 - C 10 or a C2 - C6 dialkylamino group; alternatively, dimethylamino, diethylamino, dipropylamino, pyrrolidino, piperidino, diphenylamino, xylidino, bis - xylidino or dibenzylamino; alternatively, dimethylamino, diethylamino or dipropylamino; alternatively, pyrrolidino or piperidino; alternatively, diphenylamino, xylidino, bis - xylidino; or alternatively, dibenzylamino. The hydrocarbyl aluminum (or alkyl aluminum) compound having the formula AlX 2 3-n R 1 n and / or Al2X 2 6-q R 1 q (wherein at least a part (or all) of X 2 in which may be a carboxamido anion) of the specific carboxamido anion in the hydrocarbyl aluminum (or alkyl aluminum) compound can be a C2 - C 20 carboxamido anion, a C2 - C 10A carboxamide anion or a C2 to C6 carboxamide anion; alternatively, a dimethylformamide anion, a diethylformamide anion, a dimethylacetamide anion, a diethylacetamide anion, a 2-pyrrolidone anion, a valerolactam anion or a caprolactam anion; alternatively, a dimethylformamide anion, a diethylformamide anion, a dimethylacetamide anion, a diethylacetamide anion; alternatively, a 2-pyrrolidone anion, a valerolactam anion or a caprolactam anion; alternatively, a dimethylformamide anion; alternatively, a dimethylacetamide anion; alternatively, a 2-pyrrolidone anion; alternatively, a valerolactam anion; or alternatively, a caprolactam anion. When the hydrocarbylaluminum (or alkylaluminum) compound having the formula AlX 2 3-n R 1 n and / or Al2X 2 6-q R 1 q has at least a part (or all) of X 2 as an alkoxide, a carboxylate, a dihydrocarbylamino group and / or a carboxamide anion, the molar ratio of the alkoxide, carboxide, amino group and / or amide anion to aluminum can be in the range of 0.1:1 to 1:1, 0.1:1 to 0.75:1 or 0.1:1 to 0.5:1.

[0070] In the aspect where the hydrocarbylaluminum (or alkylaluminum) compound has the formula AlX 2 3-n R 1 n or Al2X 2 6-q R 1 q and at least a part (or all) of X 2 is an alkoxide, a carboxylate, a dihydrocarbylamino group and / or a carboxamide anion, the hydrocarbylaluminum (or alkylaluminum) compound having the formula AlX 2 3-n R 1 n or Al2X 2 6-q R 1 q can be generated in-situ. These in-situ generated hydrocarbylaluminum (or alkylaluminum) compounds can be obtained by reacting a suitable alcohol, carboxylic acid or simple ester of a carboxylic acid, amine and / or amide with a compound having the formula AlX 2 3-n R 1 n or Al2X 2 6-q R 1q formed by contact with an alkylaluminum compound, wherein i) each R 1 is independently any alkyl or hydrocarbyl group as described herein for a hydrocarbylaluminum (or alkylaluminum) compound having the formula AlX 2 3-n R 1 n or Al2X 2 6-q R 1 q ii) each X can independently be any halogen group as described herein for a hydrocarbylaluminum (or alkylaluminum) compound having the formula AlX 1 group, iii) n can have any value as described herein for a hydrocarbylaluminum (or alkylaluminum) compound having the formula AlX 2 2 3-n 1 R n 2 or Al2X 6-q 1 R q 2 3-n 1 n R 2 6-q or Al2X 6-q 1 R q 2 3-n 1 n R 2 6-q or Al2X 1 q R 20 10 and iv) q can have any value as described herein for a hydrocarbylaluminum (or alkylaluminum) compound having the formula AlX 20 carboxylic acids, C2 to C 10Carboxylic acid or C2 - C6 carboxylic acid; alternatively, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, benzoic acid, methylbenzoic acid, dimethylbenzoic acid or phenylacetic acid; alternatively, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid or caprylic acid; alternatively, benzoic acid, methylbenzoic acid or dimethylbenzoic acid; or alternatively, phenylacetic acid. Generally, the alcohol of the alcohol - derived moiety of a simple ester of a carboxylic acid can be methanol and / or ethanol; alternatively, methanol or ethanol. The amine that can be used to generate an in - situ - formed hydrocarbylaluminum (or alkylaluminum) compound having a dihydrocarbylamido group can be C2 - C 20 amine, C2 - C 10 amine or C2 - C6 amine; alternatively, dimethylamine, diethylamine, dipropylamine, pyrrolidine, piperidine, diphenylamine, dimethylaniline, bis - dimethylphenylamine or dibenzylamine; alternatively, dimethylamine, diethylamine or dipropylamine; alternatively, pyrrolidine or piperidine; alternatively, diphenylamine, dimethylaniline, bis - dimethylphenylamine; or alternatively, dibenzylamine. The amide that can be used to generate an in - situ - formed hydrocarbylaluminum (or alkylaluminum) compound having a carboxamido anion can be C2 - C 20 amide, C2 - C 10 amide or C2 - C6 amide; alternatively, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, 2 - pyrrolidone, valerolactam or caprolactam; alternatively, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide; alternatively, 2 - pyrrolidone, valerolactam or caprolactam; alternatively, dimethylformamide; alternatively, dimethylacetamide; alternatively, 2 - pyrrolidone; alternatively, valerolactam; or alternatively, caprolactam. The alcohol, carboxylic acid, carboxylic acid ester, amine and / or amide used to prepare an in - situ - formed hydrocarbylaluminum (or alkylaluminum) compound having the formula AlX 2 3-n R 1 n or Al2X 2 6-q R 1 q (where at least a part (or all) of X 2 is an alkoxide, carboxylate, dihydrocarbylamido group and / or carboxamido anion) and the hydrocarbylaluminum (or alkylaluminum) compound having the formula AlX 2 3-n R 1 n or Al2X 2 6-q R 1 q can have a molar ratio in the range of 0.1:1 to 1:1, 0.1:1 to 0.75:1 or 0.1:1 to 0.5:1.

[0071] Generally, the in-situ generated hydrocarbylaluminum (or alkylaluminum) compound having the formula AlX 2 3-n R 1 n or Al2X 2 6-q R 1 q can be formed in any manner that produces the desired in-situ generated hydrocarbylaluminum (or alkylaluminum) compound. In one aspect, the in-situ generated hydrocarbylaluminum (or alkylaluminum) compound having the formula AlX 2 3-n R 1 n or Al2X 2 6-q R 1 q (where at least a part (or all) of X 2 is an alkoxide, carboxylate, dihydrocarbylamino group, and / or carboxamide anion) of the hydrocarbylaluminum (or alkylaluminum) compound can be formed by 1) contacting an alcohol, carboxylic acid or simple ester of a carboxylic acid, amine, and / or amide with a suitable or (desired) hydrocarbylaluminum (or alkylaluminum) compound having the formula AlX 2 3-n R 1 n and / or Al2X 2 6-q R 1 q and then contacting the in-situ generated hydrocarbylaluminum (or alkylaluminum) compound with the zirconium compound component of the catalyst system.

[0072] The aluminoxane compounds of hydrocarbyl metal (or alkyl metal, or hydrocarbyl aluminum, or alkyl aluminum) compounds that can be used as catalyst systems can comprise the following, can consist essentially of the following, or can be the following: 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 any combination thereof. In some non-limiting aspects, the aluminoxane can comprise the following, can consist essentially of the following, or can be the following: methylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutylaluminoxane, tert-butylaluminoxyl, or any combination thereof; alternatively, 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.

[0073] Non-limiting exemplary hydrocarbyl aluminum (or alkyl aluminum) compounds that can be used in the catalyst systems for the methods described herein can comprise the following, can consist essentially of the following, or can be the following: Al(CH3)3, Al(C2H5)3, Al(C3H7)3, Al(C4H9)3, Al(C5H 11 )3, Al(C6H 13 )3, Al(C8H 17)3. Al(C2H5)2Cl, Al(C2H5)2Br, Al(C2H5)2I, Al(C2H5)Cl2, Al(C2H5)Br2, Al(C2H5)I2, AlC2H5(OC2H5)2, AlC2H5(OC3H7)2, AlC2H5(OC4H9)2, Al(OC2H5)2Cl, Al(OC3H7)2Cl, Al(OC4H9)2Cl, Al(OC2H5)Cl2, Al(OC3H7)Cl2, Al(OC4H9)Cl2, AlC2H5(OCOC2H5)2, AlC2H5(OCOC3H7)2, AlC2H5(OCOC4H9)2, Al(OCOC2H5)2Cl, Al(OCOC3H7)2Cl, Al(OCOC4H9)2Cl, Al(OCOC2H5)Cl2, Al(OCOC3H7)Cl2, Al(OCOC4H9)Cl2, Al(C2H5)2OC2H5, Al(C2H5)2OC3H7, Al(C2H5)2OC4H9, Al(C2H5)2N(C2H5)2, Al(C2H5)2N(C3H7)2, Al(C2H5)2N(C4H9)2, Al2(CH3)3Cl3, Al2(CH3)3Br3, Al2(C2H5)3Cl3, Al2(C2H5)3Br3, Al2(C2H5)3I3, Al2(C2H5)2BrCl2, Al2(C3H7)3Cl3, Al2(C4H9)3Cl3, Al2(C5H7)3Cl3, Al2(OCOC4H9)3Cl3, or any combination thereof. In some aspects, the hydrocarbylaluminum (or alkylaluminum) compound can comprise the following, can consist essentially of the following, or can be the following: Al(CH3)3, Al(C2H5)3, Al(C3H7)3, Al(C4H9)3, Al(C5H 11 )3, Al(C6H 13 )3, Al(C8H 17)3. Al(C2H5)2Cl, Al(C2H5)2Br, Al(C2H5)2I, Al(C2H5)Cl2, Al(C2H5)Br2, Al(C2H5)I2, Al2(CH3)3Cl3, Al2(CH3)3Br3, Al2(C2H5)3Cl3, Al2(C2H5)3Br3, Al2(C2H5)3I3, Al2(C2H5)2BrCl2, Al2(C3H7)3Cl3, Al2(C4H9)3Cl3, Al2(C5H7)3Cl3 or any combination thereof; alternatively, AlC2H5(OC2H5)2, AlC2H5(OC3H7)2, AlC2H5(OC4H9)2, AlC2H5(OCOC2H5)2, AlC2H5(OCOC3H7)2, AlC2H5(OCOC4H9)2, Al(C2H5)2OC2H5, Al(C2H 5)2 OC3H7, Al(C2H5)2OC4H9, Al(C2H5)2N(C2H5)2, Al(C2H5)2N(C3H7)2, Al(C2H5)2N(C4H9)2 or any combination thereof; alternatively, AlC2H5(OC2H5)2, AlC2H5(OC3H7)2, AlC2H5(OC4H9)2 or any combination thereof; or alternatively, AlC2H5(OCOC2H5)2, AlC2H5(OCOC3H7)2, AlC2H5(OCOC4H9)2, Al(C2H5)2OC2H5, Al(C2H5)2OC3H7, Al(C2H5)2OC4H9 or any combination thereof; alternatively, Al(C2H5)2N(C2H5)2, Al(C2H5)2N(C3H7)2, Al(C2H5)2N(C4H9)2 or any combination thereof. In other respects, the hydrocarbyl aluminum (or alkyl aluminum) compound may include the following, may consist essentially of the following, or may be the following: Al2(CH3)3Cl3, Al2(CH3)3Br3, Al2(C2H5)3Cl3, Al2(C2H5)3Br3, Al2(C2H5)3I3, Al2(C2H5)2BrCl2, Al2(C3H7)3Cl3, Al2(C4H9)3Cl3, Al2(C5H7)3Cl3 or any combination thereof; or alternatively, Al(C2H5)3, Al(C2H5)2Cl, Al(C2H5)Cl2, Al2(C2H5)3Cl3 or any combination thereof.

[0074] The molar ratio of the metal of the metal hydrocarbon (or hydrocarbyl aluminum, or alkyl aluminum) compound to the zirconium of the zirconium compound (also referred to herein as the M:Zr molar ratio) can be any value that provides a catalyst system capable of forming an oligomeric product. In one aspect, the minimum M:Zr (or Al:Zr) molar ratio can be 0.1:1, 0.2:1, 0.6:1, 1:1, 2:1, 10:1; alternatively or additionally, the maximum M:Zr (or Al:Zr) molar ratio can be 100:1, 75:1, 50:1, 25:1, 15:1 or 10:1. Generally, the M:Zr (or Al:Zr) molar ratio can be within the range of any minimum M:Zr (or Al:Zr) molar ratio disclosed herein to any maximum M:Zr (or Al:Zr) molar ratio disclosed herein. Thus, suitable non-limiting ranges for the M:Zr (or Al:Zr) molar ratio can be in the range of 0.1:1 to 100:1, 0.2:1 to 75:1, 0.6:1 to 25:1, 1:1 to 50:1, 2:1 to 25:1, 1:1 to 15:1, 2:1 to 10:1, 10:1 to 50:1 or 10:1 to 25:1. Other suitable M:Zr (or Al:Zr) molar ranges will be apparent from the present disclosure.

[0075] In some aspects, the catalyst system can further comprise a neutral nonionic organic modifier (or having a neutral nonionic organic modifier as a component). Generally, the neutral nonionic organic modifier can be any neutral nonionic organic modifier that in combination with the zirconium compound and the metal hydrocarbon compound can form an oligomeric product. The neutral nonionic organic modifier can include the following, consist essentially of the following, or can be the following: ethers, esters, ketones, aldehydes, alcohols, acid anhydrides, acyl chlorides, nitriles, thioethers, disulfides, phosphines, amines or amides; alternatively, ethers; alternatively, esters; alternatively, ketones; alternatively, aldehydes; alternatively, alcohols; alternatively, thioethers; alternatively, disulfides; alternatively, nitriles; alternatively, phosphines; alternatively, amines; or alternatively, amides.

[0076] The ethers that can be used as neutral nonionic organic modifiers can be C2 to C 20 ethers, C2 to C 15 ethers or C2 to C 10 ethers. The thioethers that can be used as neutral nonionic organic modifiers can be C2 to C 20 thioethers, C2 to C 15 thioethers or C2 to C 10 thioethers. The disulfides that can be used as neutral nonionic organic modifiers can be C2 to C 20 disulfides, C2 to C 15 disulfides or C2 to C 10 disulfides. The ether can have the structure R 11 OR 12。 The thioether may have the structure R 11 SR 12 。 The disulfide may have the structure R 11 SSR 12 。 Each R of the ether, thioether, and / or disulfide 11 and R 12 can each independently be C1 to C 15 、 C1 to C 10 or C1 to C5 hydrocarbyl; C1 to C 15 、 C1 to C 10 or C1 to C5 alkyl; C5 to C 15 or C5 to C 10 cycloalkyl; C6 to C 15 or C6 to C 10 aryl; or C7 to C 15 or C7 to C 10Arylalkyl. In non-limiting aspects, ethers that can be used as neutral nonionic organic modifiers can include the following, can consist essentially of the following, or can be the following: dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, xylene ether, bisxylene ether, tetrahydrofuran, tetrahydropyran, dioxane, furan, benzofuran, isobenzofuran, dibenzofuran, or any combination thereof. In some aspects, ethers that can be used as neutral nonionic organic modifiers can include the following, can consist essentially of the following, or can be the following: dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, xylene ether, bisxylene ether, or any combination thereof; alternatively, tetrahydrofuran, tetrahydropyran, dioxane, or any combination thereof; alternatively, furan, benzofuran, isobenzofuran, dibenzofuran, or any combination thereof; alternatively, diethyl ether; alternatively, dipropyl ether; alternatively, dibutyl ether; alternatively, diphenyl ether; alternatively, xylene ether; alternatively, bisxylene ether, tetrahydrofuran; alternatively, tetrahydropyran; alternatively, dioxane; alternatively, furan; alternatively, benzofuran; alternatively, isobenzofuran; or alternatively, dibenzofuran. In non-limiting aspects, sulfides that can be used as neutral nonionic organic modifiers can include the following, consist essentially of the following, or can be the following: dimethyl sulfide, diethyl sulfide, dipropyl sulfide, dihexyl sulfide, dioctyl sulfide, dicyclohexyl sulfide, diphenyl sulfide, thiophene, methylthiophene (e.g., 2-methylthiophene or 3-methylthiophene), dimethylthiophene (e.g., 2,3-dimethylthiophene), ethylthiophene, benzothiophene, tetrahydrothiophene, thiopyran, or any combination thereof; alternatively, dimethyl sulfide, diethyl sulfide, dipropyl sulfide, dibutyl sulfide, dihexyl sulfide, dioctyl sulfide, dicyclohexyl sulfide, diphenyl sulfide, or any combination thereof; alternatively, thiophene, methylthiophene (e.g., 2-methylthiophene or 3-methylthiophene), dimethylthiophene (e.g., 2,3-dimethylthiophene), ethylthiophene, benzothiophene, tetrahydrothiophene, thiopyran, or any combination thereof; alternatively, dimethyl sulfide; alternatively, diethyl sulfide; alternatively, dibutyl sulfide; alternatively, dihexyl sulfide; alternatively, dioctyl sulfide; alternatively, dicyclohexyl sulfide; alternatively, diphenyl sulfide; alternatively, thiophene; alternatively, tetrahydrothiophene; or alternatively, thiourea.In one aspect, the disulfide can include, consist essentially of, or be: dimethyl disulfide, diethyl disulfide, dipropyl disulfide, dibutyl disulfide, dihexyl disulfide, dioctyl disulfide, dicyclohexyl disulfide, ethyl methyl disulfide, diphenyl disulfide, methyl phenyl disulfide, or any combination thereof; alternatively, dimethyl disulfide, diethyl disulfide, dipropyl disulfide, dibutyl disulfide, dihexyl disulfide, dioctyl disulfide, dicyclohexyl disulfide, ethyl methyl disulfide, diphenyl disulfide, methyl phenyl disulfide, or any combination thereof; alternatively, dimethyl disulfide; alternatively, diethyl disulfide; alternatively, dibutyl disulfide; alternatively, dioctyl disulfide; or alternatively, diphenyl disulfide.

[0077] The ester that can be used as a neutral nonionic organic modifier can be a C3 to C 20 ester, a C3 to C 15 ester, or a C3 to C 10 ester. The ester can have the structure R 13 (C=O)OR 14 . The R 13 and R 14 of the ester can independently be a C1 to C 15 , a C1 to C 10 or a C1 to C5 hydrocarbyl; a C1 to C 15 , a C1 to C 10 or a C1 to C5 alkyl; a C5 to C 15 or a C5 to C 10 cycloalkyl; a C6 to C 15 or a C6 to C 10 aryl; or a C7 to C 15 or a C7 to C 10 aralkyl. The ester that can be used as a neutral nonionic organic modifier can be a C1 to C 15 , a C1 to C 10 or a C1 to C5 hydrocarbyl, a C1 to C 15 , a C1 to C 10 or a C1 to C5 alkyl, a C6 to C 15 or a C6 to C 10 aryl, or a C7 to C 15 or a C7 to C 10 aralkyl carboxylate of a C1 to C 15 , a C1 to C 10 or a C1 to C5 hydrocarbyl, a C1 to C 15 , a C1 to C 10 or a C1 to C5 alkyl, a C5 to C 15 or a C5 to C 10 cycloalkyl, a C6 to C 15 or a C6 to C 10Aryl or C7 to C 15 or C7 to C 10 aralkyl esters. In a non-limiting aspect, the esters that can be used as neutral nonionic organic modifiers can include the following, consist essentially of the following, or can be the following: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, phenyl, tolyl, xylyl or benzyl acetate, propionate, butyrate, valerate, caproate, heptanoate, octanoate, nonanoate, decanoate, benzoate, methylbenzoate, dimethylbenzoate or naphthenate; alternatively, acetate, propionate, butyrate, valerate, caproate, heptanoate, octanoate, nonanoate, decanoate of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or tridecyl; alternatively, phenyl, tolyl, xylyl or benzyl acetate, propionate, butyrate, valerate, caproate, heptanoate, octanoate, nonanoate or decanoate; or alternatively, benzoate, methylbenzoate, dimethylbenzoate or naphthenate of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or tridecyl. In some aspects, the esters that can be used as neutral nonionic organic modifiers can be C4 to C 20 、C4 to C 15 or C4 to C 10 cyclic esters; alternatively, butyrolactone, valerolactone, o-(hydroxymethyl)benzoic acid lactone or any combination thereof; alternatively, butyrolactone; alternatively, valerolactone; or alternatively, o-(hydroxymethyl)benzoic acid lactone.

[0078] The aldehydes that can be used as neutral nonionic organic modifiers can be C2 to C 20 、C2 to C 15 or C2 to C 10 aldehydes. The ketones that can be used as neutral nonionic organic modifiers can be C3 to C 20 、C3 to C 15 or C3 to C 10 ketones. The aldehyde can have the structure R 15 (C=O)H. The ketone can have the R 15 (C=O)R 16 structure. The R 15 of the aldehyde and the R 15 and R 16 of the ketone can independently be C1 to C 15 、C1 to C 10 or C1 to C5 hydrocarbon groups; C1 to C 15 、C1 to C 10 or C1 to C5 alkyl groups; C5 to C 15 or C5 to C 10 cycloalkyl groups; C6 to C15 or C6 to C 10 aryl; or C7 to C 15 or C7 to C 10 aralkyl. In a non-limiting aspect, aldehydes that can be used as neutral nonionic organic modifiers can include, consist essentially of, the following: formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, tolualdehyde, xylaldehyde, furfural, or any combination thereof; alternatively, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, or any combination thereof; alternatively, benzaldehyde, tolualdehyde, xylaldehyde, or any combination thereof; alternatively, formaldehyde; alternatively, acetaldehyde; alternatively, propionaldehyde; alternatively, butyraldehyde; alternatively, benzaldehyde; alternatively, tolualdehyde; alternatively, xylaldehyde; alternatively, furfural. Ketones that can be used as neutral nonionic organic modifiers can include, consist essentially of, or can be the following: acetone, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, acetophenone, propiophenone, benzophenone, or any combination thereof; alternatively, acetone, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, or any combination thereof; alternatively, acetophenone, propiophenone, benzophenone, or any combination thereof; alternatively, acetone; alternatively, butanone; alternatively, pentanone; alternatively, hexanone; alternatively, heptanone; alternatively, octanone; alternatively, nonanone; alternatively, decanone; alternatively, acetophenone; alternatively, propiophenone; or alternatively, benzophenone.

[0079] The acyl halides that can be used as neutral nonionic organic modifiers can be C2 to C 20 , C2 to C 15 or C2 to C 10 acyl halides. The acid anhydrides that can be used as neutral nonionic organic modifiers can be C2 to C 20 , C2 to C 15 or C2 to C 10 acid anhydrides. The acyl halides can have the structure R 17 (C=O)X 10 . The acid anhydrides can have the R 17 (C=O)O(C=O)R 17 structure. The X 10 of the acyl halides can be chlorine, bromine, or iodine; alternatively, chlorine; alternatively, bromine; or alternatively, iodine. Each R 17 of the acyl halides and acid anhydrides can independently be C1 to C 15 , C1 to C 10 or C1 to C5 hydrocarbyl; C1 to C 15 , C1 to C 10 or C1 to C5 alkyl; C5 to C 15 or C5 to C 10 cycloalkyl; C6 to C15 or C6 to C 10 aryl; or C7 to C 15 or C7 to C 10 aralkyl. In a non-limiting aspect, acyl halides that can be used as neutral nonionic organic modifiers can include the following, consist essentially of the following, or can be the following: acetyl chloride, acetyl bromide, propionyl chloride, propionyl bromide, butyryl chloride, valeryl chloride, hexanoyl chloride, benzoyl chloride, benzoyl bromide, methylbenzoyl chloride, dimethylbenzoyl chloride, or any combination thereof; alternatively, acetyl chloride, acetyl bromide, propionyl chloride, propionyl bromide, butyryl chloride, valeryl chloride, hexanoyl chloride, or any combination thereof; alternatively, benzoyl chloride, benzoyl bromide, methylbenzoyl chloride, dimethylbenzoyl chloride, or any combination thereof; alternatively, acetyl chloride; alternatively, acetyl bromide; alternatively, propionyl chloride; alternatively, propionyl bromide; alternatively, butyryl chloride; alternatively, valeryl chloride; alternatively, hexanoyl chloride; alternatively, benzoyl chloride; alternatively, benzoyl bromide; alternatively, methylbenzoyl chloride; or alternatively, dimethylbenzoyl chloride.

[0080] In a non-limiting aspect, acid anhydrides that can be used as neutral nonionic organic modifiers can be acetic anhydride, propionic anhydride, butyric anhydride, hexanoic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride, benzoic anhydride, methylbenzoic anhydride, dimethylbenzoic anhydride, phthalic anhydride, isophthalic anhydride, or any combination thereof; alternatively, acetic anhydride, propionic anhydride, butyric anhydride, hexanoic anhydride; alternatively, maleic anhydride, succinic anhydride, glutaric anhydride, or any combination thereof; alternatively, benzoic anhydride, methylbenzoic anhydride, dimethylbenzoic anhydride, or any combination thereof; alternatively, phthalic anhydride, isophthalic anhydride, or any combination thereof; alternatively, acetic anhydride; alternatively, propionic anhydride; alternatively, butyric anhydride; alternatively, hexanoic anhydride; alternatively, maleic anhydride; alternatively, succinic anhydride; alternatively, glutaric anhydride; alternatively, benzoic anhydride; alternatively, methylbenzoic anhydride; alternatively, dimethylbenzoic anhydride; alternatively, phthalic anhydride; or alternatively, isophthalic anhydride.

[0081] Nitriles that can be used as neutral nonionic organic modifiers can be C2 to C 20 、C2 to C 15 or C2 to C 10 nitriles. The nitrile can have an R 18 CN structure. The R 18 of the nitrile can be C1 to C 15 、C1 to C 10 or C1 to C5 hydrocarbyl; C1 to C 15 、C1 to C 10 or C1 to C5 alkyl; C5 to C 15 or C5 to C 10Naphthenyl; C6 to C 15 or C6 to C 10 Aryl; or C7 to C 15 or C7 to C 10 Aralkyl. In a non-limiting aspect, the nitriles that can be used as neutral nonionic organic modifiers can include the following, consist essentially of the following, or can be the following: acetonitrile, propionitrile, butyronitrile, benzonitrile, or any combination thereof; alternatively, acetonitrile; alternatively, propionitrile; alternatively, butyronitrile; or alternatively, benzonitrile.

[0082] The phosphines that can be used as neutral nonionic organic modifiers can be C3 to C 20 、C3 to C 15 or C3 to C 10 phosphines. The phosphine can have the (R 19 )3P structure. The amine can have the (R 19 )3N structure. Each R 19 of the phosphine can independently be C1 to C 15 、C1 to C 10 or C1 to C5 hydrocarbon group; C1 to C 15 、C1 to C 10 or C1 to C5 alkyl group; C5 to C 15 or C5 to C 10 naphthenyl; C6 to C 15 or C6 to C 10 aryl; or C7 to C 15 or C7 to C 10 aralkyl. In a non-limiting aspect, the phosphines that can be used as neutral nonionic organic modifiers can include the following, consist essentially of the following, or can be the following: trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, trioctylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, or any combination thereof; alternatively, trimethylphosphine, triethylphosphine, tributylphosphine, trihexylphosphine, trioctylphosphine, or any combination thereof; alternatively, tricyclopentylphosphine, tricyclohexylphosphine, or any combination thereof; alternatively, triethylphosphine; alternatively, tributylphosphine; alternatively, trihexylphosphine; alternatively, trioctylphosphine; alternatively, tricyclopentylphosphine; alternatively, tricyclohexylphosphine; or alternatively, triphenylphosphine.

[0083] The amines that can be used as neutral nonionic organic modifiers can be C1 to C 20 、C1 to C 15 or C1 to C 10 amines. The amine can have the structure H2NR 20 、HN(R 20 )2、N(R 20 )3, or any combination thereof; alternatively, H2NR 20; Alternatively, HN(R 20 )2; or alternatively, N(R 20 )3. Each R 20 in the amine having the structure H2NR 20 )2 or N(R 20 )3 can be independently C1 to C 20 , C1 to C 15 , or C1 to C5 hydrocarbyl; C1 to C 10 , C1 to C 15 , or C1 to C5 alkyl; C5 to C 10 , or C5 to C 15 cycloalkyl; C6 to C 10 , or C6 to C 15 aryl; or C7 to C 10 , or C7 to C 15 , or C7 to C 10Arylalkyl. In non-limiting aspects, amines that can be used as neutral nonionic organic modifiers can include, consist essentially of, or can be: methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, cyclopentylamine, cyclohexylamine, piperidine, methylpiperidine, dimethylpiperidine, trimethylpiperidine, tetramethylpiperidine, aniline, benzylamine, naphthylamine, dimethylamine, diethylamine, dibutylamine, diphenylamine, methylaniline, trimethylamine, triethylamine, tributylamine, triphenylamine, pyridine, methylpyridine, or any combination thereof; alternatively, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, cyclopentylamine, cyclohexylamine, aniline, benzylamine, naphthylamine, dimethylamine, diethylamine, dibutylamine, diphenylamine, methylaniline, or any combination thereof; alternatively, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, cyclopentylamine, cyclohexylamine, aniline, benzylamine, naphthylamine, or any combination thereof; alternatively, dimethylamine, diethylamine, dibutylamine, diphenylamine, methylaniline, or any combination thereof; alternatively, piperidine, methylpiperidine, dimethylpiperidine, trimethylpiperidine, tetramethylpiperidine, or any combination thereof; alternatively, trimethylamine, triethylamine, tributylamine, triphenylamine, or any combination thereof; alternatively, pyridine, methylpyridine, or any combination thereof; alternatively, aniline, naphthylamine, or any combination thereof; alternatively, dimethylamine, diethylamine, dibutylamine, diphenylamine, methylaniline; or any combination thereof; alternatively, trimethylamine, triethylamine, tributylamine, triphenylamine, or any combination thereof; alternatively, methylamine; alternatively, ethylamine; alternatively, propylamine; alternatively, butylamine; alternatively, pentylamine; alternatively, hexylamine; alternatively, heptylamine; alternatively, octylamine; alternatively, decylamine; alternatively, cyclopentylamine; alternatively, cyclohexylamine; alternatively, piperidine; alternatively, methylpiperidine; alternatively, dimethylpiperidine; alternatively, trimethylpiperidine; alternatively, tetramethylpiperidine; alternatively, aniline; alternatively, benzylamine; alternatively, naphthylamine; alternatively, dimethylamine; alternatively, diethylamine; alternatively, dibutylamine; alternatively, diphenylamine; alternatively, methylaniline; alternatively, trimethylamine; alternatively, triethylamine; alternatively, tributylamine; alternatively, triphenylamine; alternatively, pyridine; or alternatively, methylpyridine.

[0084] Amides that can be used as neutral nonionic organic modifiers can be C2 to C 20 、C2 to C 15 or C2 to C 10 amides. The amide can have the structure H(C=O)NHR 22 、H(C=O)N(R 22 )2、R 21 (C=O)NH2、R 21 (C=O)NHR 22, R(C=O)N(R 22 )2 or any combination thereof; alternatively, H(C=O)NHR 22 or H(C=O)N(R 22 )2 or any combination thereof; alternatively, R 21 (C=O)NH2, R 21 (C=O)NHR 22 or R(C=O)N(R 22 )2 or any combination thereof; alternatively, H(C=O)NHR 22 ; alternatively, H(C=O)N(R 22 )2; alternatively, R 21 (C=O)NH2; alternatively, R 21 (C=O)NHR 22 ; or alternatively, R(C=O)N(R 22 )2. The R 21 of the amide and each R 22 can each independently be C1 to C 15 , C1 to C 10 or C1 to C5 hydrocarbyl; C1 to C 15 , C1 to C 10 or C1 to C5 alkyl; C5 to C 15 or C5 to C 10 cycloalkyl; C6 to C 15 or C6 to C 10 aryl; or C7 to C 15 or C7 to C10Arylalkyl. In non-limiting aspects, amides that can be used as neutral nonionic organic modifiers can include the following, consist essentially of the following, or can be the following: N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, N-propylformamide, N,N-dipropylformamide, N-butylformamide, N,N-dibutylformamide, N-phenylformamide, N,N-diphenylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-propylacetamide, N,N-dipropylacetamide, N-butylacetamide, N,N-dibutylacetamide, N-phenylacetamide, N,N-diphenylacetamide, N-(methylphenyl)acetamide, N,N-(dimethylphenyl)acetamide, propionamide, N-methylpropionamide, N,N-dimethylpropionamide, N-ethylpropionamide, N,N-diethylpropionamide, N-phenylpropionamide, N,N-diphenylpropionamide, butyramide, N-methylbutyramide, N,N-dimethylbutyramide, N-ethylbutyramide, N,N-diethylbutyramide, N-phenylbutyramide, N,N-diphenylbutyramide, benzamide, N-methylbenzamide, N,N-dimethylbenzamide, N-ethylbenzamide, N,N-diethylbenzamide, N-phenylbenzamide, N,N-diphenylbenzamide, methylbenzamide, N-methyl-methylbenzamide, N,N-dimethyl-methylbenzamide, N-ethyl-methylbenzamide, N,N-diethyl-methylbenzamide, N-phenyl-methylbenzamide, N,N-diphenyl-methylbenzamide, or any combination thereof; alternatively, N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-phenylacetamide, N,N-diphenylacetamide, N-methylpropionamide, N,N-dimethylpropionamide, N-methylbenzamide, N,N-dimethylbenzamide, or any combination thereof; alternatively, N-methylformamide; alternatively, N,N-dimethylformamide; alternatively, N-methylacetamide; alternatively, N,N-dimethylacetamide; alternatively, N-ethylacetamide; alternatively, N,N-diethylacetamide; alternatively, N-phenylacetamide; alternatively, N,N-diphenylacetamide; alternatively, N-methylpropionamide; alternatively, N,N-dimethylpropionamide; alternatively, N-methylbenzamide; or alternatively, N,N-dimethylbenzamide.

[0085] The alcohol that can be used as a neutral nonionic organic modifier can be a C2 to C 20 、C2 to C 15 or C2 to C 10 alcohol. The nitrile can have the structure R 23 CH2OH. The R of the alcohol nitrile23 It may be C 1 to C 15 , C1 to C 10 or C1 to C5 hydrocarbyl groups; C1 to C 15 , C1 to C 10 or C1 to C5 alkyl groups; C5 to C 15 or C5 to C 10 cycloalkyl groups; C6 to C 15 or C6 to C 10 aryl groups; or C7 to C 15 or C7 to C 10 aralkyl groups. In non-limiting aspects, the alcohols that can be used as neutral nonionic organic modifiers can include the following, consist essentially of the following, or can be the following: methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, phenol, methylphenol, dimethylphenol, ethylphenol, propylphenol, dibutylphenol, or any combination thereof; alternatively, methanol, ethanol, propanol, butanol, pentanol, or any combination thereof; alternatively, methylphenol, dimethylphenol, ethylphenol, propylphenol, dibutylphenol, or any combination thereof; alternatively, methanol; alternatively, ethanol; alternatively, propanol; alternatively, butanol; alternatively, pentanol; alternatively, methylphenol; alternatively, dimethylphenol; alternatively, ethylphenol; alternatively, propylphenol; or alternatively, dibutylphenol.

[0086] Generally, when using a neutral nonionic organic modifier, the neutral nonionic organic modifier can be utilized relative to the zirconium compound and / or the hydrocarbyl metal (or hydrocarbyl aluminum) compound. The molar ratio of the neutral nonionic organic modifier to zirconium of the zirconium compound (also referred to herein as the modifier:Zr molar ratio) and / or the molar ratio of the neutral nonionic organic modifier to the hydrocarbyl metal (or hydrocarbyl aluminum) compound (also referred to herein as the modifier:M (or modifier:Al) molar ratio) can be any ratio that can form an oligomer product when the catalyst system is contacted with ethylene. When using a neutral nonionic organic modifier relative to zirconium of the zirconium compound, the minimum modifier:Zr molar ratio can be 0.1:1, 0.5:1, 0.75:1, 0.8:1, 0.9:1, or 1:1; additionally or alternatively, the maximum modifier:Zr molar ratio can be 20:1, 15:1, 10:1, 7.5:1, or 5:1. Generally, the modifier:Zr molar ratio can be within the range of any minimum modifier:Zr molar ratio described herein to any maximum modifier:Zr molar ratio described herein. Thus, suitable non-limiting modifier:Zr molar ratios can be within the range of 0.5:1 to 20:1, 0.5:1 to 15:1, 0.75:1 to 10:1, 1:1 to 15:1, 1:1 to 10:1, 1:1 to 5:1, 0.5:1 to 5:1, 0.75:1 to 3:1, 0.8:1 to 2:1, 0.9:1, or 1.25. Other suitable modifier:Zr molar ratio ranges will be apparent from the present disclosure. When using a neutral nonionic organic modifier relative to the hydrocarbyl metal (or hydrocarbyl aluminum) compound, the minimum modifier:M (or modifier:Al) molar ratio can be 0.05:1, 0.1:1, 0.5:1, 0.75:1, 0.8:1, 0.9:1, or 1:1; additionally or alternatively, the maximum modifier:Zr molar ratio can be 5:1, 3:1, 2:1, 1.5:1, 1:1, 0.75:1, or 0.5:1. Generally, the minimum modifier:M (or modifier:Al) molar ratio can be within the range of any minimum modifier:M (or modifier:Al) molar ratio described herein to any maximum minimum modifier:M (or modifier:Al) molar ratio described herein. Thus, suitable non-limiting minimum modifier:M (or modifier:Al) molar ratios can be within the range of 0.5:1 to 5:1, 0.5:1 to 3:1, 0.75:1 to 2:1, or 0.75:1 to 1.5:1. Other suitable modifier:M (or modifier:Al) molar ratio ranges will be apparent from the present disclosure.

[0087] In one aspect, a catalyst system can be prepared first, and then i) the catalyst system is contacted with ethylene, a chain transfer agent, and an optional organic reaction medium, or ii) the catalyst system is introduced into a reaction zone. For example, in one aspect, the method can include contacting a zirconium compound with a hydrocarbyl metal (or hydrocarbyl aluminum) compound to form a catalyst system, and then i) contacting the catalyst system with ethylene, a chain transfer agent, and an optional organic reaction medium, or ii) introducing the catalyst system into a reaction zone. When a neutral nonionic organic modifier is utilized in the catalyst system, the neutral nonionic organic modifier can be contacted with the zirconium compound before contacting with the hydrocarbyl metal (or hydrocarbyl aluminum) compound, can be contacted with the hydrocarbyl metal (or hydrocarbyl aluminum) compound before contacting with the zirconium compound, or can be contacted with a mixture of the zirconium compound and the hydrocarbyl metal (or hydrocarbyl aluminum) compound. In another aspect, the neutral nonionic organic modifier, the zirconium compound, and the hydrocarbyl metal (or hydrocarbyl aluminum) compound can be contacted simultaneously to form a catalyst system.

[0088] In an alternative aspect, the catalyst system can be prepared in situ, wherein two or more components of the catalyst system are contacted i) individually (and / or simultaneously) with ethylene, a chain transfer agent, and an optional organic reaction medium, or ii) individually (and / or simultaneously) introduced into the reaction zone. For example, in one aspect, the method can include contacting i) a zirconium compound and a hydrocarbyl compound individually (and / or simultaneously) with ethylene, a chain transfer agent, and an optional organic reaction medium, or ii) introducing a zirconium compound and a hydrocarbyl compound individually (and / or simultaneously) into the reaction zone. In one aspect, when a neutral nonionic organic modifier is utilized in the catalyst system, the neutral nonionic organic modifier can be contacted with the zirconium compound first (to form a zirconium compound / neutral nonionic organic modifier mixture), and then the zirconium compound (or zirconium compound / neutral nonionic organic modifier mixture) and the hydrocarbyl metal (or hydrocarbyl aluminum) compound are contacted with ethylene, a chain transfer agent, and an optional organic reaction medium individually (and / or simultaneously) or introduced into the reaction zone individually (and / or simultaneously). In another aspect, when a neutral nonionic organic modifier is utilized in the catalyst system, the neutral nonionic organic modifier can be contacted with the hydrocarbyl metal (or hydrocarbyl aluminum) compound first (to form a hydrocarbyl metal (or hydrocarbyl aluminum) compound / neutral nonionic organic modifier mixture), and then the hydrocarbyl metal (or hydrocarbyl aluminum) compound or hydrocarbyl metal (or hydrocarbyl aluminum) compound / neutral nonionic organic modifier mixture) and the zirconium compound are contacted with ethylene, a chain transfer agent, and an optional organic reaction medium individually (and / or simultaneously) or introduced into the reaction zone individually (and / or simultaneously). In a further aspect, when a neutral nonionic organic modifier is utilized in the catalyst system, the neutral nonionic organic modifier, the zirconium compound, and the hydrocarbyl metal (or hydrocarbyl aluminum) compound can be contacted with ethylene, a chain transfer agent, and an optional organic reaction medium individually (and / or simultaneously) or introduced into the reaction zone individually (and / or simultaneously).

[0089] In a non-limiting aspect, the catalyst system can comprise a zirconium compound having the formula ZrX 1 m and the hydrocarbyl metal compound includes a hydrocarbyl metal compound having the formula AlX 2 n R 1 3-n , Al2X 2 3R 1 3, R 1 2Zn or any combination thereof. X 1 , X2 , R 1 , m, and n are described independently herein, and these independent descriptions can be used, without limitation and in any combination, to further describe a catalyst system that can include: a zirconium compound having the formula ZrX 1 m and an alkylaluminum compound including compounds having the formula AlX 2 n R 1 3-n , Al2X 2 3R 1 3, and a hydrocarbylmetal compound of a dialkylzinc compound (R 1 2Zn). In one aspect, each X 1 m of ZrX 1 can independently be chlorine or bromine and m is 4. In one aspect, the zirconium compound having the formula ZrX 1 m can include, consist essentially of, or be: ZrCl4, ZrBr4, ZrClBr3, ZrC12Br2, and ZrCl3Br; alternatively, ZrCl4 or ZrBr4; alternatively, ZrClBr3; or alternatively, ZrCl4. In one aspect, the hydrocarbylmetal compound can include compounds having the formula AlX 2 2R 1 , AlX 2 R 1 2, AlR 1 3, Al2X 2 3R 1 3, R 1 2Zn, or any combination thereof; alternatively, a hydrocarbylmetal compound of AlX 2 2R 1 , AlX 2 R 1 2, AlR 1 3, Al2X 2 3R 1 3, or any combination thereof. X 2 and R 1 are described independently herein, and these independent descriptions can be used, without limitation and in any combination, to further describe a catalyst system that can include: a zirconium compound having the formula ZrX 1 m and an alkylaluminum compound including compounds having the formula AlX 2 n R 1 3-n , Al2X 2 3R 1 3, R1 A metal hydrocarbon compound of an alkylaluminum compound of 2Zn or any combination thereof. In one aspect, each X of the metal hydrocarbon compound 2 can each independently be a halogen group, and each R 1 can each independently be a C2 to C4 alkyl group. In some aspects, the metal alkyl compound can comprise the following, or consist essentially of: triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylzinc or any combination thereof; alternatively, triethylaluminum and diethylaluminum chloride; alternatively, triethylaluminum and ethylaluminum dichloride; alternatively, triethylaluminum and ethylaluminum sesquichloride; alternatively, diethylaluminum chloride and ethylaluminum dichloride; alternatively, ethylaluminum sesquichloride. The non-limiting value of the molar ratio of the metal of the metal hydrocarbon compound (or aluminum of the alkylaluminum compound) to the zirconium of the zirconium compound can be in the range of 1:1 to 50:1, 1:1 to 15:1 or 10:1 to 25:1. In some non-limiting aspects, the catalyst system (or catalyst system components) may further comprise a neutral non-ionic organic modifier comprising a C2 to C 20 ester (any described herein), wherein the molar ratio of the neutral non-ionic organic modifier to the zirconium of the zirconium compound can be within any range disclosed herein (e.g., in the range of 0.5:1 to 5:1). In other non-limiting aspects, the catalyst system (or catalyst system components) may further comprise a neutral non-ionic organic modifier comprising a C2 to C 20 ether, a C2 to C 20 sulfide, a C1 to C 20 amine, a C3 to C 20 phosphine or any combination thereof (alternatively, a C2 to C 20 ether, a C2 to C 20 sulfide or any combination thereof; alternatively, a C2 to C 20 ether; alternatively (C2-C 20 sulfide; alternatively, a C1-C 20 amine; or alternatively, a C3-C 20 phosphine), wherein the molar ratio of the neutral non-ionic organic modifier to the zirconium of the zirconium compound can be any range disclosed herein (e.g., in the range of 0.5:1 to 20:1).

[0090] In another non-limiting aspect, the zirconium compound can have the formula ZrX 1 m Y 1 q and the metal hydrocarbon compound can comprise having the formula AlX 2 n R 1 3-n 、Al2X2 3R 1 A hydrocarbyl metal compound of 3 or any combination thereof. X 1 , Y 1 , X 2 , R 1 , n are independently described herein, and these independent descriptions can be used, without limitation and in any combination, to further describe a catalyst system that can include: a zirconium compound having the formula ZrX 1 m Y 1 q and a hydrocarbyl metal compound including an alkylaluminum compound having the formula AlX 2 n R 1 3-n , Al2X 2 3R 1 3 or any combination thereof. Each X in ZrX 1 m Y 1 q can independently be chlorine or bromine; alternatively, chlorine. Each Y in ZrX 1 1 m Y 1 q can independently be a C1 to C 1 hydrocarboxylate (e.g., any described herein), a C1 to C 10 hydrocarboxylate (e.g., any described herein), or a C1 to C 10 hydrocarboxylate (e.g., any described herein); alternatively, a C1 to C 15 hydrocarboxylate (e.g., any described herein); alternatively, a C1 to C 10 hydrocarboxylate (e.g., any described herein); or alternatively, a C1 to C 10 hydrocarboxylate (e.g., any described herein). For ZrX 15 1 m Y 1 q 10 , m can range from 0 to 4, q can range from 0 to 4, and m + q can be 4; alternatively, m can be 4 and q can be 0; or alternatively, m can be 0 and q can be 4. In one aspect, the zirconium compound having the formula ZrX 1 m 1 Y q 10 can include the following, can consist essentially of the following, or can be the following: tetra C1 to C 10Zirconium alkyl carboxylate; alternatively, zirconium tetra C1 to C5 alkyl carboxylate, or alternatively, Zr(O2C3H7)4. In another aspect, a zirconium compound having the formula ZrX 1 m may include the following, consist essentially of the following, or may be the following: ZrC14, ZrBr4, ZrClBr3, ZrC12Br2, and ZrC13Br; alternatively, ZrC14 or ZrBr4, or alternatively, ZrClBr3; or alternatively, ZrC14. In one aspect, the hydrocarbon metal compound may include a compound having the formula AlX 2 2R 1 , AlX 2 R 1 2, AlR 1 3, Al2X 2 3R 1 3 or any combination thereof, alternatively, AlX 2 2R 1 , AlX 2 R 1 2, AlR 1 3, Al2X 2 3R 1 3 or any combination thereof of hydrocarbon metal compounds. X 2 and R 1 are independently described herein, and these independent descriptions can be used without limitation and in any combination to further describe a catalyst system that may include: a zirconium compound having the formula ZrX 1 m and a hydrocarbon metal compound including an alkyl aluminum compound having the formula AlX 2 n R 1 3-n , Al2X 2 3R 1 3, R 1 2Zn or any combination thereof. In one aspect, each X 2 of the hydrocarbon metal compound may independently be a halogen group, and each R 1Each can independently be a C2 to C4 alkyl group. In some aspects, the alkyl metal compound can comprise the following, or consist essentially of the following: triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, or any combination thereof; alternatively, triethylaluminum and diethylaluminum chloride; alternatively, triethylaluminum and ethylaluminum dichloride; alternatively, triethylaluminum and ethylaluminum sesquichloride; alternatively, diethylaluminum chloride and ethylaluminum dichloride; alternatively, ethylaluminum sesquichloride. Non-limiting values of the molar ratio of the metal in the hydrocarbyl metal compound (or aluminum in the hydrocarbyl aluminum compound) to the zirconium of the zirconium compound can be in the range of 1:1 to 50:1, 2:1 to 25:1, or 1:1 to 15:1, and other ranges disclosed herein. In one aspect, the zirconium compound having the formula ZrX 1 m Y 1 q can be partially hydrolyzed by contacting ZrX 1 m Y 1 q with water at a water to zirconium molar ratio of 0.01:1 to 3:1, 0.1: to 2:1, or 0.25:1 to 1.75:1. In one aspect, the catalyst system (or catalyst system component) can further comprise a neutral nonionic organic modifier comprising a C2 to C 15 alcohol, a C1 to C 15 amine, a C2 to C 15 amide, or any combination thereof; alternatively, a C2 to C 15 alcohol; alternatively, a C1 to C 15 amine; or alternatively, a C2 to C 15 amide. In one aspect, the molar ratio of the neutral nonionic organic modifier to the metal in the hydrocarbyl metal compound (or aluminum in the hydrocarbyl aluminum compound) is in the range of 0.75:1 to 2:1, or 0.75:1 to 1.5:1, and other ranges disclosed herein. In one aspect, the neutral nonionic organic modifier can be contacted with the hydrocarbyl metal (or hydrocarbyl aluminum) compound before the hydrocarbyl metal (or hydrocarbyl aluminum) compound contacts the zirconium compound and / or ethylene (and / or is introduced into the reaction zone). In some aspects, the neutral nonionic organic modifier is contacted with the zirconium compound before the zirconium compound contacts ethylene and / or the hydrocarbyl metal compound (and / or is introduced into the reaction zone).

[0091] The methods described herein can utilize 1) a chain transfer agent comprising a compound having a hydrosilyl bond, a compound having a hydrosulfide bond, a compound having a hydrophosphine bond, or any combination thereof, 2) hydrogen gas, 3) a transition metal compound chain transfer agent, or any combination thereof; alternatively, 1) a chain transfer agent comprising a compound having a hydrosilyl bond, a compound having a hydrosulfide bond, a compound having a hydrophosphine bond, and 2) hydrogen gas; alternatively, a chain transfer agent comprising a compound having a hydrosilyl bond, a compound having a hydrosulfide bond, a compound having a hydrophosphine bond, or any combination thereof; alternatively, hydrogen gas; or alternatively, a transition metal compound chain transfer agent. Generally, in the process of forming an oligomer product, a chain transfer agent, hydrogen gas, and / or a transition metal compound chain transfer agent are utilized to achieve a desired effect. Desirable effects can include, relative to the same method without using 1) a chain transfer agent comprising a compound having a hydrosilyl bond, a compound having a hydrosulfide bond, a compound having a hydrophosphine bond, or any combination thereof, 2) hydrogen gas, and / or 3) a transition metal compound chain transfer agent, producing (a) less than 1 wt.% of polymer, (b) less than 1 wt.% of compounds having a weight average molecular weight greater than 1000 g / mol, or (c) any combination thereof, where wt.% is based on the total weight of the oligomer product; alternatively or additionally, producing (a) an oligomer product comprising a polymer having a lower Mw, (b) an oligomer product in which the polymer has a lower Mw maximum peak, (c) an oligomer product having a reduced amount of polymer, (d) an oligomer product having a reduced % of polymer having a molecular weight greater than 100,000, or (e) any combination thereof.

[0092] The chain transfer agent can comprise, consist essentially of, or can be: a compound having a hydrosilyl bond, a compound having a hydrosulfide bond, a compound having a hydrophosphine bond, or any combination thereof; alternatively, a compound having a hydrosilyl bond; alternatively, a compound having a hydrosulfide bond; or alternatively, a compound having a hydrophosphine bond. The reaction zone can have any molar ratio of any chain transfer agent to ethylene that provides any of the desired effects described herein. In one aspect, the reaction zone can have a minimum molar ratio of chain transfer agent to ethylene of 1 x 10 -5 :1, 5 x 10 -4 :1, 1 x 10 -4 :1, or 5 x 10 -3 :1; additionally or alternatively, 5 x 10 -1 :1, 1 x 10 -1 :1, 5 x 10 -2 :1, or 1 x 10 -2:1 maximum molar ratio of chain transfer agent to ethylene. Generally, the molar ratio of chain transfer agent to ethylene in the reaction zone can be within the range of any minimum molar ratio of chain transfer agent to ethylene described herein to any maximum molar ratio of chain transfer agent to ethylene described herein. Thus, suitable molar ratios of chain transfer agent to ethylene in the reaction zone can be from 1x10 -5 :1 to 5x10 -1 :1, 5x10 -4 :1 to 1x10 -1 :1, 1x10 -4 :1 to 5x10 -2 :1 or 5x10 -3 :1 to 1x10 -2 :1. Other suitable ranges of molar ratios of chain transfer agent to ethylene will be apparent from the present disclosure.

[0093] Compounds having a hydrosilyl bond that can be used as neutral nonionic organic modifiers can be C1 to C 40 、C1 to C 30 or C1 to C 20 compounds. In one aspect, compounds having a hydrosilyl bond that can be used as chain transfer agents can have the formula R 31 SiH3, (R 31 )2SiH2, (R 31 )3SiH, R 31 OSiH3, (R 31 O)2SiH2, (R 31 O)3SiH, or any combination thereof; alternatively, R 31 SiH3, (R 31 )2SiH2, (R 31 )3SiH, or any combination thereof; alternatively, R 31 OSiH3, (R 31 O)2SiH2, (R 31 O)3SiH, or any combination thereof; alternatively, R 31 SiH3; alternatively, (R 31 )2SiH2; alternatively, (R 31 )3SiH; alternatively, R 31 OSiH3; alternatively, (R 31 O)2SiH2; or alternatively, (R 31 O)3SiH. Each R 31 in the formula of the compound having a hydrosilyl bond can independently be a C1 to C 15 、C1 to C 10 or C1 to C5 hydrocarbyl group, C1 to C 15 、C1 to C10 or a C1 to C5 alkyl, C5 to C 15 or C5 to C 10 cycloalkyl, C6 to C 15 or C6 to C 10 aryl or C7 to C 15 or C7 to C 10 aralkyl. In a non-limiting aspect, a compound having a hydrosilyl bond (e.g., having any of the formulas described herein) can comprise the following, consist essentially of the following, or can be the following: trimethylsilane, diethylsilane, triethylsilane, tripropylsilane, dibutylsilane, tributylsilane, hexylsilane, dihexylsilane, trihexylsilane, octylsilane, dioctylsilane, trioctylsilane, decylsilane, didecylsilane, tridecylsilane, tridodecylsilane, phenylsilane, diphenylsilane, triphenylsilane, phenethylsilane, diphenethylsilane, triphenethylsilane, trimethoxysilane, triethoxysilane, 9,10-dimethyl-9,10-dihydro-9,10-disilaanthracene, tetraphenyldisilane, or any combination thereof; alternatively, trimethylsilane, diethylsilane, triethylsilane, tripropylsilane, dibutylsilane, tributylsilane, hexylsilane, dihexylsilane, trihexylsilane, octylsilane, dioctylsilane, trioctylsilane, decylsilane, didecylsilane, tridecylsilane, tridodecylsilane, phenylsilane, diphenylsilane, triphenylsilane, phenethylsilane, diphenethylsilane, triphenethylsilane, or any combination thereof; trimethylsilane, diethylsilane, triethylsilane, tripropylsilane, dibutylsilane, tributylsilane, hexylsilane, dihexylsilane, trihexylsilane, octylsilane, dioctylsilane, decylsilane, didecylsilane, phenylsilane, diphenylsilane, triphenylsilane, phenethylsilane, diphenethylsilane, or any combination thereof; alternatively, trioctylsilane, tridecylsilane, tridodecylsilane, triphenethylsilane, or any combination thereof; alternatively, trimethoxysilane, triethoxysilane, or any combination thereof; or alternatively, phenylsilane, diphenylsilane, or any combination thereof.

[0094] A compound having a silanylthio bond that can be used as a neutral nonionic organic modifier can be a C1 to C 20 , C1 to C 15 or C1 to C 10 compound. A compound having a hydrosulfide bond that can be used as a neutral nonionic organic modifier can comprise the following, consist essentially of the following, or can be the following: C1 to C 20 , C1 to C 15 or C1 to C 10 thiol, C1 to C 20 , C1 to C15 or C1 to C 10 thioglycolate, and / or C1 to C 20 、C1 to C 15 or C1 to C 10 mercapto propionate; alternatively, C1 to C 20 、C1 to C 15 or C1 to C 10 thiol; alternatively, C1 to C 20 、C1 to C 15 or C1 to C 10 thioglycolate; or alternatively, C1 to C 20 、C1 to C 15 or C1 to C 10 mercapto propionate. In one aspect, the compound having a hydrogen-sulfur bond that can be used as a chain transfer agent may have the formula R 32 SH, R 32 CO2CH2SH, R 32 CO2CH2CH2SH or any combination thereof; alternatively, R 32 CO2CH2SH, R 32 CO2CH2CH2SH or any combination thereof; alternatively, R 32 SH; alternatively, R 32 CO2CH2SH; or alternatively, R 32 CO2CH2CH2SH. R 32 in the formula of the compound having a hydrogen-sulfur bond can be C1 to C 15 、C1 to C 10 or C1 to C5 hydrocarbon group, C1 to C 15 、C1 to C 10 or C1 to C5 alkyl group, C5 to C 15 or C5 to C 10 cycloalkyl group, C6 to C 15 or C6 to C 10 aryl group or C7 to C 15 or C7 to C 10Arylalkyl. In non-limiting aspects, a compound having a hydrogen-sulfur bond (e.g., having any of the formulas described herein) can include, consist essentially of, or can be: methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, methyl thioglycolate, ethyl thioglycolate, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, or any combination thereof; alternatively, methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, or any combination thereof; alternatively, methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, or any combination thereof; alternatively, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, or any combination thereof; alternatively, methyl thioglycolate, ethyl thioglycolate, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, or any combination thereof; alternatively, ethanethiol; alternatively, propanethiol; alternatively, butanethiol; alternatively, tert-butyl mercaptan; alternatively, octanethiol; alternatively, decanethiol; alternatively, dodecanethiol; alternatively, methyl thioglycolate; or alternatively, methyl 3-mercaptopropionate.

[0095] Compounds having a hydrogen-phosphorus bond that can be used as neutral nonionic organic modifiers can be C1 to C compounds having a hydrogen-phosphorus bond 40 、C1 to C 30 or C1 to C 20 compounds. Compounds having a hydrogen-phosphorus bond that can be used as neutral nonionic organic modifiers can include, consist essentially of, or can be: C1 to C 40 、C1 to C 30 or C1 to C 20 phosphines and / or C1 to C 40 、C1 to C 30 or C1 to C 20 phosphites; alternatively, C1 to C 40 、C1 to C 30 or C1 to C 20 phosphines; or alternatively, C1 to C 40 、C1 to C 30 or C1 to C 20 phosphites. In one aspect, a compound having a hydrogen-phosphorus bond that can be used as a chain transfer agent can have the formula (R 33 )2PH, (R 33 O)2P(=O)H, or any combination thereof; alternatively, R 33 PH2; or alternatively, (R 33 O)2P(=O)H. Each R in the formula of the compound having a hydrogen-phosphorus bond 33Each can independently be C1 to C 15 、C1 to C 10 or a C1 to C5 hydrocarbyl group, C1 to C 15 、C1 to C 10 or a C1 to C5 alkyl group, C5 to C 15 or C5 to C 10 cycloalkyl, C6 to C 15 or C6 to C 10 aryl or C7 to C 15 or C7 to C 10 aralkyl. In a non-limiting aspect, a compound having a phosphorus-hydrogen bond (e.g., having any of the formulas described herein) can comprise, consist essentially of, or can be: dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dioctylphosphine, dicyclopentylphosphine, dicyclohexylphosphine, phenylphosphine, diphenylphosphine, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, dihexyl phosphite, dioctyl phosphite, diphenyl phosphite, dibenzyl phosphite, or any combination thereof; dimethylphosphine, diethylphosphine, dibutylphosphine, dioctylphosphine, dicyclopentylphosphine, dicyclohexylphosphine, phenylphosphine, diphenylphosphine, dimethyl phosphite, diethyl phosphite, diphenyl phosphite, dibenzyl phosphite, or any combination thereof; alternatively, dimethylphosphine, diethylphosphine, dibutylphosphine, dicyclopentylphosphine, dicyclohexylphosphine, dioctylphosphine, phenylphosphine, diphenylphosphine, or any combination thereof; or alternatively, dimethyl phosphite, diethyl phosphite, diphenyl phosphite, dibenzyl phosphite, or any combination thereof.

[0096] The transition metal compound chain transfer agent can comprise, consist essentially of, or can be: a Group 8 transition metal compound, a Group 9 transition metal compound, a Group 10 transition metal compound, or any combination thereof; alternatively, a Group 8 transition metal compound; alternatively, a Group 9 transition metal compound; or alternatively, a Group 10 transition metal compound. In one aspect, the reaction zone can have a minimum transition metal to ethylene molar ratio of 1x10 -9 :1, 5x10 -8 :1, 1x10 -8 :1, 5x10 -7 :1 or 1x10 -7 :1; additionally or alternatively, 5x10 -3 :1, 1x10 -3 :1, 5x10 -4 :1, 1x10 -4 :1 or 5x10 -5:1 maximum molar ratio of transition metal to ethylene. Generally, the reaction zone may have a molar ratio of transition metal to ethylene that can range from any minimum molar ratio of transition metal to ethylene described herein to any maximum molar ratio of transition metal to ethylene described herein. Thus, a suitable molar ratio of transition metal to ethylene in the reaction zone can be in the range of 1x10 -9 :1 to 5x10- 3 :1, 5x10- 8 :1 to 1x10- 3 :1, 1x10- 8 :1 to 5x10- 4 :1, 5x10- 7 :1 to 1x10 -4 :1 or 1x10 -7 :1 to 5x10 -5 :1. Other suitable ranges of the molar ratio of transition metal to ethylene in the reaction zone will be apparent from the present disclosure.

[0097] Generally, the transition metal compound chain transfer agent can have the formula MX 4 p , where M is a transition metal, X 4 is a monoanion, and p is the oxidation state of the transition metal M. The transition metal M can be a Group 8 - Group 10 transition metal; alternatively, a Group 8 - Group 9 transition metal; alternatively, a Group 8 transition metal; alternatively, a Group 9 transition metal; or alternatively, a Group 10 transition metal. In one aspect, the transition metal M can be iron, cobalt, or nickel; alternatively, iron or cobalt; alternatively, iron; alternatively, cobalt; or alternatively, nickel. Generally, for the transition metal compound chain transfer agent having the formula MX 4 p , p is an integer from 2 to 4, being 2 or 3, 2, 3, or 4. In one aspect, for each p of the transition metal compound chain transfer agent having the formula MX 4 p , it can independently be a halogen group, a carboxylate group, a β-diketonate group, a hydrocarbyloxy group, or a nitrate group; alternatively, a carboxylate group, a β-diketonate group, or a hydrocarbyloxy group; alternatively, a carboxylate group or a β-diketonate group; alternatively, a carboxylate group; or alternatively, a β-diketonate group. In one aspect, for each carboxylate group of the transition metal compound chain transfer agent having the formula MX 4 p , it can independently be a C2 to C 24 , C4 to C 19 or C5 to C 12 carboxylate group. In one aspect, for each hydrocarbyloxy group of the transition metal compound chain transfer agent having the formula MX 4 p , it can independently be a C1 to C24 , C4 to C 19 or C5 to C 12 hydroxide. In one aspect, each β-diketonate of the transition metal compound chain transfer agent having the formula MX 4 p can independently be C5 to C 24 , C5 to C 19 or C5 to C 12 β-diketonate.

[0098] Generally, each halo group of the transition metal compound chain transfer agent having the formula MX 4 p can independently be chlorine, bromine or iodine; alternatively, bromine, or alternatively, iodine. Generally, each carboxylate group of the transition metal compound chain transfer agent having the formula MX 4 p can independently be acetate, propionate, butyrate, valerate, caproate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, or dodecanoate; alternatively, valerate, caproate, heptanoate, octanoate, nonanoate, decanoate, undecanoate or dodecanoate; alternatively, valerate, caproate, heptanoate, octanoate, nonanoate, decanoate, undecanoate or dodecanoate; alternatively, caproate; alternatively, octanoate; alternatively, decanoate; or alternatively, dodecanoate. Generally, each hydrocarbyloxy group of the transition metal compound chain transfer agent having the formula MX 4 p can independently be methoxy, ethoxy, propoxy, butoxy, phenoxy, methylphenoxy or dimethylphenoxy; alternatively, methoxy, ethoxy, propoxy or butoxy; alternatively, phenoxy, methylphenoxy or dimethylphenoxy. Generally speaking, each β-diketonate of the transition metal compound chain transfer agent having the formula MX 4 p can independently be acetylacetonate (i.e., 2,4-pentanedionate), hexafluoroacetylacetonate (i.e., 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate) or benzoylacetonate; alternatively, acetylacetonate; alternatively, hexafluoroacetylacetonate; or alternatively, benzoylacetonate. In some non-limiting aspects, the transition metal compound chain transfer agent (or having the formula MX 4 pThe transition metal compound chain transfer agent) may include the following, consist essentially of the following, or may be the following: iron(II) chloride, iron(III) chloride, iron(II) acetate, iron(III) acetate, iron(II) octanoate, iron(III) octanoate, iron(II) acetylacetonate, iron(III) acetylacetonate, cobalt(II) chloride, cobalt(III) chloride, cobalt(II) acetate, cobalt(III) acetate, cobalt(II) octanoate, cobalt(III) octanoate, cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, nickel(II) chloride, nickel(II) acetate, nickel(II) octanoate or nickel(II) acetylacetonate; alternatively, iron(II) acetate, iron(III) acetate, iron(II) octanoate, iron(III) octanoate, iron(II) acetylacetonate, iron(III) acetylacetonate, cobalt(II) acetate, cobalt(III) acetate, cobalt(II) octanoate, cobalt(III) octanoate, cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, nickel(II) acetate, nickel(II) octanoate or nickel(II) acetylacetonate; alternatively, iron(II) octanoate, iron(III) octanoate, iron(II) acetylacetonate, iron(III) acetylacetonate, cobalt(II) octanoate, cobalt(III) octanoate, cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, nickel(II) octanoate or nickel(II) acetylacetonate; or alternatively, iron(III) octanoate, iron(III) acetylacetonate, cobalt(III) octanoate, cobalt(III) acetylacetonate, nickel(II) octanoate or nickel(II) acetylacetonate.

[0099] When using hydrogen, the reaction zone can have any hydrogen-to-ethylene ratio that can provide any of the desired effects described herein. In one aspect, the minimum hydrogen-to-ethylene ratio can be (0.05 g hydrogen) / (kg ethylene), (0.1 g hydrogen) / (kg ethylene), (0.25 g hydrogen) / (kg ethylene), (0.4 g hydrogen) / (kg ethylene), or (0.5 g hydrogen) / (kg ethylene); additionally or alternatively, the maximum hydrogen-to-ethylene ratio can be (5 g hydrogen) / (kg ethylene), (3 g hydrogen) / (kg ethylene), (2.5 g hydrogen) / (kg ethylene), (2 g hydrogen) / (kg ethylene), or (1.5 g hydrogen) / (kg ethylene). Generally, the reaction zone can have a hydrogen-to-ethylene ratio that can range from any of the minimum hydrogen-to-ethylene ratios described herein to any of the maximum hydrogen-to-ethylene ratios described herein. Thus, suitable reaction zone hydrogen-to-ethylene ratios can be in the range of (0.05 g hydrogen) / (kg ethylene) to (5 g hydrogen) / (kg ethylene), from (0.25 g hydrogen) / (kg ethylene) to (5 g hydrogen) / (kg ethylene), from (0.25 g hydrogen) / (kg ethylene) to (4 g hydrogen) / (kg ethylene), from (0.4 g hydrogen) / (kg ethylene) to (3 g hydrogen) / (kg ethylene), from (0.4 g hydrogen) / (kg ethylene) to (2.5 g hydrogen) / (kg ethylene), from (0.4 g hydrogen) / (kg ethylene) to (2 g hydrogen) / (kg ethylene), or from (0.5 g hydrogen) / (kg ethylene) to (2 g hydrogen) / (kg ethylene). Other suitable reaction zone hydrogen-to-ethylene ratio ranges will be apparent from the present disclosure.

[0100] The organic reaction medium that can be used in the methods described herein can be, for example, a hydrocarbon, a halogenated hydrocarbon, or a combination thereof. The hydrocarbons and halogenated hydrocarbons that can be used as the organic reaction medium can include aliphatic hydrocarbons, aromatic hydrocarbons, petroleum distillates, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, or any combination thereof. The aliphatic hydrocarbons that can be used as the organic reaction medium include C3 to C 20 aliphatic hydrocarbons; or C4 to C 15 aliphatic hydrocarbons; or C5 to C 10 aliphatic hydrocarbons. The aliphatic hydrocarbons that can be used as the organic reaction medium can be cyclic or acyclic and / or can be straight-chain or branched-chain, unless otherwise specified. Non-limiting examples of suitable acyclic aliphatic hydrocarbon organic reaction media that can be used alone or in any combination include propane, isobutane, n-butane, butane (n-butane, or a mixture of straight-chain and branched-chain C4 acyclic aliphatic hydrocarbons), pentane (n-pentane, or a mixture of straight-chain and branched-chain C5 acyclic aliphatic hydrocarbons), hexane (n-hexane, or a mixture of straight-chain and branched-chain C6 acyclic aliphatic hydrocarbons), heptane (n-heptane, or a mixture of straight-chain and branched-chain C7 acyclic aliphatic hydrocarbons), and octane (n-octane, or a mixture of straight-chain and branched-chain C8 acyclic aliphatic hydrocarbons). The aromatic hydrocarbons that can be used as the organic reaction medium include aromatic hydrocarbons or C6 to C10 Aromatic hydrocarbons. Non-limiting examples of suitable aromatic hydrocarbons that can be used alone or in any combination as an organic reaction medium include benzene, toluene, xylene (including ortho-xylene, meta-xylene, para-xylene, or mixtures thereof), and ethylbenzene. Halogenated aliphatic hydrocarbons that can be used as an organic reaction medium include C1 to C 15 halogenated aliphatic hydrocarbons or C1 to C 10 halogenated aliphatic hydrocarbons or C1 to C5 halogenated aliphatic hydrocarbons. The halogenated aliphatic hydrocarbons that can be used as an organic reaction medium can be cyclic or acyclic and / or can be straight-chain or branched, unless otherwise specified. Non-limiting examples of suitable halogenated aliphatic hydrocarbons that can be used as an organic reaction medium include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, or any combination thereof. Halogenated aromatic hydrocarbons that can be used as an organic reaction medium include C6 to C 20 halogenated aromatic hydrocarbons or 6 to C 10 halogenated aromatic hydrocarbons. Non-limiting examples of suitable halogenated aromatic hydrocarbons that can be used as an organic reaction medium include chlorobenzene, dichlorobenzene, or any combination thereof.

[0101] Generally, oligomer products can be formed under any conditions capable of forming oligomer products. Conditions that can be used to form oligomer products can include, alone or in any combination, the reaction zone pressure, the partial pressure of ethylene in the reaction zone, the reaction zone temperature, the molar ratio of zirconium to ethylene of the zirconium compound in the reaction zone, the mass ratio of ethylene to the organic reaction medium in the reaction zone, the reaction zone residence time (or average residence time), the ethylene conversion (or single-pass ethylene conversion), the Schultz-Flory K value of the oligomer product, and the selectivity of the oligomer product to normal α-olefins. The reaction zone pressure, the partial pressure of ethylene in the reaction zone, the reaction zone temperature, the molar ratio of zirconium to ethylene of the zirconium compound in the reaction zone, the mass ratio of ethylene to the organic reaction medium in the reaction zone, the reaction zone residence time (or average residence time), the ethylene conversion (or single-pass ethylene conversion), the Schultz-Flory K value of the oligomer product, and the selectivity of the oligomer product to normal α-olefins are described independently herein, and these independent descriptions of the reaction zone pressure, the partial pressure of ethylene in the reaction zone, the reaction zone temperature, the molar ratio of zirconium to ethylene of the zirconium compound in the reaction zone, the mass ratio of ethylene to the organic reaction medium in the reaction zone, the reaction zone residence time (or average residence time), the ethylene conversion (or single-pass ethylene conversion), the Schultz-Flory K value of the oligomer product, and the selectivity of the oligomer product to normal α-olefins can be used, without limitation and in any combination, to further describe the methods disclosed herein.

[0102] The oligomer product can be formed at the minimum pressure of the reaction zone below (or the reaction zone can have the following minimum pressure): 100 psi (689 kPa), 250 psi (1.72 MPa), 500 psi (3.45 MPa), 750 psi (5.17 MPa), 900 psi (6.21 MPa), or 1000 psi (6.89 MPa); alternatively or additionally, it can be formed at the maximum pressure below (or the reaction zone can have the following maximum pressure): 5000 psi (34.5 MPa), 4500 psi (31 MPa), 4,000 psi (27.6 MPa), 3500 psi (24.1 MPa), 3000 psi (20.7 MPa), 2,500 psi (17.2 MPa), 2,000 psi (13.8 MPa), 1,500 psi (10.3 MPa), 1250 psi (8.62 MPa), or 1000 psi (6.89 MPa). Generally, the oligomer product can be formed at a reaction zone pressure ranging from any minimum pressure disclosed herein to any maximum pressure disclosed herein (or the reaction zone can have a pressure ranging from any minimum pressure disclosed herein to any maximum pressure disclosed herein). In some non-limiting aspects, the oligomer product can be formed at the following reaction zone pressures (or the reaction zone can have the following pressures): from 100 psi (689 kPa) to 5000 psi (34.5 MPa), 100 psi (689 kPa) to 2,500 psi (17.2 MPa), 100 psi (689 kPa) to 1000 psi (6.89 MPa), 500 psi (3.45 MPa) to 4500 psi (31 MPa), 500 psi (3.45 MPa) to 2,500 psi (17.2 MPa), 500 psi (3.45 MPa) to 1000 psi (6.89 MPa), 750 psi (5.17 MPa) to 4500 psi (31 MPa), 900 psi (6.21 MPa) to 4,000 psi (27.6 MPa), or 1000 psi (6.89 MPa) to 3500 psi (24.1 MPa). With the present disclosure, other pressure ranges that can be utilized will be readily apparent to those skilled in the art.

[0103] The oligomer product can be formed at a minimum ethylene partial pressure in the reaction zone as follows (or the reaction zone can have the following minimum ethylene partial pressure): 100 psi (689 kPa), 250 psi (1.72 MPa), 500 psi (3.45 MPa), 750 psi (5.17 MPa), 900 psi (6.21 MPa), or 1000 psi (6.89 MPa); alternatively or additionally, it can be formed at a maximum pressure as follows (or the reaction zone can have the following maximum pressure) 5000 psi (34.5 MPa), 4500 psi (31 MPa), 4,000 psi (27.6 MPa), 3500 psi (24.1 MPa), 3000 psi (20.7 MPa), 2,500 psi (17.2 MPa), 2,000 psi (13.8 MPa), 1,500 psi (10.3 MPa), 1250 psi (8.62 MPa), or 1000 psi (6.89 MPa). Generally, the oligomer product can be formed at an ethylene partial pressure in the reaction zone ranging from any of the minimum ethylene partial pressures disclosed herein to any of the maximum ethylene partial pressures disclosed herein (or the reaction zone can have an ethylene partial pressure ranging from any of the minimum ethylene partial pressures disclosed herein to any of the maximum ethylene partial pressures disclosed herein). In some non-limiting aspects, the oligomer product can be formed at an ethylene partial pressure in the reaction zone as follows (or the reaction zone can have) the following ethylene partial pressures: from 100 psi (689 kPa) to 5000 psi (34.5 MPa), 100 psi (689 kPa) to 2,500 psi (17.2 MPa), 100 psi (689 kPa) to 1000 psi (6.89 MPa), 500 psi (3.45 MPa) to 4500 psi (31 MPa), 500 psi (3.45 MPa) to 2,500 psi (17.2 MPa), 500 psi (3.45 MPa) to 1000 psi (6.89 MPa), 750 psi (5.17 MPa) to 4500 psi (31 MPa), 900 psi (6.21 MPa) to 4,000 psi (27.6 MPa), or 1000 psi (6.89 MPa) to 3500 psi (24.1 MPa). With the present disclosure, other ethylene partial pressure ranges will be readily apparent to those skilled in the art.

[0104] The oligomer product can be formed at the minimum temperature of the reaction zone below (or the reaction zone can have the following minimum temperature): 0 °C, 25 °C, 40 °C, 50 °C, 75 °C, 100 °C or 125 °C; alternatively or additionally, it can be formed at the following maximum temperature (or the reaction zone can have the following maximum temperature) 250 °C, 200 °C, 150 °C, 125 °C, 100 °C or 90 °C. Generally, the oligomer product is formed at a reaction zone temperature ranging from any minimum temperature disclosed herein to any maximum temperature disclosed herein (or the reaction zone can have a temperature ranging from any minimum temperature disclosed herein to any maximum temperature disclosed herein). In some non-limiting aspects, the oligomer product can be formed at the following reaction zone temperatures (or the reaction zone can have the following temperatures): from 0 °C to 250 °C, from 25 °C to 200 °C, from 40 °C to 150 °C, from 40 °C to 100 °C, from 50 °C to 100 °C, from 50 °C to 150 °C, from 75 °C to 125 °C, from 75 °C to 250 °C, from 100 °C to 200 °C or from 100 °C to 200 °C. With the present disclosure, other temperature ranges that can be utilized will be readily apparent to those skilled in the art.

[0105] The oligomer product can be formed at the following molar ratio of zirconium of the minimum reaction zone zirconium compound in the reaction zone to ethylene (or the reaction zone has the following molar ratio of zirconium of the minimum reaction zone zirconium compound to ethylene): 5x10 -7 :1, 1x10 -6 :1, 5x10 -5 :1 or 2.5x10 -5 :1; additionally or alternatively, it can be formed at the following maximum molar ratio of zirconium of the reaction zone zirconium compound to ethylene (or the reaction zone has the following maximum molar ratio of zirconium of the reaction zone zirconium compound to ethylene): 7.5x10 -4 :1, 5x10 -4 :1, 2.5x10 -4 :1 or 1x10 -4 :1. Generally, the molar ratio of zirconium of the reaction zone zirconium compound to ethylene can be in the range from any minimum molar ratio of zirconium of the reaction zone zirconium compound to ethylene disclosed herein to any maximum molar ratio of zirconium of the reaction zone zirconium compound to ethylene disclosed herein. In non-limiting aspects, the molar ratio of zirconium of the reaction zone zirconium compound to ethylene can be from 5x10 -7 :1 to 1x10 -4 :1, 1x10 -6 :1 to 2.5x10 -4 :1, 5x10 -5 :1 to 5x10 -4 :1 or 2.5x10 -5 :1 to 7.5x10 -4within the range of 1. With the present disclosure, it will be readily apparent to those skilled in the art the range of the molar ratio of zirconium of other available reaction zone zirconium compounds to ethylene.

[0106] The oligomer product can be formed at the following minimum ethylene:organic reaction medium mass ratios in the reaction zone (or the reaction zone can have the following minimum ethylene:organic reaction medium mass ratios): 0.5:1, 0.75:1, 1:1, 1.25:1, or 1.5:1; additionally or alternatively, it can be formed at the following maximum ethylene:organic reaction medium mass ratios (or the reaction zone can have the following maximum ethylene:organic reaction medium mass ratios): 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, or 2:1. Generally, the oligomer product can be formed at a reaction zone ethylene:organic reaction medium mass ratio ranging from any of the minimum ethylene:organic reaction medium mass ratios disclosed herein to any of the maximum ethylene:organic reaction medium mass ratios disclosed herein (or the reaction zone can have an ethylene:organic reaction medium mass ratio ranging from any of the minimum ethylene:organic reaction medium mass ratios disclosed herein to any of the maximum ethylene:organic reaction medium mass ratios disclosed herein). In some non-limiting aspects, the oligomer product can be formed at a reaction zone ethylene:organic reaction medium mass ratio within the following ranges (or the reaction zone can have an ethylene:organic reaction medium mass ratio within the following ranges): 0.5:1 to 4.5:1, 0.75:1 to 4:1, 0.75:1 to 2:1, 1:1 to 3:1, or 1.5:1 to 2.5:1. With the present disclosure, it will be readily apparent to those skilled in the art the other available mass ratio ranges of ethylene to the organic reaction medium.

[0107] The oligomer product can be formed at any desired residence time (or average residence time) in the reaction zone (or the reaction zone can have any desired residence time (or average residence time) in the reaction zone). In one aspect, the oligomer product can be formed at a residence time (or average residence time) in the reaction zone that is used to produce a desired amount of oligomer product, a desired productivity of the catalyst system, provide a desired ethylene conversion, or any combination thereof; alternatively, to produce a desired amount of oligomer product; alternatively, a desired productivity of the catalyst system; or alternatively, to provide a desired ethylene conversion. The oligomer product can be formed at a minimum residence time (or average residence time) in the reaction zone (or the reaction zone can have a minimum residence time (or average residence time) in the reaction zone) of: 10 minutes, 20 minutes, or 30 minutes; additionally or alternatively, it can be formed at a maximum residence time (or average residence time) in the reaction zone (or the reaction zone can have a maximum residence time (or average residence time) in the reaction zone) of: 3 hours, 2.5 hours, 2 hours, or 1.5 hours. Generally, the residence time (or average residence time) in the reaction zone can be in the range from any minimum residence time (or average residence time) disclosed herein to any maximum residence time (or average residence time) disclosed herein. In some non-limiting aspects, the oligomer product can be formed at a residence time (or average residence time) in the reaction zone of 10 minutes to 2.5 hours, 20 minutes to 2 hours, 30 minutes to 2 hours, or from 30 minutes to 1.5 hours. With the present disclosure, it will be readily apparent to those skilled in the art what other ranges of residence times (or average residence times) in the reaction zone are available.

[0108] The oligomer product can have (or can be formed with) a minimum Schultz-Flory K value of 0.4, 0.45, 0.5; or 0.55; alternatively or additionally, a maximum Schultz-Flory K value of 0.9, 0.85, 0.8, 0.75, 0.7 or 0.65. The oligomer product can have (or can be formed with) a Schultz-Flory K value ranging from any of the minimum Schultz-Flory K values disclosed herein to any of the maximum Schultz-Flory K values disclosed herein. In a non-limiting aspect, the oligomer product can have (or can be formed with) a Schultz-Flory K value ranging from 0.4 to 0.9, from 0.4 to 0.8, from 0.5 to 0.8, from 0.5 to 0.7 or from 0.55 to 0.7. The Schultz-Flory K value ranges for other oligomer products are apparent from the present disclosure. In any aspect, the Schultz-Flory K value can be determined using adjacent pairs of oligomer products, where the two adjacent oligomer products are each selected from C8, C 10 , C 12 , C 14 or C 16 oligomer products. In an embodiment, the Schultz-Flory K value can be the average of any two or more Schultz-Flory K values of the oligomers described herein produced using different adjacent pairs. In some aspects, the Schultz-Flory K value can be determined using the C8 and C 10 oligomer products, C 10 and C 12 oligomer products, C 12 and C 14 oligomer products, C 14 and C 16低 oligomer products, C8, C 10 and C 12 oligomer products, or the average of any two or more of the adjacent pairs of oligomer products.

[0109] The oligomer product can be formed at any desired ethylene conversion (or single-pass ethylene conversion). The oligomer product can be formed at a minimum ethylene conversion (or single-pass ethylene conversion) of 30%, 35%, 40%, 45%, 50% or 55%; additionally or alternatively, at a maximum ethylene conversion (or single-pass ethylene conversion) of 95%, 90%, 87.5%, 85% or 80%. Generally, the oligomer product can be formed at an ethylene conversion (or single-pass ethylene conversion) that can range from any minimum ethylene conversion (or single-pass ethylene conversion) disclosed herein to any maximum ethylene conversion (or single-pass ethylene conversion) disclosed herein. In some non-limiting aspects, the oligomer product can be formed at an ethylene conversion (or single-pass ethylene conversion) ranging from 30% to 90%, from 35% to 90%, from 40% to 87.5%, from 45% to 87.5%, from 50% to 85% or from 55% to 85%. With the present disclosure, it will be readily apparent to those skilled in the art what other ranges of ethylene conversion (or single-pass ethylene conversion) can be utilized. In some aspects, the oligomer product can be formed at an ethylene conversion that provides an oligomer product that is selective for the desired linear alpha-olefin (e.g., having a percentage of linear alpha-olefins in the indicated oligomer product carbon number).

[0110] The methods described herein can produce an oligomer product that is highly selective for linear alpha-olefins. In one aspect, the C6 olefin oligomer product produced by the methods described herein can have a 1-hexene content of at least 98.5 wt.%, 98.75 wt.%, 99.0 wt.%, 99.25 wt.%. In one aspect, the 1-octene content of the C8 olefin oligomer product produced by the methods described herein can be at least 98 wt.%, 98.25 wt.%, 98.5 wt.%, 98.75 wt.% or 99.0 wt.% of 1-octene. In one aspect, the C 10 olefin oligomer product can have a 1-decene content of at least 97.5 wt.%, 97.75 wt.%, 98 wt.%, 98.25 wt.% or 98.5 wt.%. In one aspect, the C 12 olefin oligomer product can have a 1-dodecene content of at least 96.5 wt.%, 97 wt.%, 97.5 wt.%, 97.75 wt.% or 98.0 wt.%. In one aspect, the methods described herein can produce an oligomer product that can have any combination of: the 1-hexene content of any C6 olefin oligomer product described herein, the 1-octene content of any C8 olefin oligomer product described herein, any C 10The 1-decene content of the olefin oligomer product and / or the 1-octene content of any C8 olefin oligomer product described herein. In some non-limiting aspects, the oligomer product may have at least 99 wt.% of the 1-hexene content of the C6 olefin oligomer product and at least 97.5 wt.% of the C 12 1-dodecene content of the olefin oligomer product; alternatively, at least 98.5 wt.% of the 1-octene content of the C8 olefin oligomer product and at least 97.5 wt.% of the C 12 1-dodecene octene content of the olefin oligomer product; or alternatively, at least 99 wt.% of the 1-hexene content of the C6 olefin oligomer product, at least 98.5 wt.% of the 1-octene content of the C8 olefin oligomer product, at least 98 wt.% of the C 10 1-decene content of the olefin oligomer product, and at least 97.5 wt.% of the C 12 1-dodecene content of the olefin oligomer product. Other combinations of the n-alpha-olefin content of the oligomer product are apparent from the present disclosure.

[0111] In one aspect, relative to the same method that does not use 1) a chain transfer agent comprising a compound having a hydrosilyl bond, a compound having a hydrosulfide bond, a compound having a hydrophosphine bond, or any combination thereof, 2) hydrogen gas, and / or 3) a transition metal compound chain transfer agent, the methods described herein produce an oligomer product having: (a) less than 2.5 wt.%, 1 wt.%, 0.75 wt.%, 0.5 wt.%, or 0.25 wt.% polymer, (b) less than 2.5 wt.%, 1 wt.%, 0.75 wt.%, 0.5 wt.%, or 0.25 wt.% compounds having a weight average molecular weight greater than 1000 g / mol, or (c) any combination thereof. The wt.% of polymer and the weight average molecular weight of the oligomer product are based on the total weight of the oligomer product. In another, separate or combinable, aspect, relative to the same method that does not use 1) a chain transfer agent comprising a compound having a hydrosilyl bond, a compound having a hydrosulfide bond, a compound having a hydrophosphine bond, or any combination thereof, 2) hydrogen gas, and / or 3) a transition metal compound chain transfer agent, the methods described herein produce an oligomer product having: (a) an oligomer product comprising a polymer having a lower Mw, (b) an oligomer product in which the polymer has a lower Mw maximum peak, (c) an oligomer product having a reduced amount of polymer, (d) an oligomer product having a reduced % of polymer having a molecular weight greater than 100,000 molecular weight, or (e) any combination thereof. In one aspect, relative to the polymer produced by the same method that does not use 1) a chain transfer agent comprising a compound having a hydrosilyl bond, a compound having a hydrosulfide bond, a compound having a hydrophosphine bond, or any combination thereof, 2) hydrogen gas, and / or 3) a transition metal compound chain transfer agent, the amount of polymer present in the oligomer product per gram of oligomer product produced can be reduced by at least 10%, 25%, 40%, 50%, 60%, 70%, or 80%. In one aspect, relative to the polymer produced by the same method that does not use 1) a chain transfer agent comprising a compound having a hydrosilyl bond, a compound having a hydrosulfide bond, a compound having a hydrophosphine bond, or any combination thereof, 2) hydrogen gas, and / or 3) a transition metal compound chain transfer agent, the amount of polymer having a molecular weight greater than 100,000 molecular weight can be reduced by at least 10%, 25%, 40%, 50%, 60%, 70%, or 80%.

[0112] The reaction zone for forming the oligomer product can include any suitable reactor. Non-limiting examples of reactor types can include stirred tank reactors, plug flow reactors, or any combination thereof; alternatively, stirred tank reactors; alternatively, plug flow reactors; alternatively, fixed bed reactors, continuous stirred tank reactors, loop slurry reactors, solution reactors, tubular reactors, recycle reactors, or any combination thereof; alternatively, continuous stirred tank reactors; alternatively, loop slurry reactors; alternatively, solution reactors; alternatively, tubular reactors; or alternatively, recycle reactors. In one aspect, the reaction zone can have more than one reactor, which are in series and / or parallel and include any combination of reactor types and arrangements. Additionally, the oligomerization process for forming the oligomer product can be a continuous process, a semi-continuous process, or a batch process, or any reactor or vessel within the oligomerization reaction system can be operated continuously, semi-continuously, or batchwise.

[0113] Additional information regarding zirconium-based catalyst systems for the oligomerization of ethylene, including specific examples, and methods for producing oligomer products using such zirconium-based catalyst systems can be found in, but is not necessarily limited to, the following documents: US 4,361,714, US 4,377,720, US 4,396,788, US 4,409,414, US 4,410,750, US 4,434,312, US 4,434,313, US 4,442,309, US 4,486,615, US 4,783,573, US 4,855,525, US 4,886,933, US 4,966,874, US 5,260,500, US 6,576,721, US 7,897,826, US 2003 / 0153798, US 7,169,961, US 7,291,685, US 7,566,679, US 8,269,055, US 2009 / 0216057, US 2009 / 0306312, US 2010 / 0191029, US 2010 / 0292423, US 2011 / 0046429, US 2011 / 0054130, US 2011 / 0054233, US 2012 / 0184692, US 2020 / 0055799, US 2020 / 0062672, US 2020 / 0055800, US 2020 / 0062673, EP 320,571 A2, EP 444,505 A2, EP 1,749,807 A1, EP 1,752,434 A1, EP 1,780,189, EP 2,258,674 A1, WO 91 / 02707, Sekiyu Gakkaishi, Vol. 37, No. 4, 1994, pp. 337-346, Sekiyu Gakkaishi, Vol. 42, No. 4, 1999, pp. 235-245, Sekiyu Gakkaishi, Vol. 43, No. 5, 2000, pp. 328-338, Sekiyu Gakkaishi, Vol. 44, No. 1, 2001, pp. 25-35, and Sekiyu Gakkaishi, Vol. 44, No. 2, 2001, pp. 109-119.

[0114] Examples

[0115] The present disclosure is further illustrated by the following examples, which should not be construed as limiting the scope of the present disclosure in any way. After reading the description herein, various other aspects, modifications, and their equivalents will occur to those of ordinary skill in the art without departing from the spirit of the present disclosure or the scope of the appended claims.

[0116] Continuous ethylene oligomerization unit

[0117] Figure 1 Disclosed is a diagram of a continuous ethylene oligomerization unit. The continuous ethylene oligomerization unit includes a 0.5-liter autoclave (serving as a reactor), a 5-gallon high-pressure product tank, a primary catalyst system pump, a secondary catalyst system pump, an organic reaction medium pump, a hydrogen feed line, a chain transfer agent feed line, and related equipment (such as valves and pipes and other related equipment). The autoclave effluent sample port is located on the autoclave effluent line that runs between the autoclave and the high-pressure product tank. The reactor effluent line connecting the reactor and the high-pressure product tank is heat-traced and the skin temperature is maintained at the reaction temperature. The 0.5-liter autoclave includes an overhead magnetic mechanical stirrer for mixing the reaction mixture, as well as an internal cooling coil (for the flow of a heat exchange fluid) and an external heating jacket, which is used when necessary to maintain the required temperature. The continuous ethylene oligomerization unit also includes a high-pressure nitrogen feed line leading to the 0.5-liter autoclave reactor and the product tank to provide an inert atmosphere to these two vessels. The hydrogen feed line is connected to the ethylene feed line and is metered to provide the required hydrogen:ethylene ratio (when utilized), while the chain transfer agent feed line is connected to the organic reaction medium feed line on the suction side of the diluent pump and is metered to provide the required amount of chain transfer agent to the reactor. The catalyst system is fed to the reactor via one or two ISCO injection pumps (catalyst system feed pumps), while the organic reaction medium is fed from the organic reaction feed tank via the organic reaction medium pump. When the prepared catalyst system is fed into the reactor, the continuous ethylene oligomerization unit utilizes the primary catalyst system solution feed pump, and when two solutions containing one or more components of the catalyst system are fed separately to the feed line leading to the reactor, the continuous ethylene oligomerization unit utilizes the primary and secondary catalyst system feed pumps.

[0118] During continuous ethylene oligomerization, one or more catalyst system pumps (ISCO injection pumps) continuously feed one or more catalyst system solutions to the reactor at one or more required rates, the organic reaction medium pump continuously feeds the organic reaction medium to the autoclave at the required rate, and ethylene is continuously fed to the reactor at the required rate through the connected mass flow meter. The catalyst system and ethylene are introduced into the autoclave via dip tubes such that the catalyst system solution and ethylene enter the liquid contents of the autoclave at approximately the midpoint of the vertical height of the autoclave.

[0119] Example 1

[0120] In an argon atmosphere drying oven, 20 mmol of dry zirconium tetrachloride (ZrCl4) and 250 mL of dry cyclohexane were charged into a 500 mL flask equipped with a stirrer. Then the mixture was stirred at room temperature for 10 minutes. Triethylaluminum (TEA) was added to the stirred mixture, and then ethyl sesquichloride (EASC) was added to obtain a mixture having a molar ratio of EASC:TEA of 3.5:1 and a molar ratio of aluminum to zirconium of 7:1. Then the resulting mixture was heated at 70 °C for 2 hours. Then the mixture was cooled to room temperature. A 50 mL portion of the cooled mixture was transferred to a one-liter volumetric flask together with a certain amount of thiophene to achieve a molar ratio of thiophene to zirconium of 3:1. Then sufficient dry cyclohexane was charged into the one-liter volumetric flask to provide a one-liter catalyst system mixture. The resulting catalyst system mixture had a zirconium concentration per liter of cyclohexane and had a molar ratio of aluminum:zirconium of 7:1, a molar ratio of EASC:TEA of 3.5:1, and a molar ratio of thiophene:zirconium of 3:1. Then the volumetric flask of the catalyst system mixture was capped and removed from the argon atmosphere drying oven.

[0121] Run 1-1 (Comparison)

[0122] The oligomerization device as previously described is utilized only with the primary catalyst system solution pump. The high-pressure product tank is charged to the required pressure using the high-pressure N2 filling line to prepare the oligomerization reactor for ethylene oligomerization reaction. The reactor is isolated from the primary catalyst system solution pump and is also cycled through three high-pressure N2 fillings (to 800 psig - 5.5 MPa) and venting cycles. Each nitrogen purge is performed by closing the valve leading to the product tank, charging the autoclave with nitrogen via the spare inlet to a pressure of 800 psig (5.5 MPa), holding the nitrogen pressure on the autoclave for 5 minutes and then releasing the nitrogen pressure on the autoclave by opening the valve leading to the product tank. After the nitrogen release of the last nitrogen purge, the autoclave is maintained with a slight residual nitrogen pressure. Then 200 mL of the catalyst system mixture is transferred to the catalyst system ISCO injection pump of the prepared ethylene oligomerization device. Then the organic reaction medium (cyclohexane) is quickly injected into the reactor. Then the diluent pump is started at a rate of 335 mL per hour to bring the reactor to a reaction pressure of 925 psi (6.37 MPa). When the reactor reaches this reaction pressure, the overhead magnetic stirrer is started and set to approximately 1200 rpm, and the heating jacket is turned on and set to 120 °C. When the reactor reaches a stable temperature of 120 °C, the catalyst system ISCO pump is turned on and set to feed the catalyst system mixture to the reactor at a rate of 15 mL / hr. After 30 minutes, ethylene is introduced into the reactor at an initial rate of 50 grams per hour and is gradually increased to a final rate of 175 grams per hour over a 30-minute period. The internal cooling coil and external heating jacket are used as needed to maintain the oligomerization reaction temperature. After 6 hours, the oligomerization reaction is terminated by reducing the catalyst system flow rate to zero, reducing the ethylene flow rate to zero and turning off the heating jacket. When the reactor reaches room temperature, the flow rate of the organic reaction medium is reduced to zero and the liquid contents of the reactor are pressurized into the high-pressure product tank using high-pressure N2.

[0123] Then open the reactor, collect the solids inside the reactor and covering the inner reactor surface, and add them to the reactor effluent collected in the high-pressure product tank. Collect a 250-gram liquid sample from the product tank and add a known amount of an internal standard (such as nonane) to the sample. Then treat the sample with a 5 wt.% sodium hydroxide solution to deactivate the catalyst system. Then analyze the organic layer of the sodium hydroxide-treated sample using gas chromatography to determine the oligomer product distribution, Schulz-Flory K value, carbon number purity, and catalyst system productivity. Then homogenize the remaining product tank contents and take a second 250-gram sample from the product tank. Then rotary evaporate the second sample at 100 °C under -30 inches of mercury for 1 h to effectively remove all the liquid. Determine the mass of the remaining wax and polymer. Then analyze a portion of the wax using thermogravimetric analysis (TGA) to calculate the fraction of the solid sample that is polymer, using the following cut-off values: A) liquid (≤175 °C); B) wax (175 °C to 420 °C; C) polymer ≥420 °C. Analyze a second portion of the wax and polymer by HPLC to determine the molecular weight distribution of the polymer produced in the oligomerization reaction, including Mw, Mn, and Mp. Use the liquid and polymer analysis results to determine the oligomer product distribution, Schulz-Flory K value, carbon number purity, catalyst system productivity, polymer Mw, polymer Mw maximum peak, percentage of polymer in the oligomer product, percentage of polymer with Mw greater than 100,000, and percentage of oligomer product with Mw greater than 1,000 g / mol.

[0124] Run 1-2 .

[0125] In an argon atmosphere drying oven, charge a 250 mL volumetric flask with 0.1 mole of triethylsilane (chain transfer agent), and then charge enough dry cyclohexane to provide a 250 mL chain transfer agent mixture. Then cap the chain transfer agent mixture volumetric flask and remove it from the argon atmosphere drying oven.

[0126] Connect the chain transfer agent feed line to the organic reaction medium feed line on the suction side of the organic reaction medium pump. Repeat the procedure of Run 1-1, except that during the entire ethylene oligomerization reaction, the addition rate of the triethylsilane solution on the suction side of the diluent pump is metered to provide a 1x10 -3 :1 triethylsilane:ethylene molar ratio (when the ethylene flow rate is 175 grams per hour, this addition rate is approximately 15 mL per hour).

[0127] Run 1-3

[0128] In an argon atmosphere drying oven, a 250 mL volumetric flask was charged with 0.1 mmol of iron(III) octanoate (transition metal compound chain transfer agent), and then sufficient dry cyclohexane was charged to provide a 250 mL transition metal compound chain transfer agent mixture. Then the volumetric flask of the chain transfer agent mixture was capped and removed from the argon atmosphere drying oven.

[0129] The transition metal compound chain transfer agent feed line was connected to the organic reaction medium feed line on the suction side of the organic reaction medium pump. The procedure of Run 1-1 was repeated, except that during the entire ethylene oligomerization reaction, the addition amount of the iron(III) octanoate solution on the suction side of the diluent pump was metered to provide a 1x10 -6 :1 iron(III) octanoate:ethylene molar ratio (when the ethylene flow rate was 175 g / h, this addition amount was about 15 mL / h).

[0130] Run 1-4

[0131] The hydrogen feed line was connected to the ethylene feed line of the ethylene oligomerization unit. The procedure of Run 1-1 was repeated, except that hydrogen was metered into the ethylene at a certain rate during the entire ethylene oligomerization reaction to provide a hydrogen:ethylene mass ratio of (1 g of hydrogen) / (kg of ethylene).

[0132] The gas chromatography analysis and HPLC analysis of the ethylene oligomerization reactions Run 1-2, 1-3, and 1-4 using the chain transfer agent were reviewed and compared with the gas chromatography analysis and HPLC analysis of the ethylene oligomerization reaction Run 1-1. The analysis showed that compared with the ethylene oligomerization reaction Run 1-1 without using the chain transfer agent, the oligomer products produced in the ethylene oligomerization reactions Run 1-2, 1-3, and 1-4 using the chain transfer agent had less than 1 wt.% polymer and / or less than 1 wt.% of compounds with a weight average molecular weight greater than 1000 g / mol. The analysis also showed that when compared with the ethylene oligomerization reaction Run 1-1 without using the chain transfer agent, the oligomer products produced in the ethylene oligomerization reactions Run 1-2, 1-3, and 1-4 using the chain transfer agent produced such oligomer products that contained polymers with lower Mw, polymers with lower Mw maximum peaks, a reduced percentage of polymers, and / or polymers with a reduced percentage of Mw greater than 100,000. The gas chromatography analysis of the oligomer products of Runs 1-1, 1-2, 1-3, and 1-4 showed that when the chain transfer agent was utilized in the ethylene oligomerization reaction, there was no significant effect on the Schulz-Flory K value, carbon number purity, and catalyst system productivity.

[0133] Example 2

[0134] In an argon atmosphere drying oven, a first 500 mL flask equipped with a stirrer was charged with zirconium(IV) isopropyl carboxylate (60 mmol), anisole (45 mmol), and dry toluene (200 mL). Then this first mixture was stirred at room temperature for 10 minutes. In the argon drying oven, a second 500 mL flask equipped with a stirrer was charged with 2-pyrrolidone (43 mmol) and dry toluene (200 mL). Pure diethylaluminum chloride (1.2 mol) was added to this second mixture over a 30-minute period. Then this second mixture was stirred for an additional 10 minutes. Then the first mixture was transferred to a one-liter volumetric flask. Then the second mixture was added to the first mixture in the volumetric flask, and then sufficient dry toluene was charged to the volumetric flask to provide a one-liter solution of the first catalyst system mixture. After thorough mixing, a 200 mL portion of the first catalyst system mixture was transferred to a second one-liter volumetric flask together with sufficient dry toluene to provide a one-liter second catalyst system mixture. The zirconium concentration of the second catalyst system mixture thus prepared was 12 mmol / L and had an anisole:zirconium molar ratio of 0.75:1, an aluminum:zirconium molar ratio of 20:1, and a 2-pyrrolidone:aluminum ratio of 0.15:1. Then the second catalyst system mixture volumetric flask was capped and removed from the argon atmosphere drying oven.

[0135] Run 2-1 (Comparison)

[0136] The oligomerization apparatus as previously described is utilized only with a primary catalyst system solution pump. The high-pressure product tank is charged to the required pressure by using a high-pressure N2 filling line to prepare the oligomerization reactor for ethylene oligomerization reaction. The reactor is isolated from the primary catalyst system solution pump while also being cycled through three high-pressure N2 fillings (to 800 psig - 5.5 MPa) and purge cycles. Each nitrogen purge is carried out by closing the valve leading to the product tank, charging the autoclave with nitrogen via the spare inlet to a pressure of 800 psig (5.5 MPa), holding the nitrogen pressure on the autoclave for 5 minutes and then releasing the nitrogen pressure on the autoclave by opening the valve leading to the product tank. After the nitrogen release of the last nitrogen purge, the autoclave is maintained with a slight residual nitrogen pressure. Then 200 mL of the secondary catalyst system mixture is transferred to the catalyst system ISCO injection pump of the prepared ethylene oligomerization apparatus. Then the organic reaction medium (cyclohexane) is quickly injected into the reactor. Then the diluent pump is started at a rate of 485 mL per hour to bring the reactor to a reaction pressure of 450 psi (3.1 MPa). When the reactor reaches this reaction pressure, the overhead magnetic stirrer is started and set to approximately 1200 rpm, and the heating jacket is turned on and set to 70 °C. When the reactor reaches a stable temperature of 70 °C, the catalyst system ISCO pump is turned on and set to feed the catalyst system mixture to the reactor at a rate of 15 mL / hr. After 30 minutes, ethylene is introduced into the reactor at an initial rate of 50 grams per hour and gradually increased to a final rate of 175 grams per hour over a 30-minute period. The internal cooling coil and external heating jacket are used as needed to maintain the oligomerization reaction temperature. After 6 hours, the oligomerization reaction is terminated by reducing the catalyst system flow rate to zero, reducing the ethylene flow rate to zero and turning off the heating jacket. When the reactor reaches room temperature, the flow rate of the organic reaction medium is reduced to zero and the liquid contents of the reactor are pressured into the high-pressure product tank using high-pressure N2.

[0137] Then, open the reactor, collect the solids inside the reactor and covering the inner reactor surface, and add them to the reactor effluent collected in the high-pressure product tank. Collect a 250-gram liquid sample from the product tank, and add a known amount of internal standard (such as nonane) to this sample. Then, treat the sample with a 5 wt.% sodium hydroxide solution to deactivate the catalyst system. Then, analyze the organic layer of the sodium hydroxide-treated sample using gas chromatography to determine the oligomer product distribution, Schulz-Flory K value, carbon number purity, and catalyst system productivity. Then, homogenize the remaining product tank contents, and take a second 250-gram sample from the product tank. Then, rotary evaporate the second sample at 100 °C under -30 inches of mercury for 1 h to effectively remove all the liquid. Determine the mass of the remaining wax and polymer. Then, analyze a portion of the wax using thermogravimetric analysis (TGA) to calculate the fraction of the solid sample that is polymer, using the following cut-off values: A) liquid (≤ 175 °C); B) wax (175 °C to 420 °C); C) polymer ≥ 420 °C. Analyze a second portion of the wax and polymer by HPLC to determine the molecular weight distribution of the polymer produced in the oligomerization reaction, including Mw, Mn, and Mp. Use the liquid and polymer analysis results to determine the oligomer product distribution, Schulz-Flory K value, carbon number purity, catalyst system productivity, polymer Mw, polymer Mw maximum peak, percentage of polymer in the oligomer product, and percentage of polymer having

[0138] Run 2-2 .

[0139] In an argon atmosphere drying oven, charge a 250 mL volumetric flask with 0.1 mole of triethylsilane (chain transfer agent), and then charge enough dry cyclohexane to provide 250 mL of the chain transfer agent mixture. Then, cap the chain transfer agent mixture volumetric flask and remove it from the argon atmosphere drying oven.

[0140] Connect the chain transfer agent feed line to the organic reaction medium feed line on the suction side of the organic reaction medium pump. Repeat the procedure of Run 2-1, except that during the entire ethylene oligomerization reaction, the addition amount of the triethylsilane solution on the suction side of the diluent pump is metered to provide a 1x10 -3 :1 triethylsilane:ethylene molar ratio (when the ethylene flow rate is 175 grams per hour, this addition amount is approximately 15 mL per hour).

[0141] Run 2-3

[0142] In an argon atmosphere drying oven, 0.1 mmol of iron(III) octanoate (transition metal compound chain transfer agent) was loaded into a 250 mL volumetric flask, and then sufficient dry cyclohexane was loaded to provide a 250 mL transition metal compound chain transfer agent mixture. Then the volumetric flask of the chain transfer agent mixture was capped and removed from the argon atmosphere drying oven.

[0143] Connect the transition metal compound chain transfer agent feed line to the organic reaction medium feed line on the suction side of the organic reaction medium pump. Repeat the procedure of Run 2-1, except that during the entire ethylene oligomerization reaction, the addition amount of the iron(III) octanoate solution on the suction side of the diluent pump was metered to provide a 1x10 -6 :1 iron(III) octanoate:ethylene molar ratio (when the ethylene flow rate is 175 g / h, this addition amount is about 15 mL / h).

[0144] Run 2-4

[0145] Connect the hydrogen feed line to the ethylene feed line of the ethylene oligomerization unit. Repeat the procedure of Run 2-1, except that hydrogen was metered into the ethylene at a certain rate during the entire ethylene oligomerization reaction to provide a hydrogen:ethylene mass ratio of (1 g of hydrogen) / (kg of ethylene).

[0146] The gas chromatography analysis and HPLC analysis of the ethylene oligomerization reactions Runs 2-2, 2-3, and 2-4 using the chain transfer agent were reviewed and compared with the gas chromatography analysis and HPLC analysis of the ethylene oligomerization reaction Run 2-1. The analysis showed that compared with the ethylene oligomerization reaction Run 2-1 without using the chain transfer agent, the oligomer products produced in the ethylene oligomerization reactions Runs 2-2, 2-3, and 2-4 using the chain transfer agent had less than 1 wt.% polymer and / or less than 1 wt.% of compounds with a weight average molecular weight greater than 1000 g / mol. The analysis also showed that when compared with the ethylene oligomerization reaction Run 1-1 without using the chain transfer agent, the oligomer products produced in the ethylene oligomerization reactions Runs 2-2, 2-3, and 2-4 using the chain transfer agent produced such oligomer products that contained polymers with lower Mw, polymers with lower Mw maximum peaks, a reduced percentage of polymers, and / or polymers with a reduced percentage of Mw greater than 100,000. The gas chromatography analysis of the oligomer products of Runs 2-1, 2-2, 2-3, and 2-4 showed that when using the chain transfer agent in the ethylene oligomerization reaction, there was no significant effect on the Schulz-Flory K value, carbon number purity, and catalyst system productivity.

[0147] Example 3

[0148] In an argon atmosphere drying oven, zirconium tetrachloride (100 mmol), isodecyl acetate (105 mmol), and dry o-xylene (200 mL) were added to a first 500 mL flask equipped with a stirrer. Then this zirconium mixture was stirred at room temperature for 10 minutes. Then the first zirconium mixture was transferred to a one-liter volumetric flask, and then enough o-xylene was charged into this one-liter volumetric flask to provide one liter of the first zirconium solution. After thorough mixing, a 200 mL portion of the first zirconium solution was transferred together with enough dry o-xylene to a second one-liter volumetric flask to provide one liter of the second zirconium solution. The second zirconium solution had an isodecyl acetate:zirconium molar ratio of 1.05:1. Then the second zirconium solution volumetric flask was capped and removed from the argon atmosphere drying oven.

[0149] In an argon drying oven, dry o-xylene (500 mL) was charged to a second 500 mL flask equipped with a stirrer. Pure diethylaluminum chloride (1.2 mol) was added to this o-xylene over a 30-minute stirring period. Then this mixture was stirred for another 10 minutes. Then this diethylaluminum chloride solution was transferred to a one-liter volumetric flask, and then enough o-xylene was charged into this one-liter volumetric flask to provide one liter of the first zirconium solution. After thorough mixing, a 200 mL portion of the first diethylaluminum chloride solution was transferred together with enough dry o-xylene to a second one-liter volumetric flask to provide one liter of the second diethylaluminum chloride solution. Then the second diethylaluminum chloride solution volumetric flask was capped and removed from the argon atmosphere drying oven.

[0150] Run 3-1 (Comparison)

[0151] An oligomerization apparatus as previously described is utilized with the following modifications: the 500 mL autoclave is replaced with a 200 mL autoclave (which is also equipped with an overhead magnetic mechanical stirrer for mixing the reaction mixture, an internal cooling coil, and an external heating jacket), and a primary and secondary catalyst system pump is utilized simultaneously. The high-pressure product tank is charged to the desired pressure using a high-pressure N2 filling line to prepare the oligomerization reactor for ethylene oligomerization. The reactor is cycled through three high-pressure N2 fills (to 800 psig - 5.5 MPa) and vent cycles while isolated from the primary and secondary catalyst system solution pumps. Each nitrogen purge is performed by closing the valve to the product tank, charging the autoclave with nitrogen via the spare inlet to a pressure of 800 psig (5.5 MPa), holding the nitrogen pressure on the autoclave for 5 minutes and then releasing the nitrogen pressure on the autoclave by opening the valve to the product tank. After the nitrogen release of the last nitrogen purge, the autoclave is maintained with a slight residual nitrogen pressure. 200 mL of the second zirconium mixture is transferred to the primary catalyst system ISCO injection pump of the prepared ethylene oligomerization apparatus. 200 mL of the second diethylaluminum chloride solution is transferred to the secondary catalyst system ISCO injection pump of the prepared ethylene oligomerization apparatus. Then, the reactor is rapidly filled with dry organic reaction medium (o-xylene). Then, the diluent pump is started at a rate of 680 mL per hour to bring the reactor to a reaction pressure of 3000 psi (20.7 MPa). When the reactor reaches this reaction pressure, the overhead magnetic stirrer is started and set to approximately 1200 rpm, and the heating jacket is turned on and set to 165 °C. When the reactor reaches a stable temperature of 70 °C, the primary and secondary catalyst system ISCO pumps are started and set to feed the second zirconium solution and the second diethylaluminum chloride solution at a rate of 11 mL per hour. The feed rates of the zirconium solution and the diethylaluminum chloride solution provide an Al:Zr ratio of 12:1. After 30 minutes, ethylene is introduced into the reactor at an initial rate of 50 grams per hour and gradually increased to a final rate of 600 grams per hour over a 30-minute period. The internal cooling coil and the external heating jacket are used as needed to maintain the oligomerization reaction temperature. After 4 hours, the oligomerization reaction is terminated by reducing the feed flow rates of the zirconium solution and the diethylaluminum chloride solution to zero, reducing the ethylene flow rate to zero, and turning off the heating jacket. When the reactor reaches room temperature, the flow rate of the organic reaction medium is reduced to zero, and the liquid contents of the reactor are pressured into the high-pressure product tank using high-pressure N2.

[0152] Then open the reactor, collect the solids inside the reactor and covering the inner reactor surface, and add them to the reactor effluent collected in the high-pressure product tank. Collect a 250 g liquid sample from the product tank and add a known amount of internal standard (such as nonane) to the sample. Then treat the sample with 5 wt.% sodium hydroxide solution to deactivate the catalyst system. Then analyze the organic layer of the sodium hydroxide-treated sample using gas chromatography to determine the oligomer product distribution, Schulz-Flory K value, carbon number purity, and catalyst system productivity. Then homogenize the remaining product tank contents and remove a second 250 g sample from the product tank. Then rotary evaporate the second sample at 100 °C under -30 inches of mercury for 1 h to effectively remove all liquids. Determine the mass of the remaining wax and polymer. Then analyze a portion of the wax by thermogravimetric analysis (TGA) to calculate the fraction of the solid sample that is polymer, using the following cut-off values: A) liquid (≤175 °C); B) wax (175 °C to 420 °C; C) polymer ≥420 °C. Analyze the second portion of wax and polymer by HPLC to determine the molecular weight distribution of the polymer produced in the oligomerization reaction, including Mw, Mn, and Mp. Use the liquid and polymer analysis results to determine the oligomer product distribution, Schulz-Flory K value, carbon number purity, catalyst system productivity, polymer Mw, polymer Mw maximum peak, percentage of polymer in the oligomer product, percentage of polymer present.

[0153] Run 3-2 .

[0154] In an argon atmosphere drying oven, charge 360 mmol of triethylsilane (chain transfer agent) into a 250 mL volumetric flask, and then charge sufficient dry o-xylene to provide 250 mL of chain transfer agent mixture. Then cap the chain transfer agent mixture volumetric flask and remove it from the argon atmosphere drying oven.

[0155] Connect the chain transfer agent feed line to the organic reaction medium feed line on the suction side of the organic reaction medium pump. Repeat the procedure of Run 3-1, except that during the entire ethylene oligomerization reaction, the addition amount of the triethylsilane solution on the suction side of the diluent pump is metered to provide a 1x10 -3 :1 triethylsilane:ethylene molar ratio (when the ethylene flow rate is 600 g / h, this addition amount is about 15 mL / h).

[0156] Run 3-3

[0157] In an argon atmosphere drying oven, 0.36 mmol of iron(III) octanoate (transition metal compound chain transfer agent) was charged into a 250 mL volumetric flask, and then sufficient dry cyclohexane was charged to provide a 250 mL transition metal compound chain transfer agent mixture. Then the volumetric flask of the chain transfer agent mixture was capped and removed from the argon atmosphere drying oven.

[0158] Connect the transition metal compound chain transfer agent feed line to the organic reaction medium feed line on the suction side of the organic reaction medium pump. Repeat the procedure of Run 3-1, except that during the entire ethylene oligomerization reaction, the addition amount of the iron(III) octanoate solution on the suction side of the diluent pump was metered to provide a 1x10 -6 :1 iron(III) octanoate:ethylene molar ratio (when the ethylene flow rate is 175 g / h, this addition amount is about 15 mL / h).

[0159] Run 3-4

[0160] Connect the hydrogen feed line to the ethylene feed line of the ethylene oligomerization unit. Repeat the procedure of Run 3-1, except that hydrogen was metered into the ethylene at a certain rate during the entire ethylene oligomerization reaction to provide a hydrogen:ethylene mass ratio of (1 g of hydrogen) / (kg of ethylene).

[0161] The gas chromatography analysis and HPLC analysis of the ethylene oligomerization reactions Runs 3-2, 3-3, and 3-4 using the chain transfer agent were reviewed and compared with the gas chromatography analysis and HPLC analysis of the ethylene oligomerization reaction Run 3-1. The analysis showed that compared with the ethylene oligomerization reaction Run 3-1 without using the chain transfer agent, the oligomer products produced in the ethylene oligomerization reactions Runs 3-2, 3-3, and 3-4 using the chain transfer agent had less than 1 wt.% polymer and / or less than 1 wt.% of compounds with a weight average molecular weight greater than 1000 g / mol. The analysis also showed that when compared with the ethylene oligomerization reaction Run 3-1 without using the chain transfer agent, the oligomer products produced in the ethylene oligomerization reactions Runs 3-2, 3-3, and 3-4 using the chain transfer agent produced such oligomer products that contained polymers with lower Mw, polymers with lower Mw maximum peaks, a reduced percentage of polymers, and / or polymers with a reduced percentage of Mw greater than 100,000. The gas chromatography analysis of the oligomer products of Runs 3-1, 3-2, 3-3, and 3-4 showed that when using the chain transfer agent in the ethylene oligomerization reaction, there was no significant effect on the Schulz-Flory K value, carbon number purity, and catalyst system productivity.

[0162] An illustrative statement of the subject matter claimed below will now be provided. For clarity, not all features of actual embodiments are described in this specification. It will be understood that in the development of any such actual embodiment, numerous implementation-specific decisions must be made to achieve the developer's specific goals, such as compliance with system-related and business-related constraints, which will vary between different embodiments. Additionally, it will be understood that such development work, while complex and time-consuming, will be routine for those of ordinary skill in the art who benefit from this disclosure. Further, various modifications may be made within the scope of the invention as contemplated herein, and embodiments of the invention may include combinations of features other than those explicitly claimed. In particular, fluid arrangements other than those explicitly described herein are also within the scope of the invention.

[0163] Claim 1. A method comprising a) contacting: i) ethylene, ii) a catalyst system (or catalyst system component) comprising 1) a zirconium compound having the formula ZrX 1 m Y 1 q wherein each X 1 is independently a halogen group, each Y 1 is independently a hydrocarbyloxy group, a dihydrocarbylamino group, a hydrocarbylcarboxylate group, a hydrocarbylsulfonate group, or a β-diketonate group, m ranges from 0 to 4, q ranges from 0 to 4, and m + q is an integer from 2 to 4, and 2) a hydrocarbylmetal compound, iii) a chain transfer agent comprising a compound having a hydrogen-silicon bond, a compound having a hydrogen-sulfur bond, a compound having a hydrogen-phosphorus bond, or any combination thereof, and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone.

[0164] Claim 2. A method comprising a) introducing into a reaction zone: i) ethylene, ii) a catalyst system (or catalyst system component) comprising 1) a zirconium compound having the formula ZrX 1 m Y 1 q wherein each X 1 is independently a halogen group, each Y 1 is independently a hydrocarbyloxy group, a dihydrocarbylamino group, a hydrocarbylcarboxylate group, a hydrocarbylsulfonate group, or a β-diketonate group, m ranges from 0 to 4, q ranges from 0 to 4, and m + q is an integer from 2 to 4, and 2) a hydrocarbylmetal compound, iii) a chain transfer agent comprising a compound having a hydrogen-silicon bond, a compound having a hydrogen-sulfur bond, a compound having a hydrogen-phosphorus bond, or any combination thereof, and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone.

[0165] Claim 3. The method according to claim 1 or 2, wherein the chain transfer agent comprises a compound having the formula R 31 SiH3, (R 31 )2SiH2, (R 31 )3SiH, R 31 OSiH3, (R 31 O)2SiH2, (R 31 O)3SiH, R 32 SH, R 32 CO2CH2SH, R 32 CO2CH2CH2SH, R 33 PH2, (R 33 )2PH, R 33 OPH2, (R 33 O)2PH or any combination thereof, wherein each R 31 , R 32 and R 33 is independently a C1 to C 15 hydrocarbyl group.

[0166] Claim 4. The method according to any one of claims 1 - 3, wherein the reaction zone has any molar ratio of hydrogen to ethylene of the chain transfer agent disclosed herein, such as (1x10 -5 :1, 5x10 -4 :1, 1x10 -4 :1 or 5x10 -3 :1 as the minimum value; 5x10 -1 :1, 1x10 -1 :1, 5x10 -2 :1, 1x10 -2 :1 as the maximum value; in the range from 1x10 -5 :1 to 5x10 -1 :1, 5x10 -4 :1 to 1x10 -1 :1, 1x10 -4 :1 to 5x10 -2 :1 or 5x10 -3 :1 to 1x10 -2 :1; etc. other values and ranges).

[0167] Claim 5. A method comprising a) contacting: i) ethylene, ii) a catalyst system (or catalyst system components), the catalyst system (or catalyst system components) comprising 1) a zirconium compound having the formula ZrX 1 m Y 1 q wherein each X 1Each Y is independently a halogen group 1 Each is independently a hydrocarboxy group, a dihydrocarbylamino group, a hydrocarbyl carboxylate group, a hydrocarbyl sulfonate group or a β-diketonate group, m ranges from 0 to 4, q ranges from 0 to 4, and m + q is an integer from 2 to 4, and 2) a hydrocarbyl metal compound, iii) hydrogen, and iv) an optional organic reaction medium; and b) forming an oligomer product in the reaction zone.

[0168] Claim 6. A method comprising a) introducing into a reaction zone: i) ethylene, ii) a catalyst system (or catalyst system components), said catalyst system (or catalyst system components) comprising 1) a zirconium compound having the formula ZrX 1 m Y 1 q wherein each X 1 is independently a halogen group, each Y 1 is independently a hydrocarboxy group, a dihydrocarbylamino group, a hydrocarbyl carboxylate group, a hydrocarbyl sulfonate group or a β-diketonate group, m ranges from 0 to 4, q ranges from 0 to 4, and m + q is an integer from 2 to 4, and 2) a hydrocarbyl metal compound, iii) hydrogen, and iv) an optional organic reaction medium; and b) forming an oligomer product in the reaction zone.

[0169] Claim 7. The method according to claim 5 or 6, wherein the reaction zone has any mass ratio of hydrogen to ethylene disclosed herein (e.g., a minimum of (0.05 g hydrogen) / (kg ethylene), (0.1 g hydrogen) / (kg ethylene), (0.25 g hydrogen) / (kg ethylene), (0.4 g hydrogen) / (kg ethylene) or (0.5 g hydrogen) / (kg ethylene); a maximum of (5 g hydrogen) / (kg ethylene), (3 g hydrogen) / (kg ethylene), (2.5 g hydrogen) / (kg ethylene), (2 g hydrogen) / (kg ethylene) or (1.5 g hydrogen) / (kg ethylene); in the range from (0.05 g hydrogen) / (kg ethylene) to (5 g hydrogen) / (kg ethylene), from (0.25 g hydrogen) / (kg ethylene) to (5 g hydrogen) / (kg ethylene), from (0.25 g hydrogen) / (kg ethylene) to (4 g hydrogen) / (kg ethylene), from (0.4 g hydrogen) / (kg ethylene) to (3 g hydrogen) / (kg ethylene), from (0.4 g hydrogen) / (kg ethylene) to (2.5 g hydrogen) / (kg ethylene), from (0.4 g hydrogen) / (kg ethylene) to (2 g hydrogen) / (kg ethylene) or from (0.5 g hydrogen) / (kg ethylene) to (2 g hydrogen) / (kg ethylene); and other values and ranges).

[0170] Claim 8. A method comprising a) contacting: i) ethylene, ii) a catalyst system (or catalyst system components) comprising 1) a zirconium compound having the formula ZrX 1 m Y 1 q wherein each X 1 is independently a halogen group, each Y 1 is independently a hydrocarbyloxy group, a dihydrocarbylamino group, a hydrocarbylcarboxylate group, a hydrocarbylsulfonate group or a β-diketonate group, m ranges from 0 to 4, q ranges from 0 to 4, and m + q is an integer from 2 to 4, and 2) a hydrocarbylmetal compound, iii) a transition metal compound chain transfer agent, and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone.

[0171] Claim 9. A method comprising a) introducing into a reaction zone: i) ethylene, ii) a catalyst system (or catalyst system components) comprising 1) a zirconium compound having the formula ZrX 1 m Y 1 q wherein each X 1 is independently a halogen group, each Y 1 is independently a hydrocarbyloxy group, a dihydrocarbylamino group, a hydrocarbylcarboxylate group, a hydrocarbylsulfonate group or a β-diketonate group, m ranges from 0 to 4, q ranges from 0 to 4, and m + q is an integer from 2 to 4, and 2) a hydrocarbylmetal compound, iii) a transition metal compound chain transfer agent, and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone.

[0172] Claim 10. The method according to claim 8 or 9, wherein the transition metal compound chain transfer agent is any transition metal compound chain transfer agent having the formula MX 4 p where M is a transition metal, X 4 is a monoanion, and p is an integer from 2 to 4.

[0173] Claim 11. The method according to claim 10, wherein the transition metal compound chain transfer agent is any transition metal compound chain transfer agent having the formula MX4p as described herein, wherein M is iron, cobalt or nickel.

[0174] Claim 12. The method according to claim 10 or 11, wherein the transition metal compound chain transfer agent is any transition metal compound chain transfer agent having the formula MX 4 p as described herein, wherein X 4 is C4 to C19 Carboxylate group.

[0175] Claim 13. The method according to any one of Claims 8 to 12, wherein the reaction zone has any molar ratio of the transition metal of the transition metal compound chain transfer agent disclosed herein to ethylene (1x10 -9 :1, 5x10 -8 :1, 1x10 -8 :1, 5x10 -7 :1 or 1x10 -7 :1 minimum value; 5x10 -3 :1, 1x10 -3 :1, 5x10 -4 :1, 1x10 -4 :1 or 5x10 -5 :1 maximum value; from 1x10 -9 :1 to 5x10 -3 :1, 5x10 -8 :1 to 1x10 -3 :1, 1x10 -8 :1 to 5x10 -4 :1, 5x10 -7 :1 to 1x10 -4 :1 or 1x10 -7 :1 to 5x10 -5 :1 range; and other values and ranges).

[0176] Claim 14. The method according to any one of Claims 1 - 13, wherein the hydrocarbyl metal compound is any hydrocarbyl metal compound disclosed herein (e.g., comprising any metal of Groups 1, 2, 11, 12, 13 or 14 disclosed herein and other Group metals disclosed herein - and any hydrocarbyl group disclosed herein - C1 to C 20 ., C1 to C 10 or C1 to C6 hydrocarbyl groups and other more specific hydrocarbyl groups disclosed herein).

[0177] Claim 15. The method according to any one of Claims 1 - 14, wherein the metal of the hydrocarbyl metal compound: the zirconium of the zirconium compound is any value disclosed herein (e.g., 0.1:1, 0.2:1, 0.6:1, 1:1, 2:1 minimum value of 10:1; 100:1 maximum value of 75:1, 50:1, 25:1, 15:1 or 10:1; or in the range from 0.1:1 to 100:1, 0.2:1 to 75:1, 0.6:1 to 25:1, 1:1 to 50:1, 2:1 to 25:1, 1:1 to 15:1, 2:1 to 10:1, 10:1 to 50:1 or 10:1 to 25:1; and other values and ranges).

[0178] Claim 16. The method according to any one of Claims 1-15, wherein the catalyst system (or catalyst system component) further comprises a neutral non-ionic organic modifier.

[0179] Claim 17. The method according to Claim 16, wherein the neutral non-ionic organic modifier comprises any ether, ester, ketone, aldehyde, alcohol, acid anhydride, acyl chloride, nitrile, thioether, disulfide, phosphine, amine or amide as described herein.

[0180] Claim 18. The method according to Claim 16 or 17, wherein the molar ratio of the neutral non-ionic organic modifier to zirconium of the zirconium compound can have any value as described herein (for example, a minimum value of 0.1:1, 0.5:1, 0.75:1, 0.8:1, 0.9:1 or 1:1; a maximum value of 20:1, 15:1, 10:1, 7.5:1 or 5:1; or in the range from 0.5:1 to 20:1, 0.5:1 to 15:1, 0.75:1 to 10:1, 1:1 to 15:1, 1:1 to 10:1, 1:1 to 5:1, 0.5:1 to 5:1, 0.75:1 to 3:1, 0.8:1 to 2:1, 0.9:1 or 1.25; and other values and ranges).

[0181] Claim 19. The method according to any one of Claims 16-18, wherein the molar ratio of the neutral non-ionic organic modifier to the hydrocarbyl metal (or hydrocarbyl aluminum) compound can have any value as described herein (for example, a minimum value of 0.05:1, 0.1:1, 0.5:1, 0.75:1, 0.8:1, 0.9:1 or 1:1; a maximum value of 5:1, 3:1, 2:1, 1.5:1, 1:1, 0.75:1 or 0.5:1; or in the range from 0.05:1 to 5:1, 0.1 to 1:1, 0.1:1 to 0.5:1, 0.5:1 to 5:1, 0.5:1 to 3:1, 0.75:1 to 2:1 or 0.75:1 to 1.5:1; and other values and ranges).

[0182] Claim 20. The method according to any one of Claims 1-19, wherein the zirconium compound has the formula ZrX 1 m Y 1 q , wherein each X 1 is independently chlorine or bromine, and each Y 1 is independently a C1 to C 10 hydrocarbyloxy group (for example, any as described herein), a C1 to C 15 hydrocarbyl carboxylate group (for example, any as described herein) or a C1 to C 15A hydrocarbylsulfonate group (e.g., any of those described herein), m ranges from 0 to 4, q ranges from 0 to 4, and m + q = 4.

[0183] Claim 21. The method according to any one of claims 1 - 20, wherein the metal hydrocarbon compound comprises an alkylaluminum compound having the formula AlX 2 3-n R 1 n 、Al2X 2 6-q R 1 q 、R 1 2Zn or any combination thereof, wherein each R 1 is independently a C1 to C 10 alkyl group, each X 2 is independently chlorine, bromine or iodine, n is an integer from 0 to 3, and q is an integer from 0 to 6.

[0184] Claim 22. The method according to any one of claims 20 - 22, wherein the neutral nonionic organic modifier comprises any C2 to C 20 ether, C3 to C 20 ester, C3 to C 20 ketone, C2 to C 20 nitrile, C2 to C 20 sulfide, C2 to C 20 disulfide, C3 to C 20 phosphine, C1 to C 20 amine or C2 to C 20 amide described herein.

[0185] Claim 23. The method according to any one of claims 1 - 19, wherein the zirconium compound has the formula ZrX 1 m wherein each X 1 is independently chlorine or bromine and m = 4, the metal hydrocarbon compound has the formula AlX 2 n R 1 3-n 、Al2X 2 3R 1 3、R 1 2Zn or any combination thereof, wherein each X 2 is independently a halogen group and each R 1 is independently a C2 to C4 alkyl group, and the molar ratio of the metal of the metal hydrocarbon compound (aluminum of the alkylaluminum compound) to the zirconium of the zirconium compound is within any of the ranges disclosed herein (e.g., in the range of 1:1 to 50:1).

[0186] Claim 24. The method according to claim 23, wherein the catalyst system (or catalyst system component) further comprises a neutral nonionic organic modifier, the neutral nonionic organic modifier comprising C2 to C 20 esters, and wherein the molar ratio of the neutral nonionic organic modifier to the zirconium of the zirconium compound is within any of the ranges disclosed herein (e.g., in the range of 0.5:1 to 5:1), and the molar ratio of the metal of the organometallic compound (or the aluminum of the organoaluminum compound) to the zirconium of the zirconium compound is within any of the ranges disclosed herein (e.g., in the range of 10:1 to 25:1).

[0187] Claim 25. The method according to claim 24, wherein the neutral nonionic organic modifier is contacted with the zirconium compound prior to the zirconium compound contacting ethylene and / or the organometallic compound (and / or being introduced into the reaction zone).

[0188] Claim 26. The method according to claim 23 or 24, wherein the catalyst system (or catalyst system component) further comprises a neutral nonionic organic modifier, the neutral nonionic organic modifier comprising C2 to C 20 ethers, C2 to C 20 sulfides, C1 to C 20 amines, C3 to C 20 phosphines or any combination thereof, and wherein the molar ratio of the neutral nonionic organic modifier to the zirconium of the zirconium compound is within any of the ranges disclosed herein (e.g., in the range of 0.5:1 to 20:1), and the molar ratio of the metal of the organometallic compound (or the aluminum of the organoaluminum compound) to the zirconium of the zirconium compound is within any of the ranges disclosed herein (e.g., in the range of 1:1 to 15:1).

[0189] Claim 27. The method according to any one of claims 1-19, wherein the zirconium compound has the formula ZrX 1 m Y 1 q , wherein each X 1 is independently chlorine or bromine, each Y 1 is independently a C1 to C 10 hydrocarbyloxy group (e.g., any as described herein), a C1 to C 10 hydrocarbyl carboxylate group (e.g., any as described herein) or a C1 to C 15 hydrocarbyl sulfonate group (e.g., any as described herein), m is in the range of 0 to 4, q is in the range of 0 to 4, and m + q is 4, and the organometallic compound comprises a compound having the formula AlX 2 n R 1 3-n 、Al2X2 3R 1 a metal hydrocarbon compound of 3 or any combination thereof, wherein each X 2 is independently a halogen group and each R 1 is independently a C2-C4 alkyl group, and the molar ratio of the metal of the metal hydrocarbon compound (the aluminum of the hydrocarbylaluminum compound) to the zirconium of the zirconium compound is in the range of 1:1 to 50:1.

[0190] Claim 28. The method according to claim 27, wherein the zirconium compound is at least partially hydrolyzed by contacting the zirconium compound with water at any molar ratio of water to zirconium disclosed herein (for example, 0.01:1 to 3:1, 0.1: to 2:1, or 0.25:1 to 1.75:1).

[0191] Claim 29. The method according to claim 27 or 28, wherein the catalyst system (or catalyst system component) further comprises a neutral nonionic organic modifier comprising a C2-C 15 amide, and wherein the molar ratio of the neutral nonionic organic modifier to the metal of the metal hydrocarbyl compound (the aluminum of the hydrocarbylaluminum compound) is in the range of 0.1:1 to 1:1.

[0192] Claim 30. The method according to claim 29, wherein the neutral nonionic organic modifier is contacted with the metal hydrocarbyl (or hydrocarbylaluminum) compound before the metal hydrocarbyl (or hydrocarbylaluminum) compound contacts ethylene (and / or is introduced into the reaction zone).

[0193] Claim 31. The method according to any one of claims 27-30, wherein the catalyst system (or catalyst system component) further comprises a neutral nonionic organic modifier comprising a C2-C 20 ether, a C2-C 20 sulfide, a C1-C 20 amine, or any combination thereof, and wherein the neutral nonionic organic modifier:zirconium of the zirconium compound is within any range disclosed herein (for example, in the range of 0.1:1 to 10:1).

[0194] Claim 32. The method according to claim 31, wherein the neutral nonionic organic modifier is contacted with the zirconium compound before the zirconium compound contacts ethylene and / or the metal hydrocarbyl compound (and / or is introduced into the reaction zone).

[0195] The method according to any one of statements 1-32, wherein the oligomer product is formed at the reaction zone (or the reaction zone has) any molar ratio of zirconium of the reaction zone zirconium compound to ethylene described herein (for example, 5x10- 7:1, 1 x 10- 6 :1, 5 x 10 -5 :1 or 2.5 x 10- 5 :The molar ratio of zirconium in the zirconium compound in the minimum reaction zone to ethylene; 7.5 x 10- 4 :1, 5 x 10 -4 :1, 2.5 x 10 -4 :1 or 1 x 10 -4 :The molar ratio of zirconium in the zirconium compound in the maximum reaction zone to ethylene; the range is 5 x 10- 7 :1 to 1 x 10 -4 :1, 1 x 10 -6 :1 to 2.5 x 10 -4 :1, 5 x 10 -5 :1 to 5 x 10 -4 :1 or 2.5 x 10 -5 :1 to 7.5 x 10 -4 :The molar ratio of zirconium in the zirconium compound in the reaction zone; the molar ratios and ranges of zirconium in other reaction zone zirconium compounds).

[0196] Claim 34. The method according to any one of claims 1-33, wherein the oligomer product is formed at any pressure described herein (e.g., a minimum pressure of 100 psi (689 kPa), 250 psi (1.72 MPa), 500 psi (3.45 MPa), 750 psi (5.17 MPa), 900 psi (6.21 MPa), or 1000 psi (6.89 MPa); a maximum pressure of 5000 psi (34.5 MPa), 4500 psi (31 MPa), 4,000 psi (27.6 MPa), 3500 psi (24.1 MPa), 3000 psi (20.7 MPa), 2,500 psi (17.2 MPa), 2,000 psi (13.8 MPa), 1,500 psi (10.3 MPa), 1250 psi (8.62 MPa), or 1000 psi (6.89 MPa); or a pressure within the range from 100 psi (689 kPa) to 5000 psi (34.5 MPa), 100 psi (689 kPa) to 2,500 psi (17.2 MPa), 100 psi (689 kPa) to 1000 psi (6.89 MPa), 500 psi (3.45 MPa) to 4500 psi (31 MPa), 500 psi (3.45 MPa) to 2,500 psi (17.2 MPa), 500 psi (3.45 MPa) to 1000 psi (6.89 MPa), 750 psi (5.17 MPa) to 4500 psi (31 MPa), 900 psi (6.21 MPa) to 4,000 psi (27.6 MPa), or 1000 psi (6.89 MPa) to 3500 psi (24.1 MPa); and other pressures and pressure ranges), or the reaction zone has such pressure.

[0197] Claim 35. The method according to any one of Claims 1-34, wherein the oligomer product is formed at any ethylene partial pressure described herein (e.g., a minimum ethylene partial pressure of 100 psi (689 kPa), 250 psi (1.72 MPa), 500 psi (3.45 MPa), 750 psi (5.17 MPa), 900 psi (6.21 MPa) or 1000 psi (6.89 MPa); a maximum ethylene partial pressure of 5000 psi (34.5 MPa), 4500 psi (31 MPa), 4,000 psi (27.6 MPa), 3500 psi (24.1 MPa), 3000 psi (20.7 MPa), 2,500 psi (17.2 MPa), 2,000 psi (13.8 MPa), 1,500 psi (10.3 MPa), 1250 psi (8.62 MPa) or 1000 psi (6.89 MPa); or an ethylene partial pressure in the range from 100 psi (689 kPa) to 5000 psi (34.5 MPa), from 100 psi (689 kPa) to 2,500 psi (17.2 MPa), from 100 psi (689 kPa) to 1000 psi (6.89 MPa), from 500 psi (3.45 MPa) to 4500 psi (31 MPa), from 500 psi (3.45 MPa) to 2,500 psi (17.2 MPa), from 500 psi (3.45 MPa) to 1000 psi (6.89 MPa), from 750 psi (5.17 MPa) to 4500 psi (31 MPa), from 900 psi (6.21 MPa) to 4,000 psi (27.6 MPa) or from 1000 psi (6.89 MPa) to 3500 psi (24.1 MPa); and other ethylene partial pressures and ethylene partial pressure ranges), or the reaction zone has the ethylene partial pressure.

[0198] Claim 36. The method according to any one of Claims 1-35, wherein the oligomer product is formed at any temperature described herein (e.g., a minimum temperature of 0 °C, 25 °C, 40 °C, 50 °C, 75 °C, 100 °C or 125 °C; a maximum temperature of 250 °C, 200 °C, 150 °C, 125 °C, 100 °C or 90 °C; a temperature in the range from 0 °C to 250 °C, from 25 °C to 200 °C, from 40 °C to 150 °C, from 40 °C to 100 °C, from 50 °C to 100 °C, from 50 °C to 150 °C, from 75 °C to 125 °C, from 75 °C to 250 °C, from 100 °C to 200 °C or from 100 °C to 200 °C; and other temperature values and temperature ranges), or the reaction zone has the temperature.

[0199] Claim 37. The method according to any one of Claims 1 - 36, wherein the oligomer product is formed at any ethylene:organic reaction medium mass ratio described herein (e.g., a minimum ethylene:organic reaction medium mass ratio of 0.5:1, 0.75:1, 1:1, 1.25:1, or 1.5:1; a maximum ethylene:organic reaction medium mass ratio of 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, or 2:1; an ethylene:organic reaction medium mass ratio in the range from 0.5:1 to 4.5:1, from 0.75:1 to 4:1, from 0.75:1 to 2:1, from 1:1 to 3:1, or from 1.5:1 to 2.5:1; and other ethylene:organic reaction medium mass ratio values and ranges), or the reaction zone has such an ethylene:organic reaction medium mass ratio.

[0200] Claim 38. The method according to any one of Claims 1 - 37, wherein the oligomer product is formed at any reaction zone residence time (or average reaction zone residence time) described herein (e.g., a minimum reaction zone residence time (or average reaction zone residence time) of 10 minutes, 20 minutes, or 30 minutes; a maximum reaction zone residence time (or average reaction zone residence time) of 3 hours, 2.5 hours, 2 hours, or 1.5 hours; a reaction zone residence time (or average reaction zone residence time) in the range from 10 minutes to 2.5 hours, from 20 minutes to 2 hours, from 30 minutes to 2 hours, or from 30 minutes to 1.5 hours; and other reaction zone residence time (or average reaction zone residence time) values and ranges), or the reaction zone has such a reaction zone residence time (or average reaction zone residence time).

[0201] Claim 39. The method according to any one of Statements 1 - 38, wherein the oligomer product can be formed at any ethylene conversion (or single - pass ethylene conversion) described herein (e.g., a minimum ethylene conversion (or single - pass ethylene conversion) of 30%, 35%, 40%, 45%, 50%, or 55%; additionally or alternatively, a maximum ethylene conversion (or single - pass ethylene conversion) of 95%, 90%, 87.5%, 85%, or 80%; an ethylene conversion (or single - pass ethylene conversion) in the range from 30% to 90%, from 35% to 90%, from 40% to 87.5%, from 45% to 87.5%, from 50% to 85%, or from 55% to 85%; and other ethylene conversion (or single - pass ethylene conversion) values and ranges).

[0202] Claim 40. The method according to any one of Claims 1-39, wherein the oligomer product can have any Schulz-Flory K value disclosed herein (e.g., a minimum Schulz-Flory K value of 0.4, 0.45, 0.5 or 0.55; a maximum Schulz-Flory K value of 0.9, 0.85, 0.8, 0.75, 0.7 or 0.65; a Schulz-Flory K value ranging from 0.4 to 0.9, from 0.4 to 0.8, from 0.5 to 0.8, from 0.5 to 0.7 or from 0.55 to 0.7; and other Schulz-Flory K values and ranges).

[0203] Claim 41. The method according to any one of Claims 1-40, wherein, relative to the same method without using a chain transfer agent comprising a compound having a hydrosilyl bond, a compound having a hydrosulfide bond, a compound having a hydrophosphine bond or any combination thereof as described in any one of Claims 1-4, 2) hydrogen as described in any one of Claims 5-7, and / or 3) a transition metal compound chain transfer agent as described in any one of Claims 8-13, the method produces an oligomer product comprising: (a) a polymer having a lower Mw, (b) a polymer having a lower Mw maximum peak, (c) a polymer with a reduced percentage, (d) a polymer having a reduced percentage of polymer with Mw greater than 100,000, or (e) any combination thereof.

[0204] Claim 42. The method according to any one of Claims 1-41, wherein the oligomer product comprises (a) less than 1 wt% of polymer, (b) less than 1 wt.% of a compound having a weight average molecular weight greater than 1000 g / mol, or (c) any combination thereof, wherein the wt.% is based on the total weight of the oligomer product.

[0205] All publications and patents mentioned herein are incorporated herein by reference. The publications and patents mentioned herein can be used to describe and disclose, for example, the constructs and methods described in the publications, which can be used in combination with the presently described invention. The publications discussed throughout the text are provided only for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention.

Claims

1. A method, comprising: a) contacting: i) ethylene, ii) a catalyst system comprising 1) A zirconium compound having the formula ZrX 1 m Y 1 q , wherein each X 1 is independently a halogen group, each Y 1 is independently a hydrocarbyloxy group, a dihydrocarbylamino group, a hydrocarbylcarboxylate group, a hydrocarbylsulfonate group or a β-diketonate group, m is in the range of 0 to 4, q is in the range of 0 to 4, and m + q is an integer from 2 to 4, and 2) a hydrocarbon metal compound, iii) a chain transfer agent comprising a hydrosilyl bond, a compound having a hydrothio bond, a compound having a hydrophosphino bond, or any combination thereof; and iv) an optional organic reaction medium, and b) forming an oligomer product in a reaction zone; and wherein the oligomer product has a Schulz-Flory K value of 0.4 to 0.

8.

2. The method according to claim 1, wherein the chain transfer agent comprises a compound having the formula R 31 SiH3, (R 31 )2SiH2, (R 31 )3SiH, R 31 OSiH3, (R 31 O)2SiH2, (R 31 O)3SiH, R 32 SH, R 32 CO2CH2SH, R 32 CO2CH2CH2SH, R 33 PH2, (R 33 )2PH, R 33 OPH2, (R 33 O)2PH, or any combination thereof, wherein each R 31 , R 32 and R 33 is independently a C1 to C 15 hydrocarbon group.

3. The method according to claim 1, wherein the molar ratio of the chain transfer agent to ethylene in the reaction zone is in the range from 1x10 -5 :1 to 5x10 -1 :

1.

4. The method according to claim 1, wherein the oligomer product comprises (a) less than 1 wt% of polymer, (b) less than 1 wt.% of a compound having a weight average molecular weight greater than 1000 g / mol, or (c) any combination thereof, wherein the wt.% is based on the total weight of the oligomer product.

5. The method according to claim 1, wherein relative to the same method without using a chain transfer agent comprising a compound having a hydrosilyl bond, a compound having a hydrothio bond, a compound having a hydrophosphino bond, or any combination thereof, the method produces an oligomer product comprising: (a) a polymer having a lower Mw, (b) a polymer having a lower Mw maximum peak, (c) a reduced percentage of polymer, (d) a polymer having a reduced percentage of polymer with an Mw greater than 100,000 g / mol, or (e) any combination thereof.

6. The method according to claim 1, wherein the hydrocarbyl metal compound has the formula AlX 2 3-n R 1 n , Al2X 2 6-q R 1 q , R 1 2Zn or any combination thereof, wherein each R 1 is independently a C1 to C 10 alkyl group, each X 2 is independently chlorine, bromine or iodine, n is an integer from 0 to 3, and q is an integer from 0 to 6.

7. The method according to claim 1, wherein the catalyst system further comprises a neutral nonionic organic modifier.

8. The method according to claim 7, wherein the neutral nonionic organic modifier comprises an ether, an ester, a ketone, an aldehyde, an alcohol, an acid anhydride, an acyl chloride, a nitrile, a thioether, a disulfide, a phosphine, an amine, or an amide.

9. The method according to claim 1, wherein the zirconium compound has the formula ZrX 1 m , where each X 1 is independently chlorine or bromine and m is 4, and wherein the hydrocarbyl metal compound has the formula AlX 2 n R 1 3-n , Al2X 2 3R 1 3, R 1 2Zn or any combination thereof, where each X 2 is independently a halogen group and each R 1 is independently a C2 to C4 alkyl group.

10. The method according to claim 9, wherein the catalyst system further comprises a C2 to C 20 ester, a C2 to C 20 ether or a C2 to C 20 sulfide as a neutral nonionic organic modifier.

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