Ethylene oligomerization processes

Abstract

To provide novel and improved processes for ethylene oligomerization.SOLUTION: There is provided a process for producing alpha olefins, comprising contacting ethylene, a zirconium-based catalyst system comprising a hydrocarbylmetal compound, a chain transfer agent, and optionally an organic reaction medium. Chain transfer agents which can be utilized include a) hydrogen, b) a compound comprising a hydrogen silicon bond, a compound having a hydrogen sulfur bond, a compound having a hydrogen phosphorus bond, or c) a transition metal compound chain transfer agent.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a process for producing normal alpha olefins. More particularly, the present disclosure relates to an improved process for oligomerizing ethylene to normal alpha olefins. [Background technology]

[0002] Alpha olefins are important commodities in commerce. Their many applications include use as intermediates in the manufacture of detergents, as precursors to more environmentally friendly refined oils, as monomers, and as precursors to many other types of products. One method of making alpha olefins is by oligomerization of ethylene in catalytic reactions using various types of catalysts and / or catalyst systems. Some ethylene oligomerization catalyst systems produce large amounts of polymer, which can reduce the reaction system run time before reactor cleaning is required, reduce the reliability of the reaction system, and / or complicate product isolation. The uses and demand for normal alpha olefins continue to increase, and the competition for their supply is correspondingly intensifying. Thus, new and improved processes for ethylene oligomerization are desirable. Summary of the Invention

[0003] The present application relates to a method for producing a catalyst system comprising: a) contacting i) ethylene with ii) a catalyst system having the formula ZrX 1 m Y 1 q Zirconium compounds having the formula 1 is independently a halide, and each Y 1are independently a hydrocarboxyte, dihydrocarbyl azanide, hydrocarbyl carboxylate, hydrocarbyl sulfonate, or β-diketonate, 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 hydrocarbyl metal compound; iii) a chain transfer agent; and iv) optionally an organic reaction medium; and b) forming an oligomeric product in a reaction zone, wherein the oligomeric product has a Schulz-Flory K value of 0.4 to 0.8. In one embodiment, the chain transfer agent can be i) a compound containing a hydrogen silicon bond, a compound having a hydrogen sulfur bond, a compound having a hydrogen phosphorus bond, or any combination thereof; ii) hydrogen; or 3) a transition metal compound. In some embodiments, the process can produce an oligomer product comprising (a) less than 1 weight percent polymer, (b) less than 1 weight percent compounds having a weight average molecular weight greater than 1000 g / mol, or (c) any combination thereof, where weight percent is based on the total weight of the oligomer product. In another embodiment, the process can produce 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 reduced percentage of polymer having a Mw greater than 100,000, or (e) any combination thereof, compared to the same process without the use of 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.

[0004] The subject matter of this patent application can be understood by reference to the following description in conjunction with the accompanying drawings, in which like reference numerals identify like elements and in which: [Brief description of the drawings]

[0005] [Figure 1] FIG. 1 shows an example of an ethylene oligomerization unit. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] While the subject matter of this patent application is susceptible to various modifications and alternative forms, the drawings show by way of example specific embodiments described in detail herein. It is to be understood, however, that the description herein of specific embodiments is not intended to limit the claimed subject matter to the particular forms disclosed, but rather, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.

[0007] definition The following definitions are provided to more clearly define the terms used herein. Unless otherwise stated, the following definitions apply to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, 2nd Ed (1997) may be applied, unless it conflicts with any other disclosure or definition applied herein and does not make the claim to which it applies unclear or invalid. If any definition or usage provided by any document incorporated by reference herein conflicts with the definition or usage provided herein, the definition or usage provided herein shall take precedence.

[0008] Subject matter features may be described herein such that combinations of different features may be envisioned in specific aspects and / or clauses. With any aspect and / or clause and / or feature disclosed herein, all combinations that do not adversely affect the systems, compositions, processes and / or methods described herein are contemplated, regardless of the explicit description of a particular combination. Furthermore, unless otherwise stated, any aspect and / or clause and / or feature disclosed herein may be combined to describe inventive processes and systems consistent with the present disclosure.

[0009] The terms "a," "an," and "the" are intended to include plural options, e.g., at least one, or one or more, unless otherwise specified. For example, disclosure of a "trialkylaluminum compound" is intended to encompass one trialkylaluminum compound, or a mixture or combination of two or more trialkylaluminum compounds, unless otherwise specified.

[0010] Groups of elements in the periodic table are designated using the numbering scheme found in the version of the Periodic Table of the Elements published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, a group of elements may be designated using the common name assigned to that group, e.g., Group 1 elements are alkali metals, Group 2 elements are alkaline earth metals, Groups 3-12 elements are transition metals, Group 17 elements are halogens, etc.

[0011] For any particular compound disclosed herein, the general structure or name presented is also intended to encompass all structural isomers, conformers, and stereoisomers that may result from a particular set of substituents, unless otherwise stated. Thus, a general reference to a compound includes all structural isomers, unless otherwise stated. For example, a general reference to a C6 hydrocarbon refers to all hydrocarbons having 6 carbon atoms, a general reference to pentane includes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, and a general reference to a butyl group includes n-butyl, sec-butyl, iso-butyl, and tert-butyl groups. Furthermore, a reference to a general structure or name, where the context permits or requires, encompasses all enantiomers, diastereoisomers, and other optical isomers, whether enantiomeric or racemic, as well as mixtures of stereoisomers. For any particular formula or name given, the general formula or name given also encompasses all conformational isomers, positional isomers, and stereoisomers that may arise from a particular set of substituents.

[0012] A chemical "group" is described according to how the group is formally derived from a reference or "parent" compound, for example, by the number of hydrogen atoms formally removed from the parent compound to produce the group, even if the group is not actually synthesized in this manner. By way of example, an "alkyl group" may be formally derived by removing one hydrogen atom from an alkane, and an "alkylene group" may be formally derived by removing two hydrogen atoms from an alkane. Furthermore, a more general term may be used to encompass a variety of groups that are formally derived by removing any number ("one or more") of hydrogen atoms from a parent compound, which in this example may be expressed as an "alkane group," and includes "alkyl groups," "alkylene groups," and materials in which three or more hydrogen atoms have been removed from an alkane, as the case may be. Throughout, disclosure that a substituent, ligand, or other chemical moiety may constitute a particular "group" implies that the well-known rules of chemical structure and bonding are adhered to when the group is used as described. When a group is described as being "derived by," "derived from," "formed by," or "formed from," unless otherwise specified or the context requires otherwise, such terms are used in a formal sense and are not intended to reflect any particular synthetic method or procedure.

[0013] The term "hydrocarbon" whenever used in the present specification and claims refers to a compound containing only carbon and hydrogen. Other identifiers may be utilized to indicate the presence of a particular group 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 group" is used herein according to the definition laid down by IUPAC, which is a monovalent group formed by removing a hydrogen atom from a hydrocarbon. Similarly, a "hydrocarbylene group" refers to a group formed by removing two hydrogen atoms from a hydrocarbon, whether two hydrogen atoms from one carbon atom or one hydrogen atom from each of two different carbon atoms. Thus, according to the terminology used herein, a "hydrocarbon group" refers collectively to a group formed by removing one or more hydrogen atoms (as many as are necessary for the particular group) from a hydrocarbon. "Hydrocarbyl group", "hydrocarbylene group", and "hydrocarbon group" may be acyclic or cyclic groups and / or straight or branched chain. "Hydrocarbyl groups", "hydrocarbylene groups", and "hydrocarbon groups" can include rings, ring systems, aromatic rings, and aromatic ring systems that contain only carbon and hydrogen. "Hydrocarbyl groups", "hydrocarbylene groups", and "hydrocarbon groups" include, by way of example, aryl, arylene, arene, alkyl, alkylene, alkane, cycloalkyl, cycloalkylene, cycloalkane, aralkyl, aralkylene, and aralkane groups, among other groups.

[0014] The term "alkane" whenever used in the specification and claims refers to a saturated hydrocarbon compound. Other identifiers may be utilized to indicate the presence of a particular group in the alkane (e.g., a halogenated alkane indicates the presence of one or more halogen atoms replacing the same number of hydrogen atoms in the alkane). The term "alkyl group" is used herein according to the definition set forth by IUPAC, which is a monovalent group formed by removing a hydrogen atom from an alkane. Similarly, an "alkylene group" refers to a group formed by removing two hydrogen atoms from an alkane (whether two hydrogen atoms from one carbon atom or one hydrogen atom from two different carbon atoms). An "alkane group" is a general term that refers to a group formed by removing one or more hydrogen atoms (as many as are necessary for the particular group) from an alkane. An "alkyl group", "alkylene group", and "alkane group" may be acyclic or cyclic groups and / or straight or branched chain, unless otherwise specified. Primary, secondary, and tertiary alkyl groups are derived by the removal of a hydrogen atom from a primary, secondary, or tertiary carbon atom, respectively, of an alkane. An n-alkyl group can be derived by the removal of a hydrogen atom from a terminal carbon atom of a straight-chain alkane.

[0015] The term "substituted," when used to describe a compound or group, for example when referring to a substituted analog of a particular compound or group, is intended to describe a non-hydrogen moiety that formally replaces a hydrogen of the group and is intended to be non-limiting. One or more groups may also be referred to herein as "unsubstituted" or by equivalent terms such as "unsubstituted," which refers to the original group in which a non-hydrogen moiety has not replaced a hydrogen in the group. "Substituted" is intended to be non-limiting and includes inorganic or organic substituents.

[0016] The term "olefin" whenever used in the present specification and claims refers to a hydrocarbon having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. 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, unless otherwise specified. Olefins having only one, two, three, etc. carbon-carbon double bonds can be identified by the use of the terms "mono", "di", "tri", etc. in the name of the olefin. Olefins can be further identified by the position of the carbon-carbon double bond(s).

[0017] The term "alpha olefin" as used herein and in the claims refers to an olefin having a carbon-carbon double bond between the first and second carbon atoms of the longest continuous chain of carbon atoms. The term "alpha olefin" includes linear and branched alpha olefins unless otherwise specified. In the case of branched alpha olefins, the branching may be at the 2-position (vinylidene) and / or the 3-position or higher relative to the olefinic double bond. The term "vinylidene" whenever used herein and in the claims refers to an alpha olefin having a branch at the 2-position relative to the olefinic double bond. The term "alpha olefin" itself does not indicate the presence or absence of other carbon-carbon double bonds unless otherwise specified. The term "linear alpha olefin" as used herein refers to an unbranched alpha olefin having a carbon-carbon double bond between the first and second carbon atoms.

[0018] The term "normal alpha olefin" whenever used in this specification and claims refers to a straight chain aliphatic mono-olefin having a carbon-carbon double bond between a first and a second carbon atom. Note that "normal alpha olefin" is not synonymous with "linear alpha olefin" as the term "linear alpha olefin" can include straight chain olefin compounds having a double bond between the first and second carbon atoms and additional double bonds.

[0019] Cycloalkanes are saturated cyclic hydrocarbons with or without side chains, e.g., cyclobutane. Unsaturated cyclic hydrocarbons with one or more endocyclic double bonds or one triple bond are called cycloalkenes and cycloalkynes, respectively. Cycloalkenes and cycloalkynes with only one, two, three, etc. endocyclic double or triple bonds can be distinguished by the use of the terms "mono", "di", "tri", etc. in the name of the cycloalkene or cycloalkyne, respectively. Cycloalkenes and cycloalkynes can further specify the position of the endocyclic double or triple bond.

[0020] A "cycloalkyl group" is a univalent group derived by removing a hydrogen atom from a ring carbon atom of a cycloalkane. Similarly, a "cycloalkylene group" refers to a group derived by removing two hydrogen atoms from a cycloalkane, at least one of which is a ring carbon. Thus, a "cycloalkylene group" includes both groups derived from a cycloalkane in which two hydrogen atoms have been formally removed from the same ring carbon, groups derived from a cycloalkane in which two hydrogen atoms have been formally removed from two different ring carbons, and groups derived from a cycloalkane in which a first hydrogen atom has been formally removed from a ring carbon and a second hydrogen atom has been formally removed from a carbon atom that is not a ring carbon. A "cycloalkane group" refers generically to groups formed by removing one or more hydrogen atoms from a cycloalkane, at least one of which is a ring carbon, as necessary for the particular group. It should be noted that, according to the definitions provided herein, the general cycloalkane groups (including cycloalkyl and cycloalkylene groups) include those that have zero, one, or more hydrocarbyl substituents attached to the cycloalkane ring carbon atoms (e.g., methylcyclopropyl groups) and are members of the group of hydrocarbon groups. However, when referring to a cycloalkane group having a specific number of cycloalkane ring carbon atoms (e.g., cyclopentane or cyclohexane groups, among others), the base name of the cycloalkane group having the specified number of cycloalkane ring carbon atoms refers to an unsubstituted cycloalkane group (including those that do not have hydrocarbyl groups located on the cycloalkane ring carbon atoms). Thus, a substituted cycloalkane group having a specific number of ring carbon atoms (e.g., substituted cyclopentane or substituted cyclohexane, among others) refers to the respective group having one or more substituents attached to the ring carbon atoms of the cycloalkane group (including halogens, hydrocarbyl groups, or hydrocarboxy groups, among others). Where a substituted cycloalkane group having a specified number of cycloalkane ring carbon atoms is a member of the group of hydrocarbon groups (or a member of the general group of cycloalkane groups), each substituent of the substituted cycloalkane group having a specified number of cycloalkane ring carbon atoms is limited to being a hydrocarbyl substituent.The general group, specific group, and / or individual substituted cycloalkane group(s) having a particular number of ring carbon atoms that can be utilized as a member of a hydrocarbon group (or as a member of a general group of cycloalkane groups) can be readily determined and selected.

[0021] Aliphatic compounds are acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds. "Aliphatic group" is a general term for groups formed by removing one or more hydrogen atoms (as necessary for the particular group) from the carbon atoms of an aliphatic compound. Aliphatic compounds, and thus aliphatic groups, may contain organic functional group(s) and / or atom(s) other than carbon and other than hydrogen.

[0022] Aromatic compounds are compounds that contain a cyclic conjugated double bond system containing (4n+2) π electrons according to the Hückel (4n+2) rule, where n is an integer from 1 to 5. Aromatic compounds include "arenes" (hydrocarbon aromatic compounds) and "heteroarenes", also called "hetaranes" (heterocyclic aromatic compounds that are formally derived from arenes by replacing one or more methine (-C=) carbon atoms of the cyclic conjugated double bond system with a trivalent or divalent heteroatom so as to maintain the contiguous π electron system characteristic of aromatic systems and the number of out-of-plane π electrons corresponding to the Hückel (4n+2) rule). Arene compounds and heteroarene compounds are mutually exclusive members of the aromatic compound family, but compounds that have both arene and heteroarene groups are generally considered heteroarene compounds. Aromatic compounds, arenes, and heteroarenes may be monocyclic (e.g., benzene, toluene, furan, pyridine, methylpyridine) or polycyclic, unless otherwise specified. Polycyclic aromatic compounds, arenes, and heteroarenes, unless otherwise specified, include compounds in which aromatic rings may be fused (e.g., naphthalene, benzofuran, and indole), compounds in which aromatic groups may be separate and connected by bonds (e.g., biphenyl or 4-phenylpyridine), or compounds in which aromatic groups are connected by groups that contain linking atoms (e.g., the carbon of the methylene group in diphenylmethane, the oxygen of diphenylether, the nitrogen of triphenylamine, among other linking groups). As disclosed herein, the term "substituted" may be used to describe aromatic groups, arenes, or heteroarenes in which a non-hydrogen moiety formally replaces a hydrogen in the compound and is intended to be non-limiting.

[0023] "Aromatic group" refers to a collective term for groups formed by removing one or more hydrogen atoms (at least one of which is an aromatic ring carbon atom, as necessary for the particular group) from an aromatic compound. In the case of a monovalent "aromatic group", the hydrogen atom removed must be from an aromatic ring carbon. In the case of an "aromatic group" formed by removing two or more hydrogen atoms from an aromatic compound, at least one hydrogen atom must be from an aromatic hydrocarbon ring carbon. Furthermore, an "aromatic group" may have a hydrogen atom removed from the same ring of an aromatic ring or ring system (e.g., phen-1,4-ylene, pyridin-2,3-ylene, naphth-1,2-ylene, and benzofuran-2,3-ylene), from two different rings of a ring system (e.g., naphth-1,8-ylene and benzofuran-2,7-ylene), or from two isolated aromatic rings or ring systems (e.g., bis(phen-4-ylene)methane).

[0024] Arenes are aromatic hydrocarbons with or without side chains (e.g., benzene, toluene, or xylene, among others). An "aryl group" is a group derived from the formal removal of a hydrogen atom from an aromatic ring carbon of an arene. It should be noted that arenes may contain a single aromatic hydrocarbon ring (e.g., benzene, or toluene), fused aromatic rings (e.g., naphthalene or anthracene), one or more isolated aromatic rings covalently linked through bonds (e.g., biphenyl), or non-aromatic hydrocarbon group(s) (e.g., diphenylmethane). Similarly, an "arylene group" refers to a group formed by removing two hydrogen atoms from an arene, at least one of which is from an aromatic ring carbon. An "arene group" refers to a collective term for groups formed by removing one or more hydrogen atoms from an arene, at least one of which is an aromatic ring carbon, as necessary for the particular group. It should be noted that, according to the definitions provided herein, the general arene groups (including aryl and arylene groups) include those that have zero, one, or more hydrocarbyl substituents located on the aromatic hydrocarbon ring or ring carbon atoms (e.g., toluene or xylene groups, among others) and are members of the group of hydrocarbon groups. However, phenyl (or phenylene) and / or naphthyl (or naphthylene) groups refer to specific unsubstituted arene groups (not including hydrocarbyl groups located on aromatic hydrocarbon ring or ring carbon atoms). Thus, substituted phenyl or naphthyl groups refer to the respective arene groups that have one or more substituents (including halogens, hydrocarbyl groups, or hydrocarboxy groups, among others) located on the aromatic hydrocarbon ring or ring carbon atoms. When the substituted phenyl and / or naphthyl groups are members of the group of hydrocarbon groups (or members of the general group of arene groups), each substituent is limited to a hydrocarbyl substituent.One of ordinary skill in the art can readily identify and select general phenyl and / or naphthyl groups, specific phenyl and / or naphthyl groups, and / or individual substituted phenyl or naphthyl groups that may be utilized as members of the group of hydrocarbon groups (or members of the general group of arene groups).

[0025] An "aralkyl group" is an aryl-substituted alkyl group having a free valence at a non-aromatic carbon atom (e.g., benzyl, or 2-phenyleth-1-yl, among others). Similarly, an "aralkylene group" is an aryl-substituted alkylene group having two free valences at a single non-aromatic carbon atom or free valences at two non-aromatic carbon atoms, and an "aralkane group" is a generic term for aryl-substituted alkane groups having one or more free valences at a non-aromatic carbon atom(s). It should be noted that, according to the definitions provided herein, generic aralkane groups include those that have zero, one, or more hydrocarbyl substituents located on the aralkane aromatic hydrocarbon ring or ring system carbon atoms and are members of the group of hydrocarbon groups. However, a specific aralkane group specifying a specific aryl group (e.g., benzyl or 2-phenylethyl, among others) refers to a specific unsubstituted aralkane group (not including hydrocarbyl groups located on the aralkane aromatic hydrocarbon ring or ring system carbon atoms). Thus, a substituted aralkane group designating a particular aryl group refers to each aralkane group having one or more substituents, including, inter alia, halogens, hydrocarbyl groups, or hydrocarboxy groups. When a substituted aralkane group designating a particular aryl group is a member of a group of hydrocarbon groups (or a member of a general group of aralkane groups), each substituent is limited to a hydrocarbyl substituent. Substituted aralkane groups designating a particular aryl group that can be utilized as a member of a group of hydrocarbon groups (or a member of a general group of aralkane groups) can be readily identified and selected.

[0026] As used herein, the term "hydrocarbyl metal compound" refers to a compound having at least one metal-carbon bond, and the carbon atom involved in the metal-carbon bond is part of a hydrocarbyl group. "Hydrocarbyl compound" can include other non-hydrocarbyl groups such as halides, hydrocarboxylates, alkoxides, carboxylates, and azanides, among other non-hydrocarbyl groups, so long as the compound contains at least one metal-carbon bond, and the carbon atom involved in the metal-carbon bond is part of a hydrocarbyl group. Similarly, any particular "hydrocarbyl metal compound" (a compound in which the metal of the hydrocarbyl metal compound is specified) refers to a compound having at least one particular metal-carbon bond, and the carbon atom involved in the metal-carbon bond is part of a hydrocarbyl group.

[0027] "Halide" has its ordinary meaning. Thus, examples of halides include fluoride, chloride, bromide, and iodide.

[0028] The term "substituted", when used to describe a group, for example when referring to a substituted analog of a particular group, is intended to describe a non-hydrogen moiety that formally replaces a hydrogen of the group and is intended to be non-limiting. One or more groups may also be referred to herein as "unsubstituted" or by equivalent terms such as "unsubstituted", which refers to the original group in which a non-hydrogen moiety has not replaced a hydrogen in the group. "Substituted" is intended to be non-limiting and includes inorganic or organic substituents.

[0029] The term "room temperature" or "ambient temperature" is used herein to refer to any temperature between 15°C and 35°C where no external heat or cooling source is directly applied. Thus, the terms "room temperature" and "ambient temperature" encompass the individual temperatures between 15°C and 35°C and any and all ranges, subranges, and subrange combinations of temperatures where no external heat or cooling source is directly applied. The term "atmospheric pressure" is used herein to refer to the Earth's air pressure where no external pressure correcting means are utilized. Generally, except at extreme altitudes, "atmospheric pressure" is about 1 atmosphere (alternatively, about 14.7 psi or about 101 kPa). References to gaseous, liquid, and / or solid substances refer to the physical state of the substance at 25°C and atmospheric pressure.

[0030] Features provided as minimum values ​​in this disclosure may alternatively be described as "at least" the stated minimum value or "greater than or equal to" the stated minimum value for the feature disclosed herein. Features provided as maximum values ​​in this disclosure may alternatively be described as "less than or equal to" the feature disclosed herein.

[0031] In this disclosure, the usual rules of organic nomenclature prevail. For example, when referring to a substituted compound or group, reference to the substitution pattern is interpreted as indicating that the indicated group(s) are at the indicated position, and all other positions not shown are hydrogen. For example, reference to a 4-substituted phenyl group indicates that a non-hydrogen substituent is located at the 4 position, and hydrogen is located at the 2-, 3-, 5-, and 6-positions. Reference to a compound or group having substitutions at positions other than those indicated may be referred to using the word "comprising" or some other alternative wording. For example, reference to a phenyl group containing a substituent at the 4 position refers to the 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.

[0032] The term "reaction zone effluent" and its derivatives (e.g., oligomerization reaction zone effluent) generally refers to all materials that exit a reaction zone. The term "reaction zone effluent" and its derivatives may be preceded by other descriptors that qualify the portion of the reaction zone effluent to which reference is being made. For example, the term "reaction zone effluent" refers to all materials that exit the reaction zone (e.g., products and solvent or diluent, among others), while the term "olefin reaction zone effluent" refers to only the olefins in the reaction zone effluent, and the term "oligomer product reaction zone effluent" refers to the oligomer products in the reaction zone effluent.

[0033] The term oligomer refers to products containing 2-20 monomer units. The terms "oligomer product" and "oligomer product effluent" include all oligomer products made by the "oligomerization" process, but exclude other non-oligomeric components in the reaction zone effluent stream, such as unreacted monomer (ethylene), organic reaction medium, and hydrogen, among other components. The term "oligomerization", and its derivatives, refer to processes that produce oligomer products that contain at least 20%, 35%, 50%, or 60% by weight of products containing 2-20 monomer units. In one example, an "oligomerization" process using ethylene as the monomer produces a product mixture that contains at least 20%, 35%, 50%, or 60% by weight of oligomers having 4-40 carbon atoms.

[0034] The Schulz-Flory K value (also called the Schulz-Flory chain growth factor, K value) is calculated by the formula: K = X q+1 / X q where X q+1 is the number of moles of oligomeric product produced having q+1 monomer (e.g., ethylene) units, and X qis the number of moles of oligomeric product produced having q monomer (e.g., ethylene) units. In general, the Schulz-Flory K value can be determined using any two oligomers of oligomeric products that differ by one number of monomer units. However, it will be understood that product isolation and analysis may result in inaccuracies in the distribution of oligomeric products determined using a particular oligomer (e.g., incomplete recovery of gaseous and / or solid products during product isolation). One skilled in the art will recognize such issues and be able to select the appropriate oligomer on which to base the determination of the Schulz-Flory K value.

[0035] The productivity of a catalyst system is defined as grams of product produced per gram (or mole) of zirconium in the catalyst system utilized for oligomerization. The activity of a catalyst system is defined as grams of product produced per gram (or mole) of zirconium per unit of time (e.g., hour) of oligomerization. The productivity and / or activity of a catalyst system can be described in terms of various products of oligomerization and / or components of the catalyst system. For example, in an ethylene oligomerization process utilizing a catalyst system that includes a zirconium compound, the productivity of a catalyst system that may be utilized includes, among other products, (1 g of oligomer product) / (1 g of Zr).

[0036] Unless otherwise specified, the terms "contacting" and "combining," as well as derivatives thereof, may refer to any addition order, sequence, or concentration for contacting or combining two or more components of the disclosed embodiments. The combining or contacting of the oligomerization components may occur in one or more reaction zones under suitable contacting conditions, such as temperature, pressure, contact time, flow rate, etc.

[0037] The terms "catalyst system", "catalyst composition", "catalyst mixture", and the like do not depend on the actual product or composition resulting from 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 complex of the organoaluminum compound and the heteroatom ligand transition metal compound after combining these components. Thus, the terms "catalyst system", "catalyst composition", "catalyst mixture", and the like encompass not only the initial starting components of the composition, but also any product(s) that may result from contacting these initial starting components. The terms "catalyst system", "catalyst composition", "catalyst mixture", and the like may be used interchangeably throughout this disclosure.

[0038] In the present disclosure, a process can have multiple steps or can include features having multiple different elements (e.g., components of a catalyst system or components of an olefin oligomerization process, among other features). These steps and / or elements can be labeled using terms such as first, second, and third, a), b), c), etc., i), ii), iii), etc., (a), (b), (c), etc., and / or series such as (i), (ii), (iii) (among other labeling series) as necessary to provide a label for each process step and / or element. It is to be understood that the numerical or alphabetical order of the labels in a labeling series does not imply a particular order or priority of the process steps in the processes described herein, the feature(s) described herein, and / or the element(s) in the features, unless otherwise specifically indicated or necessitated by other process steps, elements, and / or element characteristics. Additionally, these label series are provided to distinguish between different process steps and / or elements within a feature, and may be used where appropriate and regardless of the label series used for a particular step, element, or feature used in this description, so long as the label series consistently distinguishes between different features, different process steps, and / or different elements of a feature.

[0039] The terms "simultaneously", "contacting simultaneously", "contacting simultaneously" and their derivatives when referring to contacting methods refer to contacting methods in which two or more specified compounds, mixtures, streams, and / or compositions are contacted by flowing them into a common junction, pot, vessel, or reactor at the same time. The terms "substantially simultaneously", "contacting substantially simultaneously", "contacting substantially simultaneously" and their derivatives when referring to contacting methods refer to contacting methods in which two or more specified compounds, mixtures, streams, and / or compositions are contacted such that during contacting of the two or more specified compounds, mixtures, streams, and / or compositions, the two or more specified compounds, mixtures, streams, and / or compositions flow into a common junction, pot, vessel, or reactor at the same time over a period of time during the contacting process. It should be noted that the terms "substantially simultaneously", "contacting substantially simultaneously", "contacting substantially simultaneously" and their derivatives do not imply that the two or more specified compounds, mixtures, streams, and / or compositions are contacted simultaneously throughout the addition of each of the two or more specified compounds, mixtures, streams, and / or compositions. The terms "substantially simultaneously," "contacting substantially simultaneously," and "contacting substantially simultaneously," and derivatives thereof, include scenarios in which the flow of one (or a whole portion) of the specified compounds, mixtures, streams, and / or compositions into a common junction, pot, vessel, or reactor may be initiated before the others, and / or the flow of one (or a whole portion) of the specified compounds, mixtures, streams, and / or compositions into a common junction, pot, vessel, or reactor may be completed, stopped, or discontinued before the other specified compounds, mixtures, streams, and / or compositions.In any aspect and / or embodiment described herein, the terms "simultaneously," "contacting simultaneously," "contacting simultaneously," and derivatives thereof may be modified by including terms providing the amount of each of the specified compounds, mixtures, streams, and / or compositions that may be contacted simultaneously to indicate the scenarios of various degrees of "substantially simultaneously," "contacting substantially simultaneously," "contacting substantially simultaneously," and derivatives thereof. For example, at least 20%, 30%, 40%, 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95% of each of the specified compounds, mixtures, streams, and / or compositions may be "contacted simultaneously" or "contacted simultaneously." In general, the percentage of a specified compound, mixture, stream, and / or composition that may be "contacted simultaneously" or "contacted simultaneously" may be on a weight basis (wt%), a volume basis (vol%), or a molar basis (mol%). Unless otherwise specified, the terms "substantially simultaneously," "contacting substantially simultaneously," "contacting substantially simultaneously," and derivatives thereof, of specified compounds, mixtures, streams, and / or compositions shall mean that at least 50% of each of the specified compounds, mixtures, streams, and / or compositions are "contacted simultaneously" or can be "contacted simultaneously."

[0040] Additionally, it should be noted that the terms "concurrently," "contacting simultaneously," "contacting simultaneously," "contacting substantially simultaneously," "contacting substantially simultaneously," and derivatives thereof, with respect to a method or process of contacting, are distinct from a process or method in which one or more first substances (e.g., compounds, mixtures, streams, and / or compositions) are already present in a pot, vessel, or reactor, and one or more other compounds, mixtures, streams, and / or compositions are added to the pot, vessel, or reactor. In this case, the first substance in the pot, vessel, or reactor does not flow into the pot, vessel, or reactor in parallel with the other compounds, mixtures, streams, and / or compositions and the substances in the pot. Thus, the first substance and the other compounds, mixtures, streams, and / or compositions cannot be said to "contact simultaneously," "contact simultaneously," "contact substantially simultaneously," or "contact substantially simultaneously" with the other component(s).

[0041] The term "contacting" is used herein to describe systems, compositions, processes, and methods of contacting or combining components together in any order, in any manner, and for any length of time, unless otherwise specified. For example, components may be combined by blending or mixing using any suitable technique. As used herein, "contacting" two or more components may result in a reaction product mixture or a reaction mixture.

[0042] As used herein, the term "reactor" refers to a single piece of equipment, such as a vessel in which a reaction takes place, but excludes associated equipment such as piping, pumps, etc. that are external to the vessel. Examples of reactors include stirred tank reactors (e.g., continuous stirred tank reactors), plug flow reactors, or any other type of reactor. As used herein, "reactor system" refers to any piece of equipment in which a desired reaction takes place, including, but not limited to, the reactor, associated piping, associated pumps, and any other associated equipment. Note that in some cases, a "reactor" can also be a "reactor system." For example, in some cases, a polyethylene loop reactor can be considered a reactor system. The terms "reactor" and "reactor system" can be qualified to refer to more specific "reactors" and "reactor systems" by the use of additional qualifying terms. For example, the use of the terms "oligomerization reactor" and "oligomerization reactor system" indicates that the desired reaction in the reactor and / or reactor system is oligomerization.

[0043] As used herein, the term "reaction zone" refers to a portion of a reaction system where all of the necessary reactants and reaction conditions are present so that the reaction can occur at a desired rate. That is, a reaction zone begins where the necessary reactants and reaction conditions are present to maintain the reaction within 25 percent of the average reaction rate, and the reaction system ends where the conditions do not maintain the reaction rate within 25 percent of the average reaction rate (based on the volume average of the reaction rate of the reaction zone). For example, for an ethylene oligomerization process, a reaction zone begins at a point where there is sufficient ethylene and an active catalyst system under sufficient reaction conditions (e.g., temperature and / or pressure, among others) to maintain the production of oligomer products at a desired rate, and the reaction zone ends at a point where the catalyst system is deactivated, there is not enough ethylene to sustain the production of oligomer products, or other reaction conditions (e.g., temperature and / or pressure, among others) are not sufficient to maintain the production of oligomer products or the desired rate of oligomer product production. As used herein, a "reaction zone" may include one or more reactors. The term "reaction zone" may be qualified to refer to a more specific "reaction zone" by the use of additional qualifying terms. For example, use of the term "oligomerization reaction zone" indicates that the desired reaction within the "reaction zone" is oligomerization.

[0044] The term "reaction system" refers to all of the equipment for producing a product. The term "reaction system" includes the reactor, reaction zone, and all associated equipment, associated process lines, and control equipment that can control the reaction by moving the necessary component(s) into and out of the reaction system. As used herein, a "reaction system" can include one or more reactor zones, one or more reactors, and associated equipment for producing a product. The term "reaction system" can be qualified to refer to a more specific "reaction system" by the use of additional qualifying terms. For example, the use of the term "oligomerization reaction system" indicates that the "reaction system" is related to oligomerization.

[0045] All publications and patents mentioned herein are incorporated by reference herein for the purpose of describing and disclosing, e.g., the constructs and methodology described in the publications that might be used in connection with the inventions described herein.

[0046] Detailed Description of the Invention Disclosed herein is a process comprising: a) contacting: i) ethylene; ii) a catalyst system comprising: 1) a zirconium compound; and 2) a hydrocarbyl metal compound; iii) a chain transfer agent comprising: a silyl hydride compound; a compound having a hydrogen-sulfur bond; a compound having a hydrogen-phosphorus bond; or any combination thereof; and iv) optionally an organic reaction medium; and b) forming an oligomeric product in a reaction zone. Disclosed herein is a process comprising: a) contacting: i) ethylene; ii) a catalyst system comprising: 1) a zirconium compound; and 2) a hydrocarbyl metal compound; iii) hydrogen; and iv) optionally an organic reaction medium; and b) forming an oligomeric product in a reaction zone. Further disclosed herein is a process comprising: a) contacting: i) ethylene; ii) a catalyst system comprising: 1) a zirconium compound; and 2) a hydrocarbyl metal compound; iii) a transition metal compound chain transfer agent; and iv) optionally an organic reaction medium; and b) forming an oligomeric product in the reaction zone. Also disclosed herein is a process comprising: a) introducing to a reaction zone: i) ethylene; ii) a catalyst system or catalyst system components comprising: 1) a zirconium compound; and 2) a hydrocarbyl metal compound; iii) a chain transfer agent comprising: a silyl hydride compound, a compound having a hydrogen sulfur bond, a compound having a hydrogen phosphorus bond, or any combination thereof; and iv) optionally an organic reaction medium; and b) forming an oligomeric product in the reaction zone. Also disclosed herein is a process comprising: a) introducing to a reaction zone: i) ethylene; ii) a catalyst system or catalyst system components comprising: 1) a zirconium compound; and 2) a hydrocarbyl metal compound; iii) hydrogen; and iv) optionally an organic reaction medium; and b) forming an oligomeric product in the reaction zone.Further disclosed herein is a process comprising: a) introducing to a reaction zone: i) ethylene; ii) a catalyst system or catalyst system components comprising: 1) a zirconium compound; and 2) a hydrocarbyl metal compound; iii) a transition metal compound chain transfer agent; and iv) optionally an organic reaction medium; and b) forming an oligomeric product in the reaction zone.

[0047] In one embodiment, the oligomeric product can be formed, the reaction zone can have, or the reaction zone can operate under conditions that allow the oligomeric product to be formed. In general, the catalyst system, the elements of the catalyst system (e.g., zirconium compounds, hydrocarbyl metal compounds, and any other catalyst system elements described herein), the chain transfer agent, hydrogen, transition metal compound chain transfer agent, optional organic reaction medium, the oligomeric product, the conditions under which the oligomeric product is formed, the conditions the reaction zone can have, the conditions under which the reaction can operate, and / or any other catalyst system and / or process elements described herein are independent elements of the processes described herein and are described herein independently. These independently described elements can be utilized in any combination without limitation to further describe the processes provided herein.

[0048] In one embodiment, the zirconium compound of the catalyst system has 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 It may have the formula ZrX 1 mY 1 q , ZrX 1 m , or ZrY 1 q X of the zirconium compound having 1 , Y 1 , m, and q are independent elements of the zirconium compound and are independently described herein. 1 , Y 1 The independent descriptions of X, m, and q may be utilized in any combination without limitation to further describe the zirconium compound. 1 may independently be a halide. In one embodiment, each Y 1 may be independently a hydrocarboxyte, a dihydrocarbyl azanide, a hydrocarbyl carboxylate, a hydrocarbyl sulfonate, or a β-diketonate; alternatively a hydrocarboxyte, a hydrocarbyl carboxylate, a hydrocarbyl sulfonate, or a β-diketonate; alternatively a hydrocarboxyte, a hydrocarbyl carboxylate, or a hydrocarbyl sulfonate; alternatively a hydrocarbyl carboxylate or a hydrocarbyl sulfonate; alternatively a hydrocarboxyte; alternatively a dihydrocarbyl azanide; alternatively a hydrocarbyl carboxylate; alternatively a hydrocarbyl sulfonate; or alternatively a β-diketonate. In one embodiment, m may be in the range of 0 to 4; alternatively in the range of 2 to 4; alternatively 2; alternatively 3; or alternatively 4. In one embodiment, q may be in the range of 0 to 4; alternatively in the range of 2 to 4; alternatively 2; alternatively 3; or alternatively 4. Alternatively, m+q is 2; alternatively, 3; or alternatively, 4.

[0049] Zirconium Compound X 1 Each halide that may be utilized as may independently be a fluoride, chloride, bromide, or iodide; alternatively, chloride, bromide, or iodide; alternatively, chloride; alternatively, bromide; or alternatively, iodide.

[0050] Zirconium Compound Y 1 The hydrocarboxylates that can be used are C1-C 20 , C1~C 10 or a C1-C5 hydrocarboxylate. 1 is the formula - OR 2 The formula - OR 2 R of a hydrocarboxylate having 2 is C1~C 20 , C1~C 10 or a C1 to C5 hydrocarbyl group. - OR 2 R of a hydrocarboxylate having 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 is C1-C 20 , C1~C 10 or a C1 to C5 alkyl group. 2 Cycloalkyl groups are C4-C 20 , C5~C 15 , or C5~C 10 R may be a cycloalkyl group. 2 The aryl group is C6-C 20 , C6~C 15 Or C6~C 10 R may be an aryl group. 2 Aralkyl groups are C7-C 20 , C7~C 15 Or C7~C 10 In one embodiment, the formula - OR 2 R of a hydrocarboxylate having 2The group can be methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, phenyl, toluyl, xylyl, benzyl, or ethylphenyl; alternatively, methyl, ethyl, propyl, butyl, or pentyl; alternatively, cyclopentyl or cyclohexyl; alternatively, phenyl, toluyl, or xylyl; or alternatively, benzyl or ethylphenyl. In one embodiment, each hydrocarboxylate Y of the zirconium compound can be 1 may be methoxide, ethoxide, propoxide, butoxide, pentoxide, cyclopentoxide, cyclohexoxide, phenoxide, toroxide, xyloxide, benzoxide, or ethylphenoxide; alternatively, methoxide, ethoxide, propoxide, butoxide, or pentoxide; alternatively, cyclopentoxide or cyclohexoxide; alternatively, phenoxide, toroxide, or xyloxide; or alternatively, benzoxide or ethylphenoxide.

[0051] Zirconium Compound Y 1 The hydrocarbyl carboxylates that can be used are C1-C 20 , C1~C 15 , C1~C 10 or a C1-C5 hydrocarbyl carboxylate. 1 The hydrocarbyl carboxylates which may be utilized are represented by the formula - OC(=O)R 3 The zirconium compound Y 1 The hydrocarbyl sulfonates that can be used are C1-C 20 , C1~C 10 or C1-C5 hydrocarbyl sulfonate. 1 The hydrocarbyl sulfonates which may be utilized are of the formula - OS(=O)2R 3 The formula - OC(=O)R 3 and / or hydrocarboxylates having the formula- OS(=O)2R 3 R of hydrocarbyl sulfonates having 3 is C1~C 20 , C1~C 15 , C1~C 10 or a C1 to C5 hydrocarbyl group. - OC(=O)R 3 and / or hydrocarboxylates having the formula - OS(=O)2R 3 R of hydrocarbyl sulfonates having 3 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 3 The alkyl group is C1-C 20 , C1~C 10 or a C1 to C5 alkyl group. 3 Cycloalkyl groups are C4-C 20 , C5~C 15 , or C5~C 10 R may be a cycloalkyl group. 3 The aryl group is C6-C 20 , C6~C 15 Or C6~C 10 R may be an aryl group. 3 Aralkyl groups are C7-C 20 , C7~C 15 Or C7~C 10 It may be an aralkyl group. - OC(=O)R 3 and / or hydrocarboxylates having the formula - OS(=O)2R 3 R of hydrocarbyl sulfonates having 3The group can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, cyclopentyl, cyclohexyl, phenyl, toluoyl, xylyl, benzyl, or ethylphenyl; alternatively, methyl, ethyl, propyl, butyl, pentyl, hexyl, or heptyl; alternatively, cyclopentyl or cyclohexyl; alternatively, phenyl, toluoyl, or xylyl; or alternatively, benzyl or ethylphenyl. Y of the zirconium compound 1 Each hydrocarboxylate that may be utilized as Y may be acetate, propanoate, butanoate, pentonate, hexanoate, heptanoate, octanoate, cyclopentyl acetate, cyclohexyl acetate, benzoate, methyl benzoate, dimethyl benzoate, phenyl acetate, or phenyl propanoate; alternatively acetate, propanoate, butanoate, pentonate, hexanoate, heptanoate, or octanoate; alternatively cyclopentyl acetate or cyclohexyl acetate; alternatively benzoate, methyl benzoate, or dimethyl benzoate; or alternatively phenyl acetate or phenyl propanoate. Y of the zirconium compound 1 Each hydrocarbyl sulfonate that may be utilized may be methyl sulfonate, ethyl sulfonate, propyl sulfonate, butyl sulfonate, pentyl sulfonate, hexyl sulfonate, heptyl sulfonate, cyclopentyl sulfonate, cyclohexyl sulfonate, phenyl sulfonate, toluyl sulfonate, xylyl sulfonate, benzyl sulfonate, or ethyl phenyl sulfonate; alternatively, methyl sulfonate, ethyl sulfonate, propyl sulfonate, butyl sulfonate, pentyl sulfonate, hexyl sulfonate, or heptyl sulfonate; alternatively, cyclopentyl sulfonate or cyclohexyl sulfonate; alternatively, phenyl sulfonate, toluyl sulfonate, or xylyl sulfonate.

[0052] Zirconium Compound Y 1 The dihydrocarbyl azanides that can be used are C2-C 30 , C2~C 20 , or C2~C 15 The zirconium compound Y may be a dihydrocarbyl azanide. 1 The dihydrocarbyl azanide which may be utilized is represented by the formula - N(R 4 In some embodiments, the compound may have the formula - N(R 4 Each R of the dihydrocarbyl azanide having 4 The hydrocarbyl groups may independently 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. Each R 4 The alkyl group is independently C1 to C 15 , C1~C 10 or a C1 to C5 alkyl group. 4 The cycloalkyl groups are independently C4 to C 15 , or C5~C 15 Each R may be a cycloalkyl group. 4 The aryl groups are independently C6 to C 20 , C6~C 15 Or C6~C 10 Each R may be an aryl group. 4 The aralkyl groups are independently C7 to C 20 , C7~C 15 Or C7~C 10 It may be an aralkyl group. - N(R 4 Each R of the dihydrocarbyl azanide having 4The hydrocarbyl groups may be independently methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, phenyl, toluoyl, xylyl, benzyl, or ethylphenyl; alternatively, methyl, ethyl, propyl, butyl, or pentyl; alternatively, cyclopentyl or cyclohexyl; alternatively, phenyl, toluoyl, or xylyl; or alternatively, benzyl or ethylphenyl. In one embodiment, the two R of the dihydrocarbyl azanide are 4 The groups are bonded to a hydrocarbylene group L 1 In such an embodiment, the linked R 4 The group, i.e., L 1 forms a ring or ring system that includes the azanide nitrogen atom. 1 The hydrocarbylene group is C2-C 30 , C2~C 20 , or C2~C 10 or alternatively, L 1 is C2~C 30 , C2~C 20 , or C2~C 10 In one embodiment, L may be an alkylene group. 1 can be a propylene group, a butylene group, a hexylene group, or a heptalene group. In one embodiment, Y of the zirconium compound 1 Each dihydrocarbyl azanide that may be utilized as may be dimethyl azanide, diethyl azanide, dipropyl azinide, pyrrolidine azanide, piperidine azanide, diphenyl azanide, ditoluyl azanide, dixyl azanide, or dibenzyl azanide; alternatively, dimethyl azanide, diethyl azanide, or dipropyl azinide; alternatively, pyrrolidine azanide or piperidine azanide; alternatively, diphenyl azanide, ditoluyl azanide, dixyl azanide; or alternatively, dibenzyl azanide.

[0053] Zirconium Compound Y 1 The β-diketonates that can be used are C5-C 20, C5~C 15 , or C5~C 10 In one embodiment, each β-diketonate can be independently an acetylacetonate (i.e., 2,4-pentanedionate) or a benzoylacetonate; alternatively, an acetylacetonate; or alternatively, a benzoylacetonate.

[0054] In one embodiment, the zirconium compound of the catalyst system may be a zirconium compound that has been at least partially hydrolyzed by contacting the zirconium compound with water (referred to herein as a partially hydrolyzed zirconium compound). In some embodiments, the partially hydrolyzed zirconium compound comprises, consists essentially of, or consists of a zirconium compound (any of those described herein) that has been contacted with water. In some embodiments, the zirconium compound of the partially hydrolyzed zirconium compound has the formula ZrX 1 m Y 1 q wherein each X 1 may independently be a halide (any of those disclosed herein); Y 1 is the formula - OR 2 (In the formula, R 2 is any of the R 2 a hydrocarbyl group (which may be general or specific) or - OC(=O)R 3 (In the formula, R 3 is any of the R 3 Hydrocarbyl groups (which may be general or specific), m may range from 0 to 4, q may range from 0 to 4, and m+q may be 4. In some embodiments, m may range from 0 to 3. In one embodiment, the molar ratio of water to zirconium of the zirconium compound may range from 0.01:1 to 3:1, 0.1: to 2:1, 0.25:1 to 1.75:1.

[0055] In a non-limiting embodiment, the zirconium compound of the catalyst system has the formula ZrX 1 m Y 1 q wherein each X 1 may independently be a halide (any of those disclosed herein); Y 1 is the formula - OC(=O)R 3 or - OS(=O)2R 3 (In the formula, R 3 is any of the R 3 In another non-limiting embodiment, the zirconium compound of the catalyst system can have a hydrocarbyl group (which can be 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 embodiment, the zirconium compound of the catalyst system can have a formula of ZrX 1 m wherein each X 1 can independently be a halide (any of those disclosed herein) and m can be an integer from 2 to 4, alternatively 2; or alternatively 4. In yet another non-limiting embodiment, the zirconium compound has the formula ZrY 1 q wherein each Y 1 are, independently, - OR 2 (In the formula, R 2 is C1~C 10 alkyl group) or - OC(=O)R 3 (In the formula, R 3 is C1~C 10 is an alkyl group), and q is an integer from 2 to 4, alternatively 2; alternatively 4. In another non-limiting embodiment, the zirconium compound of the catalyst system has the formula ZrX 1 m Y 1 q wherein each X 1 can independently be a halide (any of those described herein); Y 1 is the formula - OR 2 (In the formula, R 2is any of the R 2 which may be a hydrocarbyl group) or may have the formula - OC(=O)R 3 (In the formula, R 3 is any of the R 3 Hydrocarbyl groups (which may be general or specific), m may range from 0 to 4, q may range from 0 to 4, and m+q may be 4. In a further non-limiting embodiment, the zirconium compound of the catalyst system may be a partially hydrolyzed zirconium compound, the zirconium compound having the formula ZrX 1 m Y 1 q wherein each X 1 can independently be a halide (any of those described herein); Y 1 is the formula - OR 2 (In the formula, R 2 is any of the R 2 which may be a hydrocarbyl group) or may have the formula - OC(=O)R 3 (In the formula, R 3 is any of the R 3 hydrocarbyl groups (which may be general or specific), m may range from 0 to 4, q may range from 0 to 4, m+q may be 4, and the molar ratio of water to zirconium of the zirconium compound may range from 0.1: to 2:1.

[0056] Non-limiting exemplary zirconium compounds that may be utilized in the catalyst systems for the processes described herein include 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(O C4H9)3Cl, Zr(OC4H9)2Cl2, Zr(OC6H5)4, Zr(OC6H5)3Cl, Zr(OC6H5)2Cl2, Zr(OCOCH3)4, Zr(OCOCH3)3Cl, Z r(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, Z r(OCOC6H5)2Cl2, Zr(OSO3CH3)4, Zr(OSO3C2H5)4, Zr(OSO3C3H7)4, Zr(OSO3C4H9)4, Zr(OSO3C6H5)4, Zr(H 3CCOCHCOCH3)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 embodiments, the zirconium compound is 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(OC OC3H7)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 embodiments, the zirconium compound may comprise, consist essentially of, or be ZrCl4;Alternatively, it may comprise, consist essentially of, or be 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, it may comprise, consist essentially of, or be Zr(OSO3C6H5)4;

[0057] Generally, the hydrocarbyl metal compound can be any hydrocarbyl metal compound capable of forming oligomeric products in conjunction with the zirconium compound when contacted with ethylene. The hydrocarbyl metal compound of the catalyst system can comprise, consist essentially of, or be any heteroleptic or homoleptic hydrocarbyl metal compound. In one embodiment, the hydrocarbyl metal is represented by the formula (R 1 ) a M(X 2 ) b wherein R 1 is a hydrocarbyl group, and X 2is a halide or hydrocarboxylate, M is a metal, a ranges from 1 to 4, b ranges from 0 to 3, and a+b is equal to the oxidation state of the metal M. In one embodiment, the metal of the hydrocarbyl metal compound may comprise, consist essentially of, or consist of a metal of Group 1, 2, 11, 12, 13, or 14; alternatively, a metal of Group 1 or 2; alternatively, a metal of Group 12, 13, or 14; or alternatively, a metal of Group 12 or 13; alternatively, a metal of Group 1; alternatively, a metal of Group 2; alternatively, a metal of Group 12; or alternatively, a metal of Group 13. In some embodiments, the metal of the hydrocarbyl metal compound may comprise, consist essentially of, or be 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.

[0058] The hydrocarbyl group of the hydrocarbyl metal compound is C1-C 20 , C1~C 10 In one embodiment, 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-C 20 , C1~C 10 or a C1 to C6 alkyl group. The cycloalkyl group of the hydrocarbyl metal compound may be a C4 to C 20 , C4~C 15 , or C4~C 10 The aryl group of the hydrocarbyl metal compound may be a C6-C 20 , C6~C 15, or C6~C 10 The aralkyl group of the hydrocarbyl metal compound may be a C7-C 20 , C7~C 15 , or C7~C 10 It may be an aralkyl group.

[0059] In any of the embodiments disclosed herein, the hydrocarbyl metal compound of the catalyst system may be an alkyl metal compound (i.e., R 1 In one embodiment, the alkylmetal compound of the catalyst system can be an alkyllithium (R 1 Li), alkyl sodium (R 1 Na), alkyl potassium (R 1 K), alkyl magnesium compounds (R 1 2Mg or R 1 MgX 2 ), alkyl copper compounds (R 1 2Cu or R 1 CuX 2 ), alkyl zinc compounds (R 1 2Zn or R 1 ZnX 2 ), alkyl tin 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 1 5); Alternatively, alkyl lithium (R 1Li), alkyl sodium (R 1 Na), alkyl potassium (R 1 K), alkyl magnesium compounds (R 1 2Mg or R 1 MgX 2 ), alkyl zinc compounds (R 1 2Zn or R 1 ZnX 2 ), or alkylaluminum compounds (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, alkyl lithium (R 1 Li), alkyl sodium (R 1 Na), or alkyl potassium (R 1 K); alternatively, alkyl lithium (R 1 Li); alternatively, alkyl sodium (R 1 Na); alternatively, alkyl magnesium compounds (R 1 2Mg or R 1 MgX 2 Alternatively, alkyl zinc compounds (R 1 2Zn or R 1 ZnX 2 Alternatively, alkyl tin 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 alternatively, alkylaluminum compounds (AlX 2 2R 1 ,AlX 2 R 1 2. AlR 13. Al2X 2 5R 1 , Al2X 2 3R 1 3, or Al2X 2 R 1 5). In some embodiments, the alkylmetal compound of the catalyst system may comprise, consist essentially of, or be an alkyllithium (R 1 Li), alkyl sodium (R 1 Na), alkyl potassium (R 1 K), alkyl magnesium halide (R 1 MgX 2 ), dialkyl magnesium (R 1 2Mg), alkyl copper halide (R 1 CuX 2 ), dialkyl copper (R 1 2Cu), alkyl zinc halide (R 1 ZnX 2 ), dialkyl zinc (R 1 2Zn), alkyl tin halide (R 1 3SnX 2 , R 1 2SnX 2 2. R 1 2SnX 2 3. 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) Alkyl aluminum sesquihalide (Al2X 2 3R 1 3), alkylaluminum dialkoxide (AlX 2 2R 1 ), dialkylaluminum alkoxide (AlX 2 R 1 2), or aluminoxanes; alternatively, alkyllithium (R1 Li), alkyl sodium (R 1 Na), alkyl potassium (R 1 K), dialkyl magnesium (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 (AlX 2 3R 1 3); Alternatively, alkyl lithium (R 1 Li), alkyl sodium (R 1 Na), alkyl potassium (R 1 K); alternatively, alkyl magnesium halides (R 1 MgX 2 ) or dialkylmagnesium (R 1 2Mg; alternatively, dialkyltin (R 1 2Sn), tetraalkyltin (R 1 4Sn); alternatively, alkyl zinc compounds (R 1 2Zn or R 1 ZnX 2 ) and alkylaluminum compounds (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 dihalides (AlX 2 2R 1 ), dialkylaluminum halide (AlX 2 R 1 2), alkylaluminum sesquihalide (Al2X 2 3R 1 3), Trialkylaluminum (AlR1 3), or aluminoxanes; alternatively, alkyllithium (R 1 Li); alternatively, alkyl sodium (R 1 Na); alternatively, alkyl potassium (R 1 K); alternatively, alkyl magnesium halides (R 1 MgX 2 Alternatively, dialkylmagnesium (R 1 2Mg; alternatively, alkyl zinc halide (R 1 ZnX 2 Alternatively, dialkyl zinc (R 1 2Zn; alternatively, alkylaluminum dihalides (AlX 2 2R 1 Alternatively, dialkylaluminum halides (AlX 2 R 1 2); Alternatively, alkylaluminum sesquihalides (AlX 2 3R 1 3); Alternatively, alkylaluminum dialkoxides (AlX 2 2R 1 Alternatively, dialkylaluminum alkoxides (AlX 2 R 1 2); Alternatively, trialkylaluminum (AlR 1 3); or alternatively may comprise, consist essentially of, or be an aluminoxane.

[0060] Generally, each halide of any hydrocarbyl metal halide (or alkyl metal halide) can be any halide. Each halide of any alkyl metal halide disclosed herein can be, independently, a fluoride, a chloride, a bromide, or an iodide; alternatively, a chloride, a bromide, or an iodide; alternatively, a fluoride; alternatively, a chloride; alternatively, a bromide; or alternatively, an iodide.

[0061] Each alkyl group of any alkylmetal compound disclosed herein is independently C1 to C 20 , C1~C10 or a C1-C6 alkyl group. In one embodiment, each alkyl group of any alkyl metal compound disclosed herein may be, independently, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group; alternatively, a methyl group, an ethyl group, a butyl group, a hexyl group, or an octyl group. In some embodiments, each alkyl group(s) of any alkyl metal compound disclosed herein may be, independently, a methyl group, an ethyl group, a n-propyl group, a n-butyl group, an iso-butyl group, a n-hexyl group, or a n-octyl group; alternatively, a methyl group, an ethyl group, a n-butyl group, or an iso-butyl group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, a n-propyl group; alternatively, a n-butyl group; alternatively, an iso-butyl group; alternatively, a n-hexyl group; or alternatively, a n-octyl group.

[0062] Each alkoxide of any alkyl metal alkoxide disclosed herein independently comprises a C1-C 20 , C1~C 10 or a C1-C6 alkoxide. In one embodiment, each alkoxide of any alkyl metal alkoxide disclosed herein can be, independently, a methoxide, ethoxide, propoxide, butoxide, pentoxide, hexoxide, heptoxide, or octoxide; alternatively, a methoxide, ethoxide, butoxide, hexoxide, or octoxide. In some aspects, each alkoxide group of any alkyl metal alkoxide disclosed herein can independently be methoxide, ethoxide, n-propoxide, n-butoxide, iso-butoxide, n-hexoxide, or n-octoxide; alternatively, methoxide, ethoxide, n-butoxide, or iso-butoxide; alternatively, methoxide; alternatively, ethoxide; alternatively, n-propoxide; alternatively, n-butoxide; alternatively, iso-butoxide; alternatively, n-hexoxide; or alternatively, n-octoxide.

[0063] Hydrocarbyl lithium compounds (or alkyl lithium compounds) which may be utilized as the hydrocarbyl metal compounds may comprise, consist essentially of, or be methyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium; alternatively, methyl lithium; alternatively, n-butyl lithium; alternatively, sec-butyl lithium; or alternatively, tert-butyl lithium. Hydrocarbyl sodium compounds (or alkyl sodium compounds) which may be utilized as the hydrocarbyl metal compounds may comprise, consist essentially of, or be methyl sodium, n-butyl sodium, sec-butyl sodium, tert-butyl sodium; alternatively, methyl sodium; alternatively, n-butyl sodium; alternatively, sec-butyl sodium; or alternatively, tert-butyl sodium. Hydrocarbyl potassium compounds (or alkyl potassium compounds) which may be utilized as the hydrocarbyl metal compound may comprise, consist essentially of, or be methyl potassium, n-butyl potassium, sec-butyl potassium, tert-butyl potassium; alternatively, methyl potassium; alternatively, n-butyl potassium; alternatively, sec-butyl potassium; or alternatively, tert-butyl potassium.

[0064] Hydrocarbyl magnesium halides (or alkyl magnesium halides) that may be utilized as the hydrocarbyl metal compound may comprise, consist essentially of, or be methyl magnesium halides, ethyl magnesium halides, propyl magnesium halides, or butyl magnesium halides; alternatively, methyl magnesium halides; alternatively, ethyl magnesium halides; alternatively, propyl magnesium halides; alternatively, butyl magnesium halides. Dihydrocarbyl magnesium (or dialkyl magnesium) that may be utilized as the hydrocarbyl metal compound may comprise, consist essentially of, or be dimethyl magnesium, diethyl magnesium, dipropyl magnesium, or dibutyl magnesium; alternatively, dimethyl magnesium; alternatively, diethyl magnesium; alternatively, dipropyl magnesium; or alternatively, dibutyl magnesium.

[0065] The hydrocarbyl zinc halides which may be utilized as the hydrocarbyl metal compound are methyl zinc halides, ethyl zinc halides, propyl zinc halides, butyl zinc halides, pentyl zinc halides, hexyl zinc halides, cyclopentyl zinc halides, cyclohexyl zinc halides, phenyl zinc halides, touryl zinc halides, xylyl zinc halides, or benzyl zinc halides; alternatively, methyl zinc halides, ethyl zinc halides, propyl zinc halides, butyl zinc halides, pentyl zinc halides, or hexyl zinc halides; alternatively, cyclopentyl zinc halides or cyclohexyl zinc halides; Alternatively, it may comprise, consist essentially of, or be a phenyl zinc halide, a touryl zinc halide, or a xylyl zinc halide; alternatively, a methyl zinc halide; alternatively, an ethyl zinc halide; alternatively, a propyl zinc halide; alternatively, a butyl zinc halide; alternatively, a pentyl zinc halide; alternatively, a hexyl zinc halide; alternatively, a cyclopentyl zinc halide; alternatively, a cyclohexyl zinc halide; alternatively, a phenyl zinc halide; alternatively, a touryl zinc halide; alternatively, a xylyl zinc halide; or alternatively, a benzyl zinc halide.Dihydrocarbyl zincs which may be utilized as the hydrocarbyl metal compound include dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc, dipentyl zinc, dihexyl zinc, dicyclopentyl zinc, dicyclohexyl zinc, diphenyl zinc, ditouryl zinc, dixylyl zinc, or dibenzyl zinc; alternatively, dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc, dipentyl zinc, or dihexyl zinc; alternatively, dicyclopentyl zinc or dicyclohexyl zinc; alternatively, diphenyl zinc, ditouryl zinc, ditouryl zinc, or dibenzyl zinc. Alternatively, it may comprise, consist essentially of, or be dibenzyl zinc; alternatively, dimethyl zinc; alternatively, diethyl zinc; alternatively, dipropyl zinc; alternatively, dibutyl zinc; alternatively, dipentyl zinc; alternatively, dihexyl zinc; alternatively, dicyclopenyl zinc; alternatively, dicyclohexyl zinc; alternatively, diphenyl zinc; alternatively, ditouryl zinc; alternatively, dixylyl zinc; or alternatively, dibenzyl zinc.

[0066] In one embodiment, the hydrocarbyl metal compound in the catalyst system can be an alkylaluminum compound. Generally, hydrocarbyl aluminum compounds that can be utilized as the hydrocarbyl metal compound in the catalyst system are represented by 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 It may have the formula AlX 2 3-n R 1 n and Al2X 2 6-q- R 1 q X2 , R 1 , n, and q are of the formula AlX 2 3-n R 1 n and Al2X 2 6-q- R 1 q and are independently described herein. 2 , R 1 Independent descriptions of n, q and n are of the formula AlX 2 3-n R 1 n or Al2X 2 6-q- R 1 q can be used in any combination without limitation to describe hydrocarbyl aluminum compounds having the formula AlX 2 3-n R 1 n and Al2X 2 6-q R 1 q In each R 1 are independently 20 , C1~C 10 or a C1-C6 hydrocarbyl group; or alternatively a C1-C 20 , C1~C 10 or a C1-C6 alkyl group (in which case the hydrocarbylaluminum compound may be referred to as an alkylaluminum compound). 1may be independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; alternatively, methyl, ethyl, butyl, hexyl, or octyl; alternatively, methyl, ethyl, n-propyl, n-butyl, iso-butyl, n-hexyl, or n-octyl; alternatively, methyl, ethyl, n-butyl, or iso-butyl; alternatively, methyl; alternatively, ethyl; alternatively, n-propyl; alternatively, n-butyl; alternatively, iso-butyl; alternatively, n-hexyl; or alternatively, n-octyl. Formula AlX 2 3-n R 1 n and Al2X 2 6-q R 1 q In each X 2 may be, independently, fluoride, chloride, bromide, or iodide; alternatively, chloride, bromide, or iodide; alternatively, chloride; alternatively, bromide; or alternatively, iodide. Formula AlX 2 3-n R 1 n and Al2X 2 6-q R 1 q In the formula AlX, n can be in the range of 1 to 3; alternatively in the range of 1 to 2; alternatively 1; alternatively 2, or alternatively 3. 2 3-n R 1 n and Al2X 2 6-q R 1 q In the formula, q can be 1, 3, or 5; alternatively, 1; alternatively, 3; or alternatively, 5. In one embodiment, the formula AlX 2 3-n R 1 n or Al2X 2 6-q- R 1 qThe hydrocarbylaluminum (or alkylaluminum) compound having the formula (I) can comprise, consist essentially of, or be a trialkylaluminum, an alkylaluminum halide, or any combination thereof; alternatively, a trialkylaluminum; or alternatively, an alkylaluminum halide. The trialkylaluminum compound may comprise, consist essentially of, or be trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, or any combination thereof; alternatively, trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof; alternatively, triethylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or any combination thereof; alternatively, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, tri-n-octylaluminum, or any combination thereof; alternatively, trimethylaluminum; alternatively, triethylaluminum; alternatively, tripropylaluminum; alternatively, tri-n-butylaluminum; alternatively, tri-isobutylaluminum; alternatively, trihexylaluminum; or alternatively, tri-n-octylaluminum.The alkylaluminum halide may comprise, consist essentially of, or be diethylaluminum chloride, diethylaluminum bromide, ethylaluminum dichloride, ethylaluminum sesquichloride, or any combination thereof; alternatively, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, or any combination thereof; alternatively, diethylaluminum chloride; alternatively, diethylaluminum bromide; alternatively, ethylaluminum dichloride; or alternatively, ethylaluminum sesquichloride.

[0067] In some embodiments, hydrocarbylaluminum (or alkylaluminum) compounds that may be utilized as the hydrocarbyl metal compound in the catalyst system are represented by 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 ), wherein X 2 At least a portion (or all) of the formula AlX may be an alkoxide, a carboxylate, a dihydrocarbyl azanide, or a carboxamide anion; alternatively, an alkoxide; alternatively, a carboxylate; alternatively, a dihydrocarbyl azanide; or alternatively, a carboxamide anion. 2 3-n R 1 n and Al2X 2 6-q- R 1 q R 1, n, and q are as described herein as elements of the hydrocarbylaluminum (or alkylaluminum) compound; R 1 These independent descriptions of n, q and n form the formula AlX 2 3-n R 1 n or Al2X 2 6-q- R 1 q (In the formula, X 2 may be utilized in any combination without limitation to describe hydrocarbylaluminum compounds having at least a portion (or all) of an alkoxide, carboxylate, dihydrocarbyl azanide, and / or carboxamide anion. 2 If only a portion (or all) of X is an alkoxide, carboxylate, dihydrocarbyl azanide, and / or carboxamide anion, 2 The remainder of the formula AlX may be a halide; alternatively a fluoride, chloride, bromide, or iodide; alternatively a chloride, bromide, or iodide; alternatively a chloride; alternatively a bromide; or alternatively an iodide. 2 3-n R 1 n and / or Al2X 2 6-q- R 1 q (In the formula, X 2 Particular alkoxides of the hydrocarbylaluminum (or alkylaluminum) compounds having at least a C1-C 20 , C1~C 10or a C1-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, iso-butoxide, n-hexoxide, or n-octoxide; alternatively, methoxide, ethoxide, n-butoxide, or iso-butoxide; alternatively, methoxide; alternatively, ethoxide; alternatively, n-propoxide; alternatively, n-butoxide; alternatively, iso-butoxide; alternatively, n-hexoxide; or alternatively, n-octoxide. 2 3-n R 1 n and / or Al2X 2 6-q- R 1 q (In the formula, X 2 Particular carboxylates of the hydrocarbylaluminum (or alkylaluminum) compounds having at least a C2 to C6 alkyl group, at least some (or all) of which may be carboxylates, are 20 , C2~C 10 or a C2-C6 carboxylate; alternatively an acetate, propanoate, butanoate, pentonate, hexanoate, heptanoate, octanoate, benzoate, methylbenzoate, dimethylbenzoate, or phenylacetate; alternatively an acetate, propanoate, butanoate, pentonate, hexanoate, heptanoate, or octanoate; alternatively a benzoate, methylbenzoate, or dimethylbenzoate; or alternatively a phenylacetate. Formula AlX 2 3-n R 1 n and / or Al2X 2 6-q- R 1 q (In the formula, X 2Particular dihydrocarbyl azanides of the hydrocarbylaluminum (or alkylaluminum) compounds having at least a portion (or all) of 20 , C2~C 10 or C2-C6 dihydrocarbyl azanide; alternatively dimethyl azanide, diethyl azanide, dipropyl azanide, pyrrolidine azanide, piperidine azanide, diphenyl azanide, ditoluyl azanide, dixyl azanide, or dibenzyl azanide; alternatively dimethyl azanide, diethyl azanide, or dipropyl azanide; alternatively pyrrolidine azanide or piperidine azanide; alternatively diphenyl azanide, ditoluyl azanide, dixyl azanide; or alternatively dibenzyl azanide. Formula AlX 2 3-n R 1 n and / or Al2X 2 6-q- R 1 q (In the formula, X 2 Particular carboxamide anions of hydrocarbylaluminum (or alkylaluminum) compounds having at least some (or all) of the following may be carboxamide anions: 20 , C2~C 10 or a C2-C6 carboxylamide 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. Formula AlX 23-n R 1 n and / or Al2X 2 6-q- R 1 q X of a hydrocarbylaluminum (or alkylaluminum) compound having the formula 2 When at least a portion (or all) of the anions are alkoxide, carboxylate, dihydrocarbyl azanide, and / or carboxamide anions, the molar ratio of alkoxide, carboxylate, azanide, and / or amide anions 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.

[0068] The hydrocarbylaluminum (or alkylaluminum) compound has the formula AlX 2 3-n R 1 n or Al2X 2 6-q- R 1 q X 2 In embodiments where at least a portion (or all) of is an alkoxide, carboxylate, dihydrocarbyl azanide, and / or carboxamide anion, the formula AlX 2 3-n R 1 n or Al2X 2 6-q- R 1 q These in situ generated hydrocarbylaluminum (or alkylaluminum) compounds are prepared by reacting the appropriate alcohols, carboxylic acids or simple esters of carboxylic acids, amines, and / or amides with the formula AlX 2 3-n R 1 n or Al2X 2 6-q- R 1 qwherein i) each R 1 are independently represented by the formula AlX 2 3-n R 1 n or Al2X 2 6-q- R 1 q Any of the hydrocarbyl or alkyl aluminum compounds described herein having the formula 1 ii) each X 2 are independently represented by the formula AlX 2 3-n R 1 n or Al2X 2 6-q- R 1 q and iii) n can be any halide described herein for the hydrocarbylaluminum (or alkylaluminum) compounds having the formula AlX 2 3-n R 1 n or Al2X 2 6-q- R 1 q and iv) q can have any value 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 qcan take any of the values ​​described herein for the hydrocarbylaluminum (or alkylaluminum) compounds having the formula: Alcohols that can be utilized to generate the in situ generated hydrocarbylaluminum (or alkylaluminum) compounds can be methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, or octanol; alternatively, methanol, ethanol, butanol, hexanol, or octanol; alternatively, methanol, ethanol, n-propanol, n-butanol, iso-butanol, n-hexanol, or n-octanol; alternatively, methanol, ethanol, n-butanol, or iso-butanol; alternatively, methanol; alternatively, ethanol; alternatively, n-propanol; alternatively, n-butanol; alternatively, iso-butanol; alternatively, n-hexanol; or alternatively, n-octanol. Carboxylic acids or carboxylic acid simple esters that can be utilized to generate the in situ generated hydrocarbylaluminum (or alkylaluminum) compounds can be C2-C 20 , C2~C 10 or C2-C6 carboxylic acids; alternatively acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, benzoic acid, methylbenzoic acid, dimethylbenzoic acid, or phenylacetic acid; alternatively acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, or octanoic acid; alternatively benzoic acid, methylbenzoic acid, or dimethylbenzoic acid; or alternatively phenylacetic acid. Generally, the alcohol of the alcohol-derived portion of the simple ester of the carboxylic acid may be methanol and / or ethanol, alternatively methanol, or ethanol. Amines that may be utilized to generate the in situ generated hydrocarbylaluminum (or alkylaluminum) compounds with dihydrocarbyl azanides include C2-C 20 , C2~C 10Alternatively, it may be dimethylamine, diethylamine, dipropylamine, pyrrolidine, piperidine, diphenylamine, ditoluylamine, dixylamine, or dibenzylamine; alternatively, dimethylamine, diethylamine, or dipropylamine; alternatively, pyrrolidine or piperidine; alternatively, diphenylamine, ditoluylamine, dixylamine; or alternatively, dibenzylamine. Amides that may be utilized to generate the in situ generated hydrocarbylaluminum (or alkylaluminum) compounds having a carboxamide anion include C2-C 20 , C2~C 10 Alternatively, it may be 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. Formula AlX 2 3-n R 1 n or Al2X 2 6-q- R 1 q (In the formula, X 2 at least a portion (or all) of which is an alkoxide, carboxylate, dihydrocarbyl azanide, and / or carboxamide anion) of the formula AlX 2 3-n R 1 n or Al2X 2 6-q- R 1 qThe molar ratio of the hydrocarbylaluminum (or alkylaluminum) compound having the formula (I) 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.

[0069] Generally, the formula AlX 2 3-n R 1 n or Al2X 2 6-q- R 1 q The in situ generated hydrocarbylaluminum (or alkylaluminum) compound having the formula: may be formed by any method capable of producing the desired in situ generated hydrocarbylaluminum (or alkylaluminum) compound. In one embodiment, 2 3-n R 1 n or Al2X 2 6-q- R 1 q (In the formula, X 2 wherein at least a portion (or all) of said anions are alkoxide, carboxylate, dihydrocarbyl azanide, and / or carboxamide anions, can be prepared by 1) reacting an alcohol, a carboxylic acid or a simple ester of a carboxylic acid, an amine, and / or an amide with a compound of the formula AlX prior to contacting the in situ generated hydrocarbyl aluminum (or alkyl aluminum) compound with the zirconium compound component of the catalyst system. 2 3-n R 1 n and / or Al2X 2 6-q- R 1 q with a suitable (or desired) hydrocarbylaluminum (or alkylaluminum) compound having the formula:

[0070] Aluminoxane compounds that may be utilized as the hydrocarbyl metal (or alkyl metal, or hydrocarbyl aluminum, or alkyl aluminum) compound of the catalyst system may comprise, consist essentially of, or be methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propylaluminoxane, iso-propyl-aluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butylaluminoxane, 1-pentylaluminoxane, 2-ethylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or any combination thereof. In some non-limiting embodiments, the aluminoxane can comprise, consist essentially of, or be methylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutylaluminoxane, t-butylaluminoxane, or any combination thereof; alternatively, methylaluminoxane (MAO); alternatively, ethylaluminoxane; alternatively, modified methylaluminoxane (MMAO); alternatively, n-propylaluminoxane; alternatively, iso-propylaluminoxane; alternatively, n-butylaluminoxane; alternatively, sec-butylaluminoxane; alternatively, iso-butylaluminoxane; alternatively, t-butylaluminoxane; alternatively, 1-pentyl-aluminoxane; alternatively, 2-pentylaluminoxane; alternatively, 3-pentylaluminoxane; alternatively, iso-pentylaluminoxane; or alternatively, neopentylaluminoxane.

[0071] Non-limiting exemplary hydrocarbylaluminum (or alkylaluminum) compounds that may be utilized in the catalyst systems of the processes described herein include Al(CH3)3, Al(C2H5)3, Al(C3H7)3, Al(C4H9)3, Al(C5H 11 )3, Al(CH 13 )3, Al(CH 17)3, Al(C2H5)2Cl, Al(C2H5)2Br, Al(C2H5)2I, Al(C2H5)Cl2, Al(C2H5)Br2, Al(C2H5)I2, AlC2H 5(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, AlC2 H5(OCOC4H9)2, Al(OCOC2H5)2Cl, Al(OCOC3H7)2Cl, Al(OCOC4H9)2Cl, Al(OCOC2H5)Cl2, Al(OCO C3H7)Cl2, Al(OCOC4H9)Cl2, Al(C2H5)2OC2H5, Al(C2H5)2OC3H7, Al(C2H5)2OC4H9, Al(C2H5)2 N(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 embodiments, the hydrocarbylaluminum (or alkylaluminum) compound may comprise, consist essentially of, or be Al(CH3)3, Al(C2H5)3, Al(C3H7)3, Al(C4H9)3, Al(C5H 11 )3, Al(CH 13 )3, Al(CH 17)3, Al(C2H5)2Cl, Al(C2H5)2Br, Al(C2H5)2I, Al(C2H5)Cl2, Al(C2H5)Br2, Al(C2H5)I2, Al2(CH3)3Cl3, Al2(C H3)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(C2H5)2OC3H7, Al(C2H5)2OC4H9, Al(C 2H5)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, AlC2H 5(OCOC4H9)2, Al(C2H5)2OC2H5, Al(C2H5)2OC3H7, Al(C2H5)2OC4H9, or any combination thereof; alternatively, may comprise, consist essentially of, or be Al(C2H5)2N(C2H5)2, Al(C2H5)2N(C3H7)2, Al(C2H5)2N(C4H9)2, or any combination thereof.In other embodiments, the hydrocarbylaluminum (or alkylaluminum) compound can comprise, consist essentially of, or be 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, can comprise, consist essentially of, or be Al(C2H5)3, Al(C2H5)2Cl, Al(C2H5)Cl2, Al2(C2H5)3Cl3, or any combination thereof.

[0072] The molar ratio of the metal of the hydrocarbyl metal (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 results in a catalyst system capable of forming oligomeric products. In one embodiment, 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, and 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. In general, the M:Zr (or Al:Zr) molar ratio can range from 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 of M:Zr (or Al:Zr) molar ratios can 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. Other suitable M:Zr (or Al:Zr) molar ranges are readily apparent from the present disclosure.

[0073] In some embodiments, the catalyst system can further include (or have as a component) a neutral non-ionic organic modifier. In general, the neutral non-ionic organic modifier can be any neutral non-ionic organic modifier that can form an oligomeric product in combination with the zirconium compound and the hydrocarbyl metal compound. The neutral non-ionic organic modifier can include, consist essentially of, or be an ether, ester, ketone, aldehyde, alcohol, anhydride, acid chloride, nitrile, sulfide, disulfide, phosphine, amine, or amide; alternatively, an ether; alternatively, an ester, alternatively, a ketone; alternatively, an aldehyde; alternatively, an alcohol; alternatively, a sulfide; alternatively, a disulfide, alternatively, a nitrile; alternatively, a phosphine; alternatively, an amine; or alternatively, an amine.

[0074] Ethers that can be used as neutral nonionic organic modifiers are C2-C 20 , C2~C 15 , or C2~C 10 The sulfides that can be used as neutral nonionic organic modifiers are C2-C 20 , C2~C 15 , or C2~C 10 Disulfides that can be used as neutral nonionic organic modifiers include C2-C 20 , C2~C 15 , or C2~C 10 The ether may be a disulfide. 11 OR 12 The sulfide may have the structure R 11 S.R. 12 The disulfide may have the structure R 11 SSR 12 The ether, sulfide, and / or disulfide R 11 and R 12 are independently 15 , C1~C 10 or a C1 to C5 hydrocarbyl group, a C1 to C 15 , C1~C 10, or C1-C5 alkyl group, C5-C 15 Or C5~C 10 Cycloalkyl groups, C6-C 15 Or C6~C 10 Aryl group, or C7-C 15 Or C7~C 10In a non-limiting embodiment, the ether that can be utilized as the neutral nonionic organic modifier can comprise, consist essentially of, or be dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, ditolyl ether, dixylyl ether, tetrahydrofuran, tetrahydropyran, dioxane, furan, benzofuran, isobenzofuran, dibenzofuran, or any combination thereof. In some embodiments, an ether that may be utilized as a neutral non-ionic organic modifier may comprise, consist essentially of, or be dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, ditolyl ether, dixylyl 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, alternatively, ditolyl ether; alternatively, dixylyl ether, tetrahydrofuran; alternatively, tetrahydropyran; alternatively, dioxane; alternatively, furan; alternatively, benzofuran; alternatively, isobenzofuran; or alternatively, dibenzofuran.In non-limiting embodiments, sulfides that can be utilized as neutral nonionic organic modifiers include 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 embodiment, the disulfide may comprise, 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.

[0075] The esters that can be used as neutral nonionic organic modifiers are C3-C 20 , C3~C 15 , or C3~C 10 The ester may be an ester having the structure R 13 (C=O)OR 14 The R of the ester may have the following structure: 13 and R 14 are independently 15 , C1~C 10 or a C1 to C5 hydrocarbyl group, a C1 to C 15 , C1~C 10 , or C1-C5 alkyl group, C5-C 15 Or C5~C 10 Cycloalkyl groups, C6-C 15 Or C6~C 10 Aryl group, or C7-C 15 Or C7~C 10 The esters that can be used as neutral nonionic organic modifiers include C1-C 15 , C1~C 10 , or C1-C5 hydrocarbyl, C1-C 15 , C1~C10 , or C1-C5 alkyl, C5-C 15 Or C5~C 10 Cycloalkyl, C6-C 15 Or C6~C 10 Aryl or C1-C 15 , C1~C 10 , or C1-C5 hydrocarbyl, C1-C 15 , C1~C 10 , or C1-C5 alkyl, C6-C 15 Or C6~C 10 Aryl or C7~C 15 Or C7~C 10 Aralkyl carboxylic acids C7-C 15 Or C7~C 10It can be an aralkyl ester. In a non-limiting embodiment, the ester that can be utilized as the neutral nonionic organic modifier can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, phenyl, toluyl, xylyl, or benzyl acetate, propionate, butanoate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, benzoate, methyl benzoate, dimethyl benzoate, or naphthanoate; alternatively, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or tridecyl, acetate. Alternatively, the ester may comprise, consist essentially of, or be a phenyl, toluyl, xylyl, or benzyl acetate, propionate, butanoate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, or decanoate; or alternatively, a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or tridecyl benzoate, methyl benzoate, dimethyl benzoate, or naphthanoate. In some embodiments, the esters that may be utilized as neutral nonionic organic modifiers are C4-C 20 , C4~C 15 , or C4~C 10 It may be a cyclic ester; alternatively, butyrolactone, valerolactone, phthalide, or any combination thereof; alternatively, butyrolactone; alternatively, valerolactone; or alternatively, a phthalide.

[0076] Aldehydes that can be used as neutral nonionic organic modifiers are C2-C 20 , C2~C 15 , or C2~C 10 The neutral nonionic organic modifier may be an aldehyde. The ketones that may be utilized as the neutral nonionic organic modifier may be C3-C 20, C3~C 15 , or C3~C 10 The aldehyde can be a ketone. 15 (C=O)H. Ketones can have the structure R 15 (C=O)R 16 The R of the aldehyde may be 15 , and R of ketones 15 and R 16 are independently 15 , C1~C 10 or a C1 to C5 hydrocarbyl group, a C1 to C 15 , C1~C 10 , or C1-C5 alkyl group, C5-C 15 Or C5~C 10 Cycloalkyl groups, C6-C 15 Or C6~C 10 Aryl group, or C7-C 15 Or C7~C 10It may be an aralkyl group. In a non-limiting embodiment, the aldehyde that can be utilized as the neutral nonionic organic modifier can comprise or consist essentially of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, tolualdehyde, xylylaldehyde, furaldehyde, or any combination thereof; alternatively, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, or any combination thereof; alternatively, benzaldehyde, tolualdehyde, xylylaldehyde, or any combination thereof; alternatively, formaldehyde; alternatively, acetaldehyde; alternatively, propionaldehyde; alternatively, butyraldehyde; alternatively, benzaldehyde; alternatively, tolualdehyde; alternatively, xylylaldehyde; alternatively, furaldehyde. Ketones that may be utilized as the neutral nonionic organic modifier may include, consist essentially of, or be propanone, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, phenylethanone, phenylpropanone, benzophenone, or any combination thereof; alternatively, propanone, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, or any combination thereof; alternatively, phenylethanone, phenylpropanone, benzophenone, or any combination thereof; alternatively, propanone; alternatively, butanone; alternatively, pentanone; alternatively, hexanone; alternatively, heptanone; alternatively, octanone; alternatively, nonanone; alternatively, decanone; alternatively, phenylethanone; alternatively, phenylpropanone; or alternatively, benzophenone.

[0077] Acid halides that can be used as neutral nonionic organic modifiers are C2-C 20 , C2~C 15 , or C2~C 10 The anhydrides that can be utilized as neutral nonionic organic modifiers are C2-C 20 , C2~C 15, or C2~C 10 The acid halide may be an anhydride. 17 (C=O)X 10 The anhydrides may have the structure R 17 (C=O)O(C=O)R 17 The acid halide may have the formula: 10 may be chloride, bromide, or iodide; alternatively, chloride; alternatively, bromide; or alternatively, iodide. Each R of the acid halides and anhydrides 17 are independently 15 , C1~C 10 or a C1 to C5 hydrocarbyl group, a C1 to C 15 , C1~C 10 , or C1-C5 alkyl group, C5-C 15 Or C5~C 10 Cycloalkyl groups, C6-C 15 Or C6~C 10 Aryl group, or C7-C 15 Or C7~C 10In a non-limiting embodiment, the acid halide that can be utilized as the neutral nonionic organic modifier can be acetyl chloride, acetyl bromide, propionyl chloride, propionyl bromide, butyryl chloride, valeroyl 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, valeroyl chloride, hexanoyl chloride, or any combination thereof; alternatively, benzoyl chloride, acetyl bromide, propionyl chloride, propionyl bromide, butyryl chloride, valeroyl chloride, hexanoyl chloride, or any combination thereof. Alternatively, the aromatic hydrocarbon may comprise, consist essentially of, or be 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, valeroyl chloride; alternatively, hexanoyl chloride; alternatively, benzoyl chloride; alternatively, benzoyl bromide; alternatively, methylbenzoyl chloride; or alternatively, dimethylbenzoyl chloride.

[0078] In non-limiting embodiments, anhydrides that may be utilized as the neutral nonionic organic modifier include ethanoic anhydride, propanoic anhydride, butanoic anhydride, hexanoic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride, benzoic anhydride, methylbenzoic anhydride, dimethylbenzoic anhydride, phthalic anhydride, homophthalic anhydride, or any combination thereof; alternatively, ethanoic anhydride, propanoic anhydride, butanoic anhydride, hexanoic anhydride; alternatively, maleic anhydride, succinic anhydride, glutaric anhydride, or any combination thereof; alternatively, benzoic anhydride, methylbenzoic anhydride, homophthalic anhydride, or any combination thereof. Alternatively, the anhydride may be ethylbenzoic anhydride, dimethylbenzoic anhydride, or any combination thereof; alternatively, phthalic anhydride, homophthalic anhydride, or any combination thereof; alternatively, ethanoic anhydride; alternatively, propanoic anhydride; alternatively, butanoic 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, homophthalic anhydride.

[0079] Nitriles that can be used as neutral nonionic organic modifiers are C2-C 20 , C2~C 15 , or C2~C 10 The nitrile may be a nitrile. The nitrile has the structure R 18 CN. The R of nitrile 18 is C1~C 15 , C1~C 10 or a C1 to C5 hydrocarbyl group, a C1 to C 15 , C1~C 10 , or C1-C5 alkyl group, C5-C 15 Or C5~C 10 Cycloalkyl groups, C6-C 15 Or C6~C 10 Aryl group, or C7-C 15 Or C7~C 10In a non-limiting embodiment, the nitrile that can be utilized as the neutral non-ionic organic modifier can comprise, consist essentially of, or be acetonitrile, propionitrile, butyronitrile, benzonitrile, or any combination thereof; alternatively, acetonitrile; alternatively, propionitrile; alternatively, butyronitrile; or alternatively, benzonitrile.

[0080] Phosphines that can be used as neutral nonionic organic modifiers are C3-C 20 , C3~C 15 , or C3~C 10 , a phosphine. The phosphine may have the structure (R 19 )3P. The amine may have the structure (R 19 ) 3N. Each R of the phosphine may have 19 are independently 15 , C1~C 10 or a C1 to C5 hydrocarbyl group, a C1 to C 15 , C1~C 10 , or C1-C5 alkyl group, C5-C 15 Or C5~C 10 Cycloalkyl groups, C6-C 15 Or C6~C 10 Aryl group, or C7-C 15 Or C7~C 10It may be an aralkyl group. In a non-limiting embodiment, the phosphine that can be utilized as the neutral nonionic organic modifier can comprise, consist essentially of, or be 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.

[0081] Amines that can be used as neutral nonionic organic modifiers include C1-C 20 , C1~C 15 , or C1~C 10 The amine may be an amine having the structure HNR 20 , H.N.(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. 20 , H.N.(R 20 )2, or N(R 20 ) 3 of the amine having each R 20 are independently 15 , C1~C 10 or a C1 to C5 hydrocarbyl group, a C1 to C 15 , C1~C 10 , or C1-C5 alkyl group, C5-C 15 Or C5~C10 Cycloalkyl groups, C6-C 15 Or C6~C 10 Aryl group, or C7-C 15 Or C7~C 10In a non-limiting embodiment, the amines that can be utilized as the neutral nonionic organic modifiers are methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, cyclopentylamine, cyclohexylamine, piperidine, methylpiperidine, dimethylpiperidine, trimethylpiperidine, tetramethylpiperidine, aniline, benzylamine, naphthylamine, dimethylamine, diethylamine, dibutylamine, diphenylamine, methylphenylamine, trimethylamine, triethylamine, tributylamine, triphenylamine, pyridine, picoline, or any combination thereof; alternatively, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, cyclopentylamine, cyclohexylamine, aniline, benzylamine, naphthylamine, dimethylamine, diethylamine, dibutylamine, diphenylamine, methylphenylamine, 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, methylphenylamine, 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, picoline, or any combination thereof; alternatively, aniline, naphthylamine, or any combination thereof; alternatively, dimethylamine, diethylamine, dibutylamine, diphenylamine, methylphenylamine; 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 may comprise, consist essentially of, or be trimethylpiperidine; alternatively, tetramethylpiperidine; alternatively, aniline; alternatively, benzylamine; alternatively, naphthylamine; alternatively, dimethylamine; alternatively, diethylamine; alternatively, dibutylamine; alternatively, diphenylamine; alternatively, methylphenylamine; alternatively, trimethylamine; alternatively, triethylamine; alternatively, tributylamine; alternatively, triphenylamine; alternatively, pyridine; or alternatively, picoline;

[0082] Amides that can be used as neutral nonionic organic modifiers include C2-C 20 , C2~C 15 , or C2~C 10 It can be an amide. An amide has 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 of the amide 21 and each R 22 are independently 15 , C1~C 10 or a C1 to C5 hydrocarbyl group, a C1 to C 15 , C1~C 10 , or C1-C5 alkyl group, C5-C 15 Or C5~C 10 Cycloalkyl groups, C6-C 15 Or C6~C 10 Aryl group, or C7-C 15 Or C7~C 10In a non-limiting embodiment, the amide that can be utilized as the neutral nonionic organic modifier is 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-propylacetamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-propylacetamide, N-butylformamide, N-phenylformamide, N,N-diphenylformamide, N-propylacetamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-propylacetamide, N-butylformamide, N-phenylformamide, N,N-diphenylformamide, N-propylacetamide, N-butylformamide, N-phenylformamide, N,N-diphenylformamide, N-propylacetamide, N-methylacetamide, N,N-dimethylacetamide, N- acetamide, 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-dimethyl Butylamide, 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 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, it may comprise, consist essentially of, or be 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, it may comprise, consist essentially of, or be N,N-dimethylbenzamide;

[0083] Alcohols that can be used as neutral nonionic organic modifiers include C2-C 20 , C2~C 15 , or C2~C 10 The nitrile may be an alcohol. 23 R of alcohol nitrile may have CH2OH. 23 is C1~C 15 , C1~C 10 or a C1 to C5 hydrocarbyl group, a C1 to C 15 , C1~C 10 , or C1-C5 alkyl group, C5-C 15 Or C5~C 10 Cycloalkyl groups, C6-C 15 Or C6~C 10 Aryl group, or C7-C 15 Or C7~C 10It may be an aralkyl group. In a non-limiting embodiment, the alcohol that may be utilized as the neutral nonionic organic modifier may comprise, consist essentially of, or be 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.

[0084] Generally, when a neutral non-ionic organic modifier is utilized, the neutral non-ionic organic modifier may be utilized in conjunction with a zirconium compound and / or a hydrocarbyl metal (or hydrocarbyl aluminum) compound. The molar ratio of the neutral non-ionic organic modifier to the zirconium of the zirconium compound (also referred to herein as the modifier:Zr molar ratio) and / or the molar ratio of the neutral non-ionic organic modifier to the hydrocarbyl metal (or hydrocarbyl aluminum) compound (also referred to herein as the modifier:M (or modifier:Al) molar ratio) may be any ratio that allows the catalyst system to form oligomeric products when contacted with ethylene. When a neutral non-ionic organic modifier is utilized in conjunction with the 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, and additionally or alternatively, the maximum modifier:Zr molar ratio can be 20:1, 15:1, 10:1 7.5:1, or 5:1. In general, the modifier:Zr molar ratio can range from 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 20:1, 0.5:1 to 15:1, 0.75:10:1, 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 are readily apparent from the present disclosure. When a neutral non-ionic organic modifier is utilized in conjunction with a hydrocarbyl metal (or hydrocarbyl aluminum) compound, the minimum modifier:M (or modifier:Al) molar ratio may be 0.05:1, 0.1:1, 0.5:1, 0.75:1 0.8:1, 0.9:1, or 1:1, and additionally or alternatively, the maximum modifier:Zr molar ratio may be 5:1, 3:1, 2:1, 1.5:1, 1:1, 0.75:1, or 0.5:1. In general, the minimum modifier:M (or modifier:Al) molar ratio may range from 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 in 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 are readily apparent from the present disclosure.

[0085] In one embodiment, the catalyst system can be prepared and then i) contacted with ethylene, a chain transfer agent, and an optional organic reaction medium, or ii) introduced into the reaction zone. For example, in one embodiment, the process can include contacting a zirconium compound and a hydrocarbyl metal (or hydrocarbyl aluminum) compound to form a catalyst system, which can then i) contacted with ethylene, a chain transfer agent, and an optional organic reaction medium, or ii) introduced into the reaction zone. When a neutral non-ionic organic modifier is utilized in the catalyst system, the neutral non-ionic organic modifier can be contacted with the zirconium compound before contacting the hydrocarbyl metal (or hydrocarbyl aluminum) compound, can be contacted with the hydrocarbyl metal (or hydrocarbyl aluminum) compound before contacting the zirconium compound, or can be contacted with a mixture of the zirconium compound and the hydrocarbyl metal (or hydrocarbyl aluminum) compound. In another embodiment, the neutral non-ionic organic modifier, the zirconium compound, and the hydrocarbyl metal (or hydrocarbyl aluminum) compound can be contacted simultaneously to form the catalyst system.

[0086] In alternative embodiments, the catalyst system may be prepared in-situ by contacting two or more components of the catalyst system separately (and / or simultaneously) with ethylene, a chain transfer agent, and an optional organic reaction medium, or ii) separately (and / or simultaneously) introducing the two or more components of the catalyst system into the reaction zone. For example, in one embodiment, the process may include: i) separately (and / or simultaneously) contacting a zirconium compound and a hydrocarbyl compound with ethylene, a chain transfer agent, and an optional organic reaction medium, or ii) separately (and / or simultaneously) introducing a zirconium compound and a hydrocarbyl compound into the reaction zone. In one embodiment, when a neutral non-ionic organic modifier is utilized in the catalyst system, the zirconium compound (or zirconium compound / neutral non-ionic organic modifier mixture) and the hydrocarbyl metal (or hydrocarbyl aluminum) compound can be separately (and / or simultaneously) contacted with ethylene, a chain transfer agent, and the optional organic reaction medium, or the neutral non-ionic organic modifier can be contacted with the zirconium compound (to form the zirconium compound / neutral non-ionic organic modifier mixture) prior to separately (and / or simultaneously) introducing the zirconium compound (or zirconium compound / neutral non-ionic organic modifier mixture) and the hydrocarbyl metal (or hydrocarbyl aluminum) compound to the reaction zone.In another embodiment, when a neutral non-ionic organic modifier is utilized in the catalyst system, the neutral non-ionic organic modifier can be contacted with the hydrocarbyl metal (or hydrocarbyl aluminum) compound (to form the hydrocarbyl metal (or hydrocarbyl aluminum) compound / neutral non-ionic organic modifier mixture) prior to separately (and / or simultaneously) contacting the hydrocarbyl metal (or hydrocarbyl aluminum) compound or the hydrocarbyl metal (or hydrocarbyl aluminum) compound / neutral non-ionic organic modifier mixture) and the zirconium compound with ethylene, a chain transfer agent, and the optional organic reaction medium, or prior to separately (and / or simultaneously) introducing the hydrocarbyl metal (or hydrocarbyl aluminum) compound (or the hydrocarbyl metal (or hydrocarbyl aluminum) compound / neutral non-ionic organic modifier mixture) and the zirconium compound into the reaction zone. In a further embodiment, when a neutral non-ionic organic modifier is utilized in the catalyst system, the neutral non-ionic organic modifier, the zirconium compound, and the hydrocarbyl metal (or hydrocarbyl aluminum) compound may be contacted separately (and / or simultaneously) with the ethylene, the chain transfer agent, and the optional organic reaction medium or may be introduced separately (and / or simultaneously) into the reaction zone.

[0087] In one non-limiting embodiment, the catalyst system has the formula ZrX 1 m and the hydrocarbyl metal compound may include a zirconium compound having the formula AlX 2 n R 1 3-n , Al2X 2 3R 1 3. R 1 2Zn), or any combination thereof. 1 , X 2 , R 1 , m, and n are independently described herein, and these independent descriptions are taken to represent the formula ZrX 1 m and zirconium compounds having the formula AlX2 n R 1 3-n , Al2X 2 3R 1 Alkyl aluminum compounds having 3, dialkyl zinc compounds (R 1 In one embodiment, ZrX may be utilized in any combination without limitation. 1 m Each X 1 may be independently chloride or bromide, and m is 4. In one embodiment, the formula ZrX 1 m The zirconium compound having the formula may comprise, consist essentially of, or be ZrCl4, ZrBr4, ZrClBr3, ZrCl2Br2, and ZrCl3Br; alternatively, ZrCl4 or ZrBr4; or alternatively, ZrClBr3; or alternatively, ZrCl4. In one embodiment, the hydrocarbyl metal compound has 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, AlX 2 2R 1 ,AlX 2 R 1 2. AlR 1 3. Al2X 2 3R 1 3, or any combination thereof. 2 and R 1 are described herein independently, and these independent descriptions are taken to mean the compounds of the formula ZrX 1 m and zirconium compounds having the formula AlX 2 n R 1 3-n , Al2X 2 3R 1 3. R 1To further illustrate the catalytic system, the hydrocarbyl metal compound may include an alkylaluminum compound having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 7 2 may independently be a halide, and each R 1 can be independently a C2-C4 alkyl group. In some embodiments, the alkyl metal compound can comprise 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. Non-limiting values ​​for the molar ratio of the metal of the hydrocarbyl metal compound (or the aluminum of the hydrocarbyl aluminum compound) to the zirconium of the zirconium compound can be within the range of 1:1 to 50:1, 1:1 to 15:1, or 10:1 to 25:1. In some non-limiting embodiments, the catalyst system (or catalyst system component) can comprise a C2-C 20 The catalyst system (or catalyst system components) may further include a neutral non-ionic organic modifier comprising an ester (any of those described herein), and the molar ratio of the neutral non-ionic organic modifier to the zirconium of the zirconium compound may be within any of the ranges disclosed herein (e.g., within the range of 0.5:1 to 5:1). In other non-limiting embodiments, the catalyst system (or catalyst system components) may include a C2 to C6 20 Ether, C2-C 20 Sulfides, C1-C 20 Amines, C3-C 20 phosphines, or any combination thereof (alternatively, C2-C 20 Ether, C2-C 20 sulfides, or any combination thereof; alternatively, C2 to C 20Ether; alternatively, C2-C 20 Sulfide; alternatively, C1-C 20 amine; or alternatively, C3-C 20 The molar ratio of the neutral nonionic organic modifier to the zirconium of the zirconium compound can be within any range disclosed herein (e.g., within the range of 0.5:1 to 20:1).

[0088] In another non-limiting embodiment, the zirconium compound has the formula ZrX 1 m Y 1 q and the hydrocarbyl metal compound may have the formula AlX 2 n R 1 3-n , Al2X 2 3R 1 3, or any combination thereof. 1 , Y 1 , X 2 , R 1 , n, and q are independently described herein, and these independent descriptions are taken to represent the formula ZrX 1 m Y 1 q and zirconium compounds having the formula AlX 2 n R 1 3-n , Al2X 2 3R 1 3, or any combination thereof, may be utilized in any combination without limitation. 1 m Y 1 q Each X 1 may be, independently, chloride or bromide; alternatively, chloride. 1 m Y 1 q Each Y1 are independently 10 Hydrocarboxylates (e.g., any of those described herein), C1-C 10 Hydrocarbyl carboxylates (e.g., any of those described herein), or C1-C 15 Hydrocarbyl sulfonates (e.g., any of those described herein); alternatively, C1-C 10 Hydrocarboxylates (e.g., any of those described herein); alternatively, C1-C 10 Hydrocarbyl carboxylates (e.g., any of those described herein); or alternatively, C1-C 15 It may be a hydrocarbyl sulfonate (e.g., any of those described herein). 1 m Y 1 q wherein 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 embodiment, the formula ZrX 1 m Y 1 q The zirconium compound having the formula: zirconium tetra C1-C 10 hydrocarbyl carboxylate; alternatively, zirconium tetra C1-C5 hydrocarbyl carboxylate; or alternatively, may comprise, consist essentially of, or be Zr(O2C3H7)4. In another embodiment, the compound of formula ZrX 1 m The zirconium compound having the formula may comprise, consist essentially of, or be ZrCl4, ZrBr4, ZrClBr3, ZrCl2Br2, and ZrCl3Br; alternatively, ZrCl4 or ZrBr4; or alternatively, ZrClBr3; or alternatively, ZrCl4. In one embodiment, the hydrocarbyl metal compound has the formula AlX 2 2R 1 ,AlX 2 R 1 2. AlR 1 3. Al2X2 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. 2 and R 1 are described herein independently, and these independent descriptions are taken to mean the compounds of the formula ZrX 1 m and zirconium compounds having the formula AlX 2 n R 1 3-n , Al2X 2 3R 1 3. R 1 To further illustrate the catalytic system, the hydrocarbyl metal compound may include an alkylaluminum compound having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 7 2 may independently be a halide, and each R 1may be independently a C2-C4 alkyl group. In some embodiments, the alkyl metal compound may comprise or consist essentially of 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 ​​for the molar ratio of the metal of the hydrocarbyl metal compound (or the aluminum of the hydrocarbyl aluminum compound) to the zirconium of the zirconium compound may be within the range of 1:1 to 50:1, 2:1 to 25:1, or 1:1 to 15:1, among others disclosed herein. In one embodiment, the formula ZrX 1 m Y 1 q The zirconium compound having the formula ZrX is prepared in 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. 1 m Y 1 q In one embodiment, the catalyst system (or catalyst system components) may be partially hydrolyzed by contacting the C2 to C 15 Alcohol, C1-C 15 Amines, C2-C 15 amide, or any combination thereof; alternatively, C2-C 15 Alcohol; alternatively, C1-C 15 amine; or alternatively, C2-C 15It may further comprise a neutral non-ionic organic modifier comprising an amide. In one embodiment, the molar ratio of the neutral non-ionic organic modifier to the metal of the hydrocarbyl metal compound (or the aluminum of the hydrocarbyl aluminum compound) is within the range of 0.75:1 to 2:1, or 0.75:1 to 1.5:1, among others disclosed herein. In one embodiment, the neutral non-ionic organic modifier may be contacted with the hydrocarbyl metal (or hydrocarbyl aluminum) compound before the hydrocarbyl metal (or hydrocarbyl aluminum) compound is contacted with the zirconium compound and / or ethylene (and / or introduced into the reaction zone). In some embodiments, the neutral non-ionic organic modifier is contacted with the zirconium compound before the zirconium compound is contacted with the ethylene and / or hydrocarbyl metal compound (and / or introduced into the reaction zone).

[0089] The process described herein may utilize 1) 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, 2) hydrogen, 3) a transition metal compound chain transfer agent, or any combination thereof; alternatively, 1) 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, and 2) hydrogen; alternatively, 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; alternatively, hydrogen; or alternatively, a transition metal compound chain transfer agent. In general, the chain transfer agent, hydrogen, and / or the transition metal compound chain transfer agent are utilized to achieve the desired effect in the process of forming the oligomer product. The desired effect may include the production of (a) less than 1 weight percent polymer, (b) less than 1 weight percent compounds having a weight average molecular weight greater than 1000 g / mol, or (c) any combination thereof (weight percent is based on the total weight of the oligomer product); alternatively or additionally, compared to the same process without the use of 1) 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, 2) hydrogen, and / or 3) a transition metal compound chain transfer agent, (a) an oligomer product comprising a polymer having a lower Mw, (b) an oligomer product having a lower Mw maximum peak of polymer, (c) an oligomer product having a reduced amount of polymer, (d) an oligomer product having a reduced percentage of polymer having a molecular weight greater than 100,000 molecular weight, or (e) any combination thereof.

[0090] The chain transfer agent may comprise, consist essentially of, or be 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; alternatively, a compound having a hydrogen silicon bond; alternatively, a compound having a hydrogen sulfur bond; or alternatively, a compound having a hydrogen phosphorus bond. The reaction zone may have any of the molar ratios of chain transfer agent to ethylene that can provide any of the desired effects described herein. In one embodiment, the reaction zone may have a molar ratio of 1×10 -5 :1, 5×10 -4 :1, 1×10 -4 :1, or 5×10 -3 a minimum molar ratio of chain transfer agent to ethylene of 5×10:1; additionally or alternatively, -1 :1, 1×10 -1 :1, 5×10 -2 :1, or 1×10 -2 The reaction zone may have a maximum molar ratio of chain transfer agent to ethylene of 1×10:1. In general, the reaction zone may have a molar ratio of chain transfer agent to ethylene that may range from 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, the preferred reaction zone molar ratio of chain transfer agent to ethylene is 1×10:1. -5 :1~5×10 -1 :1, 5×10 -4 :1~1×10 -1 :1, 1×10 -4 :1~5×10 -2 :1, or 5×10 -3 :1~1×10 -2 ethylene molar ratio ranges for the chain transfer agent in the reaction zone are readily apparent from this disclosure.

[0091] Compounds having hydrogen-silicon bonds that can be used as neutral nonionic organic modifiers include C1-C 40 , C1~C 30 , or C1~C 20In one embodiment, the compound having a hydrogen silicon bond that can be utilized as a chain transfer agent can be represented by 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 in the formula of the compound having a hydrogen-silicon bond 31 are independently 15 , C1~C 10 or a C1 to C5 hydrocarbyl group, a C1 to C 15 , C1~C 10 , or C1-C5 alkyl group, C5-C 15 Or C5~C 10 Cycloalkyl groups, C6-C 15 Or C6~C 10 Aryl group, or C7-C 15 Or C7~C 10It may be an aralkyl group. In a non-limiting embodiment, the compound having a hydrogen silicon bond (e.g., having any of the formulas described herein) is trimethylsilane, diethylsilane, triethylsilane, tripropylsilane, dibutylsilane, tributylsilane, hexylsilane, dihexylsilane, trihexylsilane, octylsilane, dioctylsilane, trioctylsilane, decylsilane, didecylsilane, tridecylsilane, tridodecylsilane, phenylsilane, diphenylsilane, triphenylsilane, phenethylsilane, silane, 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 Alternatively, trioctylsilane, tridecylsilane, tridodecylsilane, triphenethylsilane, or any combination thereof; alternatively, trimethoxysilane, triethoxysilane, or any combination thereof; or alternatively, may comprise, consist essentially of, or be phenylsilane, diphenylsilane, or any combination thereof.

[0092] The compounds having hydrogen-sulfur bonds that can be used as neutral nonionic organic modifiers include C1-C 20 , C1~C 15 , or C1~C 10 The compounds having hydrogen-sulfur bonds that can be used as neutral nonionic organic modifiers include C1-C 20 , C1~C 15 , or C1~C 10 Thiols, C1-C 20 , C1~C 15 , or C1~C 10 Thioglycolate and / or C1-C 20 , C1~C 15 , or C1~C 10 mercaptopropionate; alternatively, C1-C 20 , C1~C 15 , or C1~C 10 Thiol; alternatively, C1-C 20 , C1~C 15 , or C1~C 10 thioglycolate; or alternatively, C1-C 20 , C1~C 15 , or C1~C 10 In one embodiment, the compound having a hydrogen sulfur bond that can be utilized as a chain transfer agent is represented by the formula R 32 S.H., 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 in the formula of the compound with hydrogen-sulfur bond 32 is C1~C 15 , C1~C 10 or a C1 to C5 hydrocarbyl group, a C1 to C 15 , C1~C10 , or C1-C5 alkyl group, C5-C 15 Or C5~C 10 Cycloalkyl groups, C6-C 15 Or C6~C 10 Aryl group, or C7-C 15 Or C7~C 10 It can be an aralkyl group. In non-limiting embodiments, the compound having a hydrogen sulfur bond (e.g., having any of the formulas described herein) can be methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, methyl thioglycolate, ethyl thioglycolate, methyl mercaptopropionate, ethyl 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, Alternatively, the thiol-based copolymer may comprise, consist essentially of, or be hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, or any combination thereof; alternatively, methyl thioglycolate, ethyl thioglycolate, methyl mercaptopropionate, ethyl mercaptopropionate, or any combination thereof; alternatively, ethanethiol; alternatively, propanethiol; alternatively, butanethiol; alternatively, tert-butyl thiol; alternatively, octanethiol; alternatively, decanethiol; alternatively, dodecanethiol; alternatively, methyl thioglycolate; or alternatively, methyl mercaptopropionate.

[0093] The compounds having a hydrogen-phosphorus bond that can be used as a neutral nonionic organic modifier include C1-C 40 , C1~C 30 , or C1~C 20 The compounds having a hydrogen-phosphorus bond that can be used as a neutral nonionic organic modifier include C1-C 40 , C1~C 30 , or C1~C 20 Phosphine and / or C1-C 40 , C1~C 30 , or C1~C 20 Phosphite; alternatively, C1-C 40 , C1~C 30 , or C1~C 20 Phosphine; or alternatively C1-C 40 , C1~C 30 , or C1~C 20 The compound may comprise, consist essentially of, or be a phosphite. In one embodiment, the compound having a hydrogen phosphorus bond that may be utilized as a chain transfer agent is represented by the formula (R 33 )2PH, (R 33 O)P(=O)H, or any combination thereof; alternatively, R 33 PH2; or alternatively, (R 33 Each R in the formula of the compound having a hydrogen-phosphorus bond may have 33 are independently 15 , C1~C 10 or a C1 to C5 hydrocarbyl group, a C1 to C 15 , C1~C 10 , or C1-C5 alkyl group, C5-C 15 Or C5~C 10 Cycloalkyl groups, C6-C 15 Or C6~C 10 Aryl group, or C7-C 15 Or C7~C 10It may be an aralkyl group. In a non-limiting embodiment, the compound having a phosphorus hydrogen bond (e.g., having any formula described herein) is dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dioctylphosphine, dicyclopentylphosphine, dicyclohexylphosphine, phenylphosphine, diphenylphosphine, dimethylphosphine, diethylphosphine, dibutylphosphine, dihexylphosphine, dioctylphosphine, diphenylphosphine, dibenzylphosphine, or any combination thereof; dimethylphosphine, diethylphosphine, dibutylphosphine, dioctylphosphine, dicyclopentylphosphine. , dicyclohexylphosphine, phenylphosphine, diphenylphosphine, dimethylphosphine, diethylphosphine, diphenylphosphine, dibenzylphosphine, or any combination thereof; alternatively, dimethylphosphine, diethylphosphine, dibutylphosphine, dicyclopenylphosphine, dicyclohexylphosphine, dioctylphosphine, phenylphosphine, diphenylphosphine, or any combination thereof; or alternatively, may comprise, consist essentially of, or be dimethylphosphine, diethylphosphine, diphenylphosphine, dibenzylphosphine, or any combination thereof.

[0094] The transition metal compound chain transfer agent can comprise, consist essentially of, or 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 embodiment, the reaction zone is 1×10 -9 :1, 5×10 -8 :1, 1×10 -8 :1, 5×10 -7 :1, or 1×10 -7 a minimum transition metal to ethylene molar ratio of 5×10:1; additionally or alternatively, -3:1, 1×10 -3 :1, 5×10 -4 :1, 1×10 -4 :1, or 5×10 -5 In general, the reaction zone may have a transition metal to ethylene molar ratio that may range from any minimum transition metal to ethylene molar ratio described herein to any maximum transition metal to ethylene molar ratio described herein. Thus, a suitable reaction zone transition metal to ethylene molar ratio is from 1×10 -9 :1~5×10 -3 :1, 5×10 -8 :1~1×10 -3 :1, 1×10 -8 :1~5×10 -4 :1, 5×10 -7 :1~1×10 -4 :1, or 1×10 -7 :1~5×10 -5 ethylene molar ratio range may be in the range of 1:1. Other suitable reaction zone as transition metal to ethylene molar ratio ranges are readily apparent from this disclosure.

[0095] Generally, the transition metal compound chain transfer agent has the formula MX 4 p where M is a transition metal and X 4 is a monoanion and p is the oxidation state of the transition metal M. The transition metal M can be a Group 8-10 transition metal; alternatively, a Group 8-9 transition metal; alternatively, a Group 8 transition metal; alternatively, a Group 9 transition metal; or alternatively, a Group 10 transition metal. In one embodiment, the transition metal M can be iron, cobalt, or nickel; alternatively, iron or cobalt; alternatively, iron; alternatively, cobalt; or alternatively, nickel. Generally, the transition metal of the formula MX 4 p p of the transition metal compound chain transfer agent having the formula MX 4 pEach p of the transition metal compound chain transfer agent having formula MX can be independently a halide, a carboxylate, a beta-dionate, a hydrocarboxylate, or a nitrate; alternatively, a carboxylate, a beta-dionate, or a hydrocarboxylate; alternatively, a carboxylate or a beta-dionate; alternatively, a carboxylate; or alternatively, a beta-dionate. 4 p Each carboxylate group of the transition metal compound chain transfer agent having, independently, a C2 to C 24 , C4~C 19 , or C5~C 12 In one embodiment, the compound of formula MX 4 p Each hydrocarboxylate of the transition metal compound chain transfer agent is independently selected from the group consisting of C1 to C 24、 C4~C 19 , or C5~C 12 In one embodiment, the compound of formula MX 4 p Each beta-dionate group of the transition metal compound chain transfer agent having, independently, a C5 to C 24 , C5~C 19 , or C5~C 12 It may be a beta-dionate.

[0096] Generally, the formula MX 4 p Each halide of the transition metal compound chain transfer agent having the formula MX can be independently chlorine, bromine, or iodine; alternatively, bromine; or alternatively, iodine. 4 pEach carboxylate of the transition metal compound chain transfer agent having the formula MX may independently be acetate, propionate, butyrate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, or dodecanoate; alternatively, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, or dodecanoate; alternatively, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, or dodecanoate; alternatively, hexanoate; alternatively, octanoate; alternatively, decanoate; or alternatively, dodecanoate. Generally, the transition metal compound chain transfer agent having the formula MX may be an acetate, propionate, butyrate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, or dodecanoate. 4 p Each hydrocarboxylate of the transition metal compound chain transfer agent having the formula MX may independently be a methoxide, an ethoxide, a propoxide, a butoxide, a phenoxide, a methylphenoxide, or a dimethylphenoxide; alternatively, a methoxide, an ethoxide, a propoxide, or a butoxide; alternatively, a phenoxide, a methylphenoxide, or a dimethylphenoxide. 4 p Each β-diketonate of the transition metal compound chain transfer agent having the formula MX can be independently an acetylacetonate (i.e., 2,4-pentanedionate), a hexafluoroacetylacetonate (i.e., 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate), or a benzoylacetonate; alternatively, an acetylacetonate; alternatively, a hexafluoroacetylacetonate; or alternatively, a benzoylacetonate. In some non-limiting embodiments, the transition metal compound chain transfer agent (or β-diketonate of the formula MX 4 p(transition metal compound chain transfer agent having) is 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; alternatively, may comprise, consist essentially of, or be iron(III) octanoate, iron(III) acetylacetonate, cobalt(III) octanoate, cobalt(III) acetylacetonate, nickel(II) octanoate, or nickel(II) acetylacetonate.

[0097] When hydrogen is utilized, the reaction zone can have any of the hydrogen to ethylene ratios that can provide any of the desired effects described herein. In one embodiment, 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), and 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). In general, 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 may be in the range of (0.05 g hydrogen) / (kg ethylene) to (5 g hydrogen) / (kg ethylene), (0.25 g hydrogen) / (kg ethylene) to (5 g hydrogen) / (kg ethylene), (0.25 g hydrogen) / (kg ethylene) to (4 g hydrogen) / (kg ethylene), (0.4 g hydrogen) / (kg ethylene) to (3 g hydrogen) / (kg ethylene), (0.4 g hydrogen) / (kg ethylene) to (2.5 g hydrogen) / (kg ethylene), (0.4 g hydrogen) / (kg ethylene) to (2 g hydrogen) / (kg ethylene), or (0.5 g hydrogen) / (kg ethylene) to (2 g hydrogen) / (kg ethylene). Other suitable reaction zone hydrogen to ethylene ratio ranges are readily apparent from the present disclosure.

[0098] The organic reaction medium that may be utilized in the processes described herein may be, for example, a hydrocarbon, a halogenated hydrocarbon, or a combination thereof. Hydrocarbons and halogenated hydrocarbons that may be used as organic reaction media may include aliphatic hydrocarbons, aromatic hydrocarbons, petroleum distillates, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, or any combination thereof. Aliphatic hydrocarbons that may be useful as organic reaction media include those having a C3-C 20 Aliphatic hydrocarbons, or C4-C 15Aliphatic hydrocarbons, or C5-C 10 Aliphatic hydrocarbons include. Aliphatic hydrocarbons that may be used as organic reaction media may be cyclic or acyclic, and / or straight-chain or branched, unless otherwise specified. Non-limiting examples of suitable acyclic aliphatic hydrocarbon organic reaction media that may be utilized alone or in any combination include propane, iso-butane, n-butane, butane (n-butane or a mixture of straight-chain and branched C4 acyclic aliphatic hydrocarbons), pentane (n-pentane or a mixture of straight-chain and branched C5 acyclic aliphatic hydrocarbons), hexane (n-hexane or a mixture of straight-chain and branched C6 acyclic aliphatic hydrocarbons), heptane (n-heptane or a mixture of straight-chain and branched C7 acyclic aliphatic hydrocarbons), and octane (n-octane or a mixture of straight-chain and branched C8 acyclic aliphatic hydrocarbons). Aromatic hydrocarbons that may be useful as organic reaction media include aromatic hydrocarbons, or C6 to C8 acyclic aliphatic hydrocarbons. 10 Non-limiting examples of suitable aromatic hydrocarbons that may be utilized alone or in any combination as the organic reaction medium include benzene, toluene, xylene (including ortho-xylene, meta-xylene, para-xylene, or mixtures thereof), and ethylbenzene. Halogenated aliphatic hydrocarbons that may be useful as the organic reaction medium include C1-C 15 Halogenated aliphatic hydrocarbons, or C1-C 10 Halogenated aliphatic hydrocarbons include halogenated aliphatic hydrocarbons, or C1-C5 halogenated aliphatic hydrocarbons. Halogenated aliphatic hydrocarbons that may be used as organic reaction media may be cyclic or acyclic, and / or straight or branched chain, unless otherwise specified. Non-limiting examples of suitable halogenated aliphatic hydrocarbons that may be utilized as organic reaction media include methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, or any combination thereof. Halogenated aromatic hydrocarbons that may be useful as organic reaction media include C6-C 20 Halogenated aromatic hydrocarbons, or C6-C 10Non-limiting examples of suitable halogenated aromatic hydrocarbons that may be used as the organic reaction medium include chlorobenzene, dichlorobenzene, or any combination thereof.

[0099] Generally, the oligomer product may be formed using any conditions capable of forming the oligomer product. The conditions that may be utilized to form the oligomer product may include, alone or in any combination, the reaction zone pressure, the reaction zone ethylene partial pressure, the reaction zone temperature, the molar ratio of zirconium to ethylene in 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 alpha olefins. The reaction zone pressure, reaction zone ethylene partial pressure, 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 alpha olefins are described herein independently, and these independent descriptions of the reaction zone pressure, reaction zone ethylene partial pressure, 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 alpha olefins may be utilized in any combination without limitation to further describe the processes disclosed herein.

[0100] The oligomeric product may be formed (or the reaction zone may have) a minimum reaction zone 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); alternatively or additionally, 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). Generally, the oligomer product can be formed (or the reaction zone can have) a reaction zone pressure ranging from any minimum pressure disclosed herein to any maximum pressure disclosed herein. In some non-limiting embodiments, the oligomer product can be formed at a pressure ranging 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 ( The reaction zone may be formed with (or may have) a reaction zone pressure of from 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 from 1000 psi (6.89 MPa) to 3500 psi (24.1 MPa). Other pressure ranges that may be utilized will be readily apparent to those of skill in the art upon reading this disclosure.

[0101] The oligomeric products may be formed (or the reaction zone may have) a reaction zone 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); alternatively or additionally, 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). Generally, the oligomer product can be formed (or the reaction zone can have) an ethylene partial pressure ranging from any minimum ethylene partial pressure disclosed herein to any maximum ethylene partial pressure disclosed herein. In some non-limiting embodiments, the oligomer product can be formed at a reaction zone ethylene partial pressure ranging 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), or any combination thereof. The reaction zone may be formed (or may have) an ethylene partial pressure in the range of 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). Other ranges of ethylene partial pressures will be readily apparent to those of skill in the art upon reading this disclosure.

[0102] The oligomeric product may be formed (or the reaction zone may have) a minimum reaction zone temperature of 0° C., 25° C., 40° C., 50° C., 75° C., 100° C., or 125° C.; alternatively or additionally, the oligomeric product may be formed (or the reaction zone may have) a maximum temperature of 250° C., 200° C., 150° C., 125° C., 100° C., or 90° C. In general, the oligomeric product may be formed (or the reaction zone may have) a reaction zone temperature ranging from any minimum temperature disclosed herein to any maximum temperature disclosed herein. In some non-limiting embodiments, the oligomeric product can be formed (or the reaction zone can have) a reaction zone temperature of 0° C. to 250° C., 25° C. to 200° C., 40° C. to 150° C., 40° C. to 100° C., 50° C. to 100° C., 50° C. to 150° C., 75° C. to 125° C., 75° C. to 250° C., 100° C. to 200° C., or 100° C. to 200° C. Other temperature ranges that can be utilized will be readily apparent to one of skill in the art upon reading this disclosure.

[0103] The oligomer product is 5 × 10 -7 :1, 1×10 -6 :1, 5×10 -5 :1, or 2.5×10 -5 a minimum molar ratio of zirconium to ethylene in the zirconium compound in the reaction zone of 7.5×10 -4 :1, 5×10 -4 :1, 2.5×10 -4 :1, or 1×10 -4 The reaction zone may be formed (or the reaction zone may have) a maximum molar ratio of zirconium to ethylene in the zirconium compound of the reaction zone of 1:1. Generally, the molar ratio of zirconium to ethylene in the zirconium compound of the reaction zone may range from a minimum molar ratio of zirconium to ethylene in any of the zirconium compounds of the reaction zone disclosed herein to a maximum molar ratio of zirconium to ethylene in any of the zirconium compounds of the reaction zone disclosed herein. In a non-limiting embodiment, the molar ratio of zirconium to ethylene in the zirconium compound of the reaction zone is 5×10 -7 :1~1×10 -4 :1, 1×10-6 : 1~2.5×10 -4 :1, 5×10 -5 :1~5×10 -4 :1, or 2.5×10 -5 : 1~7.5×10 -4 The molar ratio of zirconium to ethylene in other reaction zone zirconium compounds that may be utilized will be readily apparent to those of skill in the art upon reading this disclosure.

[0104] Oligomeric products may be formed (or the reaction zone may have) minimum ethylene:organic reaction medium mass ratios in the reaction zone of 0.5:1, 0.75:1, 1:1, 1.25:1, or 1.5:1; additionally or alternatively, maximum ethylene:organic reaction medium mass ratios of 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, or 2:1. In general, oligomeric products may be formed (or the reaction zone may have) in reactions with ethylene:organic reaction medium mass ratios ranging from any minimum ethylene:organic reaction medium mass ratio disclosed herein to any maximum ethylene:organic reaction medium mass ratio disclosed herein. In some non-limiting embodiments, oligomeric products can be formed in reactions (or reaction zones can have) ethylene:organic reaction medium mass ratios in the ranges of 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. Other ranges of ethylene:organic reaction medium mass ratios that can be utilized will be readily apparent to those of skill in the art upon reading this disclosure.

[0105] The oligomer product may be formed (or the reaction zone may have) any desired reaction zone residence time (or average reaction zone residence time). In one embodiment, the oligomer product may be formed (or the reaction zone may have) a reaction zone residence time (or average reaction zone residence time) that results in a desired amount of oligomer product, a desired catalyst system productivity, a desired ethylene conversion, or any combination thereof, alternatively, that results in a desired amount of oligomer product, alternatively, that results in a desired catalyst system productivity, or alternatively, that results in a desired ethylene conversion. The oligomer product may be formed (or the reaction zone may have) a minimum reaction zone residence time (or average reaction zone residence time) of 10 minutes, 20 minutes, or 30 minutes; additionally or alternatively, a maximum reaction zone residence time (or average reaction zone residence time) of 3 hours, 2.5 hours, 2 hours, or 1.5 hours. Generally, the reaction zone residence time (or average reaction zone residence time) can range from any minimum reaction zone residence time (or average reaction zone residence time) disclosed herein to any maximum reaction zone residence time (or average reaction zone residence time) disclosed herein. In some non-limiting embodiments, the oligomeric product can be formed at reaction zone residence times (or average reaction zone residence times) ranging from 10 minutes to 2.5 hours, 20 minutes to 2 hours, 30 minutes to 2 hours, or 30 minutes to 1.5 hours. Other ranges of reaction zone residence times (or average reaction zone residence times) that can be utilized will be readily apparent to one of skill in the art upon reading this disclosure.

[0106] The oligomeric 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 oligomeric product can have (or can be formed with) a Schultz-Flory K value ranging from any minimum Schultz-Flory K value disclosed herein to any maximum Schultz-Flory K value disclosed herein. In non-limiting embodiments, the oligomeric product can have (or can be formed with) a Schultz-Flory K value within the range of 0.4-0.9, 0.4-0.8, 0.5-0.8, 0.5-0.7, or 0.55-0.7. Other oligomer product Schultz-Flory K value ranges are readily apparent from the present disclosure. In any embodiment, the Schultz-Flory K values ​​are determined based on whether adjacent oligomer products are both C8, C 10 , C 12 , C 14 , or C 16 The Schultz-Flory K value can be determined using adjacent pairs of oligomer products selected from the oligomer products. In one embodiment, the Schultz-Flory K value can be the average of any two or more Schultz-Flory K values ​​using different adjacent pairs of product oligomers as described herein. In some aspects, the Schultz-Flory K value is determined using the C8 and C9 values. 10 Oligomeric products, C 10 and C 12 Oligomeric products, C 12 and C 14 Oligomeric products, C 14 and C 16 Oligomeric products, C8, C 10 , and C 12 The oligomeric product, or the average of any two or more adjacent pairs of oligomeric products, may be used to determine the degree of oligomeric binding.

[0107] The oligomer products can be formed at any desired ethylene conversion (or single pass ethylene conversion). The oligomer products 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%. In general, the oligomer products can be formed at ethylene conversions (or single pass ethylene conversions) 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 embodiments, the oligomer product may be formed at an ethylene conversion (or single pass ethylene conversion) ranging from 30% to 90%, 35% to 90%, 40% to 87.5%, 45% to 87.5%, 50% to 85%, or 55% to 85%. Other ranges of ethylene conversion (or single pass ethylene conversion) that may be utilized will be readily apparent to one of ordinary skill in the art upon reading this disclosure. In some embodiments, the oligomer product may be formed at an ethylene conversion that results in an oligomer product having a desired selectivity to normal alpha olefins (e.g., the percentage of normal alpha olefins at a particular oligomer product carbon number).

[0108] The processes described herein can produce oligomer products with high selectivity to normal alpha olefins. In one embodiment, the C6 olefin oligomer products produced by the processes 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 embodiment, the C8 olefin oligomer products produced by the processes described herein can have a 1-octene content of at least 98 wt%, 98.25 wt%, 98.5 wt%, 98.75 wt%, or 99.0 wt% of at least 1-octene content. In one embodiment, the C6 olefin oligomer products produced by the processes described herein can have a 1-octene content of at least 98 wt%, 98.25 wt%, 98.5 wt%, 98.75 wt%, or 99.0 wt% of at least 1-octene content. 10The olefin oligomer product may have a 1-decene content of at least 97.5%, 97.75%, 98%, 98.25%, or 98.5% by weight. In one embodiment, the C 1-decene produced by the process described herein is 12 The olefin oligomer product may have a 1-dodecene content of at least 96.5%, 97%, 97.5%, 97.75%, or 98.0% by weight. In one embodiment, the process described herein produces any C6 olefin oligomer product 1-hexene content described herein, any C8 olefin oligomer product 1-octene content described herein, any C9 olefin oligomer product 1-octene content described herein, any C10 olefin oligomer product 1-octene content described herein, any C11 olefin oligomer product 1-octene content described herein, any C20 olefin oligomer product 1-octene content described herein, any C30 olefin oligomer product 1-octene content described herein, any C40 olefin oligomer product 1-octene content described herein, any C50 olefin oligomer product 1-octene content described herein, any C60 olefin oligomer product 1-octene content described herein, any C70 olefin oligomer product 1-octene content described herein, any C80 olefin oligomer product 1-octene content described herein, any C90 olefin oligomer product 1-octene content described herein, any C100 olefin oligomer product 1-octene content described herein, any C110 olefin oligomer product 1-octene content described herein, any C120 olefin oligomer product 1-octene content described herein, any C130 olefin oligomer product 1-octene content described herein, any C140 olefin oligomer product 1-octene content described herein, any C150 olefin oligomer product 1-octene content described herein, any C160 olefin oligomer product 1-octene content described herein, any C170 olefin oligomer product 1-octene content described herein, any C180 olefin oligomer product 1-octene content described herein, any C190 olefin oligomer product 1-octene content described herein, any C200 olefin 10 An oligomer product can be produced that can have any combination of an olefin oligomer product 1-decene content, and / or any of the C8 olefin oligomer product 1-octene content described herein. In some non-limiting embodiments, the oligomer product can have a C6 olefin oligomer product 1-hexene content of at least 99% by weight and a C8 olefin oligomer product 1-octene content of at least 97.5% by weight. 12 olefin oligomer product 1-dodecene content; alternatively, a C olefin oligomer product 1-octene content of at least 98.5 wt.% and a C 12 olefin oligomer product 1-dodecene octene content; or alternatively, a C6 olefin oligomer product 1-hexene content of at least 99% by weight, a C8 olefin oligomer product 1-octene content of at least 98.5% by weight, a C 10 Olefin oligomer product 1-decene content, and at least 97.5 wt.% C 12 The olefin oligomer product may have a 1-dodecene content. Other combinations of normal alpha olefin content of the oligomer product are readily apparent from this disclosure.

[0109] In one aspect, the process described herein can produce an oligomer product having (a) less than 2.5 wt%, 1 wt%, 0.75 wt%, 0.5 wt%, or 0.25 wt% of polymer, (b) less than 2.5 wt%, 1 wt%, 0.75 wt%, 0.5 wt%, or 0.25 wt% of a compound having a weight average molecular weight greater than 1000 g / mol, or (c) any combination thereof, compared to the same process without the use of a chain transfer agent comprising 1) 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, 2) hydrogen, and / or 3) a transition metal compound chain transfer agent. The weight percent of polymer and the weight average molecular weight of the oligomer product are based on the total weight of the oligomer product. In separate or combinable aspects, the processes described herein can produce (a) an oligomer product comprising a polymer having a lower Mw, (b) an oligomer product having a polymer with a lower Mw maximum peak, (c) an oligomer product having a reduced amount of polymer, (d) an oligomer product having a reduced percentage of polymer having a molecular weight greater than 100,000 molecular weight, or (e) any combination thereof, as compared to the same process without the use of a chain transfer agent comprising 1) 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, 2) hydrogen, and / or 3) a transition metal compound chain transfer agent. In one embodiment, the amount of polymer present in the oligomer product per gram of oligomer product produced may be reduced by at least 10%, 25%, 40%, 50%, 60%, 70%, or 80% compared to polymer produced in connection with the same process without the use of a chain transfer agent comprising 1) 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, 2) hydrogen, and / or 3) a transition metal compound chain transfer agent.In one embodiment, the amount of polymer having a molecular weight greater than 100,000 molecular weight may be reduced by at least 10%, 25%, 40%, 50%, 60%, 70%, or 80% compared to polymer produced in connection with the same process without the use of 1) 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, 2) hydrogen, and / or 3) a transition metal compound chain transfer agent.

[0110] The reaction zone in which the oligomer product is formed may include any suitable reactor. Non-limiting examples of reactor types may include a stirred tank reactor, a plug flow reactor, or any combination thereof; alternatively, a stirred tank reactor; alternatively, a plug flow reactor; alternatively, a fixed bed reactor, a continuous stirred tank reactor, a loop slurry reactor, a solution reactor, a tubular reactor, a recirculating reactor, or any combination thereof; alternatively, a continuous stirred tank reactor; alternatively, a loop slurry reactor; alternatively, a solution reactor; alternatively, a tubular reactor; or alternatively, a recirculating reactor. In one embodiment, the reaction zone may have two or more reactors in series and / or parallel, including any combination of reactor types and configurations. Furthermore, the oligomerization process used to form the oligomer product may be a continuous process, a semi-continuous process, or a batch process, or the reactors or vessels in the oligomerization reaction system may be operated continuously, semi-continuously, or batchwise.

[0111] Additional information regarding zirconium-based catalyst systems for oligomerizing ethylene, including specific examples, and processes utilizing zirconium-based catalyst systems to produce oligomeric products can be found in, but is not limited to, 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, US7,291,685, US7,566,679, US8,269,055, US2009 / 0216057, US2009 / 0306312, US20 10 / 0191029, US2010 / 0292423, US2011 / 0046429, US2011 / 0054130, US2011 / 0054233, US2012 / 01 84692, US2020 / 0055799, US2020 / 0062672, US2020 / 0055800, US2020 / 0062673, EP320,571A2, EP 444,505A2, EP1,749,807A1, EP1,752,434A1, EP1,780,189, EP2,258,674A1, WO91 / 02707, Sekiyu 37, No. 4, 1994, pp. 337-346, Sekiyu Gakkaishi, Vol. 42, No. 4, 1999, pp. 235-245, Sekiyu Gakkaishi, Vol. 43, No. 5, 200o, pp. 328-338, Sekiyu Gakkaishi, Vol. 44, No. 1, 2001, pp. 25-35, and Sekiyu Gakkaishi, Vol. 44, No. 2, 2001, pp. 109-119. EXAMPLES

[0112] 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. Upon reading the description of this specification, various other embodiments, modifications, and their equivalents may be suggested to those skilled in the art without departing from the spirit of the present disclosure or the scope of the appended claims.

[0113] Ethylene Oligomerization Unit FIG. 1 shows a diagram of a continuous ethylene oligomerization apparatus. The continuous ethylene oligomerization apparatus includes a 0.5 liter autoclave (which functions 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 supply line, a chain transfer agent supply line, and associated equipment (e.g., valves and piping, among other associated equipment). An 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 to maintain the surface temperature at the reaction temperature. The 0.5 liter autoclave includes an overhead magnetic mechanical stirrer to provide mixing of the reaction mixture, as well as internal cooling coils (to pass heat exchange fluid) and external heating jackets that are utilized as needed to maintain the desired temperature. The continuous ethylene oligomerization apparatus also includes high pressure nitrogen supply lines to the 0.5 liter autoclave reactor and the product tank to provide an inert atmosphere to both vessels. A hydrogen supply line is connected to the ethylene supply line and metered to provide the desired hydrogen:ethylene ratio (if utilized), while a chain transfer agent supply line is connected to the organic reaction medium supply line at the suction side of the diluent pump and metered to provide the desired amount of chain transfer agent to the reactor. The catalyst system is fed to the reactor via one or two ISCO syringe pumps (catalyst system feed pumps) and the organic reaction medium is fed from an organic reaction feed tank via an organic reaction medium pump. The continuous ethylene oligomerizer utilizes a primary catalyst system solution feed pump as the prepared catalyst system is fed to the reactor. The continuous ethylene oligomerizer utilizes primary and secondary catalyst system feed pumps as two solutions containing one or more components of the catalyst system are fed separately into the feed lines to the reactor.

[0114] During continuous ethylene oligomerization, the catalyst system pump(s) (ISCO syringe pumps) continuously feed the catalyst system solution(s) to the reactor at the desired rate(s), the organic reaction medium pump continuously feeds the organic reaction medium to the autoclave at the desired rate, and ethylene is continuously fed to the reactor through a connected mass flow meter at the desired rate. The catalyst system and ethylene are introduced into the autoclave via a dip tube such that the catalyst system solution and ethylene enter the liquid contents of the autoclave at approximately the midpoint of the autoclave's vertical height.

[0115] Example 1 In an argon atmosphere drybox, a 500 mL flask equipped with a stirrer is charged with 20 mmol of zirconium tetrachloride anhydrous (ZrCl4) and 250 mL of dry cyclohexane. The mixture is then stirred for 10 minutes at room temperature. To the stirred mixture, triethylaluminum (TEA) is added followed by ethylaluminum sesquichloride (EASC) to obtain a mixture having an EASC:TEA molar ratio of 3.5:1 and an aluminum to zirconium molar ratio of 7:1. The resulting mixture is then heated at 70°C for 2 hours. The mixture is then cooled to room temperature. 50 mL of the cooled mixture is transferred to a 1-L volumetric flask along with thiophene in an amount to provide a thiophene:zirconium molar ratio of 3:1. The 1-L volumetric flask is then charged with enough dry cyclohexane to obtain 1 liter of catalyst system mixture. The zirconium concentration of the catalyst system mixture thus prepared per liter of cyclohexane is an aluminum to zirconium molar ratio of 7:1, an EASC:TEA molar ratio of 3.5:1, and a thiophene:zirconium molar ratio of 3:1. The volumetric flask of catalyst system mixture is then capped and removed from the argon atmosphere drybox.

[0116] Run 1-1 (Comparison) Utilize the oligomerization apparatus described above using only the primary catalyst system solution pump. Prepare the oligomerization reactor for ethylene oligomerization by filling the high pressure product tank to the desired pressure using the high pressure N2 fill line. Also, subject the reactor to three high pressure N2 fill (up to 800 psig-5.5 MPa) and vent cycles while isolated from the primary catalyst system solution pump. Each nitrogen purge is performed by closing the valve leading to the product tank, filling the autoclave with nitrogen through the reserve inlet port to a pressure of 800 psig (5.5 MPa), holding the autoclave nitrogen pressure for 5 minutes, and then opening the valve leading to the product tank to release the autoclave nitrogen pressure. Maintain the autoclave with a slight residual nitrogen pressure after the nitrogen from the last nitrogen purge is released. Then transfer 200 mL of the catalyst system mixture to the catalyst system ISCO syringe pump of the prepared ethylene oligomerization apparatus. The reactor is then quickly filled with the organic reaction medium (cyclohexane). The diluent pump is then turned on at a rate of 335 mL per hour to bring the reactor to a reaction pressure of 925 psi (6.37 MPa). Once the reactor has reached 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. Once the reactor has reached 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 / hour. After 30 minutes, ethylene is introduced to the reactor at an initial rate of 50 grams / hour, gradually increasing over 30 minutes to a final rate of 175 grams / hour. The oligomerization temperature is maintained by using an internal cooling coil and an external heating jacket as needed. After 6 hours, the oligomerization is terminated by reducing the catalyst system flow rate to 0, reducing the ethylene flow rate to 0, and turning off the heating jacket. Once the reactor is at room temperature, the organic reaction medium flow rate is reduced to 0, and the liquid contents of the reactor are pumped into the high pressure product tank using high pressure N2.

[0117] The reactor is then opened and the solids within the reactor that cover the reactor interior surfaces are collected and added to the reactor effluent collected in the pressurized product tank. A 250 gram liquid sample of the product tank is collected and a known amount of an internal standard (e.g., nonane) is added to the sample. This sample is then treated with a 5 wt. % sodium hydroxide solution to deactivate the catalyst system. The organic layer of the sodium hydroxide treated sample is then analyzed using gas chromatography analysis to determine the oligomer product distribution, Schulz-Flory K value, carbon number purity, and catalyst system productivity. The remaining contents of the product tank are then homogenized and a second 250 gram sample of the product tank is taken. The second sample is then subjected to rotary evaporation at -30 in Hg and 100°C for 1 hour to effectively remove all liquid. The mass of the remaining wax and polymer is determined. A portion of the wax is then analyzed by thermogravimetric analysis (TGA) and the percentage of the solid sample that is polymer is calculated using cutoffs of A) liquid (≦175° C.), B) wax (175° C.-420° C.), and C) polymer ≧420° C. A second portion of the wax and polymer is analyzed by HPLC to determine the molecular weight distribution of the polymer produced in the oligomerization, including Mw, Mn, and Mp. The results of the liquid and polymer analyses are used 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.

[0118] Run 1-2. In an argon atmosphere drybox, a 250 mL volumetric flask is charged with 0.1 moles of triethylsilane (the chain transfer agent), followed by enough dry cyclohexane to obtain 250 mL of the chain transfer agent mixture. The volumetric flask with the chain transfer agent mixture is then capped and removed from the argon atmosphere drybox.

[0119] Connect the chain transfer agent supply line to the organic reaction medium supply line at the suction side of the organic reaction medium pump. Repeat the procedure of Run 1-1, but maintain a molar ratio of triethylsilane to ethylene of 1×10 throughout the ethylene oligomerization. -3 Add a metered amount of triethylsilane solution (approximately 15 mL / hr for an ethylene flow rate of 175 grams / hr) to the suction side of the diluent pump.

[0120] Run 1-3 In an argon atmosphere drybox, a 250 mL volumetric flask is charged with 0.1 mmol of iron(III) octanoate (transition metal compound chain transfer agent) followed by sufficient dry cyclohexane to obtain 250 mL of the transition metal compound chain transfer agent mixture. The volumetric flask of chain transfer agent mixture is then capped and removed from the argon atmosphere drybox.

[0121] Connect the transition metal compound chain transfer agent supply line to the organic reaction medium supply line at the suction side of the organic reaction medium pump. Repeat the procedure of Run 1-1, but maintain the molar ratio of iron(III) octanoate to ethylene at 1×10 throughout the ethylene oligomerization. -6 Add a weighed amount of iron(III) octanoate solution (approximately 15 mL / hr for an ethylene flow rate of 175 grams / hr) to the suction side of the diluent pump.

[0122] Run 1-4 The hydrogen supply line is connected to the ethylene supply line of the ethylene oligomerization unit. The procedure of Run 1-1 is repeated, except that hydrogen is metered into the ethylene at a rate such that the hydrogen to ethylene mass ratio is (1 g hydrogen) / (kg ethylene) throughout the ethylene oligomerization.

[0123] Gas chromatography and HPLC analyses of ethylene oligomerization runs 1-2, 1-3, and 1-4 using chain transfer agents were reviewed and compared to gas chromatography and HPLC analyses of ethylene oligomerization run 1-1. These analyses show that the oligomer products produced in ethylene oligomerization runs 1-2, 1-3, and 1-4 using chain transfer agents have less than 1 wt. % polymers and / or less than 1 wt. % compounds having a weight average molecular weight greater than 1000 g / mol, as compared to ethylene oligomerization run 1-1, which did not utilize a chain transfer agent. These analyses also show that the oligomer products produced in ethylene oligomerization runs 1-2, 1-3, and 1-4 using chain transfer agents produce oligomer products including polymers having lower Mw, polymers having lower Mw maximum peaks, a reduced percentage of polymers, and / or a reduced percentage of polymers having Mw greater than 100,000, as compared to ethylene oligomerization run 1-1, which did not utilize a chain transfer agent. Gas chromatographic analysis of the oligomer products of runs 1-1, 1-2, 1-3, and 1-4 indicates that there is no significant discernible effect on the Schulz-Flory K value, carbon number purity, and productivity of the catalyst system when chain transfer agents are utilized in ethylene oligomerization.

[0124] Example 2 In an argon atmosphere drybox, a first 500 mL flask equipped with a stirrer is charged with zirconium(IV) isopropyl carboxylate (60 mmol), anisole (45 mmol), and dry toluene (200 mL). This first mixture is then stirred for 10 minutes at room temperature. In an argon drybox, a second 500 mL flask equipped with a stirrer is charged with 2-pyrrolidone (43 mmol) and dry toluene (200 mL). Neat diethylaluminum chloride (1.2 mol) is added to this second mixture over 30 minutes. This second mixture is then stirred for an additional 10 minutes. The first mixture is then transferred to a 1 liter volumetric flask. The second mixture is then added to the first mixture in the volumetric flask, and then enough dry toluene is charged to the volumetric flask to obtain a 1 liter solution of the first catalyst system mixture. After thorough mixing, 200 mL of the first catalyst system mixture is transferred to a second 1-L volumetric flask along with sufficient dry toluene to obtain 1 liter of the second catalyst system mixture. The zirconium concentration of the second catalyst system mixture thus prepared is 12 mmol / liter, with an anisole to zirconium molar ratio of 0.75:1, an aluminum:zirconium molar ratio of 20:1, and a 2-pyrrolidone:Al ratio of 0.15:1. The volumetric flask of the second catalyst system mixture is then capped and removed from the argon atmosphere drybox.

[0125] Run 2-1 (comparison) Utilize the previously described oligomerization apparatus using only the primary catalyst system solution pump. Prepare the oligomerization reactor for ethylene oligomerization by filling the high pressure product tank to the desired pressure using the high pressure N2 filling line. Also, subject the reactor to three high pressure N2 filling (up to 800 psig-5.5 MPa) and venting cycles while isolated from the primary catalyst system solution pump. Each nitrogen purge is performed by closing the valve leading to the product tank, filling the autoclave with nitrogen through the reserve inlet port to a pressure of 800 psig (5.5 MPa), holding the nitrogen pressure in the autoclave for 5 minutes, and then opening the valve leading to the product tank to release the nitrogen pressure in the autoclave. Maintain the autoclave with a slight residual nitrogen pressure after the nitrogen from the last nitrogen purge is released. Then transfer 200 mL of the second catalyst system mixture to the catalyst system ISCO syringe pump of the prepared ethylene oligomerization apparatus. The reactor is then quickly filled with the organic reaction medium (cyclohexane). The diluent pump is then turned on at a rate of 485 mL per hour to bring the reactor to a reaction pressure of 450 psi (3.1 MPa). Once the reactor has reached 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. Once the reactor has reached 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 / hour. After 30 minutes, ethylene is introduced to the reactor at an initial rate of 50 grams / hour, gradually increasing over 30 minutes to a final rate of 175 grams / hour. The oligomerization temperature is maintained by using an internal cooling coil and an external heating jacket as needed. After 6 hours, the oligomerization is terminated by reducing the catalyst system flow rate to 0, reducing the ethylene flow rate to 0, and turning off the heating jacket. Once the reactor is at room temperature, the organic reaction medium flow rate is reduced to 0, and the liquid contents of the reactor are pumped into the high pressure product tank using high pressure N2.

[0126] The reactor is then opened and the solids within the reactor that cover the reactor interior surfaces are collected and added to the reactor effluent collected in the pressurized product tank. A 250 gram liquid sample of the product tank is collected and a known amount of an internal standard (e.g., nonane) is added to the sample. This sample is then treated with a 5 wt. % sodium hydroxide solution to deactivate the catalyst system. The organic layer of the sodium hydroxide treated sample is then analyzed using gas chromatography analysis to determine the oligomer product distribution, Schulz-Flory K value, carbon number purity, and catalyst system productivity. The remaining contents of the product tank are then homogenized and a second 250 gram sample of the product tank is taken. The second sample is then subjected to rotary evaporation at -30 in Hg and 100°C for 1 hour to effectively remove all liquid. The mass of the remaining wax and polymer is determined. A portion of the wax is then analyzed by thermogravimetric analysis (TGA) and the percentage of the solid sample that is polymer is calculated using cutoffs of A) liquid (≦175° C.), B) wax (175° C.-420° C.), and C) polymer ≧420° C. A second portion of the wax and polymer is analyzed by HPLC to determine the molecular weight distribution of the polymer produced in the oligomerization, including Mw, Mn, and Mp. The results of the liquid and polymer analyses are used to determine the oligomer product distribution, Schulz-Flory K value, carbon number purity, catalyst system productivity, polymer Mw, polymer Mw maximum peak, and the percentage of polymer in the oligomer product.

[0127] Run 2-2. In an argon atmosphere drybox, a 250 mL volumetric flask is charged with 0.1 moles of triethylsilane (the chain transfer agent), followed by enough dry cyclohexane to obtain 250 mL of the chain transfer agent mixture. The volumetric flask with the chain transfer agent mixture is then capped and removed from the argon atmosphere drybox.

[0128] Connect the chain transfer agent supply line to the organic reaction medium supply line at the suction side of the organic reaction medium pump. Repeat the procedure of Run 2-1, except that the molar ratio of triethylsilane to ethylene is 1×10 throughout the ethylene oligomerization. -3 Add a metered amount of triethylsilane solution (approximately 15 mL / hr for an ethylene flow rate of 175 grams / hr) to the suction side of the diluent pump.

[0129] Run 2-3 In an argon atmosphere drybox, a 250 mL volumetric flask is charged with 0.1 mmol of iron(III) octanoate (transition metal compound chain transfer agent) followed by sufficient dry cyclohexane to obtain 250 mL of the transition metal compound chain transfer agent mixture. The volumetric flask of chain transfer agent mixture is then capped and removed from the argon atmosphere drybox.

[0130] Connect the transition metal compound chain transfer agent supply line to the organic reaction medium supply line on the suction side of the organic reaction medium pump. Repeat the procedure of Run 2-1, but maintain the molar ratio of iron(III) octanoate to ethylene at 1×10 throughout the ethylene oligomerization. -6 Add a weighed amount of iron(III) octanoate solution (approximately 15 mL / hr for an ethylene flow rate of 175 grams / hr) to the suction side of the diluent pump.

[0131] Run 2-4 The hydrogen supply line is connected to the ethylene supply line of the ethylene oligomerization unit. The procedure of Run 2-1 is repeated, except that hydrogen is metered into the ethylene at a rate such that the hydrogen to ethylene mass ratio is (1 g hydrogen) / (kg ethylene) throughout the ethylene oligomerization.

[0132] Gas chromatography and HPLC analyses of ethylene oligomerization runs 2-2, 2-3, and 2-4 using chain transfer agents were reviewed and compared to gas chromatography and HPLC analyses of ethylene oligomerization run 2-1. These analyses show that the oligomer products produced in ethylene oligomerization runs 2-2, 2-3, and 2-4 using chain transfer agents have less than 1 wt. % polymers and / or less than 1 wt. % compounds having a weight average molecular weight greater than 1000 g / mol, as compared to ethylene oligomerization run 2-1, which did not utilize a chain transfer agent. These analyses also show that the oligomer products produced in ethylene oligomerization runs 2-2, 2-3, and 2-4 using chain transfer agents produce oligomer products including polymers having lower Mw, polymers having lower Mw maximum peaks, a reduced percentage of polymers, and / or a reduced percentage of polymers having Mw greater than 100,000, as compared to ethylene oligomerization run 1-1, which did not utilize a chain transfer agent. Gas chromatographic analysis of the oligomer products of runs 2-1, 2-2, 2-3, and 2-4 indicates that there is no significant discernible effect on the Schulz-Flory K value, carbon number purity, and productivity of the catalyst system when chain transfer agents are utilized in ethylene oligomerization.

[0133] Example 3 In an argon atmosphere drybox, a first 500 mL flask equipped with a stirrer is charged with zirconium tetrachloride (100 mmol), isodecyl acetate (105 mmol), and dry ortho-xylene (200 mL). This zirconium mixture is then stirred at room temperature for 10 minutes. The first zirconium mixture is then transferred to a 1-liter volumetric flask, which is then charged with enough ortho-xylene to obtain a 1-liter solution of the first zirconium solution. After thorough mixing, 200 mL of the first zirconium solution is transferred to a second 1-liter volumetric flask along with enough dry ortho-xylene to obtain a 1-liter solution of the second zirconium solution. The second zirconium solution has an isodecyl acetate:Zr molar ratio of 1.05:1. The volumetric flask of the second zirconium solution is then capped and removed from the argon atmosphere drybox.

[0134] In an argon drybox, a second 500 mL flask equipped with a stirrer is charged with dry ortho-xylene (500 mL). Neat diethylaluminum chloride (1.2 mol) is added to the ortho-xylene over 30 minutes while stirring. The mixture is then stirred for an additional 10 minutes. The diethylaluminum chloride solution is then transferred to a 1-liter volumetric flask, which is then charged with enough ortho-xylene to obtain a 1-liter solution of the first zirconium solution. After thorough mixing, 200 mL of the first diethylaluminum chloride solution is transferred to a second 1-liter volumetric flask along with enough dry ortho-xylene to obtain a 1-liter solution of the second diethylaluminum chloride solution. The volumetric flask of the second diethylaluminum chloride solution is then capped and removed from the argon atmosphere drybox.

[0135] Run 3-1 (Comparison) The oligomerization apparatus described above is utilized with the following modifications: the 500 mL autoclave is replaced with a 200 mL autoclave (also equipped with an overhead magnetic mechanical stirrer to effect mixing of the reaction mixture, as well as an internal cooling coil and an external heating jacket), and both the primary and secondary catalyst system pumps are utilized. The oligomerization reactor is prepared for ethylene oligomerization by filling the high pressure product tank to the desired pressure using the high pressure N2 fill line. The reactor is also subjected to three high pressure N2 fill (up 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 leading to the product tank, filling the autoclave with nitrogen through the reserve inlet port to a pressure of 800 psig (5.5 MPa), holding the autoclave nitrogen pressure for 5 minutes, and then opening the valve leading to the product tank to release the autoclave nitrogen pressure. After the nitrogen from the final nitrogen purge is released, the autoclave is maintained with a slight residual nitrogen pressure. Transfer 200 mL of the second zirconium mixture to the primed ethylene oligomerizer primary catalyst system ISCO syringe pump. Transfer 200 mL of the second diethylaluminum chloride solution to the primed ethylene oligomerizer secondary catalyst system ISCO syringe pump. The reactor is then quickly filled with dry organic reaction medium (ortho-xylene). The diluent pump is then turned on at a rate of 680 mL per hour to bring the reactor to a reaction pressure of 3000 psi (20.7 MPa). Once the reactor has reached this reaction pressure, start the overhead magnetic stirrer and set it to approximately 1200 rpm, and turn on the heating jacket and set it to 165°C. Once the reactor has reached a stable temperature of 70°C, turn on the primary and secondary catalyst system ISCO pumps and set them to feed the second zirconium solution and the second diethylaluminum chloride solution at a rate of 11 mL / hour. The feed rates of the zirconium solution and the diethylaluminum chloride solution give an Al:Zr ratio of 12: 1. After 30 minutes, ethylene is introduced into the reactor at an initial rate of 50 grams / hour and gradually increased to a final rate of 600 grams / hour over 30 minutes.The oligomerization temperature is maintained by using internal cooling coils and an external heating jacket as needed. After 4 hours, the oligomerization is terminated by reducing the zirconium solution flow rate and the diethylaluminum chloride solution feed rate to zero, reducing the ethylene flow rate to zero, and turning off the heating jacket. Once the reactor is at room temperature, the organic reaction medium flow rate is reduced to zero and the liquid contents of the reactor are pumped into the high pressure product tank using high pressure N2.

[0136] The reactor is then opened and the solids within the reactor that cover the reactor interior surfaces are collected and added to the reactor effluent collected in the pressurized product tank. A 250 gram liquid sample of the product tank is collected and a known amount of an internal standard (e.g., nonane) is added to the sample. This sample is then treated with a 5 wt. % sodium hydroxide solution to deactivate the catalyst system. The organic layer of the sodium hydroxide treated sample is then analyzed using gas chromatography analysis to determine the oligomer product distribution, Schulz-Flory K value, carbon number purity, and catalyst system productivity. The remaining contents of the product tank are then homogenized and a second 250 gram sample of the product tank is taken. The second sample is then subjected to rotary evaporation at -30 in Hg and 100°C for 1 hour to effectively remove all liquid. The mass of the remaining wax and polymer is determined. A portion of the wax is then analyzed by thermogravimetric analysis (TGA) and the percentage of the solid sample that is polymer is calculated using cutoffs of A) liquid (≦175° C.), B) wax (175° C.-420° C.), and C) polymer ≧420° C. A second portion of the wax and polymer is analyzed by HPLC to determine the molecular weight distribution of the polymer produced in the oligomerization, including Mw, Mn, and Mp. The results of the liquid and polymer analyses are used to determine the oligomer product distribution, Schulz-Flory K value, carbon number purity, catalyst system productivity, polymer Mw, polymer Mw maximum peak, and the percentage of polymer in the oligomer product.

[0137] Run 3-2. In an argon atmosphere drybox, a 250 mL volumetric flask is charged with 360 mmol of triethylsilane (the chain transfer agent), followed by sufficient dry ortho-xylene to obtain 250 mL of the chain transfer agent mixture. The volumetric flask with the chain transfer agent mixture is then capped and removed from the argon atmosphere drybox.

[0138] Connect the chain transfer agent supply line to the organic reaction medium supply line at the suction side of the organic reaction medium pump. Repeat the procedure of Run 3-1, except that the molar ratio of triethylsilane to ethylene is 1×10 throughout the ethylene oligomerization. -3 Add a metered amount of triethylsilane solution (approximately 15 mL / hr for an ethylene flow rate of 600 grams / hr) to the suction side of the diluent pump.

[0139] Run 3-3 In an argon atmosphere drybox, a 250 mL volumetric flask is charged with 0.36 mmol of iron(III) octanoate (transition metal compound chain transfer agent) followed by sufficient dry cyclohexane to obtain 250 mL of the transition metal compound chain transfer agent mixture. The volumetric flask of chain transfer agent mixture is then capped and removed from the argon atmosphere drybox.

[0140] Connect the transition metal compound chain transfer agent supply line to the organic reaction medium supply line at the suction side of the organic reaction medium pump. Repeat the procedure of Run 3-1, but maintain the molar ratio of iron(III) octanoate to ethylene at 1×10 throughout the ethylene oligomerization. -6 Add a weighed amount of iron(III) octanoate solution (approximately 15 mL / hr for an ethylene flow rate of 175 grams / hr) to the suction side of the diluent pump.

[0141] Run 3-4 The hydrogen supply line is connected to the ethylene supply line of the ethylene oligomerization unit. The procedure of Run 3-1 is repeated, except that hydrogen is metered into the ethylene at a rate such that the hydrogen to ethylene mass ratio is (1 g hydrogen) / (kg ethylene) throughout the ethylene oligomerization.

[0142] Gas chromatography and HPLC analyses of ethylene oligomerization runs 3-2, 3-3, and 3-4 using chain transfer agents were reviewed and compared to gas chromatography and HPLC analyses of ethylene oligomerization run 3-1. These analyses show that the oligomer products produced in ethylene oligomerization runs 3-2, 3-3, and 3-4 using chain transfer agents have less than 1 wt.% polymers and / or less than 1 wt.% compounds having a weight average molecular weight greater than 1000 g / mol, as compared to ethylene oligomerization run 3-1, which did not utilize a chain transfer agent. These analyses also show that the oligomer products produced in ethylene oligomerization runs 3-2, 3-3, and 3-4 using chain transfer agents produce oligomer products including polymers having lower Mw, polymers having lower Mw maximum peaks, a reduced percentage of polymers, and / or a reduced percentage of polymers having Mw greater than 100,000, as compared to ethylene oligomerization run 3-1, which did not utilize a chain transfer agent. Gas chromatographic analysis of the oligomer products of Runs 3-1, 3-2, 3-3, and 3-4 indicates that there is no significant discernible effect on the Schulz-Flory K value, carbon number purity, and productivity of the catalyst system when chain transfer agents are utilized in ethylene oligomerization.

[0143] The following provides exemplary clauses of the subject matter claimed herein. For clarity, not all features of actual implementations are described herein. It can be appreciated that the development of such actual implementations will require numerous implementation-specific decisions to be made to achieve the developer's particular goals, such as compliance with system-related and business-related constraints that may vary from implementation to implementation. It can also be appreciated that such a development effort, even if complex and time-consuming, will be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure. Moreover, various modifications can be made within the scope of the invention contemplated herein, and embodiments of the invention can include combinations of features other than those expressly claimed. In particular, flow configurations other than those expressly described herein are within the scope of the invention.

[0144] Article 1. a) contacting i) ethylene with ii) a catalyst system (or catalyst system component) having the formula ZrX 1 m Y 1 q Zirconium compounds having the formula 1 is independently a halide, and each Y 1 is independently a hydrocarboxyte, dihydrocarbyl azanide, hydrocarbyl carboxylate, hydrocarbyl sulfonate, or β-diketonate, 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 hydrocarbyl metal 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) optionally an organic reaction medium; and b) forming oligomeric products in a reaction zone.

[0145] Article 2. a) providing in a reaction zone: i) ethylene; and ii) a catalyst system (or catalyst system components) having the formula: 1) ZrX1 m Y 1 q Zirconium compounds having the formula 1 is independently a halide, and each Y 1 is independently a hydrocarboxyte, dihydrocarbyl azanide, hydrocarbyl carboxylate, hydrocarbyl sulfonate, or β-diketonate, 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 hydrocarbyl metal 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) optionally an organic reaction medium; and b) forming an oligomeric product in a reaction zone.

[0146] Article 3. The chain transfer agent is represented by the formula R 31 SiH3, (R 31 )2SiH2, (R 31 )3SiH,R 31 OSiH3, (R 31 O)2SiH2, (R 31 O)3SiH,R 32 S.H., 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 are independently 15 3. The process according to clause 1 or 2, wherein the R is a hydrocarbyl group.

[0147] Article 4. The reaction zone may be any of the chain transfer agents disclosed herein, such as, for example, 1×10 molar ratios of hydrogen to ethylene, among other values ​​and ranges. -5 :1, 5×10 -4 :1, 1×10 -4 :1, or 5×10 -3 :1 min;5×10 -1 :1, 1×10 -1 :1, 5×10 -2 :1, or 1×10 -2 :1 max;1×10 -5 :1~5×10 -1 :1, 5×10 -4 :1~1×10 -1 :1, 1×10 -4 :1~5×10 -2 :1, or 5×10 -3 :1~1×10 -2 4. The process according to any one of clauses 1 to 3, wherein the process has a range of:

[0148] Article 5. a) contacting i) ethylene with ii) a catalyst system (or catalyst system component) having the formula ZrX 1 m Y 1 q Zirconium compounds having the formula 1 is independently a halide, and each Y 1 is independently a hydrocarboxyte, dihydrocarbyl azanide, hydrocarbyl carboxylate, hydrocarbyl sulfonate, or β-diketonate, 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 hydrocarbyl metal compound; iii) hydrogen; and iv) optionally an organic reaction medium; and b) forming oligomeric products in a reaction zone.

[0149] Article 6. a) providing in a reaction zone: i) ethylene; and ii) a catalyst system (or catalyst system components) having the formula: 1) ZrX 1 m Y 1 q Zirconium compounds having the formula 1 is independently a halide, and each Y 1 is independently a hydrocarboxyte, dihydrocarbyl azanide, hydrocarbyl carboxylate, hydrocarbyl sulfonate, or β-diketonate, 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 hydrocarbyl metal compound; iii) hydrogen; and iv) optionally an organic reaction medium; and b) forming oligomeric products in said reaction zone.

[0150] Article 7. The reaction zone may be configured to have any of the hydrogen to ethylene mass ratios 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), among other values ​​and ranges; 7. The process of claim 5 or 6, wherein the hydrogen permeability is within the range of (0.25g hydrogen) / (kg ethylene) to (5g hydrogen) / (kg ethylene), (0.25g hydrogen) / (kg ethylene) to (5g hydrogen) / (kg ethylene), (0.25g hydrogen) / (kg ethylene) to (4g hydrogen) / (kg ethylene), (0.4g hydrogen) / (kg ethylene) to (3g hydrogen) / (kg ethylene), (0.4g hydrogen) / (kg ethylene) to (2.5g hydrogen) / (kg ethylene), (0.4g hydrogen) / (kg ethylene) to (2g hydrogen) / (kg ethylene), or (0.5g hydrogen) / (kg ethylene) to (2g hydrogen) / (kg ethylene).

[0151] Article 8. a) contacting i) ethylene with ii) a catalyst system (or catalyst system component) having the formula ZrX 1 m Y 1 q Zirconium compounds having the formula 1 is independently a halide, and each Y 1 is independently a hydrocarboxyte, dihydrocarbyl azanide, hydrocarbyl carboxylate, hydrocarbyl sulfonate, or β-diketonate, 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 hydrocarbyl metal compound; iii) a transition metal compound chain transfer agent; and iv) optionally an organic reaction medium; and b) forming oligomeric products in a reaction zone.

[0152] Article 9. a) providing in a reaction zone: i) ethylene; and ii) a catalyst system (or catalyst system components) having the formula: 1) ZrX 1 m Y 1 q Zirconium compounds having the formula 1 is independently a halide, and each Y 1 is independently a hydrocarboxyte, dihydrocarbyl azanide, hydrocarbyl carboxylate, hydrocarbyl sulfonate, or β-diketonate, 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) said catalyst system (or catalyst system components) comprising a hydrocarbyl metal compound, iii) a transition metal compound chain transfer agent, and iv) optionally an organic reaction medium; and b) forming an oligomeric product in said reaction zone.

[0153] Article 10. The transition metal compound chain transfer agent has the formula MX 4p wherein M is the transition metal; and X 4 10. The process according to clause 8 or 9, wherein:

[0154] Article 11. The transition metal compound chain transfer agent has the formula MX 4 p wherein M is iron, cobalt, or nickel.

[0155] Article 12. The transition metal compound chain transfer agent has the formula MX 4 p Any transition metal compound chain transfer agent having the formula: 4 is C4~C 19 12. The process according to clause 10 or 11, wherein the compound is a carboxylate.

[0156] Article 13. The reaction zone may be any of the transition metal to ethylene molar ratios of the transition metal compound chain transfer agents disclosed herein, including 1×10 to 1×10, among other values ​​and ranges. -9 :1, 5×10 -8 :1, 1×10 -8 :1, 5×10 -7 :1, or 1×10 -7 :1 min;5×10 -3 :1, 1×10 -3 :1, 5×10 -4 :1, 1×10 -4 :1, or 5×10 -5 :1 max;1×10 -9 :1~5×10 -3 :1, 5×10 -8 :1~1×10 -3 :1, 1×10 -8 :1~5×10 -4 :1, 5×10 -7 :1~1×10 -4 :1, or 1×10 -7 :1~5×10-5 The process according to any one of clauses 8 to 12, comprising:

[0157] Article 14. The hydrocarbyl metal compound may be any of the hydrocarbyl metal compounds disclosed herein (e.g., any of the metals disclosed herein (including metals of Groups 1, 2, 11, 12, 13, or 14, among other metal groups disclosed herein), and any of the hydrocarbyl groups (C1-C 20 , C1~C 10 or C1 to C6 hydrocarbyl groups, and other more specific hydrocarbyl groups disclosed herein), the process of any one of clauses 1 to 13.

[0158] Article 15. 15. The process of any one of clauses 1-14, wherein the metal of the hydrocarbyl metal compound and the zirconium of the zirconium compound have any value disclosed herein (e.g., a minimum of 0.1:1, 0.2:1, 0.6:1, 1:1, 2:1 and 10:1; a maximum of 100:1, 75:1, 50:1 and 25:1, 15:1 and 10:1; or within the ranges 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, among other values ​​and ranges).

[0159] Article 16. 16. The process of any one of clauses 1-15, wherein the catalyst system (or catalyst system component) further comprises a neutral non-ionic organic modifier.

[0160] Article 17. 17. The process of clause 16, wherein the neutral nonionic organic modifier comprises any ether, ester, ketone, aldehyde, alcohol, anhydride, acid chloride, nitrile, sulfide, disulfide, phosphine, amine, or amide disclosed herein.

[0161] Article 18. 18. The process of clause 16 or 17, wherein the molar ratio of the neutral nonionic organic modifier to zirconium of the zirconium compound can be any value described herein (e.g., a minimum of 0.1:1, 0.5:1, 0.75:1 0.8:1, 0.9:1, or 1:1; a maximum of 20:1, 15:1, 10:1 7.5:1, or 5:1; or within the ranges of 0.5:1 20:1, 0.5:1 to 15:1, 0.75:10:1, 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, among other values ​​and ranges).

[0162] Article 19. 19. The process of any one of clauses 16-18, wherein the molar ratio of the neutral nonionic organic modifier to the hydrocarbyl metal (or hydrocarbyl aluminum) compound can be any value described herein (e.g., a minimum of 0.05:1, 0.1:1, 0.5:1, 0.75:1 0.8:1, 0.9:1, or 1:1; a maximum of 5:1, 3:1, 2:1, 1.5:1, 1:1, 0.75:1, or 0.5:1; or within the ranges of 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, among other values ​​and ranges).

[0163] Article 20. The zirconium compound has the formula ZrX 1 m Y 1 q wherein each X 1 is independently chloride or bromide, and each Y1 are independently 10 Hydrocarboxylates (e.g., any of those described herein), C1-C 15 Hydrocarbyl carboxylates (e.g., any of those described herein), or C1-C 15 20. The process of any one of clauses 1-19, wherein the hydrocarbyl sulfonate is a hydrocarbyl sulfonate (such as any 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.

[0164] Article 21. 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 are independently 10 is an alkyl group, 2 21. The process of any one of clauses 1-20, wherein is independently chloride, bromide, or iodide; n is an integer from 0 to 3; and q is an integer from 0 to 6.

[0165] Article 22. The neutral nonionic organic modifier is any one of C2 to C4 20 Ether, C3-C 20 Esters, C3-C 20 Ketones, C2-C 20 Nitriles, C2-C 20 Sulfides, C2-C 20 Disulfides, C3-C 20 Phosphine, C1-C 20 Amine, or C2-C 20 23. The process of any one of clauses 20 to 22, comprising an amide.

[0166] Article 23. The zirconium compound has the formula ZrX 1 m (In the formula, each 1 is independently chloride or bromide and m is 4, and said 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 (wherein each X 2 is independently a halide, and each R 1 are independently a C2 to C4 alkyl group, and the molar ratio of the metal of the hydrocarbyl metal compound (or the aluminum of the hydrocarbyl aluminum compound) to the zirconium of the zirconium compound is within any of the ranges disclosed herein (e.g., within the range of 1:1 to 50:1).

[0167] Article 24. The catalyst system (or catalyst system component) is 20 24. The process of claim 23, further comprising a neutral nonionic organic modifier comprising an ester, 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., within the range of 0.5:1 to 5:1), and the molar ratio of the metal of the hydrocarbyl metal compound (or the aluminum of the hydrocarbyl aluminum compound) to the zirconium of the zirconium compound is within any of the ranges disclosed herein (e.g., within the range of 10:1 to 25:1).

[0168] Article 25. 25. The process of claim 24, wherein the neutral non-ionic organic modifier is contacted with the zirconium compound before the zirconium compound is contacted with ethylene and / or the hydrocarbyl metal compound (and / or introduced into the reaction zone).

[0169] Article 26. The catalyst system (or catalyst system component) is 20 Ether, C2-C 20 Sulfides, C1-C 20 Amines, C3-C 20 25. The process of claim 23 or 24, further comprising a neutral non-ionic organic modifier comprising a phosphine, a phosphine, or any combination thereof, wherein the molar ratio of the neutral non-ionic organic modifier to the zirconium of the zirconium compound is within any of the ranges disclosed herein (e.g., within the range of 0.5:1 to 20:1), and the molar ratio of the metal of the hydrocarbyl metal compound (or the aluminum of the hydrocarbyl aluminum compound) to the zirconium of the zirconium compound is within any of the ranges disclosed herein (e.g., within the range of 1:1 to 15:1).

[0170] Article 27. The zirconium compound has the formula ZrX 1 m Y 1 q (In the formula, each 1 is independently chloride or bromide, and each Y 1 are independently 10 Hydrocarboxylates (e.g., any of those described herein), C1-C 10 Hydrocarbyl carboxylates (e.g., any of those described herein), or C1-C 15 a hydrocarbyl sulfonate (e.g., any 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 hydrocarbyl metal compound has the formula AlX 2 n R 1 3-n , Al2X 2 3R 1 3, or any combination thereof (wherein each X 2 is independently a halide, and each R 1are independently a C2 to C4 alkyl group), and the molar ratio of the metal of the hydrocarbyl metal compound (or the aluminum of the hydrocarbyl aluminum compound) to the zirconium of the zirconium compound is in the range of 1:1 to 50:1.

[0171] Article 28. 28. The process of claim 27, wherein the zirconium compound is at least partially hydrolyzed by contacting the zirconium compound with water using any of the molar ratios of water to zirconium disclosed herein (e.g., 0.01:1 to 3:1, 0.1: to 2:1, 0.25:1 to 1.75:1).

[0172] Article 29. The catalyst system (or catalyst system component) is 15 29. The process of claim 27 or 28, further comprising a neutral non-ionic organic modifier comprising an amide, wherein the molar ratio of the neutral non-ionic organic modifier to the metal of the hydrocarbyl metal compound (or aluminum of the hydrocarbyl aluminum compound) is in the range of 0.1:1 to 1:1.

[0173] Article 30. 30. The process of clause 29, wherein the neutral non-ionic organic modifier is contacted with the hydrocarbyl metal (or hydrocarbyl aluminum) compound before the hydrocarbyl metal (or hydrocarbyl aluminum) compound is contacted with ethylene (and / or introduced into the reaction zone).

[0174] Article 31. The catalyst system (or catalyst system component) is 20 Ether, C2-C 20 Sulfides, C1-C 2031. The process of any one of clauses 27-30, further comprising a neutral non-ionic organic modifier comprising an amine, a tertiary amine, or any combination thereof, wherein the neutral non-ionic organic modifier and the zirconium of the zirconium compound are within any range disclosed herein (e.g., within the range of 0.1:1 to 10:1).

[0175] Article 32. 32. The process of claim 31, wherein the neutral non-ionic organic modifier is contacted with the zirconium compound before the zirconium compound is contacted with ethylene and / or the hydrocarbyl metal compound (and / or introduced into the reaction zone).

[0176] The oligomer product may be produced in any of the molar ratios of zirconium to ethylene of the zirconium compound of the reaction zone described herein (e.g., 5×10 to 10×10 molar ratios of zirconium to ethylene of the zirconium compound of the reaction zone, among other molar ratios and ranges of zirconium to ethylene of the zirconium compound of the reaction zone). -7 :1, 1×10 -6 :1, 5×10 -5 :1, or 2.5×10 -5 The minimum molar ratio of zirconium to ethylene in the zirconium compound in the reaction zone is 7.5×10:1; -4 :1, 5×10 -4 :1, 2.5×10 -4 :1, or 1×10 -4 The maximum molar ratio of zirconium to ethylene in the zirconium compound in the reaction zone is 5×10 -7 :1~1×10 -4 :1, 1×10 -6 : 1~2.5×10 -4 :1, 5×10 -5 :1~5×10 -4 :1, or 2.5×10 -5 : 1~7.5×10 -4 33. The process of any one of clauses 1 to 32, wherein the zirconium compound in the reaction zone is (or the reaction zone has) a molar ratio of zirconium to ethylene in the reaction zone ranging from 0.5:1 to 1.

[0177] Article 34. The oligomer product may be subjected to any of the pressures 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), among other pressures and pressure ranges. si(689kPa)~5000psi(34.5MPa), 100psi(689kPa)~2,500psi(17.2MPa), 100psi(689kPa)~1000psi(6.8 9MPa), 500psi(3.45MPa)~4500psi(31MPa), 500psi(3.45MPa)~2,500psi(17.2MPa), 500psi(3.45MPa)~1 34. The process of any one of clauses 1-33, wherein the reaction zone is formed at (or has a pressure in the range of) 1,000 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).

[0178] Article 35. The oligomer product may be produced at any of the ethylene partial pressures 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), among other ethylene partial pressures and pressure ranges; or 100psi (689kPa) ~ 5000psi (34.5MPa), 100psi (689kPa) ~ 2,500psi (17.2MPa), 100psi (689kPa) ~ 1000psi (6. 89MPa), 500psi(3.45MPa)~4500psi(31MPa), 500psi(3.45MPa)~2,500psi(17.2MPa), 500psi(3.45MPa)~100 35. The process of any one of clauses 1-34, wherein the reaction zone is formed at (or has an ethylene partial pressure in the range of) 0 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).

[0179] Article 36. 36. The process of any one of clauses 1-35, wherein the oligomeric product is formed at (or the reaction zone has) any of the temperatures described herein (e.g., minimum temperatures of 0°C, 25°C, 40°C, 50°C, 75°C, 100°C, or 125°C; maximum temperatures of 250°C, 200°C, 150°C, 125°C, 100°C, or 90°C; temperatures ranging from 0°C to 250°C, 25°C to 200°C, 40°C to 150°C, 40°C to 100°C, 50°C to 100°C, 50°C to 150°C, 75°C to 125°C, 75°C to 250°C, 100°C to 200°C, or 100°C to 200°C, among other temperature values ​​and ranges).

[0180] Article 37. 37. The process of any one of clauses 1-36, wherein the oligomeric product is formed at (or the reaction zone has) any of the ethylene:organic reaction medium mass ratios 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 ranging from 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, among other ethylene:organic reaction medium mass ratio values ​​and ranges).

[0181] Article 38. 38. The process of any one of clauses 1-37, wherein the oligomeric product is formed at (or the reaction zone has) any of the reaction zone residence times (or average reaction zone residence times) 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) ranging from 10 minutes to 2.5 hours, 20 minutes to 2 hours, 30 minutes to 2 hours, or 30 minutes to 1.5 hours, among other reaction zone residence time (or average reaction zone residence time) values ​​and ranges).

[0182] Article 39. 39. The process of any one of clauses 1-38, wherein the oligomeric products can be formed at any of the ethylene conversions (or single pass ethylene conversions) 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) ranging from 30% to 90%, 35% to 90%, 40% to 87.5%, 45% to 87.5%, 50% to 85%, or 55% to 85%, among other ethylene conversion (or single pass ethylene conversion) values ​​and ranges).

[0183] Article 40. 40. The process of any one of clauses 1-39, wherein the oligomeric 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, 0.4 to 0.8, 0.5 to 0.8, 0.5 to 0.7, or 0.55 to 0.7, among other Schulz-Flory K values ​​and ranges).

[0184] Article 41. 41. The process of any one of clauses 1-40, wherein the process produces an oligomeric 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 reduced percentage of polymer having a Mw greater than 100,000; or (e) any combination thereof, compared to the same process without the use of a) 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, as described in any one of clauses 1-4, 2) hydrogen as described in any one of clauses 5-7, and / or 3) a transition metal compound chain transfer agent as described in any one of clauses 8-13.

[0185] Article 42. 42. The process of any one of clauses 1-41, wherein the oligomer product comprises: (a) less than 1 wt. % polymer; (b) less than 1 wt. % compounds having a weight average molecular weight greater than 1000 g / mol; or (c) any combination thereof, wherein the wt. % is based on a total weight of the oligomer product.

[0186] All publications and patents mentioned herein are incorporated herein by reference. The publications and patents mentioned herein may be used, for example, for the purpose of describing and disclosing constructs and methodologies described therein that may be used in connection with the inventions described herein. Publications mentioned throughout the text are provided solely for their disclosure prior to the filing date of this application. Nothing herein should be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention.

Claims

1. a) contacting, i) ethylene; ii) a catalyst system comprising: 1) Formula ZrX １ ｍ Y １ ｑ Zirconium compounds having the formula １ is independently a halide; １ is independently a hydrocarboxyte, a dihydrocarbyl azanide, a hydrocarbyl carboxylate, a hydrocarbyl sulfonate, or a β-diketonate; 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) the catalyst system, comprising a hydrocarbyl metal compound; iii) a chain transfer agent comprising a compound having a hydrogen-silicon bond, a hydrogen-sulfur bond, a compound having a hydrogen-phosphorus bond, or any combination thereof; iv) optionally, said contacting with an organic reaction medium; and b) forming an oligomeric product in a reaction zone; The process wherein the oligomeric product has a Schulz-Flory K value of 0.4 to 0.

8.

2. The chain transfer agent is represented by the formula R ３１ SiH ３ , (R ３１ ) ２ SiH ２ , (R ３１ ) ３ SiH,R ３１ OSiH3, (R ３１ O) ２ SiH ２ , (R ３１ O) ３ SiH,R ３２ S.H., R. ３２ CO ２ CH ２ S.H., R. ３２ CO ２ CH ２ CH ２ S.H., R. ３３ PH ２ , (R ３３ ) ２ P.H., R. ３３ OPH ２ , (R ３３ O) ２ or any combination thereof, wherein each R ３１ , R ３２ , and R ３３ are independently １ ~C １５ The process of claim 1 wherein the alkyl group is a hydrocarbyl group.

3. The reaction zone is 1×10 －５ : 1 to 5 x 10 －１ 2. The process of claim 1, wherein the molar ratio of the chain transfer agent to ethylene is in the range of 1:

1.

4. 2. The process of claim 1, wherein the oligomeric product comprises: (a) less than 1 weight percent polymer; (b) less than 1 weight percent compounds having a weight average molecular weight greater than 1000 g / mol; or (c) any combination thereof, wherein the weight percent is based on the total weight of the oligomeric product.

5. 2. The process of claim 1, wherein the process produces an oligomeric 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 reduced percentage of polymer having a Mw greater than 100,000 g / mol; or (e) any combination thereof, compared to the same process without the use of the 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.

6. The hydrocarbyl metal compound has the formula AlX ２ ３－ｎ R １ ｎ , Al ２ X ２ ６－ｑ－ R １ ｑ , R １ ２ Zn, or any combination thereof, wherein each R １ are independently １ ~C １０ is an alkyl group, ２ 2. The process of claim 1, wherein is independently chloride, bromide, or iodide; n is an integer from 0 to 3; and q is an integer from 0 to 6.

7. 10. The process of claim 1, wherein the catalyst system further comprises a neutral non-ionic organic modifier.

8. 8. The process of claim 7, wherein the neutral non-ionic organic modifier comprises an ether, ester, ketone, aldehyde, alcohol, anhydride, acid chloride, nitrile, sulfide, disulfide, phosphine, amine, or amide.

9. The zirconium compound has the formula ZrX １ ｍ (In the formula, each １ is independently chloride or bromide and m is 4, and said hydrocarbyl metal compound has the formula AlX ２ ｎ R １ ３－ｎ , Al ２ X ２ ３ R １ ３ , R １ ２ Zn, or any combination thereof (wherein each X ２ is independently a halide; １ are independently ２ ~C ４ 2. The process of claim 1 , wherein the alkyl group is an alkyl group.

10. The catalyst system contains C as a neutral non-ionic organic modifier. ２ ~C ２０ Estelle, C. ２ ~C ２０ Ether, or C ２ ~C ２０ 10. The process of claim 9 further comprising a sulfide.

11. The zirconium compound has the formula ZrY １ ｑ (In the formula, each Y １ are, independently, － OR ２ and R ２ is C １ ~C １０ Alkyl group or － O.C.(=O)R ３ and R ３ is C １ ~C １０ and q is an integer from 2 to 4; and the hydrocarbyl metal compound has the formula AlX ３ ｎ R １ ３－ｎ , Al ２ X ３ ３ R １ ３ or any combination thereof, ２ is independently a halide; １ are independently ２ ~C ４ 2. The process of claim 1 , wherein the alkyl group is an alkyl group.

12. a) contacting, i) ethylene; ii) a catalyst system comprising: 1) Formula ZrX １ ｍ Y １ ｑ Zirconium compounds having the formula １ is independently a halide; １ is independently a hydrocarboxyte, a dihydrocarbyl azanide, a hydrocarbyl carboxylate, a hydrocarbyl sulfonate, or a β-diketonate; 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) the catalyst system, comprising a hydrocarbyl metal compound; iii) hydrogen; and iv) optionally, said contacting with an organic reaction medium; and b) forming an oligomeric product in a reaction zone; The process wherein the oligomeric product has a Schulz-Flory K value of 0.4 to 0.

8.

13. 13. The process of claim 12, wherein the reaction zone has a hydrogen to ethylene mass ratio in the range of (0.05 g hydrogen) / (kg ethylene) to (5 g hydrogen) / (kg ethylene).

14. 13. The process of claim 12, wherein the oligomeric product comprises: (a) less than 1 weight percent polymer; (b) less than 1 weight percent compounds having a weight average molecular weight greater than 1000 g / mol; or (c) any combination thereof, wherein the weight percent is based on the total weight of the oligomeric product.

15. 13. The process of claim 12, wherein the process produces an oligomeric 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 reduced percentage of polymer having a Mw greater than 100,000 g / mol; or (e) any combination thereof, compared to the same process without the use of hydrogen.

16. The hydrocarbyl metal compound has the formula AlX ２ ３－ｎ R １ ｎ , Al ２ X ２ ６－ｑ－ R １ ｑ , R １ ２ Zn, or any combination thereof, wherein each R １ are independently １ ~C １０ is an alkyl group, ２ 13. The process of claim 12, wherein is independently chloride, bromide, or iodide; n is an integer from 0 to 3; and q is an integer from 0 to 6.

17. The process of claim 12, wherein the catalyst system further comprises a neutral non-ionic organic modifier.

18. 18. The process of claim 17, wherein the neutral non-ionic organic modifier comprises an ether, ester, ketone, aldehyde, alcohol, anhydride, acid chloride, nitrile, sulfide, disulfide, phosphine, amine, or amide.

19. The zirconium compound has the formula ZrX １ ｍ (In the formula, each １ is independently chloride or bromide and m is 4, and said hydrocarbyl metal compound has the formula AlX ２ ｎ R １ ３－ｎ , Al ２ X ２ ３ R １ ３ , R １ ２ Zn, or any combination thereof (wherein each X ２ is independently a halide; １ are independently ２ ~C ４ 13. The process of claim 12, wherein the alkyl group is an alkyl group.

20. The catalyst system contains C as a neutral non-ionic organic modifier. ２ ~C ２０ Estelle, C. ２ ~C ２０ Ether, or C ２ ~C ２０ 20. The process of claim 19 further comprising a sulfide.

21. The zirconium compound has the formula ZrY １ ｑ (In the formula, each Y １ are, independently, － OR ２ and R ２ is C １ ~C １０ Alkyl group or － O.C.(=O)R ３ and R ３ is C １ ~C １０ and q is an integer from 2 to 4; and the hydrocarbyl metal compound has the formula AlX ３ ｎ R １ ３－ｎ , Al ２ X ３ ３ R １ ３ or any combination thereof, ３ is independently a halide; １ are independently ２ ~C ４ 13. The process of claim 12, wherein the alkyl group is an alkyl group.

22. a) contacting, i) ethylene; ii) a catalyst system comprising: 1) Formula ZrX １ ｍ Y １ ｑ Zirconium compounds having the formula １ is independently a halide; １ is independently a hydrocarboxyte, a dihydrocarbyl azanide, a hydrocarbyl carboxylate, a hydrocarbyl sulfonate, or a β-diketonate; 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) the catalyst system, comprising a hydrocarbyl metal compound; iii) a transition metal compound chain transfer agent; and iv) optionally, said contacting with an organic reaction medium; and b) forming an oligomeric product in a reaction zone; The process wherein the oligomeric product has a Schulz-Flory K value of 0.4 to 0.

8.

23. The transition metal compound chain transfer agent has the formula MX ４ ｐ wherein M is a transition metal; and X ４ 23. The process of claim 22, wherein is a monoanion and p is an integer from 2 to 4.

24. 24. The process of claim 23, wherein M is iron, cobalt, or nickel.

25. X ４ But, C ４ ~C １９ 24. The process of claim 23, wherein the carboxylate is a carboxylate.

26. The reaction zone is 1×10 －８ ~1×10 －３ 24. The process of claim 23, wherein the chain transfer agent has a metal to ethylene molar ratio in the range of:

27. 23. The process of claim 22, wherein the oligomeric product comprises: (a) less than 1 weight percent polymer; (b) less than 1 weight percent compounds having a weight average molecular weight greater than 1000 g / mol; or (c) any combination thereof, wherein the weight percent is based on the total weight of the oligomeric product.

28. 23. The process of claim 22, wherein the process produces an oligomeric 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 reduced percentage of polymer having a Mw greater than 100,000 g / mol; or (e) any combination thereof, compared to the same process without the use of the transition metal compound chain transfer agent.

29. The hydrocarbyl metal compound has the formula AlX ２ ３－ｎ R １ ｎ , Al ２ X ２ ６－ｑ－ R １ ｑ , R １ ２ Zn, or any combination thereof, wherein each R １ are independently １ ~C １０ is an alkyl group, ２ 23. The process of claim 22, wherein is independently chloride, bromide, or iodide; n is an integer from 0 to 3; and q is an integer from 0 to 6.

30. 23. The process of claim 22, wherein the catalyst system further comprises a neutral non-ionic organic modifier.

31. 31. The process of claim 30, wherein the neutral non-ionic organic modifier comprises an ether, ester, ketone, aldehyde, alcohol, anhydride, acid chloride, nitrile, sulfide, disulfide, phosphine, amine, or amide.

32. The zirconium compound has the formula ZrX １ ｍ (In the formula, each １ is independently chloride or bromide and m is 4, and said hydrocarbyl metal compound has the formula AlX ２ ｎ R １ ３－ｎ , Al ２ X ２ ３ R １ ３ , R １ ２ Zn, or any combination thereof (wherein each X ２ is independently a halide; １ are independently ２ ~C ４ 23. The process of claim 22, wherein the alkyl group is an alkyl group.

33. The catalyst system contains C as a neutral non-ionic organic modifier. ２ ~C ２０ Estelle, C. ２ ~C ２０ Ether, or C ２ ~C ２０ 33. The process of claim 32 further comprising a sulfide.

34. The zirconium compound has the formula ZrY １ ｑ (In the formula, each Y １ are, independently, － OR ２ and R ２ is C １ ~C １０ Alkyl group or － O.C.(=O)R ３ and R ３ is C １ ~C １０ and q is an integer from 2 to 4, and said hydrocarbyl metal compound has the formula AlX ３ ｎ R １ ３－ｎ , Al ２ X ３ ３ R １ ３ or any combination thereof, ２ is independently a halide; １ are independently ２ ~C ４ 23. The process of claim 22, wherein the alkyl group is an alkyl group.

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