Ethylene oligomerization process

Abstract

A method for producing alpha-olefins, comprising contacting ethylene, a zirconium-based catalyst system comprising a hydrocarbyl metal compound, a chain transfer agent, and an optional organic reaction medium. Available chain transfer agents include: a) hydrogen; b) compounds comprising hydrogen-silicon bonds; compounds having hydrogen-sulfur bonds; compounds having hydrogen-phosphorus bonds; or c) transition metal compound chain transfer agents.

Description

Technical Field

[0001] The present disclosure relates to processes for producing normal alpha olefins. More specifically, the present disclosure relates to improved processes for oligomerizing ethylene to normal alpha olefins. Background Art

[0002] Alpha-olefins are important commercial products. 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 the oligomerization of ethylene in a catalytic reaction involving various types of catalysts and / or catalyst systems. Some ethylene oligomerization catalyst systems produce large amounts of polymer, which can reduce the time the reaction system can be run before the reactor needs to be cleaned, reduce the reliability of the reaction system, and / or complicate product separation. The use and demand for normal alpha-olefins continues to increase, and competition to supply them has increased accordingly. Therefore, new and improved processes for the oligomerization of ethylene are desirable. Summary of the invention

[0003] The present application relates to a method comprising: a) contacting: i) ethylene, ii) a catalyst system comprising 1) a catalyst having the formula ZrX 1 m Y 1 q A zirconium compound wherein each X 1 are independently halogen, each Y 1are each independently a hydrocarboxide, 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) a hydrocarbyl metal compound; iii) a chain transfer agent; and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone; and wherein the oligomer product has a Schulz-Flory K value of 0.4 to 0.8. In one aspect, 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 aspects, the method can produce an oligomer product comprising (a) less than 1 wt% of a polymer, (b) less than 1 wt.% of a compound having a weight average molecular weight greater than 1000 g / mol, or (c) any combination thereof, wherein the wt.% is based on the total weight of the oligomer product. In another aspect, relative to the same method without using a chain transfer agent 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, the method 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 polymers, (d) a polymer having a reduced percentage of polymers having a Mw greater than 100,000, or (e) any combination thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0004] The subject matter of the present application may be understood by reference to the following description in conjunction with the accompanying drawings, wherein like reference numerals refer to like elements, and wherein:

[0005] Figure 1 An example of an ethylene oligomerization unit is illustrated.

[0006] Although the subject matter of the present application is susceptible to various modifications and alternative forms, the accompanying drawings illustrate specific embodiments described in detail by way of example herein. However, it should be understood that the description of specific embodiments herein is not intended to limit the claimed subject matter to the particular forms disclosed, but on the contrary, the present invention will cover all modifications, equivalents and alternative forms falling within the spirit and scope of the present invention as defined by the appended claims.

[0007] definition

[0008] In order to more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to the present disclosure. If a term is used in the present disclosure but is not specifically defined herein, the definition in the 2nd edition of IUPAC Chemical Terminology (IUPAC Compendium of Chemical Terminology) (1997) can be applied, as long as the definition does not conflict with any other disclosure or definition applied herein, or does not make any claim to which the definition is applied unclear or invalid. If any definition or usage provided by any file incorporated herein by reference conflicts with the definition or usage provided herein, then the definition or usage provided herein shall prevail.

[0009] Herein, the features of the subject matter may be described so that in a particular aspect and / or statement, a combination of different features may be envisioned. For each aspect, and / or statement, and / or feature disclosed herein, all combinations that do not adversely affect the systems, compositions, processes, and / or methods described herein are contemplated with or without explicit description of a particular combination. In addition, unless otherwise expressly stated, any aspect, and / or statement, and / or feature disclosed herein may be combined to describe methods and systems of the present invention consistent with the present disclosure.

[0010] Unless expressly indicated otherwise, the terms "a", "an", and "the" are intended to include multiple alternatives, such as at least one alternative, or one or more alternatives. For example, unless otherwise indicated, disclosure of "a trialkylaluminum compound" is intended to cover one trialkylaluminum compound, or a mixture or combination of more than one trialkylaluminum compound.

[0011] The element groups of the periodic table are indicated using the numbering scheme found in the version of the periodic table published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, the element groups may be indicated using the common name assigned to the group; for example, alkali metals indicate Group 1 elements, alkaline earth metals indicate Group 2 elements, transition metals indicate Groups 3-12 elements, and halogens indicate Group 17 elements, etc.

[0012] For any particular compound disclosed herein, unless otherwise indicated, the general structure or name presented is also intended to encompass all structural isomers, conformational isomers, and stereoisomers that may arise from a particular set of substituents. Thus, unless otherwise expressly indicated, a general reference to a compound includes all structural isomers; for example, a reference to C 6A general reference to hydrocarbons 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 butyl includes n-butyl, sec-butyl, isobutyl and tert-butyl. In addition, when the context permits or requires, reference to a general structure or name encompasses all enantiomers, diastereomers and other optical isomers (whether in enantiomeric or racemic form), as well as mixtures of stereoisomers. For any specific formula or name provided, any general formula or name provided also encompasses all conformational isomers, regioisomers and stereoisomers that may result from a particular set of substituents.

[0013] Chemical "groups" are described according to how the group is formally derived from a reference or "parent" compound, such as by the number of hydrogen atoms formally removed from the parent compound to produce the group, even if the group is not literally synthesized in this way. For example, an "alkyl" can be formally derived by removing one hydrogen atom from an alkane, while an "alkylene" can be formally derived by removing two hydrogen atoms from an alkane. In addition, more general terms can be used to cover various groups formally derived by removing any number ("one or more") of hydrogen atoms from a parent compound, which in this example can be described as an "alkane group", and it covers "alkyl", "alkylene", and the material has three or more hydrogen atoms removed from the alkane as the case may be. Throughout this article, the disclosure that a substituent, ligand or other chemical moiety can constitute a specific "group" means that when the group is used as described, the well-known chemical structure and bonding rules are followed. When a group is described as "derived from," "derived from," "formed from," or "formed from," these terms are used in a formal sense and are not intended to reflect any particular synthetic method or procedure, unless otherwise indicated or the context requires otherwise.

[0014] Whenever used in this specification and claims, the term "hydrocarbon" refers to a compound containing only carbon and hydrogen. Other identifiers can be used to indicate the presence of a specific group in a hydrocarbon (for example, a halogenated hydrocarbon indicates that one or more halogen atoms replace an equal number of hydrogen atoms in the hydrocarbon). The term "hydrocarbon group" is used herein according to the definition specified by IUPAC: a monovalent group formed by removing one hydrogen atom from a hydrocarbon. Similarly, "alkylene" refers to a group formed by removing two hydrogen atoms from a hydrocarbon (removing two hydrogen atoms from one carbon atom or removing one hydrogen atom from each of two different carbon atoms). Therefore, according to the terms used herein, "hydrocarbon group" refers to a generalized group formed by removing one or more hydrogen atoms (necessary for a specific group) from a hydrocarbon. "Hydrocarbon group", "alkylene group" and "hydrocarbon group" can be acyclic or cyclic groups, and / or can be straight or branched. "Hydrocarbon group", "alkylene group" and "hydrocarbon group" can contain rings, ring systems, aromatic rings and aromatic ring systems containing only carbon and hydrogen. For example, "hydrocarbyl," "hydrocarbylene," and "hydrocarbyl group" include as members other groups such as aryl, arylene, aromatic, alkyl, alkylene, alkane, cycloalkyl, cycloalkylene, cycloalkane, aralkyl, aralkylene, and aralkane groups.

[0015] Whenever used in this specification and claims, the term "alkane" refers to a saturated hydrocarbon compound. Other identifiers may be used to indicate the presence of a specific group in an alkane (e.g., a halogenated alkane indicates the presence of one or more halogen atoms replacing an equal number of hydrogen atoms in an alkane). The term "alkyl" is used herein according to the definition specified by IUPAC: a monovalent group formed by removing a hydrogen atom from an alkane. Similarly, an "alkylene" refers to a group formed by removing two hydrogen atoms from an alkane (removing two hydrogen atoms from one carbon atom or removing one hydrogen atom from each of two different carbon atoms). An "alkane group" is a general term and refers to a group formed by removing one or more hydrogen atoms (necessary for a specific group) from an alkane. Unless otherwise specified, "alkyl", "alkylene" and "alkane group" may be acyclic or cyclic groups, and / or may be straight or branched. Primary, secondary and tertiary alkyl groups are obtained by removing hydrogen atoms from primary, secondary or tertiary carbon atoms of an alkane, respectively. An n-alkyl group can be obtained by removing a hydrogen atom from the terminal carbon atom of a straight chain alkane.

[0016] The term "substituted" when used to describe a compound or group, for example, when referring to a substituted analog of a particular compound or group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in the group, and is intended to be non-limiting. A group or groups may also be referred to herein as "unsubstituted," or referred to by equivalent terms such as "non-substituted," which refers to the original group in which a non-hydrogen moiety does not replace a hydrogen in the group. "Substituted" is intended to be non-limiting and includes inorganic or organic substituents.

[0017] Whenever used in this specification and claims, the term "olefin" refers to a hydrocarbon with at least one carbon-carbon double bond, which is not a part of an aromatic ring or aromatic ring system. Unless otherwise specifically provided, the term "olefin" includes aliphatic and aromatic, cyclic and acyclic and / or straight and branched hydrocarbons with at least one carbon-carbon double bond, which is not a part of an aromatic ring or ring system. Olefins with only one, only two, only three, etc. carbon-carbon double bonds can be identified by using the terms "single", "two", "three", etc. in the name of the olefin. Olefins can be further identified by the position of one or more carbon-carbon double bonds.

[0018] The term "alpha olefin" used in this specification and claims refers to an olefin having a carbon-carbon double bond between the first carbon atom and the second carbon atom of the longest continuous carbon atom chain. Unless otherwise expressly stated, the term "alpha olefin" includes straight-chain and branched alpha olefins. In the case of branched alpha olefins, the branch can be at the 2 position (vinylidene) and / or 3 position or higher relative to the olefin double bond. Whenever used in this specification and claims, the term "vinylidene" refers to an alpha olefin having a branch at the 2 position relative to the olefin double bond. Unless expressly stated, the term "alpha olefin" itself does not indicate the presence or absence of other carbon-carbon double bonds. As used herein, the term "straight-chain alpha olefin" refers to a non-branched alpha olefin having a carbon-carbon double bond between the first and second carbon atoms.

[0019] Whenever used in this specification and claims, the term "normal alpha-olefin" refers to a linear aliphatic monoolefin having a carbon-carbon double bond between the first carbon atom and the second carbon atom. It should be noted that "normal alpha-olefin" is not synonymous with "linear alpha-olefin" because the term "linear alpha-olefin" can include linear olefin compounds having a double bond between the first carbon atom and the second carbon atom and additional double bonds.

[0020] "Cycloalkanes" are saturated cyclic hydrocarbons with or without side chains, such as 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, only two, only three, etc., endocyclic double or triple bonds may be identified by using the terms "mono," "di," "tri," etc. in the name of the cycloalkenes or cycloalkynes, respectively. Cycloalkenes and cycloalkynes may further identify the location of the endocyclic double or triple bonds.

[0021] "Cycloalkyl" is a monovalent group obtained by removing one hydrogen atom from a ring carbon atom of a cycloalkane. Similarly, "cycloalkylene" refers to a group obtained by removing two hydrogen atoms from a cycloalkane, at least one of which is a ring carbon. Thus, "cycloalkylene" includes: a group obtained from a cycloalkane in which two hydrogen atoms are formally removed from the same ring carbon; a group obtained from a cycloalkane in which two hydrogen atoms are formally removed from two different ring carbons; and a group obtained from a cycloalkane in which the first hydrogen atom is formally removed from a ring carbon and the second hydrogen atom is formally removed from a carbon atom that is not a ring carbon. "Cycloalkane group" refers to a generalized group formed by removing one or more hydrogen atoms (required for the specific group and at least one of which is a ring carbon) from a cycloalkane. It should be noted that, according to the definitions provided herein, general cycloalkane groups (including cycloalkyl and cycloalkylene) include cycloalkane groups having zero, one or more than one hydrocarbyl substituents attached to the cycloalkane ring carbon atoms (e.g., methylcyclopropyl) and are members of the group of hydrocarbyl groups. However, when referring to cycloalkane groups having a specified number of cycloalkane ring carbon atoms (e.g., cyclopentane groups or cyclohexane groups, etc.), the basic name of the cycloalkane group having the defined number of cycloalkane ring carbon atoms refers to the unsubstituted cycloalkane group (including no hydrocarbyl groups located on the cycloalkane group ring carbon atoms). Therefore, substituted cycloalkane groups having a specified number of ring carbon atoms (e.g., substituted cyclopentane or substituted cyclohexane, etc.) refer to the corresponding groups having one or more substituents attached to the cycloalkane group ring carbon atoms (including other substituents such as halogen, hydrocarbyl or hydrocarbyloxy groups). When a substituted cycloalkane group having a defined number of cycloalkane ring carbon atoms is a member of a group of hydrocarbon groups (or a member of a general group of cycloalkane groups), each substituent in the substituted cycloalkane group having a defined number of cycloalkane ring carbon atoms is limited to a hydrocarbon substituent. One can readily discern and select the general group, specific group, and / or one or more monosubstituted cycloalkane groups having a specific number of ring carbon atoms that can be used as a member of the hydrocarbon group (or a member of a general group of cycloalkane groups).

[0022] Aliphatics are acyclic or cyclic, saturated or unsaturated carbon compounds other than aromatic compounds. An "aliphatic group" is a broad group formed by removing one or more hydrogen atoms (necessary for the specific group) from a carbon atom of an aliphatic compound. Thus, aliphatics and aliphatic groups may contain one or more organic functional groups and / or one or more atoms other than carbon and hydrogen.

[0023] An "aromatic" compound is a compound containing a cyclic conjugated double bond system that follows the Hückel (4n+2) rule and contains (4n+2) π electrons, where n is an integer from 1 to 5. Aromatic compounds include "aromatic hydrocarbons" (hydrocarbon aromatic compounds) and "heteroaromatic hydrocarbons" (also known as "heteroaromatic hydrocarbons (hetarenes)") (heteroaromatic compounds formally derived from aromatic hydrocarbons by replacing one or more methine (-C=) carbon atoms in the cyclic conjugated double bond system with trivalent or divalent heteroatoms, in such a way that the continuous π electron system characteristic of the aromatic system and the number of out-of-plane π electrons corresponding to the Hückel rule (4n+2) are retained). Although aromatic hydrocarbon compounds and heteroaromatic hydrocarbon compounds are mutually exclusive members of the group of aromatic compounds, compounds having both aromatic hydrocarbon groups and heteroaromatic hydrocarbon groups are generally regarded as heteroaromatic hydrocarbon compounds. Unless otherwise specified, aromatic compounds, aromatic hydrocarbons and heteroaromatic hydrocarbons can be monocyclic (e.g., benzene, toluene, furan, pyridine, methylpyridine) or polycyclic. Unless otherwise specified, polycyclic aromatic compounds, aromatic hydrocarbons, and heteroaromatic hydrocarbons include compounds in which aromatic rings can be fused (e.g., naphthalene, benzofuran, and indole), compounds in which aromatic groups can be separated and connected by bonds (e.g., biphenyl or 4-phenylpyridine), or compounds in which aromatic groups are connected by groups containing connecting atoms (e.g., the carbon of the methylene group in diphenylmethane; the oxygen of diphenyl ether; the nitrogen of triphenylamine; and other connecting groups). As disclosed herein, the term "substituted" can be used to describe an aromatic group, aromatic hydrocarbon, or heteroaromatic hydrocarbon in which a non-hydrogen moiety formally replaces a hydrogen in the compound, and is intended to be non-limiting.

[0024] "Aromatic group" refers to a broad group formed by removing one or more hydrogen atoms (as required by the specific group and at least one of which is an aromatic ring carbon atom) from an aromatic compound. For a monovalent "aromatic group", the removed hydrogen atom must come from an aromatic ring carbon. For an "aromatic group" formed by removing more than one hydrogen atom from an aromatic compound, at least one hydrogen atom must come from an aromatic hydrocarbon ring carbon. In addition, an "aromatic group" may have hydrogen atoms removed from the same ring of an aromatic ring or ring system (e.g., benzene-1,4-subunit, pyridine-2,3-subunit, naphthalene-1,2-subunit, and benzofuran-2,3-subunit), hydrogen atoms removed from two different rings of a ring system (e.g., naphthalene-1,8-subunit and benzofuran-2,7-subunit), or hydrogen atoms removed from two separate aromatic rings or ring systems (e.g., bis(benzene-4-subunit)methane).

[0025] Aromatic hydrocarbons are aromatic hydrocarbons (e.g., benzene, toluene, or xylene, etc.) with or without side chains. "Aryl" refers to a group obtained by formally removing a hydrogen atom from an aromatic ring carbon of an aromatic hydrocarbon. It should be noted that an aromatic hydrocarbon may contain a single aromatic hydrocarbon ring (e.g., benzene or toluene), contain a fused aromatic ring (e.g., naphthalene or anthracene), and contain one or more separated aromatic rings covalently linked via a bond (e.g., biphenyl) or one or more non-aromatic hydrocarbon groups (e.g., diphenylmethane). Similarly, "arylene" refers to a group formed by removing two hydrogen atoms (at least one of which is from an aromatic ring carbon) from an aromatic hydrocarbon. "Aromatic hydrocarbon group" refers to a generalized group formed by removing one or more hydrogen atoms (according to the needs of a specific group and at least one of which is an aromatic ring carbon atom) from an aromatic hydrocarbon. It should be noted that, according to the definitions provided herein, general aromatic hydrocarbon groups (including aryl and arylene) include those having zero, one or more than one hydrocarbon substituents located on the aromatic hydrocarbon ring or ring system carbon atoms (e.g., toluene groups or xylene groups, etc.) and are members of the group of hydrocarbon groups. However, phenyl (or phenylene) and / or naphthyl (or naphthylene) refer to specific unsubstituted aromatic hydrocarbon groups (excluding hydrocarbon groups located on aromatic hydrocarbon rings or ring system carbon atoms). Therefore, substituted phenyl or substituted naphthyl refers to the corresponding aromatic hydrocarbon group having one or more substituents located on the aromatic hydrocarbon ring or ring system carbon atoms (including halogen, hydrocarbon group or hydrocarbon oxide group, etc.). When substituted phenyl and / or substituted naphthyl are members of the group of hydrocarbon groups (or members of the general group of aromatic hydrocarbon groups), each substituent is limited to hydrocarbon substituents. 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 substituted naphthyl groups that can be used as members of the group of hydrocarbon groups (or members of the general group of aromatic hydrocarbon groups).

[0026] "Aralkyl" is an alkyl group substituted with an aryl group having a free valence on a non-aromatic carbon atom (e.g., benzyl, or 2-phenylethyl-1-yl, etc.). Similarly, "aralkylene" is an alkylene group substituted with an aryl group having two free valences on a single non-aromatic carbon atom or having a free valence on two non-aromatic carbon atoms, and "aralkane group" is an alkane group substituted with a generalized aryl group having one or more free valences on one or more non-aromatic carbon atoms. It should be noted that, according to the definition provided herein, general aralkane groups include those having zero, one or more than one alkyl substituents located on the aromatic hydrocarbon ring or ring system carbon atom of the aralkane and are members of the group of alkyl groups. However, a specific aralkane group specifying a specific aryl group (e.g., phenyl or 2-phenylethyl in benzyl, etc.) refers to a specific unsubstituted aralkane group (not including an alkyl group located on the aromatic hydrocarbon ring or ring system carbon atom of the aralkane). Thus, a substituted aralkyl group designating a particular aryl group refers to the corresponding aralkyl group with one or more substituents, including halogen, alkyl or alkyloxy groups, etc. When a substituted aralkyl group designating a particular aryl group is a member of the group of alkyl groups (or a member of the general group of aralkyl groups), each substituent is limited to alkyl substituents. One can easily identify and select a substituted aralkyl group designating a particular aryl group that can be used as a member of the group of alkyl groups (or a member of the general group of aralkyl groups).

[0027] As used herein, the term "hydrocarbylmetal compound" refers to a compound having at least one metal-carbon bond, wherein the carbon atom participating in the metal-carbon bond is part of a hydrocarbyl group. A "hydrocarbyl compound" may contain other non-hydrocarbyl groups, such as halides, alkoxides, alkoxylates, carboxylates, and amides, as long as the compound contains at least one metal-carbon bond (wherein the carbon atom participating in the metal-carbon bond is part of a hydrocarbyl group). Similarly, any specific "hydrocarbylmetal compound" (a compound specifying the metal of the hydrocarbylmetal compound) refers to a compound having at least one specific metal-carbon bond, wherein the carbon atom participating in the metal-carbon bond is part of a hydrocarbyl group.

[0028] "Halo" has the usual meaning; thus, examples of halo include fluoro, chloro, bromo, and iodo.

[0029] The term "substituted" when used to describe a group (e.g., when referring to a substituted analog of a particular group) is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in the group, and is intended to be non-limiting. A group or groups may also be referred to herein as "unsubstituted," or referred to by equivalent terms such as "non-substituted," which refers to the original group in which a non-hydrogen moiety does not replace a hydrogen in the group. "Substituted" is intended to be non-limiting and includes inorganic or organic substituents.

[0030] The term "room temperature" or "ambient temperature" is used herein to describe any temperature from 15°C to 35°C, where no external source of heat or cooling is directly applied. Therefore, the terms "room temperature" and "ambient temperature" encompass individual temperatures and any and all ranges, subranges, and subrange combinations of temperatures from 15°C to 35°C, where no external source of heating or cooling is directly applied. The term "atmospheric pressure" is used herein to describe the earth's air pressure without the use of an external pressure regulating device. In general, unless implemented at extreme altitudes on the earth, "atmospheric pressure" is about 1 atmosphere (alternatively, about 14.7psi or about 101kPa). References to gaseous, liquid, and / or solid materials refer to the physical state of the material at 25°C and atmospheric pressure.

[0031] Features provided as minimum values ​​within the present disclosure may alternatively be expressed as "at least" or "greater than or equal to" any recited minimum value of features disclosed herein. Features provided as maximum values ​​within the present disclosure may alternatively be expressed as "less than or equal to" the maximum value of features disclosed herein.

[0032] In the present disclosure, the general rules of organic nomenclature shall prevail. For example, when referring to a substituted compound or group, the reference to the substitution pattern is used to indicate that the indicated group is located at the indicated position and all other unindicated positions are hydrogen. For example, the reference to the phenyl substituted by 4- indicates that the non-hydrogen substituent is located at the 4th position and hydrogen is located at the 2nd, 3rd, 5th and 6th positions. The reference to the compound or group in which there is a substitution at a position other than the indicated position can be referred to using inclusion or some other alternative language. For example, the reference to the phenyl containing a substituent at the 4th position refers to a group having a non-hydrogen substituent at the 4th position and having hydrogen or any non-hydrogen substituent at the 2nd, 3rd, 5th and 6th positions.

[0033] The term "reaction zone effluent" and its derivatives (e.g., oligomerization reaction zone effluent) generally refer to all materials exiting from the reaction zone. The term "reaction zone effluent" and its derivatives may also be preceded by other descriptors that limit the portion of the reaction zone effluent being referred to. For example, the term "reaction zone effluent" refers to all materials (e.g., products and solvent or diluent, etc.) that exit the reaction zone, while the term "olefin reaction zone effluent" refers only to 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.

[0034] The term oligomer refers to a product containing 2 to 20 monomer units. The terms "oligomer product" and "oligomer product effluent" include all oligomer products made by the "oligomerization" process, but do not include other non-oligomer components of the reaction zone effluent stream, such as unreacted monomers (ethylene), organic reaction medium and hydrogen and other components. The term "oligomerization" and its derivatives refer to a method for producing an oligomer product containing at least 20wt.%, 35wt.%, 50wt.% or 60wt.% of a product containing 2 to 20 monomer units. In one example, the "oligomerization" process using ethylene as a monomer produces a product mixture containing at least 20wt.%, 35wt.%, 50wt.% or 60wt.% of oligomers with 4 to 40 carbon atoms.

[0035] The Schulz-Flory (Schulz-Flory) K value (sometimes referred to as the Schulz-Flory chain growth factor, K value) can be defined as the equation: K = Xq + 1 / Xq, where Xq + 1 is the number of moles of oligomer product produced having q + 1 monomer (e.g., ethylene) units, and Xq is the number of moles of oligomer product produced having q monomer (e.g., ethylene) units. In general, the Schulz-Flory K value can be determined using any two oligomers of oligomer products that differ by 1 in the number of monomer units. However, it is understood that product separation and analysis can result in inaccuracies in the distribution of oligomer products determined using a particular oligomer (e.g., incomplete recovery of gaseous products and / or solid products during product separation). One of ordinary skill in the art will recognize such issues and can select appropriate oligomers as the basis for determining the Schulz-Flory K value.

[0036] Catalyst system productivity is defined as the grams of product produced per gram (or mole) of zirconium in the catalyst system used in the oligomerization reaction. Catalyst system activity is defined as the grams of product produced per gram (or mole) of zirconium per unit time (e.g., hour) of oligomerization reaction. The productivity and / or activity of the catalyst system can be expressed in terms of the various products of the oligomerization reaction and / or the components of the catalyst system. For example, in an ethylene oligomerization process utilizing a catalyst system comprising a zirconium compound, available catalyst system productivity includes (g oligomer product) / (g Zr) and other productivity.

[0037] Unless otherwise indicated, the terms "contacting" and "combining" and their derivatives may refer to any order of addition, sequence, or concentration for contacting or combining two or more components of the disclosed embodiments. The combining or contacting of the oligomeric components may occur in one or more reaction zones under suitable contacting conditions such as temperature, pressure, contact time, flow rate, etc.

[0038] The terms "catalyst system", "catalyst composition", "catalyst mixture", etc. do not depend on the actual products or compositions produced by the contact or reaction of the initial components of the disclosed or claimed catalyst composition / mixture / system, the nature of the active catalytic sites, or the fate of the organoaluminum compound and the heteroatom ligand transition metal compound complex after combining these components. Thus, the terms "catalyst system", "catalyst composition", "catalyst mixture", etc. encompass the initial starting components of the composition as well as any products that may be produced by contacting these initial starting components. The terms "catalyst system", "catalyst composition", "catalyst mixture", etc. may be used interchangeably throughout this disclosure.

[0039] In the present disclosure, a process may have multiple steps or may include features having many different elements (e.g., components in a catalyst system or components and other features in an olefin oligomerization process). These steps and / or elements may be designated as necessary using the terms first, second, and third, etc., series a), b), c), etc., i), ii), iii), etc., (a), (b), (c), etc., and / or (i), (ii), (iii), etc. (and other designated series) to provide a designation for each process step and / or element. It should be understood that unless otherwise expressly stated or required by other process steps, elements, and / or element features, the designated numerical or alphabetical ordering within the designated series does not imply a particular order or preference for process steps in the methods described herein, one or more features described herein, and / or one or more elements in the features. In addition, these designated series are provided to distinguish different process steps and / or elements in the features and may be utilized as necessary without regard to the designated series for the specific steps, elements, or features utilized in this specification, as long as the designated series always distinguishes different features, different process steps, and / or different elements of the features.

[0040] The terms "simultaneous," "contacting simultaneously," "contacting simultaneously," and their derivatives, when referring to a contacting method, refer to a contacting method in which the two or more listed compounds, mixtures, streams, and / or compositions are contacted by flowing into a common junction, tank, container, or reactor, etc., at the same time. The terms "substantially simultaneous," "contacting substantially simultaneously," "contacting substantially simultaneously," and their derivatives, when referring to a contacting method, refer to a contacting method in which during the contacting of two or more listed compounds, mixtures, streams, and / or compositions, the two or more listed compounds, mixtures, streams, and / or compositions are contacted such that, for a period of time during the contacting, the two or more listed compounds, mixtures, streams, and / or compositions flow into a common junction, tank, container, or reactor at the same time. It should be noted that the terms "substantially simultaneous," "contacting substantially simultaneously," "contacting substantially simultaneously," and their derivatives, do not mean that the two or more listed compounds, mixtures, streams, and / or compositions are contacted simultaneously during the entire addition of each of the two or more listed compounds, mixtures, streams, and / or compositions. The terms "substantially simultaneously," "contacting substantially simultaneously," "contacting substantially simultaneously," and their derivatives encompass situations in which one (or less than all) of the listed compounds, mixtures, streams, and / or compositions may begin entering a common junction, tank, container, or reactor before the other listed compounds, mixtures, streams, and / or compositions before the flow of one (or less than all) of the listed compounds, mixtures, streams, and / or compositions into a common junction, tank, container, or reactor may be completed, stopped, or interrupted. In any aspect and / or embodiment described herein, the terms "simultaneously," "contacting simultaneously," "contacting simultaneously," and their derivatives may be modified by incorporating terms that provide for the amounts of each of the listed compounds, mixtures, streams, and / or compositions that may be contacted simultaneously, indicating situations of varying degrees of "substantially simultaneously," "contacting substantially simultaneously," "contacting substantially simultaneously," and their derivatives. For example, at least 20%, 30%, 40%, 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95% of each of the listed compounds, mixtures, streams, and / or compositions can be "contacted simultaneously" or "contacted simultaneously." In general, the percentages of the listed compounds, mixtures, streams, and / or compositions that can be "contacted simultaneously" or "contacted simultaneously" can be by weight (wt.%), volume (vol.%), or mole (mol%).Unless otherwise indicated, reference to listed compounds, mixtures, streams and / or compositions "substantially simultaneously," "contacted substantially simultaneously," "contacted substantially simultaneously," and their derivatives shall mean that at least 50% of each of the listed compounds, mixtures, streams and / or compositions may be "contacted simultaneously" or "contacted simultaneously."

[0041] It should be further noted that "simultaneously," "contacting simultaneously," "contacting simultaneously," "contacting substantially simultaneously," "contacting substantially simultaneously," and their derivatives when referring to a contacting method or process are distinct from methods or processes in which one or more first materials (e.g., compounds, mixtures, streams, and / or compositions) are already present in a tank, vessel, or reactor and one or more other compounds, mixtures, streams, and / or compositions are added to the tank, vessel, or reactor. In this case, the first material in the tank, container, or reactor does not flow into the tank, container, or reactor simultaneously with the other compounds, mixtures, streams, and / or compositions and the material in the tank. Thus, the first material and the other compounds, mixtures, streams, and / or compositions cannot be said to be "contacted simultaneously," "contacted substantially simultaneously," with one or more other components.

[0042] Unless otherwise indicated, the term "contacting" is used herein to describe systems, compositions, processes and methods in which components are contacted or combined together in any order, in any manner and for any length of time. For example, the components can be combined by blending or mixing using any suitable technique. Herein, "contacting" two or more components can produce a reaction product mixture or a reaction mixture.

[0043] In this specification, the word "reactor" refers to a single piece of equipment, such as a container, in which a reaction occurs, but does not include any associated equipment outside the container, such as piping, pumps, etc. Examples of reactors include stirred tank reactors (e.g., continuous stirred tank reactors), plug flow reactors, or any other type of reactor. In this specification, a "reactor system" refers to any part of the equipment in which the desired reaction occurs, including but not limited to the reactor, associated piping, associated pumps, and any other associated equipment. It should be noted that in some cases, a "reactor" may also be a "reactor system." For example, in some cases, a polyethylene loop reactor may be considered a reactor system. The terms "reactor" and "reactor system" can be defined by using additional defining terms to refer to more specific "reactors" and "reactor systems." For example, the use of the terms "oligomerization reactor" and "oligomerization reactor system" indicates that the desired reaction within the reactor and / or reactor system is an oligomerization reaction.

[0044] In this specification, the term "reaction zone" refers to a part of a reaction system where all necessary reaction components and reaction conditions are present so that the reaction can occur at a desired rate. That is, the reaction zone begins where the necessary reaction components and reaction conditions are present to maintain the reaction within 25% of the average reaction rate, and the reaction system ends where the conditions cannot maintain the reaction rate within 25% of the average reaction rate (based on the volume average of the reaction rate of the reaction zone). For example, with respect to an ethylene oligomerization process, the reaction zone begins at a point where there is enough ethylene and an active catalyst system to maintain the production of oligomer products at a desired rate under sufficient reaction conditions (e.g., temperature and / or pressure, etc.), and the reaction zone ends at a point where the catalyst system is deactivated, there is not enough ethylene to maintain the production of oligomer products, or other reaction conditions (e.g., temperature and / or pressure, etc.) are not sufficient to maintain the production of oligomer products or the desired production rate of oligomer products. In this specification, a "reaction zone" may include one or more reactors. The term "reaction zone" may be defined by using additional limiting terms to refer to a more specific "reaction zone". For example, use of the term "oligomerization reaction zone" indicates that the desired reaction within the "reaction zone" is an oligomerization reaction.

[0045] The term "reaction system" refers to all equipment for producing a product. The term "reaction system" includes reactors, reaction zones, and all associated equipment, associated process lines, and control equipment that can bring necessary components into and out of the reaction system and control the reaction. In this specification, a "reaction system" may include one or more reactor zones, one or more reactors, and associated equipment for producing a product. The term "reaction system" may be limited by the use of additional limiting terms to refer to a more specific "reaction system." For example, the term "oligomerization reaction system" is used to indicate that the "reaction system" involves an oligomerization reaction.

[0046] All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which might be used in connection with the presently described invention. DETAILED DESCRIPTION

[0047] Disclosed herein is a method 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) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone. Also disclosed herein is a method comprising a) contacting: i) ethylene; ii) a catalyst system comprising 1) a zirconium compound and 2) a hydrocarbyl metal compound; iii) hydrogen; and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone. Further disclosed herein is a method 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) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone. Also disclosed herein is a process comprising a) introducing into 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) an optional organic reaction medium; and b) forming an oligomer product in the reaction zone. Also disclosed herein is a process comprising a) introducing into 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) an optional organic reaction medium; and b) forming an oligomer product in the reaction zone. Further disclosed herein is a process comprising a) introducing into 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) an optional organic reaction medium; and b) forming an oligomer product in the reaction zone.

[0048] In one aspect, the oligomer product can be formed under the condition that can form the oligomer product, and the reaction zone can have the condition that can form the oligomer product, or the reaction zone can be operated under the condition that can form the oligomer product.In general, catalyst system, the key element of catalyst system (for example, zirconium compound, hydrocarbyl metal compound and any other catalyst system element as described herein), chain transfer agent, hydrogen, transition metal compound chain transfer agent, optional organic reaction medium, oligomer product, the condition that forms the oligomer product, the condition that reaction zone can have, the condition that reaction can operate and / or any other catalyst system as described herein and / or method key element are independent key elements of the method described herein and are independently described in this article.These independently described key elements can be used for further describing the method provided herein in any combination and not restrictively.

[0049] In one aspect, the zirconium compound of the catalyst system can have the formula ZrX 1 m Y 1 q , ZrX 1 m , ZrY 1 q or any combination thereof; alternatively, ZrX 1 m Y 1 q Alternatively, ZrX 1 m ; or alternatively, ZrY 1 q . With the formula ZrX 1 m Y 1 q , ZrX 1 m or ZrY 1 q Zirconium compounds X 1 , Y 1 X, m and q are independent elements of the zirconium compound and are described independently herein. 1 , Y 1 The independent descriptions of X, m, and q may be used in any combination without limitation to further describe the zirconium compound. 1 Each Y may be independently a halogen group. 1Each may be independently a hydrocarbon oxide, a dihydrocarbylamino, a hydrocarbon carboxylate, a hydrocarbon sulfonate or a β-diketonate; alternatively, a hydrocarbon oxide, a hydrocarbon carboxylate, a hydrocarbon sulfonate or a β-diketonate; alternatively, a hydrocarbon oxide, a hydrocarbon carboxylate or a hydrocarbon sulfonate; alternatively, a hydrocarbon carboxylate or a hydrocarbon sulfonate; alternatively, a hydrocarbon oxide; alternatively, a dihydrocarbylamino; alternatively, a hydrocarbon carboxylate; alternatively, a hydrocarbon sulfonate; or alternatively, a β-diketonate. In one embodiment, m may be in the range of from 0 to 4; alternatively in the range of from 2 to 4; alternatively 2; alternatively 3; or alternatively 4. In one embodiment, q may be in the range of from 0 to 4; alternatively in the range of from 2 to 4; alternatively 2; alternatively 3; or alternatively 4. wherein m+q is an integer from 2 to 4; alternatively 2; alternatively 3; or alternatively 4.

[0050] X can be used as zirconium compound 1 Each halo of may independently be fluoro, chloro, bromo, or iodo; alternatively, chloro, bromo, or iodo; alternatively, chloro; alternatively, bromo; or alternatively, iodo.

[0051] Y can be used as zirconium compound 1 The oxyhydroxide can be C 1 To C 20 , C 1 To C 10 or C 1 To C 5 Hydroxyl radical. The hydrocarbon oxide Y 1 Can have a - OR 2 . With the formula - OR 2 The R of the alkoxide 2 Can be C 1 To C 20 , C 1 To C 10 or C 1 To C 5 A hydrocarbon group having the formula - OR 2 The hydrocarbyl group may be an alkyl, cycloalkyl, aryl, or aralkyl group; alternatively, an alkyl or aryl group; alternatively, an alkyl group; alternatively, a cycloalkyl group; alternatively, an aryl group; or alternatively, an aralkyl group. 2 The alkyl group can be C 1 To C 20 , C 1 To C 10 or C 1 To C 5 Alkyl. 2 The cycloalkyl group may be C 4 To C20 , C 5 To C 15 or C 5 To C 10 Cycloalkyl. 2 The aryl group can be C 6 To C 20 , C 6 To C 15 or C 6 To C 10 Aryl. 2 The aralkyl group may be C 7 To C 20 , C 7 To C 15 or C 7 To C 10 In one aspect, a arylalkyl group having the formula - OR 2 The R of the alkoxide 2 The group can be methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, benzyl or ethylphenyl; alternatively, methyl, ethyl, propyl, butyl or pentyl; alternatively, cyclopentyl or cyclohexyl; alternatively, phenyl, tolyl or xylyl; or alternatively, benzyl or ethylphenyl. In one aspect, each alkoxide Y of the zirconium compound 1 Each can be methaneoxide, ethaneoxide, propaneoxide, butaneoxide, pentaneoxide, cyclopentaneoxide, cyclohexaneoxide, phenoxide, tolueneoxide, xyleneoxide, benzyloxide or ethylphenoxide; alternatively, methaneoxide, ethaneoxide, propaneoxide, butaneoxide or pentaneoxide; alternatively, cyclopentaneoxide or cyclohexaneoxide; alternatively, phenoxide, tolueneoxide or xyleneoxide; or alternatively, benzyloxide or ethylphenoxide.

[0052] Y can be used as zirconium compound 1 The alkyl carboxylate may be C 1 To C 20 Hydrocarbyl carboxylate, C 1 To C 15 Hydrocarbyl carboxylate, C 1 To C 10 Hydrocarboxylate or C 1 To C 5 Hydrocarbyl carboxylate. Can be used as zirconium compound Y 1 The hydrocarbyl carboxylate may have the formula -OC (=O)R 3 Y can be used as a zirconium compound 1 The alkyl sulfonate group may be C 1 To C 20 Alkyl sulfonate, C 1 To C 10Alkyl sulfonate or C 1 To C 5 Hydrocarbon sulfonate. Can be used as zirconium compound Y 1 The alkyl sulfonate group may have the formula - OS(=O) 2 R 3 . With the formula - OC(=O)R 3 The hydrocarbon carboxylates and / or the hydrocarbon carboxylates having the formula - OS(=O) 2 R 3 The R of the alkyl sulfonate 3 Can be C 1 To C 20 , C 1 To C 15 , C 1 To C 10 or C 1 To C 5 A hydrocarbon group having the formula - OC(=O)R 3 The hydrocarbon carboxylates and / or the hydrocarbon carboxylates having the formula - OS(=O) 2 R 3 The R of the alkyl sulfonate 3 The hydrocarbyl group may be an alkyl, cycloalkyl, aryl, or aralkyl group; alternatively, an alkyl or aryl group; alternatively, an alkyl group; alternatively, a cycloalkyl group; alternatively, an aryl group; or alternatively, an aralkyl group. 3 The alkyl group can be C 1 To C 20 Alkyl, C 1 To C 10 Alkyl or C 1 To C 5 Alkyl. 3 The cycloalkyl group may be C 4 To C 20 Cycloalkyl, C 5 To C 15 Cycloalkyl or C 5 To C 10 Cycloalkyl. 3 The aryl group can be C 6 To C 20 Aryl, C 6 To C 15 Aryl or C 6 To C 10 Aryl. 3 The aralkyl group may be C 7 To C 20 Aralkyl, C 7 To C 15 Arylalkyl or C 7 To C 10Arylalkyl. - OC(=O)R 3 The hydrocarbon carboxylates and / or the hydrocarbon carboxylates having the formula - OS(=O) 2 R 3 The R of the alkyl sulfonate 3 The group may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, benzyl or ethylphenyl; alternatively, methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl; alternatively, cyclopentyl or cyclohexyl; alternatively, phenyl, tolyl or xylyl; or alternatively, benzyl or ethylphenyl. 1 Each hydrocarbon carboxylate of can be acetate, propionate, butyrate, valerate, hexanoate, heptanoate, octanoate, cyclopentylacetate, cyclohexylacetate, benzoate, methylbenzoate, dimethylbenzoate, phenylacetate or phenylpropionate; alternatively, acetate, propionate, butyrate, valerate, hexanoate, heptanoate or octanoate; alternatively, cyclopentylacetate or cyclohexylacetate; alternatively, benzoate, methylbenzoate or dimethylbenzoate; or alternatively, phenylacetate or phenylpropionate. Y can be used as the zirconium compound 1 Each hydrocarbyl sulfonate of can be methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, pentylsulfonate, hexylsulfonate, heptylsulfonate, cyclopentylsulfonate, cyclohexylsulfonate, phenylsulfonate, toluenesulfonate, xylenesulfonate, benzylsulfonate or ethylphenylsulfonate; alternatively, methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, pentylsulfonate, hexylsulfonate or heptylsulfonate; alternatively, cyclopentylsulfonate or cyclohexylsulfonate; alternatively, phenylsulfonate, toluenesulfonate or xylenesulfonate.

[0053] Y can be used as zirconium compound 1 The dialkylamino radical may be C 2 To C 30 Dialkylamino, C 2 To C 20 Dialkylamino or C 2 To C 15 Dialkylamino radical. Can be used as Y in zirconium compounds 1 The dialkylamino radical may have the formula - N(R 4 ) 2 In some embodiments, a compound having the formula - N(R 4 ) 2 Each R of the dialkylamino radical 4The hydrocarbon groups may each independently be alkyl, cycloalkyl, aryl, or aralkyl; alternatively, alkyl or aryl; alternatively, alkyl; alternatively, cycloalkyl; alternatively, aryl; or alternatively, aralkyl. Each R 4 The alkyl groups may be independently C 1 To C 15 Alkyl, C 1 To C 10 Alkyl or C 1 To C 5 Alkyl. Each R 4 The cycloalkyl groups may be independently C 4 To C 15 Cycloalkyl or C 5 To C 15 Cycloalkyl. Each R 4 The aryl groups can be independently C 6 To C 20 Aryl, C 6 To C 15 Aryl or C 6 To C 10 Aryl. Each R 4 The aralkyl groups may be independently C 7 To C 20 Aralkyl, C 7 To C 15 Arylalkyl or C 7 To C 10 Arylalkyl. - N(R 4 ) 2 Each R of the dialkylamino radical 4 The hydrocarbon radicals may each independently be methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, benzyl, or ethylphenyl; alternatively, methyl, ethyl, propyl, butyl, or pentyl; alternatively, cyclopentyl or cyclohexyl; alternatively, phenyl, tolyl, or xylyl; or alternatively, benzyl or ethylphenyl. In one aspect, the two R 4 The groups can be linked to form alkylene groups L 1 In this regard, the connected R 4 Group, i.e. L 1 , forming a ring or ring system comprising an amino nitrogen atom. In some aspects, L 1 The alkylene group may be C 2 To C 30 Alkylidene, C 2 To C 20 Alkylene or C 2 To C 10 or, alternatively, L 1 Can be C 2 To C30 Alkylene, C 2 To C 20 Alkylene or C 2 To C 10 In one aspect, L 1 It can be propylene, butylene, hexylene or heptylene. In one aspect, Y can be used for the zirconium compound. 1 Each dialkylamino group of can be dimethylamino, diethylamino, dipropylamino, pyrrolidineamino, piperidineamino, diphenylamino, ditolylamino, dixylylamino or dibenzylamino; alternatively, dimethylamino, diethylamino or dipropylamino; alternatively, pyrrolidineamino or piperidineamino; alternatively, diphenylamino, ditolylamino, dixylylamino; or alternatively, dibenzylamino.

[0054] Y can be used in zirconium compounds 1 The β-diketone radical can be C 5 To C 20 β-diketone, C 5 To C 15 β-diketone or C 5 To C 10 β-diketonate. In one aspect of an embodiment, each β-diketonate can independently be acetylacetonate (ie, 2,4-pentanedione) or benzoylacetonate; alternatively, acetylacetonate; or alternatively, benzoylacetonate.

[0055] In one embodiment, the zirconium compound of the catalyst system can be an at least partially hydrolyzed zirconium compound obtained by contacting a 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 described herein) contacted with water. In some embodiments, the zirconium compound of the partially hydrolyzed zirconium compound can have the formula ZrX 1 m Y 1 q , where each X 1 can be independently halogen (any disclosed herein), Y 1 Can have the formula - OR 2 (where R 2 It can be any R described herein. 2 Hydrocarbon group (general or specific) or - OC(=O)R 3 (where R 3 It can be any R described herein. 3Hydrocarbyl (general or specific), m can be in the range of 0 to 4, q can be in the range of 0 to 4, and m+q can be 4. In some embodiments, m can be in the range of 0 to 3. In one embodiment, the molar ratio of water to zirconium of the zirconium compound can be in the range of 0.01:1 to 3:1, 0.1: to 2:1, 0.25:1 to 1.75:1.

[0056] In non-limiting aspects, the zirconium compound of the catalyst system may have the formula ZrX 1 m Y 1 q , where each X 1 can be independently halogen (any disclosed herein), Y 1 Can have a - OC(=O)R 3 or - OS(=O) 2 R 3 , where R 3 It can be any R described herein. 3 A hydrocarbyl group (general or specific), m can be in the range of 0 to 4, q can be in the range of 0 to 4, and m+q can be 4. In another non-limiting aspect, the zirconium compound of the catalyst system can have the formula ZrX 1 m , where each X 1 Each may independently be a halide (any disclosed herein) and m may be an integer from 2 to 4, alternatively 2; or alternatively 4. In yet another non-limiting aspect, the zirconium compound may have the formula ZrY 1 q , where each Y 1 All independently - OR 2 , where R 2 C 1 To C 10 Alkyl or -OC(=O)R 3 , where R 3 It is C 1 To C 10 alkyl, and q is an integer from 2 to 4, alternatively 2; alternatively 4. In another non-limiting aspect, the zirconium compound of the catalyst system may have the formula ZrX 1 m Y 1 q , where each X 1 can be independently halogen (any of those described herein), Y 1 Can have the formula -OR 2 , where R 2It can be any R described herein. 2 A hydrocarbon group may have the formula -OC (=O)R 3 , where R 3 It can be any R described herein. 3 A hydrocarbyl group (general or specific), m can be in the range of 0 to 4, q can be in the range of 0 to 4, and m+q can be 4. In a further non-limiting embodiment, the zirconium compound of the catalyst system can be a partially hydrolyzed zirconium compound, wherein the zirconium compound can have the formula ZrX 1 m Y 1 q , where each X 1 can be independently halogen (any of those described herein), Y 1 Can have the formula - OR 2 , where R 2 It can be any R described herein. 2 A hydrocarbon group may have the formula -OC (=O)R 3 , where R 3 It can be any R described herein. 3 Hydrocarbyl (general or specific), m may be in the range of 0 to 4, q may be in the range of 0 to 4, m+q may be 4, and the molar ratio of water to zirconium of the zirconium compound may be in the range of 0.1: to 2:1.

[0057] Non-limiting exemplary zirconium compounds that can be used in the catalyst systems of the methods described herein can include, can consist essentially of, or can be: ZrCl 4 , ZrBr 4 , ZrI 4 , ZrBr 2 Cl 2 、ZrBrCl 3 、Zr(OC 2 H 5 ) 4 、Zr(OC 2 H 5 ) 3 Cl、Zr(OC 2 H 5 ) 2 Cl 2 、Zr(OC 3 H 7 ) 4 、Zr(OC 3 H 7 ) 3 Cl、Zr(OC 3 H7 ) 2 Cl 2 、Zr(OC 4 H 9 ) 4 、Zr(OC 4 H 9 ) 3 Cl、Zr(OC 4 H 9 ) 2 Cl 2 、Zr(OC 6 H 5 ) 4 、Zr(OC 6 H 5 ) 3 Cl、Zr(OC 6 H 5 ) 2 Cl 2 、Zr(OCOCH 3 ) 4 、Zr(OCOCH 3 ) 3 Cl、Zr(OCOCH 3 ) 2 Cl 2 、Zr(OCOC 2 H 5 ) 4 、Zr(OCOC 2 H 5 ) 3 Cl、Zr(OCOC 2 H 5 ) 2 Cl 2 、Zr(OCOC 3 H 7 ) 4 、Zr(OCOC 3 H 7 ) 3 Cl、Zr(OCOC 3 H 7 ) 2 Cl 2 、Zr(OCOC 4 H 9 ) 4 、Zr(OCOC 4 H 9 ) 3 Cl、Zr(OCOC 4 H 9 ) 2 Cl 2 、Zr(OCOC 6 H5 ) 4 , Zr(OCOC 6 H 5 ) 3 Cl, Zr(OCOC 6 H 5 ) 2 Cl 2 , Zr(OSO 3 CH 3 ) 4 , Zr(OSO 3 C 2 H 5 ) 4 , Zr(OSO 3 C 3 H 7 ) 4 , Zr(OSO 3 C 4 H 9 ) 4 , Zr(OSO 3 C 6 H 5 ) 4 , Zr(H 3 CCOCHCOCH 3 ) 4 , ZrCl 2 (H 3 CCOCHCOCH 3 ) 2 , Zr((H 5 C 6 )COCHCO(C 5 F 5 )) 4 , ZrCl 2 ((H 5 C 6 )COCHCO(C 5 F 5 )) 2 , Zr((CH 3 ) 2 N) 4 , Zr((C 2 H 5 ) 2 N) 4 , Zr((C 3 H 7 ) 2 N) 4 or Zr(C 4 H 9 ) 2 N) 4In some aspects, the zirconium compound can include, can consist essentially of, or can be: ZrCl 4 , ZrBr 4 , ZrI 4 , ZrBr 2 Cl 2 or ZrBrCl 3 Alternatively, Zr(OC 2 H 5 ) 4 、Zr(OC 2 H 5 ) 3 Cl、Zr(OC 2 H 5 ) 2 Cl 2 、Zr(OC 3 H 7 ) 4 、Zr(OC 3 H 7 ) 3 Cl、Zr(OC 3 H 7 ) 2 Cl 2 、Zr(OC 4 H 9 ) 4 、Zr(OC 4 H 9 ) 3 Cl、Zr(OC 4 H 9 ) 2 Cl 2 、Zr(OC 6 H 5 ) 4 、Zr(OC 6 H 5 ) 3 Cl or Zr(OC 6 H 5 ) 2 Cl 2 Alternatively, Zr(OC 2 H 5 ) 4 、Zr(OC 3 H 7 ) 4 、Zr(OC 4 H 9 ) 4 or Zr(OC 6 H 5 ) 4 Alternatively, Zr(OC 2 H5 ) 3 Cl, Zr(OC 2 H 5 ) 2 Cl 2 , Zr(OC 3 H 7 ) 3 Cl, Zr(OC 3 H 7 ) 2 Cl 2 , Zr(OC 4 H 9 ) 3 Cl, Zr(OC 4 H 9 ) 2 Cl 2 , Zr(OC 6 H 5 ) 3 Cl or Zr(OC 6 H 5 ) 2 Cl 2 ; Alternatively, Zr(OCOCH 3 ) 4 , Zr(OCOCH 3 ) 3 Cl, Zr(OCOCH 3 ) 2 Cl 2 , Zr(OCOC 2 H 5 ) 4 , Zr(OCOC 2 H 5 ) 3 Cl, Zr(OCOC 2 H 5 ) 2 Cl 2 , Zr(OCOC 3 H 7 ) 4 , Zr(OCOC 3 H 7 ) 3 Cl, Zr(OCOC 3 H 7 ) 2 Cl 2 , Zr(OCOC 4 H 9 ) 4 , Zr(OCOC 4 H 9 ) 3 Cl, Zr(OCOC 4H 9 ) 2 Cl 2 、Zr(OCOC 6 H 5 ) 4 、Zr(OCOC 6 H 5 ) 3 Cl or Zr(OCOC 6 H 5 ) 2 Cl 2 ; Alternatively, Zr(OCOCH 3 ) 4 、Zr(OCOC 2 H 5 ) 4 、Zr(OCOC 3 H 7 ) 4 、Zr(OCOC 4 H 9 ) 4 or Zr(OCOC 6 H 5 ) 4 ; Alternatively, Zr(OCOCH 3 ) 3 Cl, Zr(OCOCH 3 ) 2 Cl 2 、Zr(OCOC 2 H 5 ) 3 Cl, Zr(OCOC 2 H 5 ) 2 Cl 2 、Zr(OCOC 3 H 7 ) 3 Cl, Zr(OCOC 3 H 7 ) 2 Cl 2 、Zr(OCOC 4 H 9 ) 3 Cl, Zr(OCOC 4 H 9 ) 2 Cl 2 、Zr(OCOC 6 H 5 ) 3 Cl or Zr(OCOC 6 H 5 ) 2 Cl 2Alternatively, Zr(OSO 3 CH 3 ) 4 、Zr(OSO 3 C 2 H 5 ) 4 、Zr(OSO 3 C 3 H 7 ) 4 、Zr(OSO 3 C 4 H 9 ) 4 or Zr(OSO 3 C 6 H 5 ) 4 Alternatively, Zr(H 3 CCOCHCOCH 3 ) 4 、ZrCl 2 (H 3 CCOCHCOCH 3 ) 2 、Zr((H 5 C 6 )COCHCO(C 5 H 5 )) 4 or ZrCl 2 ((H 5 C 6 )COCHCO(C 5 H 5 )) 2 Alternatively, Zr(H 3 CCOCHCOCH 3 ) 4 or Zr((H 5 C 6 )COCHCO(C 5 H 5 )) 4 ; Alternatively, ZrCl 2 (H 3 CCOCHCOCH 3 ) 2 or ZrCl 2 ((H 5 C 6 )COCHCO(C 5 H 5 )) 2 ; or alternatively, Zr((CH 3 ) 2 N) 4 、Zr((C 2H 5 ) 2 N) 4 or Zr((C 3 H 7 ) 2 N) 4 、Zr(C 4 H 9 ) 2 N) 4 In other aspects, the zirconium compound can comprise, can consist essentially of, or can be: ZrCl 4 Alternatively, Zr(OC 2 H 5 ) 4 Alternatively, Zr(OC 3 H 7 ) 4 Alternatively, Zr(OC 4 H 9 ) 4 Alternatively, Zr(OC 6 H 5 ) 4 Alternatively, Zr(OCOCH 3 ) 4 ; Alternatively, Zr(OCOC 2 H 5 ) 4 ; Alternatively, Zr(OCOC 3 H 7 ) 4 ; Alternatively, Zr(OCOC 4 H 9 ) 4 ; Alternatively, Zr(OCOC 6 H 5 ) 4 Alternatively, Zr(OSO 3 CH 3 ) 4 Alternatively, Zr(OSO 3 C 2 H 5 ) 4 Alternatively, Zr(OSO 3 C 3 H 7 ) 4 Alternatively, Zr(OSO 3 C 4 H 9 ) 4 ; or alternatively, or Zr(OSO 3 C 6 H 5 )4 .

[0058] In general, the hydrocarbyl metal compound can be any hydrocarbyl metal compound that can form an oligomer product in combination 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 aspect, the hydrocarbyl metal can have the formula (R 1 ) a M(X 2 ) b , where R 1 is a hydrocarbon group, X 2 is a halide or an oxyhydroxide, M is a metal, a is in the range of 1 to 4, b is in the range of 0 to 3, and a+b is equal to the oxidation state of the metal M. In one aspect, the metal of the hydrocarbyl metal compound may include, may consist essentially of, or may consist of: a Group 1, Group 2, Group 11, Group 12, Group 13, or Group 14 metal; alternatively, a Group 1 or Group 2 metal; alternatively, a Group 12, Group 13, or Group 14 metal; or alternatively, a Group 12 or Group 13 metal; alternatively, a Group 1 metal; alternatively, a Group 2 metal; alternatively, a Group 12 metal; or alternatively, a Group 13 metal. In some aspects, the metal of the hydrocarbyl metal compound can comprise, consist essentially of, or can 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.

[0059] The hydrocarbon group of the hydrocarbon metal compound can be C 1 To C 20 Hydrocarbon, C 1 To C 10 Hydrocarbon or C 1 To C 6 In one aspect, the hydrocarbyl group of the hydrocarbyl metal compound can be an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; alternatively, an alkyl group; alternatively, a cycloalkyl group; alternatively, an aryl group; or alternatively, an aralkyl group. The alkyl group of the hydrocarbyl metal compound can be C 1 To C 20 Alkyl, C 1 To C 10 Alkyl or C 1 To C 6 The cycloalkyl group of the hydrocarbyl metal compound may be C 4 To C 20 Cycloalkyl, C4 To C 15 Cycloalkyl or C 4 To C 10 The aryl group of the hydrocarbyl metal compound may be C 6 To C 20 Aryl, C 6 To C 15 Aryl or C 6 To C 10 Aryl. The aralkyl group of the hydrocarbyl metal compound may be C 7 To C 20 Aralkyl, C 7 To C 15 Arylalkyl or C 7 To C 10 Aralkyl.

[0060] In any aspect disclosed herein, the hydrocarbyl metal compound of the catalyst system can be an alkyl metal compound (i.e., wherein R 1 In one embodiment, the alkyl metal compound of the catalyst system may comprise, may consist essentially of, or may be: an alkyl lithium (R 1 Li), alkyl sodium (R 1 Na), alkyl potassium (R 1 K), alkyl magnesium compounds (R 1 2 Mg or R 1 MgX 2 ), alkyl copper compounds (R 1 2 Cu or R 1 XOt 2 ), alkyl zinc compounds (R 1 2 Zn or R 1 ZnX 2 ), alkyl tin compounds (R 1 4 Sn, R 1 2 Sn, R 1 3 S X 2 , R 1 2 S X 2 2 , R 1 2 S X 2 3 , R 1 2 Sn or R 1 S X 2 ) or alkyl aluminum compounds (AlX2 2 R 1 、AlX 2 R 1 2 , AlR 1 3 、Al 2 X 2 5 R 1 、Al 2 X 2 3 (R 1 ) 3 or Al 2 X 2 R 1 5 ); Alternatively, alkyl lithium (R 1 Li), alkyl sodium (R 1 Na), alkyl potassium (R 1 K), alkyl magnesium compounds (R 1 2 Mg or R 1 MgX 2 ), alkyl zinc compounds (R 1 2 Zn or R 1 ZnX 2 ) or alkyl aluminum compounds (AlX 2 2 R 1 、AlX 2 R 1 2 , AlR 1 3 、Al 2 X 2 5 R 1 、Al 2 X 2 3 R1 3 or Al 2 X 2 R 1 5 ); Alternatively, alkyl lithium (R 1 Li), alkyl sodium (R 1 Na) or alkyl potassium (R 1 K); alternatively, an alkyl lithium (R 1 Li); alternatively, alkyl sodium (R 1 Na); alternatively, an alkyl magnesium compound (R 1 2 Mg or R 1 MgX2 ); Alternatively, an alkyl zinc compound (R 1 2 Zn or R 1 ZnX 2 ); Alternatively, an alkyl tin compound (R 1 4 Sn, R 1 2 Sn, R 1 3 S X 2 , R 1 2 S X 2 2 , R 1 2 S X 2 3 , R 1 2 Sn or R 1 S X 2 ); or alternatively, an alkyl aluminum compound (AlX 2 2 R 1 、AlX 2 R 1 2 , AlR 1 3 、Al 2 X 2 5 R 1 、Al 2 X 2 3 R 1 3 or Al 2 X 2 R 1 5 In some aspects, the alkyl metal compound of the catalyst system can comprise, can consist essentially of, or can be: an alkyl lithium (R 1 Li), alkyl sodium (R 1 Na), alkyl potassium (R 1 K), alkyl magnesium halide (R 1 MgX 2 ), dialkyl magnesium (R 1 2 Mg), alkyl copper halide (R 1 XOt 2 ), dialkyl copper (R 1 2 Cu), alkyl zinc halide (R 1 ZnX 2 ), dialkyl zinc (R1 2 Zn), alkyl tin halides (R 1 3 S X 2 , R 1 2 S X 2 2 , R 1 2 S X 2 3 , R 1 2 Sn or R 1 S X 2 ), dialkyltin (R 1 2 Sn), tetraalkyltin (R 1 4 Sn), alkyl aluminum dihalide (AlX 2 2 R 1 ), dialkylaluminum halides (AlX 2 R 1 2 ), trialkylaluminum (AlR 1 3 ), alkyl aluminum sesquihalides (Al 2 X 2 3 R 1 3 ), alkylaluminum dialkoxide (AlX 2 2 R 1 ), dialkylaluminum alkoxide (AlX 2 R 1 2 ) or aluminoxane; alternatively, alkyl lithium (R 1 Li), alkyl sodium (R 1 Na), alkyl potassium (R 1 K), dialkyl magnesium (R 1 2 Mg), dialkyl zinc (R 1 2 Zn), alkyl aluminum dihalide (AlX 2 2 R 1 ), dialkylaluminum halides (AlX 2 R 1 2 ), trialkylaluminum (AlR 1 3 ) or alkyl aluminum sesquihalide (Al 2 X 2 3 R 13 ); Alternatively, alkyl lithium (R 1 Li), alkyl sodium (R 1 Na), alkyl potassium (R 1 K); Alternatively, an alkyl magnesium halide (R 1 MgX 2 ) or dialkyl magnesium (R 1 2 Mg); alternatively, dialkyltin (R 1 2 Sn), tetraalkyltin (R 1 4 Sn); alternatively, an alkyl zinc compound (R 1 2 Zn or R 1 ZnX 2 ) and alkyl aluminum compounds (AlX 2 2 R 1 、AlX 2 R 1 2 , AlR 1 3 、Al 2 X 2 5 R 1 、Al 2 X 2 3 R 1 3 or Al 2 X 2 R 1 5 ); Alternatively, alkylaluminum dihalide (AlX 2 2 R 1 ), dialkylaluminum halides (AlX 2 R 1 2 ), alkyl aluminum sesquihalides (Al 2 X 2 3 R 1 3 ), trialkylaluminum (AlR 1 3 ) or aluminoxane; alternatively, alkyl lithium (R 1 Li); alternatively, alkyl sodium (R 1 Na); alternatively, alkyl potassium (R 1 K); Alternatively, an alkyl magnesium halide (R 1 MgX 2 ); Alternatively, dialkyl magnesium (R1 2 Mg); alternatively, an alkyl zinc halide (R 1 ZnX 2 ); Alternatively, dialkylzinc (R 1 2 Zn); alternatively, alkylaluminum dihalide (AlX 2 2 R 1 ); Alternatively, dialkylaluminum halide (AlX 2 R 1 2 ); Alternatively, alkyl aluminum sesquihalides (Al 2 X 2 3 R 1 3 ); Alternatively, alkylaluminum dialkoxide (AlX 2 2 R 1 ); Alternatively, dialkylaluminum alkoxide (AlX 2 R 1 2 ); Alternatively, trialkylaluminum (AlR 1 3 ); or alternatively, aluminoxane.

[0061] In general, 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 fluorine, chlorine, bromine or iodine; alternatively, chlorine, bromine or iodine; alternatively, fluorine; alternatively, chlorine; alternatively, bromine; or alternatively, iodine.

[0062] Each alkyl group of any alkyl metal compound disclosed herein may independently be C 1 To C 20 Alkyl, C 1 To C 10 Alkyl or C 1 To C 6 Alkyl. In one aspect, each alkyl group of any alkyl metal compound disclosed herein can independently be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl; alternatively, methyl, ethyl, butyl, hexyl or octyl. In some aspects, each one or more alkyl groups of any alkyl metal compound disclosed herein can independently be methyl, ethyl, n-propyl, n-butyl, isobutyl, n-hexyl or n-octyl; alternatively, methyl, ethyl, n-butyl or isobutyl; alternatively, methyl; alternatively, ethyl; alternatively, n-propyl; alternatively, n-butyl; alternatively, isobutyl; alternatively, n-hexyl; or alternatively, n-octyl.

[0063] Each alkoxide group of any alkyl metal alkoxide disclosed herein may independently be C 1 To C 20 Alkoxy, C 1 To C 10 Alkoxy or C 1 To C 6 Alkoxides. In one aspect, each alkoxide of any alkylmetal alkoxide disclosed herein can independently be methaneoxide, ethaneoxide, propaneoxide, butaneoxide, pentaneoxide, hexaneoxide, heptaneoxide, or octanoxide; alternatively, methaneoxide, ethaneoxide, butaneoxide, hexaneoxide, or octanoxide. In some aspects, each alkoxide group of any alkyl metal alkoxide disclosed herein can independently be methaneoxide, ethaneoxide, n-propaneoxide, n-butaneoxide, isobutaneoxide, n-hexaneoxide, or n-octaneoxide; alternatively, methaneoxide, ethaneoxide, n-butaneoxide, or isobutaneoxide; alternatively, methaneoxide; alternatively, ethaneoxide; alternatively, n-propaneoxide; alternatively, n-butaneoxide; alternatively, isobutaneoxide; alternatively, n-hexaneoxide; or alternatively, n-octaneoxide.

[0064] The hydrocarbyl lithium compound (or alkyl lithium compound) useful as the hydrocarbyl metal compound may include, may consist essentially of, or may 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. The hydrocarbyl sodium compound (or alkyl sodium compound) useful as the hydrocarbyl metal compound may include, may consist essentially of, or may 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. The hydrocarbyl potassium compound (or alkyl potassium compound) useful as the hydrocarbyl metal compound may include, may consist essentially of, or may 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.

[0065] The hydrocarbyl magnesium halide (or alkyl magnesium halide) that can be used as the hydrocarbyl metal compound can include, can consist essentially of, or can be methyl magnesium halide, ethyl magnesium halide, propyl magnesium halide or butyl magnesium halide; alternatively, methyl magnesium halide; alternatively, ethyl magnesium halide; alternatively, propyl magnesium halide; alternatively, butyl magnesium halide. The dihydrocarbyl magnesium (or dialkyl magnesium) that can be used as the hydrocarbyl metal compound can include, can consist essentially of, or can be dimethyl magnesium, diethyl magnesium, dipropyl magnesium or dibutyl magnesium; alternatively, dimethyl magnesium; alternatively, diethyl magnesium; alternatively, dipropyl magnesium; or alternatively, dibutyl magnesium.

[0066] The hydrocarbyl zinc halide useful as the hydrocarbyl metal compound may include, may consist essentially of, or may be a methyl zinc halide, an ethyl zinc halide, a propyl zinc halide, a butyl zinc halide, an pentyl zinc halide, a hexyl zinc halide, a cyclopentyl zinc halide, a cyclohexyl zinc halide, a phenyl zinc halide, a tolyl zinc halide, a xylyl zinc halide, or a benzyl zinc halide; alternatively, a methyl zinc halide, an ethyl zinc halide, a propyl zinc halide, a butyl zinc halide, an pentyl zinc halide, or a hexyl zinc halide; alternatively, a cyclopentyl zinc halide or cyclohexylzinc halide; alternatively, phenylzinc halide, tolylzinc halide or xylylzinc halide; alternatively, methylzinc halide; alternatively, ethylzinc halide; alternatively, propylzinc halide; alternatively, butylzinc halide; alternatively, pentylzinc halide; alternatively, hexylzinc halide; alternatively, cyclopentylzinc halide; alternatively, cyclohexylzinc halide; alternatively, phenylzinc halide; alternatively, tolylzinc halide; alternatively, xylylzinc halide; or alternatively, benzylzinc halide. The dihydrocarbyl zinc useful as the hydrocarbyl metal compound may include, may consist essentially of, or may be dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc, diamyl zinc, dihexyl zinc, dicyclopentyl zinc, dicyclohexyl zinc, diphenyl zinc, ditolyl zinc, dixylyl zinc, or dibenzyl zinc; alternatively, dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc, diamyl zinc, or dihexyl zinc; alternatively, dicyclopentyl zinc or dicyclohexyl zinc; Alternatively, diphenylzinc, xylylzinc, bis-xylylzinc; alternatively, or dibenzylzinc; alternatively, dimethylzinc; alternatively, diethylzinc; alternatively, dipropylzinc; alternatively, dibutylzinc; alternatively, diamylzinc; alternatively, dihexylzinc; alternatively, dicyclopentylzinc; alternatively, dicyclohexylzinc; alternatively, diphenylzinc; alternatively, xylylzinc; alternatively, bis-xylylzinc; or alternatively, dibenzylzinc.

[0067] In one aspect, the hydrocarbyl metal compound in the catalyst system can be an alkyl aluminum compound. Generally speaking, the hydrocarbyl aluminum compound that can be used as the hydrocarbyl metal compound in the catalyst system can have the formula AlX 2 3-n R 1 n 、Al 2 X 2 6-q R 1 q or any combination thereof; alternatively, AlX 2 n R 1 3-n ; or alternatively, Al 2 X 2 q R 1 6-q . Formula AlX 2 3-n R 1 n and Al 2 X 2 6-q R 1 q X 2 , R 1 , n and q are of the formula AlX 2 3-n R 1 n and Al 2 X 2 6-q R 1 q The hydrocarbyl aluminum compound is an independent element of the present invention and is described independently herein. 2 , R 1 The independent descriptions of n and q may be used without limitation and in any combination to describe a compound having the formula AlX 2 3-n R 1 n or Al 2 X 2 6-q R 1 q Hydrocarbyl aluminum compounds. In the formula AlX 2 3-n R 1 n and Al 2 X 2 6-q R 1 q In each R 1 Can be independently C1 To C 20 Hydrocarbon, C 1 To C 10 Hydrocarbon or C 1 To C 6 or alternatively, C 1 To C 20 Alkyl, C 1 To C 10 Alkyl or C 1 To C 6 In one aspect, each R 1 Each can be independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl; alternatively, methyl, ethyl, butyl, hexyl, octyl; alternatively, methyl, ethyl, n-propyl, n-butyl, isobutyl, n-hexyl or n-octyl; alternatively, methyl, ethyl, n-butyl or isobutyl; alternatively, methyl; alternatively, ethyl; alternatively, n-propyl; alternatively, n-butyl; alternatively, isobutyl; alternatively, n-hexyl; or alternatively, n-octyl. In the formula AlX 2 3-n R 1 n and Al 2 X 2 6-q R 1 q In each X 2 Each may independently be fluorine, chlorine, bromine or iodine; alternatively, chlorine, bromine or iodine; alternatively, chlorine; alternatively, bromine; or alternatively iodine. In the formula AlX 2 3-n R 1 n and Al 2 X 2 6-q R 1 q In the formula AlX, n may 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 Al 2 X 2 6-q R 1 q In one aspect, q may be 1, 3 or 5; alternatively 1, alternatively 3; or alternatively 5. 2 3-n R 1 nor Al 2 X 2 6-q R 1 q The hydrocarbyl aluminum (or alkyl aluminum) compound may include, may consist essentially of, or may be composed of: a trialkyl aluminum, an alkyl aluminum halide, or any combination thereof, alternatively, a trialkyl aluminum; or alternatively, an alkyl aluminum halide. The trialkylaluminum compound may include, may consist essentially of, or may be trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, or any combination thereof; alternatively, trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof; alternatively, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or 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, triisobutylaluminum; alternatively, trihexylaluminum; or alternatively, tri-n-octylaluminum. The alkylaluminum halide may include, may consist essentially of, or may 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.

[0068] In some aspects, the hydrocarbyl aluminum (or alkyl aluminum) compound useful as the hydrocarbyl metal compound in the catalyst system may have the formula AlX 2 3-n R 1 n 、Al 2 X 2 6-q R 1 q or any combination thereof (alternatively AlX 2 n R 1 3-n ; or alternatively Al 2 X 2 q R 1 6-q ), where X 2At least a portion (or all) of can be an alkoxide, carboxylate, dialkylamino or carboxamide anion; alternatively, an alkoxide; alternatively, a carboxylate; alternatively, a dialkylamino; or alternatively, or a carboxamide anion. Formula AlX 2 3 -n R 1 n and Al 2 X 2 6-q R 1 q R 1 , n and q are described herein as elements of a hydrocarbyl aluminum (or alkyl aluminum) compound, and R 1 These independent descriptions of n and q may be used without limitation and in any combination to describe compounds having the formula AlX 2 3-n R 1 n or Al 2 X 2 6-q R 1 q (Where X 2 At least a portion (or all) of the anions are alkoxy, carboxylate, dialkylamino and / or carboxamide anions. 2 When only a portion (or all) of X is an alkoxy, carboxylate, dialkylamino and / or carboxamide anion, X 2 The remainder of can be halo; alternatively, fluorine, chlorine, bromine or iodine; alternatively, chlorine, bromine or iodine; alternatively, chlorine; alternatively, bromine; or alternatively, iodine. 2 3-n R 1 n and / or Al 2 X 2 6- q R 1 q (Where X 2 The specific alkoxide of the hydrocarbyl aluminum (or alkyl aluminum) compound may be C 1 To C 20 Alkoxy, C 1 To C 10 Alkoxy or C 1 To C 6alkoxide; alternatively, methane oxide, ethane oxide, propane oxide, butane oxide, pentane oxide, hexane oxide, heptane oxide or octane oxide; alternatively, methane oxide, ethane oxide, butane oxide, hexane oxide or octane oxide; alternatively, methane oxide, ethane oxide, n-propane oxide, n-butane oxide, isobutane oxide, n-hexane oxide or n-octane oxide; alternatively, methane oxide, ethane oxide, n-butane oxide or isobutane oxide; alternatively, methane oxide; alternatively, ethane oxide; alternatively, n-propane oxide; alternatively, n-butane oxide; alternatively, isobutane oxide; alternatively, n-hexane oxide; or alternatively, n-octane oxide. AlX 2 3-n R 1 n and / or Al 2 X 2 6-q R 1 q( Where X 2 The specific carboxyl groups of the hydrocarbyl aluminum (or alkyl aluminum) compound may be C2 to C20 carboxyl groups, C2 to C10 carboxyl groups, C 2 To C 6 carboxylate; alternatively, acetate, propionate, butyrate, valerate, hexanoate, heptanoate, octanoate, benzoate, methylbenzoate, dimethylbenzoate or phenyllactate; alternatively, acetate, propionate, butyrate, valerate, hexanoate, heptanoate or octanoate; alternatively, benzoate, methylbenzoate or dimethylbenzoate; or alternatively, phenylacetate. AlX 2 3-n R 1 n and / or Al 2 X 2 6-q R 1 q (Where X 2 The specific dihydrocarbylamino radical of the hydrocarbyl aluminum (or alkyl aluminum) compound may be C 2 To C 20 , C 2 To C 10 or C 2 To C 6dialkylamino; alternatively, dimethylamino, diethylamino, dipropylamino, pyrrolidineamino, piperidineamino, diphenylamino, ditolylamino, bis-xylylamino or dibenzylamino; alternatively, dimethylamino, diethylamino or dipropylamino; alternatively, pyrrolidineamino or piperidineamino; alternatively, diphenylamino, ditolylamino, bis-xylylamino; or alternatively, dibenzylamino. AlX 2 3-n R 1 n and / or Al 2 X 2 6-q R 1 q (Where X 2 The specific carboxamide anion of the hydrocarbyl aluminum (or alkyl aluminum) compound may be C 2 To C 20 Carboxamide anion, C 2 To C 10 Carboxamide anion or C 2 To C 6 carboxamide anion; alternatively, dimethylformamide anion, diethylformamide anion, dimethylacetamide anion, diethylacetamide anion, 2-pyrrolidone anion, valerolactam anion or caprolactam anion; alternatively, dimethylformamide anion, diethylformamide anion, dimethylacetamide anion, diethylacetamide anion; alternatively, 2-pyrrolidone anion, valerolactam anion or caprolactam anion; alternatively, dimethylformamide anion; alternatively, dimethylacetamide anion; alternatively, 2-pyrrolidone anion; alternatively, valerolactam anion; or alternatively, caprolactam anion. When having the formula AlX 2 3-n R 1 n and / or Al 2 X 2 6-q R 1 q Hydrocarbyl aluminum (or alkyl aluminum) compound X 2 When at least a portion (or all) of is alkoxide, carboxylate, dialkylamino and / or carboxamide anion, the molar ratio of alkoxide, carboxide, amino and / or amide anion to aluminum can be in the range of 0.1:1 to 1:1, 0.1:1 to 0.75:1 or 0.1:1 to 0.5:1.

[0069] wherein the hydrocarbyl aluminum (or alkyl aluminum) compound has the formula AlX 2 3-n R 1 n or Al 2 X 2 6-q R 1 q And X 2 In the aspect that at least a portion (or all) of the anions are alkoxy, carboxylate, dialkylamino and / or carboxamide anions, the anions have the formula AlX 2 3-n R 1 n or Al 2 X 2 6-q R 1 q The hydrocarbyl aluminum (or alkyl aluminum) compounds can be generated in situ. These hydrocarbyl aluminum (or alkyl aluminum) compounds generated in situ can be prepared by reacting an appropriate alcohol, carboxylic acid or simple ester, amine and / or amide of a carboxylic acid with a hydrocarbon having the formula AlX 2 3-n R 1 n or Al 2 X 2 6-q R 1 q A hydrocarbyl aluminum (or alkyl aluminum) compound is contacted to form, wherein i) each R 1 Each of them is independently 2 3-n R 1 n or Al 2 X 2 6-q R 1 q The hydrocarbyl aluminum (or alkyl aluminum) compound is any hydrocarbyl or alkyl R described 1 group, ii) each X 2 can be independently used for the present invention for AlX 2 3-n R 1 n or Al 2 X 2 6-q R 1 q Any of the halogen groups described for the hydrocarbyl aluminum (or alkyl aluminum) compounds of the formula AlX 2 3-n R 1 n or Al2 X 2 6-q R 1 q any value described herein for the hydrocarbyl aluminum (or alkyl aluminum) compound of formula AlX 2 3-n R 1 n or Al 2 X 2 6-q R 1 q The alcohol that can be used to generate the in situ generated hydrocarbyl aluminum (or alkyl aluminum) compound 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, isobutanol, n-hexanol, or n-octanol; alternatively, methanol, ethanol, n-butanol, or isobutanol; alternatively, methanol; alternatively, ethanol; alternatively, n-propanol; alternatively, n-butanol; alternatively, isobutanol; alternatively, n-hexanol; or alternatively, n-octanol. The carboxylic acid or simple ester of the carboxylic acid that can be used to generate the in situ generated hydrocarbyl aluminum (or alkyl aluminum) compound can be C 2 To C 20 Carboxylic acid, C 2 To C 10 Carboxylic acid or C 2 To C 6 carboxylic acid; alternatively, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, benzoic acid, methyl benzoic acid, dimethyl benzoic acid or phenylacetic acid; alternatively, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid or octanoic acid; alternatively, benzoic acid, methyl benzoic acid or dimethyl benzoic acid; or alternatively, phenylacetic acid. In general, the alcohol of the alcohol-derived portion of the simple ester of the carboxylic acid can be methanol and / or ethanol; alternatively, methanol or ethanol. Amines that can be used to generate the in situ generated hydrocarbyl aluminum (or alkyl aluminum) compound having a dihydrocarbylamino group can be C 2 To C 20 Amine, C 2 To C 10 Amine or C 2 To C 6 Amine; alternatively, dimethylamine, diethylamine, dipropylamine, pyrrolidine, piperidine, diphenylamine, dimethylaniline, dimethylphenylamine, or dibenzylamine; alternatively, dimethylamine, diethylamine, or dipropylamine; alternatively, pyrrolidine or piperidine; alternatively, diphenylamine, dimethylaniline, dimethylphenylamine; or alternatively, dibenzylamine. Amides that can be used to generate the in situ generated hydrocarbyl aluminum (or alkyl aluminum) compound with a carboxamide anion can be C 2 To C20 Amide, C 2 To C 10 Amide or C 2 To C 6 amide; alternatively, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, 2-pyrrolidone, valerolactam or caprolactam; alternatively, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide; alternatively, 2-pyrrolidone, valerolactam or caprolactam; alternatively, dimethylformamide; alternatively, dimethylacetamide; alternatively, 2-pyrrolidone; alternatively, valerolactam; or alternatively, caprolactam. For preparing the in situ generated AlX 2 3-n R 1 n or Al 2 X 2 6-q R 1 q (Where X 2 Alcohols, carboxylates, carboxylates, amines and / or amides of hydrocarbyl aluminum (or alkyl aluminum) compounds of which at least a portion (or all) is an alkoxide, carboxylate, dihydrocarbylamide and / or carboxamide anion and having a formula AlX 2 3-n R 1 n or Al 2 X 2 6-q R 1 q The molar ratio of the hydrocarbyl aluminum (or alkyl aluminum) compound can be in the range of 0.1:1 to 1:1, 0.1:1 to 0.75:1, or 0.1:1 to 0.5:1.

[0070] Generally speaking, the in-situ generated 2 3-n R 1 n or Al 2 X 2 6-q R 1 q The hydrocarbyl aluminum (or alkyl aluminum) compound can be formed in any manner that produces the desired in situ generated hydrocarbyl aluminum (or alkyl aluminum) compound. In one aspect, the in situ generated hydrocarbyl aluminum (or alkyl aluminum) compound has the formula AlX 2 3-n R 1 n or Al 2 X 2 6-q R 1 q(Where X 2 Hydrocarbyl aluminum (or alkyl aluminum) compounds in which at least a portion (or all) of the anions are alkoxide, carboxylate, dihydrocarbylamide and / or carboxamide anions can be prepared 1) by reacting an alcohol, a carboxylic acid or a simple ester, amine and / or amide of a carboxylic acid with an appropriate or (desired) hydrocarbon compound having the formula AlX 2 3-n R 1 n and / or Al 2 X 2 6-q R 1 q The in situ generated hydrocarbyl aluminum (or alkyl aluminum) compound is then contacted with the zirconium compound component of the catalyst system.

[0071] The aluminoxane compound that can be used as the hydrocarbyl metal (or alkyl metal, or hydrocarbyl aluminum, or alkyl aluminum) compound of the catalyst system can comprise, can consist essentially of, or can be methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, tert-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, or any combination thereof. In some non-limiting aspects, the aluminoxane can include, can consist essentially of, or can be methylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutylaluminoxane, tert-butylaluminoxane, or any combination thereof; alternatively, methylaluminoxane (MAO); alternatively, ethylaluminoxane; alternatively, modified methylaluminoxane (MMAO); alternatively, n-propylaluminoxane; alternatively, isopropylaluminoxane; alternatively, n-butylaluminoxane; alternatively, sec-butylaluminoxane; alternatively, isobutylaluminoxane; alternatively, tert-butylaluminoxane; alternatively, 1-pentylaluminoxane; alternatively, 2-pentylaluminoxane; alternatively, 3-pentylaluminoxane; alternatively, isopentylaluminoxane; or alternatively, neopentylaluminoxane.

[0072] Non-limiting exemplary hydrocarbyl aluminum (or alkyl aluminum) compounds useful in the catalyst systems of the methods described herein may include, may consist essentially of, or may be: Al(CH 3 ) 3 、Al(C 2 H 5 ) 3 、Al(C 3 H 7 ) 3 、Al(C4 H 9 ) 3 、Al(C 5 H 11 ) 3 、Al(C 6 H 13 ) 3 、Al(C 8 H 17 ) 3 、Al(C 2 H 5 ) 2 Cl、Al(C 2 H 5 ) 2 Br、Al(C 2 H 5 ) 2 I、Al(C 2 H 5 )Cl 2 、Al(C 2 H 5 )Br 2 、Al(C 2 H 5 )I 2 、AlC 2 H 5 (OC 2 H 5 ) 2 、AlC 2 H 5 (OC 3 H 7 ) 2 、AlC 2 H 5 (OC 4 H 9 ) 2 、Al(OC 2 H 5 ) 2 Cl、Al(OC 3 H 7 ) 2 Cl、Al(OC 4 H 9 ) 2 Cl、Al(OC 2 H 5 )Cl 2 、Al(OC 3 H 7 )Cl 2 、Al(OC 4 H 9 )Cl 2 、AlC 2 H5 (OCOC 2 H 5 ) 2 、AlC 2 H 5 (OCOC 3 H 7 ) 2 、AlC 2 H 5 (OCOC 4 H 9 ) 2 、Al(OCOC 2 H 5 ) 2 Cl、Al(OCOC 3 H 7 ) 2 Cl、Al(OCOC 4 H 9 ) 2 Cl、Al(OCOC 2 H 5 )Cl 2 、Al(OCOC 3 H 7 )Cl 2 、Al(OCOC 4 H 9 )Cl 2 、Al(C 2 H 5 ) 2 OC 2 H 5 、Al(C 2 H 5 ) 2 OC 3 H 7 、Al(C 2 H 5 ) 2 OC 4 H 9 、Al(C 2 H 5 ) 2 N(C 2 H 5 ) 2 、Al(C 2 H 5 ) 2 N(C 3 H 7 ) 2 、Al(C 2 H 5 ) 2 N(C 4 H 9 )2 、Al 2 (CH 3 ) 3 Cl 3 、Al 2 (CH 3 ) 3 Br 3 、Al 2 (C 2 H 5 ) 3 Cl 3 、Al 2 (C 2 H 5 ) 3 Br 3 、Al 2 (C 2 H 5 ) 3 I 3 、Al 2 (C 2 H 5 ) 2 BrCl 2 、Al 2 (C 3 H 7 ) 3 Cl 3 、Al 2 (C 4 H 9 ) 3 Cl 3 、Al 2 (C 5 H 7 ) 3 Cl 3 、Al 2 (OCOC 4 H 9 ) 3 Cl 3 or any combination thereof. In some aspects, the hydrocarbyl aluminum (or alkyl aluminum) compound may include, may consist essentially of, or may be: Al(CH 3 ) 3 、Al(C 2 H 5 ) 3 、Al(C 3 H 7 ) 3 、Al(C 4 H 9 ) 3 、Al(C 5 H 11 ) 3、Al(C 6 H 13 ) 3 、Al(C 8 H 17 ) 3 、Al(C 2 H 5 ) 2 Cl、Al(C 2 H 5 ) 2 Br、Al(C 2 H 5 ) 2 I、Al(C 2 H 5 )Cl 2 、Al(C 2 H 5 )Br 2 、Al(C 2 H 5 )I 2 、Al 2 (CH 3 ) 3 Cl 3 、Al 2 (CH 3 ) 3 Br 3 、Al 2 (C 2 H 5 ) 3 Cl 3 、Al 2 (C 2 H 5 ) 3 Br 3 、Al 2 (C 2 H 5 ) 3 I 3 、Al 2 (C 2 H 5 ) 2 BrCl 2 、Al 2 (C 3 H 7 ) 3 Cl 3 、Al 2 (C 4 H 9 ) 3 Cl 3 、Al 2 (C 5 H 7 )3 Cl 3 or any combination thereof; alternatively, AlC 2 H 5 (OC 2 H 5 ) 2 , AlC 2 H 5 (OC 3 H 7 ) 2 , AlC 2 H 5 (OC 4 H 9 ) 2 , AlC 2 H 5 (OCOC 2 H 5 ) 2 , AlC 2 H 5 (OCOC 3 H 7 ) 2 , AlC 2 H 5 (OCOC 4 H 9 ) 2 、Al(C 2 H 5 ) 2 OC 2 H 5 、Al(C 2 H 5)2 OC 3 H 7 、Al(C 2 H 5 ) 2 OC 4 H 9 、Al(C 2 H 5 ) 2 N(C 2 H 5 ) 2 、Al(C 2 H 5 ) 2 N(C 3 H 7 ) 2 、Al(C 2 H 5 ) 2 N(C 4 H 9 ) 2 or any combination thereof; alternatively, AlC2 H 5 (OC 2 H 5 ) 2 , AlC 2 H 5 (OC 3 H 7 ) 2 , AlC 2 H 5 (OC 4 H 9 ) 2 or any combination thereof; or alternatively, AlC 2 H 5 (OCOC 2 H 5 ) 2 , AlC 2 H 5 (OCOC 3 H 7 ) 2 , AlC 2 H 5 (OCOC 4 H 9 ) 2 、Al(C 2 H 5 ) 2 OC 2 H 5 、Al(C 2 H 5 ) 2 OC 3 H 7 、Al(C 2 H 5 ) 2 OC 4 H 9 or any combination thereof; alternatively, Al(C 2 H 5 ) 2 N(C 2 H 5 ) 2 、Al(C 2 H 5 ) 2 N(C 3 H 7 ) 2 、Al(C 2 H 5 ) 2 N(C 4 H 9 ) 2Or any combination thereof. In other aspects, the hydrocarbyl aluminum (or alkyl aluminum) compound may include, may consist essentially of, or may be: Al 2 (CH 3 ) 3 Cl 3 、Al 2 (CH 3 ) 3 Br 3 、Al 2 (C 2 H 5 ) 3 Cl 3 、Al 2 (C 2 H 5 ) 3 Br 3 、Al 2 (C 2 H 5 ) 3 I 3 、Al 2 (C 2 H 5 ) 2 BrCl 2 、Al 2 (C 3 H 7 ) 3 Cl 3 、Al 2 (C 4 H 9 ) 3 Cl 3 、Al 2 (C 5 H 7 ) 3 Cl 3 or any combination thereof; or alternatively, Al(C 2 H 5 ) 3 、Al(C 2 H 5 ) 2 Cl、Al(C 2 H 5 )Cl 2 、Al 2 (C 2 H 5 ) 3 Cl 3 or any combination thereof.

[0073] The molar ratio of the metal of the hydrocarbylmetal (or hydrocarbylaluminum, or alkylaluminum) compound to the zirconium of the zirconium compound (also referred to herein as the M:Zr molar ratio) can be any value that provides a catalyst system that can form an oligomer product. In one aspect, the minimum M:Zr (or Al:Zr) molar ratio can be 0.1:1, 0.2:1, 0.6:1, 1:1, 2:1, 10:1; alternatively or in addition, 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 be within the range of any minimum M:Zr (or Al:Zr) molar ratio disclosed herein to any maximum M:Zr (or Al:Zr) molar ratio disclosed herein. Thus, suitable non-limiting ranges for the M:Zr (or Al:Zr) molar ratio can be in the range of 0.1:1 to 100:1, 0.2:1 to 75:1, 0.6:1 to 25:1, 1:1 to 50:1, 2:1 to 25:1, 1:1 to 15:1, 2:1 to 10:1, 10:1 to 50:1, or 10:1 to 25: 1. Other suitable M:Zr (or Al:Zr) molar ranges will be apparent from this disclosure.

[0074] In some aspects, the catalyst system may further comprise a neutral nonionic organic modifier (or have a neutral nonionic organic modifier as a component). In general, the neutral nonionic organic modifier may be any neutral nonionic organic modifier that can form an oligomeric product in combination with the zirconium compound and the hydrocarbyl metal compound. The neutral nonionic organic modifier may include, consist essentially of, or may 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.

[0075] The ethers useful as neutral nonionic organic modifiers may be C 2 To C 20 Ether, C 2 To C 15 Ether or C 2 To C 10 Ether. The thioether that can be used as a neutral nonionic organic modifier can be C 2 To C 20 Sulfide, C 2 To C 15 Sulfide or C 2 To C 10 Sulfide. The disulfide that can be used as a neutral nonionic organic modifier can be C 2 To C 20Disulfide, C 2 To C 15 Disulfide or C 2 To C 10 The disulfide may have the structure R 11 OR 12 The thioether may have the structure R 11 SR 12 The disulfide may have the structure R 11 SSR 12 Each R of the ether, thioether and / or disulfide 11 and R 12 Can be independently C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Hydrocarbon; C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Alkyl; C 5 To C 15 or C 5 To C 10 Cycloalkyl; C 6 To C 15 or C 6 To C 10 Aryl; or C 7 To C 15 or C 7 To C 10Aralkyl. In non-limiting aspects, ethers useful as neutral nonionic organic modifiers may include, may consist essentially of, or may be dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, xylyl ether, bisxylyl ether, tetrahydrofuran, tetrahydropyran, dioxane, furan, benzofuran, isobenzofuran, dibenzofuran, or any combination thereof. In some aspects, ethers useful as neutral nonionic organic modifiers may include, may consist essentially of, or may be dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, xylyl ether, bisxylyl 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, xylyl ether; alternatively, bisxylyl ether, tetrahydrofuran; alternatively, tetrahydropyran; alternatively, dioxane; alternatively, furan; alternatively, benzofuran; alternatively, isobenzofuran; or alternatively, dibenzofuran. In non-limiting aspects, thioethers useful as neutral nonionic organic modifiers may include, consist essentially of, or may be 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, dicyclohexyl sulfide, diphenyl sulfide, or any combination thereof; alternatively, thiophene, methylthiophene (e.g., 2-methylthiophene or 3-methylthiophene), dimethylthiophene (e.g., 2,3-dimethylthiophene), ethylthiophene, benzothiophene, tetrahydrothiophene, thiopyran, or any combination thereof; alternatively, dimethyl sulfide; alternatively, diethyl sulfide; alternatively, dibutyl sulfide; alternatively, dihexyl sulfide; alternatively, dioctyl sulfide; alternatively, dicyclohexyl sulfide; alternatively, diphenyl sulfide; alternatively, thiophene; alternatively, tetrahydrothiophene; or alternatively, thiourea.In one aspect, the disulfide can include, consist essentially of, or can 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.

[0076] Esters useful as neutral nonionic organic modifiers may be C 3 To C 20 Ester, C 3 To C 15 Ester or C 3 To C 10 The ester may have the structure R 13 (C=O)OR 14 The ester R 13 and R 14 Can be independently C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Hydrocarbon; C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Alkyl; C 5 To C 15 or C 5 To C 10 Cycloalkyl; C 6 To C 15 or C 6 To C 10 Aryl; or C 7 To C 15 or C 7 To C 10 Aralkyl. Esters useful as neutral nonionic organic modifiers may be C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Hydrocarbon, C 1 To C 15 , C1 To C 10 or C 1 To C 5 Alkyl, C 6 To C 15 or C 6 To C 10 Aryl, or C 7 To C 15 or C 7 To C 10 Aralkyl carboxylic acid C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Hydrocarbon, C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Alkyl, C 5 To C 15 or C 5 To C 10 Cycloalkyl, C 6 To C 15 or C 6 To C 10 Aryl or C 7 To C 15 or C 7 To C 10 Aralkyl Esters. In non-limiting aspects, esters useful as neutral nonionic organic modifiers may include, consist essentially of, or may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, phenyl, tolyl, xylyl, or benzyl acetate, propionate, butyrate, valerate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, benzoate, methylbenzoate, dimethylbenzoate, or naphthoate; alternatively, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, phenyl, tolyl, xylyl, or benzyl acetate, propionate, butyrate, valerate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, benzoate, methylbenzoate, dimethylbenzoate, or naphthoate; Alternatively, phenyl, tolyl, xylyl or benzyl acetate, propionate, butyrate, valerate, hexanoate, heptanoate, octanoate, nonanoate or decanoate; or alternatively, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or tridecyl benzoate, methyl benzoate, dimethyl benzoate or naphthoate. In some aspects, the ester useful as the neutral nonionic organic modifier may be C 4 To C 20 , C4 To C 15 or C 4 To C 10 Cyclic esters; alternatively, butyrolactone, valerolactone, o-hydroxymethylbenzoic acid lactone or any combination thereof; alternatively, butyrolactone; alternatively, valerolactone; or alternatively, o-hydroxymethylbenzoic acid lactone.

[0077] Aldehydes useful as neutral nonionic organic modifiers may be C 2 To C 20 , C 2 To C 15 or C 2 To C 10 Aldehydes. Ketones useful as neutral nonionic organic modifiers may be C 3 To C 20 , C 3 To C 15 or C 3 To C 10 Ketone. The aldehyde may have the structure R 15 (C=O)H. The ketone may have R 15 (C=O)R 16 Structure. The R 15 and the R 15 and R 16 Can be independently C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Hydrocarbon; C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Alkyl; C 5 To C 15 or C 5 To C 10 Cycloalkyl; C 6 To C 15 or C 6 To C 10 Aryl; or C 7 To C 15 or C 7 To C 10Aralkyl. In non-limiting aspects, aldehydes useful as neutral nonionic organic modifiers may include, consist essentially of, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, tolualdehyde, xylene carboxaldehyde, furfural, or any combination thereof; alternatively, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, or any combination thereof; alternatively, benzaldehyde, tolualdehyde, xylene carboxaldehyde, or any combination thereof; alternatively, formaldehyde; alternatively, acetaldehyde; alternatively, propionaldehyde; alternatively, butyraldehyde; alternatively, benzaldehyde; alternatively, tolualdehyde; alternatively, xylene carboxaldehyde; alternatively, furfural. Ketones useful as neutral nonionic organic modifiers may include, consist essentially of, or may be acetone, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, acetophenone, propiophenone, benzophenone, or any combination thereof; alternatively, acetone, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, or any combination thereof; alternatively, acetophenone, propiophenone, benzophenone, or any combination thereof; alternatively, acetone; alternatively, butanone; alternatively, pentanone; alternatively, hexanone; alternatively, heptanone; alternatively, octanone; alternatively, nonanone; alternatively, decanone; alternatively, acetophenone; alternatively, propiophenone; or alternatively, benzophenone.

[0078] The acyl halide useful as a neutral nonionic organic modifier may be C 2 To C 20 , C 2 To C 15 or C 2 To C 10 Acid halide. Acid anhydrides that can be used as neutral nonionic organic modifiers can be C 2 To C 20 , C 2 To C 15 or C 2 To C 10 Anhydride. An acyl halide may have the structure R 17 (C=O)X 10 The anhydride may have R 17 (C=O)O(C=O)R 17 Structure. Acyl halide X 10 can be chlorine, bromine or iodine; alternatively, chlorine; alternatively, bromine; or alternatively, iodine. Each R of the acyl halide and anhydride 17 Can be independently C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Hydrocarbon; C 1 To C 15 , C 1To C 10 or C 1 To C 5 Alkyl; C 5 To C 15 or C 5 To C 10 Cycloalkyl; C 6 To C 15 or C 6 To C 10 Aryl; or C 7 To C 15 or C 7 To C 10 Aralkyl. In non-limiting aspects, the acyl halide useful as the neutral nonionic organic modifier may include, consist essentially of, or may be acetyl chloride, acetyl bromide, propionyl chloride, propionyl bromide, butyryl chloride, valeryl chloride, hexanoyl chloride, benzoyl chloride, benzoyl bromide, methylbenzoyl chloride, dimethylbenzoyl chloride, or any combination thereof; alternatively, acetyl chloride, acetyl bromide, propionyl chloride, propionyl bromide, butyryl chloride, valeryl chloride, hexanoyl chloride, or any combination thereof; alternatively, benzoyl chloride, benzoyl bromide, methylbenzoyl chloride, dimethylbenzoyl chloride, or any combination thereof; alternatively, acetyl chloride; alternatively, acetyl bromide; alternatively, propionyl chloride; alternatively, propionyl bromide; alternatively, butyryl chloride; alternatively, valeryl chloride; alternatively, hexanoyl chloride; alternatively, benzoyl chloride; alternatively, benzoyl bromide; alternatively, methylbenzoyl chloride; or alternatively, dimethylbenzoyl chloride.

[0079] In non-limiting aspects, the anhydride that can be used as the neutral nonionic organic modifier can be acetic anhydride, propionic anhydride, butyric anhydride, caproic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride, benzoic anhydride, methylbenzoic anhydride, dimethylbenzoic anhydride, phthalic anhydride, homophthalic anhydride, or any combination thereof; alternatively, acetic anhydride, propionic anhydride, butyric anhydride, caproic anhydride; alternatively, maleic anhydride, succinic anhydride, glutaric anhydride, or any combination thereof; alternatively, benzoic anhydride, methylbenzoic anhydride, dimethylbenzoic anhydride, phthalic anhydride, homophthalic anhydride, or any combination thereof; Alternatively, phthalic anhydride, homophthalic anhydride, or any combination thereof; alternatively, acetic anhydride; alternatively, propionic anhydride; alternatively, butyric anhydride; alternatively, caproic 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.

[0080] Nitriles useful as neutral nonionic organic modifiers may be C 2 To C 20 , C 2 To C 15or C 2 To C 10 The nitrile may have R 18 CN structure. 18 Can be C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Hydrocarbon; C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Alkyl; C 5 To C 15 or C 5 To C 10 Cycloalkyl; C 6 To C 15 or C 6 To C 10 Aryl; or C 7 To C 15 or C 7 To C 10 Aralkyl. In non-limiting aspects, nitriles useful as neutral nonionic organic modifiers can include, consist essentially of, or can be acetonitrile, propionitrile, butyronitrile, benzonitrile, or any combination thereof; alternatively, acetonitrile; alternatively, propionitrile; alternatively, butyronitrile; or alternatively, benzonitrile.

[0081] Phosphines useful as neutral nonionic organic modifiers may be C 3 To C 20 , C 3 To C 15 or C 3 To C 10 The phosphine may have (R 19 ) 3 P structure. The amine may have (R 19 ) 3 N structure. Each R of the phosphine 19 Can be independently C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Hydrocarbon; C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Alkyl; C 5 To C 15or C 5 To C 10 Cycloalkyl; C 6 To C 15 or C 6 To C 10 Aryl; or C 7 To C 15 or C 7 To C 10 Aralkyl. In non-limiting aspects, phosphines useful as neutral nonionic organic modifiers may include, consist essentially of, or may 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.

[0082] Amines useful as neutral nonionic organic modifiers may be C 1 To C 20 , C 1 To C 15 or C 1 To C 10 Amine. The amine may have the structure H 2 NR 20 、HN(R 20 ) 2 、N(R 20 ) 3 or any combination thereof; alternatively, H 2 NR 20 ; Alternatively, HN(R 20 ) 2 ; or alternatively, N(R 20 ) 3 . With structure H 2 NR 20 、HN(R 20 ) 2 or N(R 20 ) 3 Each R of the amine 20 Can be independently C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Hydrocarbon; C 1 To C 15 , C1 To C 10 or C 1 To C 5 Alkyl; C 5 To C 15 or C 5 To C 10 Cycloalkyl; C 6 To C 15 or C 6 To C 10 Aryl; or C 7 To C 15 or C 7 To C 10Aralkyl. In non-limiting aspects, amines useful as neutral nonionic organic modifiers may include, consist essentially of, or may be methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, cyclopentylamine, cyclohexylamine, piperidine, methylpiperidine, dimethylpiperidine, trimethylpiperidine, tetramethylpiperidine, aniline, benzylamine, naphthylamine, dimethylamine, diethylamine, dibutylamine, diphenylamine, methylaniline, trimethylamine, triethylamine, tributylamine, triphenylamine, pyridine, picoline, or any combination thereof; alternatively, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, cyclopentylamine, cyclohexylamine, piperidine, methylpiperidine, dimethylpiperidine, trimethylpiperidine, tetramethylpiperidine, aniline, benzylamine, naphthylamine, dimethylamine, diethylamine, dibutylamine, diphenylamine, methylaniline, trimethylamine, triethylamine, tributylamine, triphenylamine, pyridine, picoline, or any combination thereof; amine, octylamine, decylamine, cyclopentylamine, cyclohexylamine, aniline, benzylamine, naphthylamine, dimethylamine, diethylamine, dibutylamine, diphenylamine, methylaniline or any combination thereof; alternatively, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, cyclopentylamine, cyclohexylamine, aniline, benzylamine, naphthylamine or any combination thereof; alternatively, dimethylamine, diethylamine, dibutylamine, diphenylamine, methylaniline or any combination thereof; alternatively, piperidine, methylpiperidine, dimethylpiperidine, trimethylpiperidine, tetramethylpiperidine or any combination thereof; alternatively, trimethylamine, triethylamine, Alternatively, amine, 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, methylaniline; or any combination thereof; alternatively, trimethylamine, triethylamine, tributylamine, triphenylamine, or any combination thereof; alternatively, methylamine; alternatively, ethylamine; alternatively, propylamine; alternatively, butylamine; alternatively, pentylamine; alternatively, hexylamine; alternatively, heptylamine; alternatively, octylamine; alternatively, decylamine ; alternatively, cyclopentylamine; alternatively, cyclohexylamine; alternatively, piperidine; alternatively, methylpiperidine; alternatively, dimethylpiperidine; alternatively, trimethylpiperidine; alternatively, tetramethylpiperidine; alternatively, aniline; alternatively, benzylamine; alternatively, naphthylamine; alternatively, dimethylamine; alternatively, diethylamine; alternatively, dibutylamine; alternatively, diphenylamine; alternatively, methylaniline; alternatively, trimethylamine; alternatively, triethylamine; alternatively, tributylamine; alternatively, triphenylamine; alternatively, pyridine; or alternatively, methylpyridine.

[0083] Amides useful as neutral nonionic organic modifiers may be C 2 To C 20 , C 2 To C 15 or C 2 To C 10 Amide. The amide may have the structure H(C=O)NHR 22 、H(C=O)N(R 22 ) 2 , R 21(C=O)NH 2 , 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)NH 2 , 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)NH 2 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 can be independently C1 to C 15 , C 1 To C 10 or C 1 To C 5 Hydrocarbon; C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Alkyl; C 5 To C 15 or C 5 To C 10 Cycloalkyl; C 6 To C 15 or C 6 To C 10 Aryl; or C 7 To C 15 or C 7 to C10Aralkyl. In non-limiting aspects, amides useful as neutral nonionic organic modifiers may include, consist essentially of, or may be N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, N-propylformamide, N,N-dipropylformamide, N-butylformamide, N,N-dibutylformamide, N-phenylformamide, N,N-diphenylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-propylacetamide, N,N-dipropylacetamide, N-butylacetamide, N,N-dibutylformamide, N-phenylformamide, N,N-diphenylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-propylacetamide, N,N-dipropylacetamide, N-butylacetamide, N,N -Dibutylacetamide, N-phenylacetamide, N,N-diphenylacetamide, N-(methylphenyl)acetamide, N,N-(dimethylphenyl)acetamide, propionamide, N-methylpropionamide, N,N-dimethylpropionamide, N-ethylpropionamide, N,N-diethylpropionamide, N-phenylpropionamide, N,N-diphenylpropionamide, butanamide, N-methylbutanamide, N,N-dimethylbutanamide, N-ethylbutanamide, N,N-diethylbutanamide, N-phenylbutanamide, N,N-diphenylbutanamide, benzamide, N-methylbenzamide, N,N-dimethylbenzamide, N-ethylbenzamide, N,N- diethylbenzamide, N-phenylbenzamide, N,N-diphenylbenzamide, methylbenzamide, N-methyl-methylbenzamide, N,N-dimethyl-methylbenzamide, N-ethyl-methylbenzamide, N,N-diethyl-methylbenzamide, N-phenyl-methylbenzamide, N,N-diphenyl-methylbenzamide or any combination thereof; alternatively, N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-phenylacetamide, N,N-diphenylacetamide, N-methylpropionamide, N ,N-dimethylpropionamide, N-methylbenzamide, N,N-dimethylbenzamide or any combination thereof; alternatively, N-methylformamide; alternatively, N,N-dimethylformamide; alternatively, N-methylacetamide; alternatively, N,N-dimethylacetamide; alternatively, N-ethylacetamide; alternatively, N,N-diethylacetamide; alternatively, N-phenylacetamide; alternatively, N,N-diphenylacetamide; alternatively, N-methylpropionamide; alternatively, N,N-dimethylpropionamide; alternatively, N-methylbenzamide; or alternatively, N,N-dimethylbenzamide.

[0084] Alcohols that can be used as neutral nonionic organic modifiers can be C 2 To C 20 , C 2 To C 15 or C 2 To C 10The nitrile may have the structure R 23 CH 2 OH. The R 23 Can be C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Hydrocarbon; C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Alkyl; C 5 To C 15 or C 5 To C 10 Cycloalkyl; C 6 To C 15 or C 6 To C 10 Aryl; or C 7 To C 15 or C 7 To C 10 Aralkyl. In non-limiting aspects, alcohols useful as neutral nonionic organic modifiers may include, consist essentially of, or may 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.

[0085] In general, when a neutral nonionic organic modifier is used, the neutral nonionic organic modifier may be utilized relative to the zirconium compound and / or the hydrocarbyl metal (or hydrocarbyl aluminum) compound. The molar ratio of the neutral nonionic organic modifier to the zirconium of the zirconium compound (also referred to herein as the modifier:Zr molar ratio) and / or the molar ratio of the neutral nonionic organic modifier to the hydrocarbyl metal (or hydrocarbyl aluminum) compound (also referred to herein as the modifier:M (or modifier:Al) molar ratio) may be any ratio that can form an oligomer product when the catalyst system is contacted with ethylene. When a neutral nonionic organic modifier is utilized relative to the zirconium of the zirconium compound, the minimum modifier:Zr molar ratio may be 0.1:1, 0.5:1, 0.75:1, 0.8:1, 0.9:1, or 1:1; additionally or alternatively, the maximum modifier:Zr molar ratio may be 20:1, 15:1, 10:1, 7.5:1, or 5:1. Typically, the modifier: Zr molar ratio can be in the range of any minimum modifier: Zr molar ratio described herein to any maximum modifier: Zr molar ratio described herein. Thus, suitable non-limiting modifier: Zr molar ratios can be in the range of 0.5: 1 to 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 apparent from this disclosure. When a neutral nonionic organic modifier is utilized relative to the 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; 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 may range from 0.5: 1 to 5: 1, 0.5: 1 to 3: 1, 0.75: 1 to 2: 1, or 0.75: 1 to 1.5: 1. Other suitable modifier:M (or modifier:Al) molar ratio ranges will be apparent from this disclosure.

[0086] In one aspect, the catalyst system can be prepared first, and then i) the catalyst system is contacted with ethylene, a chain transfer agent, and an optional organic reaction medium or ii) the catalyst system is introduced into a reaction zone. For example, in one aspect, the method can include contacting a zirconium compound with a hydrocarbyl metal (or hydrocarbyl aluminum) compound to form a catalyst system, and then i) the catalyst system is contacted with ethylene, a chain transfer agent, and an optional organic reaction medium, or ii) the catalyst system is introduced into a reaction zone. When a neutral nonionic organic modifier is utilized in the catalyst system, the neutral nonionic organic modifier can be contacted with the zirconium compound before contacting 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. On the other hand, the neutral nonionic organic modifier, the zirconium compound, and the hydrocarbyl metal (or hydrocarbyl aluminum) compound can be contacted simultaneously to form the catalyst system.

[0087] In alternative aspects, the catalyst system can be prepared in situ, wherein two or more components of the catalyst system are i) contacted separately (and / or simultaneously) with ethylene, a chain transfer agent, and an optional organic reaction medium, or ii) introduced separately (and / or simultaneously) into a reaction zone. For example, in one aspect, the method can include i) contacting a zirconium compound and a hydrocarbyl compound separately (and / or simultaneously) with ethylene, a chain transfer agent, and an optional organic reaction medium, or ii) introducing a zirconium compound and a hydrocarbyl compound separately (and / or simultaneously) into a reaction zone. In one aspect, when a neutral nonionic organic modifier is utilized in the catalyst system, the neutral nonionic organic modifier can be contacted with the zirconium compound first (to form a zirconium compound / neutral nonionic organic modifier mixture) before the zirconium compound (or zirconium compound / neutral nonionic organic modifier mixture) and the hydrocarbyl metal (or hydrocarbyl aluminum) compound are contacted with ethylene, a chain transfer agent, and an optional organic reaction medium separately (and / or simultaneously) or the zirconium compound (or zirconium compound / neutral nonionic organic modifier mixture) and the hydrocarbyl metal (or hydrocarbyl aluminum) compound are introduced separately (and / or simultaneously) into the reaction zone. On the other hand, when a neutral nonionic organic modifier is utilized in the catalyst system, the neutral nonionic organic modifier may be contacted with a hydrocarbyl metal (or hydrocarbyl aluminum) compound (to form a hydrocarbyl metal (or hydrocarbyl aluminum) compound / neutral nonionic organic modifier mixture) before the hydrocarbyl metal (or hydrocarbyl aluminum) compound or the hydrocarbyl metal (or hydrocarbyl aluminum) compound / neutral nonionic organic modifier mixture) and the zirconium compound are contacted with ethylene, a chain transfer agent, and an optional organic reaction medium, or the hydrocarbyl metal (or hydrocarbyl aluminum) compound (or the hydrocarbyl metal or hydrocarbyl aluminum) compound / neutral nonionic organic modifier mixture) and the zirconium compound are introduced into the reaction zone, either separately (and / or simultaneously). In a further aspect, when a neutral nonionic organic modifier is utilized in the catalyst system, the neutral nonionic organic modifier, the zirconium compound, and the hydrocarbyl metal (or hydrocarbyl aluminum) compound may be contacted separately (and / or simultaneously) with ethylene, a chain transfer agent, and an optional organic reaction medium or introduced separately (and / or simultaneously) into the reaction zone.

[0088] In one non-limiting aspect, the catalyst system may comprise a catalyst having the formula ZrX 1 m The zirconium compound and the hydrocarbyl metal compound include those having the formula AlX 2 n R 1 3-n 、Al 2 X 2 3 R 1 3 , R 12 Zn or any combination thereof. 1 , X 2 , R 1 , m and n are described independently herein, and these independent descriptions may be used without limitation and in any combination to further describe a catalyst system that may include: a catalyst having the formula ZrX 1 m Zirconium compounds and compounds having the formula AlX 2 n R 1 3-n 、Al 2 X 2 3 R 1 3 Alkyl aluminum compounds, dialkyl zinc compounds (R 1 2 In one aspect, ZrX 1 m Each X 1 Each of the above compounds may be independently chlorine or bromine and m is 4. In one aspect, the compound of formula ZrX 1 m The zirconium compound may include, consist essentially of, or may be: ZrCl 4 , ZrBr 4 、ZrClBr 3 、ZrC1 2 Br 2 and ZrCl 3 Br; alternatively, ZrCl 4 or ZrBr 4 ; Alternatively, ZrClBr 3 ; or alternatively, ZrCl 4 In one aspect, the hydrocarbyl metal compound may include a compound having the formula AlX 2 2 R 1 、AlX 2 R 1 2 , AlR 1 3 、Al 2 X 2 3 R 1 3 , R 1 2 Zn or any combination thereof; alternatively, AlX 2 2 R 1 、AlX2 R 1 2 , AlR 1 3 、Al 2 X 2 3 R 1 3 Or any combination thereof. 2 and R 1 are described independently herein, and these independent descriptions may be used without limitation and in any combination to further describe a catalyst system that may include: a catalyst having the formula ZrX 1 m Zirconium compounds and compounds having 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. In one aspect, each X of the hydrocarbyl metal compound 2 can be independently halogen, and each R 1 Can be independently C 2 To C 4 Alkyl. In some aspects, the alkyl metal compound may include, 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 ​​of 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 in the range of 1:1 to 50:1, 1:1 to 15:1, or 10:1 to 25:1. In some non-limiting aspects, the catalyst system (or catalyst system component) may further include a neutral nonionic organic modifier comprising C 2 To C 20 ester (any described herein), wherein the molar ratio of the neutral nonionic organic modifier to the zirconium of the zirconium compound can be in any range disclosed herein (e.g., in the range of 0.5:1 to 5:1). In other non-limiting aspects, the catalyst system (or catalyst system component) can further include a neutral nonionic organic modifier comprising C2 To C 20 Ether, C 2 To C 20 Sulfide, C 1 To C 20 Amine, C 3 To C 20 Phosphine or any combination thereof (alternatively, C 2 To C 20 Ether, C 2 To C 20 sulfide or any combination thereof; alternatively, C 2 To C 20 ether; alternatively (C 2 -C 20 thioether; alternatively, C 1 -C 20 Amine; or alternatively, C 3 -C 20 phosphine), wherein the molar ratio of the neutral nonionic organic modifier to the zirconium of the zirconium compound can be any range disclosed herein (e.g., in the range of 0.5:1 to 20:1).

[0089] In another non-limiting aspect, the zirconium compound can have the formula ZrX 1 m Y 1 q And the hydrocarbyl metal compound may include a compound having the formula AlX 2 n R 1 3-n 、Al 2 X 2 3 R 1 3 Or any combination thereof. 1 , Y 1 , X 2 , R 1 , n are described independently herein, and these independent descriptions may be used without limitation and in any combination to further describe a catalyst system that may include: having the formula ZrX 1 m Y 1 q Zirconium compounds and compounds having the formula AlX 2 n R 1 3-n 、Al 2 X 2 3 R 1 3Or any combination thereof, a hydrocarbyl metal compound of an alkyl aluminum compound. ZrX 1 m Y 1 q Each X in 1 Each may independently be chlorine or bromine; alternatively, chlorine. ZrX 1 m Y 1 q Each Y 1 Can be independently C 1 To C 10 Oxygen (e.g., any described herein), C 1 To C 10 A hydrocarbyl carboxylate (e.g., any described herein) or a C 1 To C 15 alkyl sulfonate (such as any described herein); alternatively, C 1 To C 10 alkoxide (such as any described herein); alternatively, C 1 To C 10 A hydrocarbyl carboxylate (such as any described herein); or alternatively, C 1 To C 15 Hydrocarbyl sulfonate (such as any described herein). For ZrX 1 m Y 1 q , m can be in the range of 0 to 4, q can be in the range of 0 to 4, and m+q can be 4; alternatively, m can be 4 and q can be 0; or alternatively, m can be 0 and q can be 4. In one aspect, a ZrX 1 m Y 1 q The zirconium compound may include, may consist essentially of, or may be: 1 To C 10 zirconium hydrocarbyl carboxylate; alternatively, tetra-C 1 To C 5 zirconium hydrocarbyl carboxylate, or alternatively, Zr(O 2 C 3 H 7 ) 4 On the other hand, having the formula ZrX 1 m The zirconium compound may include, consist essentially of, or may be: ZrCl 4 , ZrBr 4 、ZrClBr 3 、ZrC1 2Br 2 and ZrCl 3 Br; alternatively, ZrCl 4 or ZrBr 4 , or alternatively, ZrClBr 3 ; or alternatively, ZrCl 4 In one aspect, the hydrocarbyl metal compound may include a compound having the formula AlX 2 2 R 1 、AlX 2 R 1 2 , AlR 1 3 、Al 2 X 2 3 R 1 3 or any combination thereof, alternatively, AlX 2 2 R 1 、AlX 2 R 1 2 , AlR 1 3 、Al 2 X 2 3 R 1 3 Or any combination thereof. 2 and R 1 are described independently herein, and these independent descriptions may be used without limitation and in any combination to further describe a catalyst system that may include: a catalyst having the formula ZrX 1 m Zirconium compounds and compounds having 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. In one aspect, each X of the hydrocarbyl metal compound 2 can be independently halogen, and each R 1 Can be independently C 2 To C 4Alkyl. In some aspects, the alkyl metal compound may include, 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 ​​of the molar ratio of the metal in the hydrocarbyl metal compound (or the aluminum of the hydrocarbyl aluminum compound) to the zirconium of the zirconium compound may be in the range of 1:1 to 50:1, 2:1 to 25:1, or 1:1 to 15:1, as well as other ranges disclosed herein. In one aspect, a compound having the formula ZrX 1 m Y 1 q The zirconium compounds can be obtained by making ZrX 1 m Y 1 q The catalyst system (or catalyst system components) may further comprise a neutral nonionic organic modifier comprising C 2 To C 15 Alcohol, C 1 To C 15 Amine, C 2 To C 15 Amide or any combination thereof; alternatively, C 2 To C 15 Alcohol; alternatively, C 1 To C 15 Amine; or alternatively, C 2 To C 15 In one aspect, the molar ratio of the neutral nonionic organic modifier to the metal of the hydrocarbyl metal compound (or the aluminum of the hydrocarbyl aluminum compound) is between 0.75:1 and 2:1 or between 0.75:1 and 1.5:1, as well as other ranges disclosed herein. In one aspect, the neutral nonionic organic modifier can be contacted with the hydrocarbyl metal (or hydrocarbyl aluminum) compound before the hydrocarbyl metal (or hydrocarbyl aluminum) compound contacts the zirconium compound and / or ethylene (and / or is introduced into the reaction zone). In some aspects, the neutral nonionic organic modifier is contacted with the zirconium compound before the zirconium compound contacts ethylene and / or the hydrocarbyl metal compound (and / or is introduced into the reaction zone).

[0090] The methods described herein may utilize 1) a chain transfer agent comprising a compound having a hydrogen-silicon bond, a compound having a hydrogen-sulfide 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-sulfide 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-sulfide 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, in the process of forming an oligomer product, a chain transfer agent, hydrogen, and / or a transition metal compound chain transfer agent are utilized to achieve the desired effect. Desirable effects may include producing (a) less than 1 wt.% polymer, (b) less than 1 wt.% compound having a weight average molecular weight greater than 1000 g / mol, or (c) any combination thereof, relative to the same process not using 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, wherein the wt.% is based on the total weight of the oligomer product; alternatively or additionally, producing (a) an oligomer product comprising a polymer having a lower Mw, (b) an oligomer product wherein the polymer has a lower Mw maximum peak, (c) an oligomer product having a reduced amount of polymer, (d) an oligomer product having a reduced % of polymer having a molecular weight greater than 100,000 molecular weight, or (e) any combination thereof.

[0091] The chain transfer agent may include, consist essentially of, or may 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 molar ratio of chain transfer agent to ethylene that can provide any desired effect described herein. In one aspect, the reaction zone may have 1x10 -5 :1, 5x10 -4 :1, 1x10 -4 :1 or 5x10 -3 :1 minimum chain transfer agent to ethylene molar ratio; additionally or alternatively, 5x10 -1 :1, 1x10 -1 :1, 5x10 -2 :1 or 1x10 -2:1 maximum chain transfer agent to ethylene molar ratio. Generally speaking, the chain transfer agent to ethylene molar ratio of the reaction zone can be in the range of any minimum chain transfer agent to ethylene molar ratio described herein to any maximum chain transfer agent to ethylene molar ratio described herein. Thus, a suitable reaction zone chain transfer agent to ethylene molar ratio can be in the range of 1x10 -5 :1 to 5x10 -1 :1, 5x10 -4 :1 to 1x10 -1 :1, 1x10 -4 :1 to 5x10 -2 :1 or 5x10 -3 :1 to 1x10 -2 Other suitable reaction zone chain transfer agent to ethylene molar ratio ranges are apparent from this disclosure.

[0092] The compound having a hydrogen-silicon bond that can be used as a neutral nonionic organic modifier can be a C 1 To C 40 , C 1 To C 30 or C 1 To C 20 In one aspect, the compound having a hydrogen-silicon bond that can be used as a chain transfer agent can have the formula R 31 S H 3 , (R 31 ) 2 S H 2 , (R 31 ) 3 SiH、R 31 OSiH3、(R 31 O) 2 S H 2 , (R 31 O) 3 SiH or any combination thereof; alternatively, R 31 S H 3 , (R 31 ) 2 S H 2 , (R 31 ) 3 SiH or any combination thereof; alternatively, R 31 OSiH3、(R 31 O) 2 S H 2 , (R 31 O) 3 SiH or any combination thereof; alternatively, R 31 S H 3 ; Alternatively, (R 31 )2 S H 2 ; Alternatively, (R 31 ) 3 SiH; alternatively, R 31 OSiH3; alternatively, (R 31 O) 2 S H 2 ; or alternatively, (R 31 O) 3 SiH. Each R in the formula of the compound having a hydrogen-silicon bond 31 Can be independently C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Hydrocarbon, C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Alkyl, C 5 To C 15 or C 5 To C 10 Cycloalkyl, C 6 To C 15 or C 6 To C 10 Aryl or C 7 To C 15 or C 7 To C 10Aralkyl. In non-limiting aspects, compounds having a hydrogen-silicon bond (e.g., having any of the formulas described herein) can include, consist essentially of, or can be trimethylsilane, diethylsilane, triethylsilane, tripropylsilane, dibutylsilane, tributylsilane, hexylsilane, dihexylsilane, trihexylsilane, octylsilane, dioctylsilane, trioctylsilane, decylsilane, didecylsilane, tridecylsilane, tridodecylsilane, benzene 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, diphenylethylsilane, triphenylethylsilane, or any combination thereof; trimethylsilane, diethylsilane, triethylsilane, tripropylsilane, dibutylsilane, tributylsilane, hexylsilane, dihexylsilane, trihexylsilane , octylsilane, dioctylsilane, decylsilane, didecylsilane, phenylsilane, diphenylsilane, triphenylsilane, phenethylsilane, diphenylethylsilane or any combination thereof; alternatively, trioctylsilane, tridecylsilane, tridodecylsilane, triphenylethylsilane or any combination thereof; alternatively, trimethoxysilane, triethoxysilane or any combination thereof; or alternatively, phenylsilane, diphenylsilane or any combination thereof.

[0093] The compounds having a silicon-sulfur bond that can be used as neutral nonionic organic modifiers can be C 1 To C 20 , C 1 To C 15 or C 1 To C 10 Compounds. Compounds having hydrogen-sulfide bonds useful as neutral nonionic organic modifiers may include, consist essentially of, or may be: C 1 To C 20 , C 1 To C 15 or C 1 To C 10 Thiol, C 1 To C 20 , C 1 To C 15 or C 1 To C 10Thioglycolate, and / or C 1 To C 20 , C 1 To C 15 or C 1 To C 10 Mercaptopropionate; alternatively, C 1 To C 20 , C 1 To C 15 or C 1 To C 10 Thiol; alternatively, C 1 To C 20 , C 1 To C 15 or C 1 To C 10 Thioglycolate; or alternatively, C 1 To C 20 , C 1 To C 15 or C 1 To C 10 In one aspect, the compound having a hydrogen-sulfide bond that can be used as a chain transfer agent can have the formula R 32 SH, R 32 CO 2 CH 2 SH, R 32 CO 2 CH 2 CH 2 SH or any combination thereof; alternatively, R 32 CO 2 CH 2 SH, R 32 CO 2 CH 2 CH 2 SH or any combination thereof; alternatively, R 32 SH; alternatively, R 32 CO 2 CH 2 SH; or alternatively, R 32 CO 2 CH 2 CH 2 SH. R in the formula of a compound having a hydrogen-sulfur bond 32 Can be C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Hydrocarbon, C 1 To C 15 , C 1 To C10 or C 1 To C 5 Alkyl, C 5 To C 15 or C 5 To C 10 Cycloalkyl, C 6 To C 15 or C 6 To C 10 Aryl or C 7 To C 15 or C 7 To C 10 Aralkyl. In non-limiting aspects, compounds having hydrogen-sulfide bonds (e.g., having any formula described herein) can include, consist essentially of, or can be methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, undecyl mercaptan, dodecyl mercaptan, methyl thioglycolate, ethyl thioglycolate, methyl mercaptopropionate, ethyl mercaptopropionate, or any combination thereof; alternatively, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, undecyl mercaptan, dodecyl mercaptan, or any combination thereof; Alternatively, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, pentyl mercaptan or any combination thereof; alternatively, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decanyl mercaptan, undecanyl mercaptan, dodecanyl mercaptan or any combination thereof; alternatively, methyl thioglycolate, ethyl thioglycolate, methyl mercaptopropionate, ethyl mercaptopropionate or any combination thereof; alternatively, ethyl mercaptan; alternatively, propyl mercaptan; alternatively, butyl mercaptan; alternatively, tert-butyl mercaptan; alternatively, octyl mercaptan; alternatively, decanyl mercaptan; alternatively, dodecanyl mercaptan; alternatively, methyl thioglycolate; or alternatively, methyl mercaptopropionate.

[0094] The compound having a hydrogen-phosphorus bond that can be used as a neutral nonionic organic modifier can be a C 1 To C 40 , C 1 To C 30 or C 1 To C 20 Compounds. Compounds having hydrogen-phosphorus bonds useful as neutral nonionic organic modifiers may include, consist essentially of, or may be: C 1 To C 40 , C 1 To C 30 or C 1 To C 20 Phosphine and / or C 1 To C 40 , C 1 To C30 or C 1 To C 20 Phosphite; alternatively, C 1 To C 40 , C 1 To C 30 or C 1 To C 20 Phosphine; or alternatively, C 1 To C 40 , C 1 To C 30 or C 1 To C 20 In one aspect, the compound having a hydrogen-phosphorus bond that can be used as a chain transfer agent can have the formula (R 33 ) 2 PH, (R 33 O) 2 P(=O)H or any combination thereof; alternatively, R 33 PH 2 ; or alternatively, (R 33 O) 2 P(=O)H. Each R in the formula of the compound having a hydrogen-phosphorus bond 33 Can be independently C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Hydrocarbon, C 1 To C 15 , C 1 To C 10 or C 1 To C 5 Alkyl, C 5 To C 15 or C 5 To C 10 Cycloalkyl, C 6 To C 15 or C 6 To C 10 Aryl or C 7 To C 15 or C 7 To C 10Aralkyl. In non-limiting aspects, compounds having a phosphorus-hydrogen bond (e.g., having any of the formulas described herein) can include, consist essentially of, or can be dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dioctylphosphine, dicyclopentylphosphine, dicyclohexylphosphine, phenylphosphine, diphenylphosphine, dimethylphosphite, diethylphosphite, dibutylphosphite, dihexylphosphite, dioctylphosphite, diphenylphosphite, dibenzylphosphite, or any combination thereof; dimethylphosphine , diethyl phosphine, dibutyl phosphine, dioctyl phosphine, dicyclopentyl phosphine, dicyclohexyl phosphine, phenyl phosphine, diphenyl phosphite, dimethyl phosphite, diethyl phosphite, diphenyl phosphite, dibenzyl phosphite, or any combination thereof; alternatively, dimethyl phosphine, diethyl phosphine, dibutyl phosphine, dicyclopentyl phosphine, dicyclohexyl phosphine, dioctyl phosphine, phenyl phosphine, diphenyl phosphite, or any combination thereof; or alternatively, dimethyl phosphite, diethyl phosphite, diphenyl phosphite, dibenzyl phosphite, or any combination thereof.

[0095] The transition metal compound chain transfer agent may include, consist essentially of, or may be a Group 8 transition metal compound, a Group 9 transition metal compound, a Group 10 transition metal compound, or any combination thereof; alternatively, a Group 8 transition metal compound; alternatively, a Group 9 transition metal compound; or alternatively, a Group 10 transition metal compound. In one aspect, the reaction zone may have 1x10 -9 :1, 5x10 -8 :1, 1x10 -8 :1, 5x10 -7 :1 or 1x10 -7 :1 minimum transition metal to ethylene molar ratio; additionally or alternatively, 5x10 -3 :1, 1x10 -3 :1, 5x10 -4 :1, 1x10 -4 :1 or 5x10 -5 In general, the reaction zone may have a transition metal to ethylene molar ratio that can 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 may have a transition metal to ethylene molar ratio that can range from 1 x 10 -9 :1 to 5x10- 3 :1, 5x10- 8 :1 to 1x10- 3 :1, 1x10- 8 :1 to 5x10- 4 :1, 5x10- 7 :1 to 1x10 -4:1 or 1x10 -7 :1 to 5x10 -5 Other suitable ranges of transition metal to ethylene molar ratios for the reaction zone are apparent from this disclosure.

[0096] Generally, transition metal compound chain transfer agents may have the formula MX 4 p , where M is a transition metal, X 4 is a single anion, 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 aspect, the transition metal M can be iron, cobalt, or nickel; alternatively, iron or cobalt; alternatively, iron; alternatively, cobalt; or alternatively, nickel. In general, a compound having the formula MX 4 p The transition metal compound chain transfer agent p is an integer from 2 to 4, and is 2 or 3, 2, 3 or 4. In one aspect, the transition metal compound chain transfer agent having the formula MX 4 p Each p of the transition metal compound chain transfer agent can independently be a halide, carboxylate, β-diketonate, oxylate or nitrate; alternatively, a carboxylate, β-diketonate or oxylate; alternatively, a carboxylate or β-diketonate; alternatively, a carboxylate; or alternatively, a β-diketonate. In one aspect, the compound of formula MX 4 p Each carboxylate group of the transition metal compound chain transfer agent can be independently C 2 To C 24 , C 4 To C 19 or C 5 To C 12 In one aspect, a carboxylate having the formula MX 4 p Each oxyalkyl group of the transition metal compound chain transfer agent can be independently C 1 To C 24 , C 4 To C 19 or C 5 To C 12 In one aspect, a compound having the formula MX 4 p Each β-diketonate of the transition metal compound chain transfer agent can be independently C 5 To C 24 , C 5 To C 19 or C 5 To C 12β-diketone.

[0097] Generally speaking, MX 4 p Each halide group of the transition metal compound chain transfer agent of the formula may independently be chlorine, bromine or iodine; alternatively, bromine, or alternatively, iodine. In general, a transition metal compound of the formula MX 4 p Each carboxylate of the transition metal compound chain transfer agent can be independently 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. In general, the compound having the formula MX 4 p Each oxyhydroxide of the transition metal compound chain transfer agent can be independently methoxy, ethoxy, propoxy, butoxy, phenoxy, methylphenoxy or dimethylphenoxy; alternatively, methoxy, ethoxy, propoxy or butoxy; alternatively, phenoxy, methylphenoxy or dimethylphenoxy. In general, the transition metal compound chain transfer agent of formula MX 4 p Each β-diketonate of the transition metal compound chain transfer agent can be independently acetylacetonate (i.e., 2,4-pentanedione), hexafluoroacetylacetonate (i.e., 1,1,1,5,5,5-hexafluoro-2,4-pentanedione) or benzoylacetonate; alternatively, acetylacetonate; alternatively, hexafluoroacetylacetonate; or alternatively, benzoylacetonate. In some non-limiting aspects, the transition metal compound chain transfer agent (or having the formula MX 4 pThe transition metal compound chain transfer agent) may include, consist essentially of, or may be iron (II) chloride, iron (III) chloride, iron (II) acetate, iron (III) acetate, iron (II) octoate, iron (III) octoate, iron (II) acetylacetonate, iron (III) acetylacetonate, cobalt (II) chloride, cobalt (III) chloride, cobalt (II) acetate, cobalt (III) acetate, cobalt (II) octoate, cobalt (III) octoate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, nickel (II) chloride, nickel (II) acetate, nickel (II) octoate, or nickel (II) acetylacetonate; alternatively, iron (II) acetate, iron (III) acetate, iron (II) octoate, iron (III) octoate, iron (II) acetylacetonate, iron (III) acetylacetonate Alternatively, iron (II) octoate, iron (III) octoate, iron (II) octoate, iron (III) acetylacetonate, iron (III) acetylacetonate, cobalt (II) octoate, cobalt (III) acetylacetonate, nickel (II) acetate, nickel (II) octoate or nickel (II) acetylacetonate; or alternatively, iron (III) octoate, iron (III) octoate, iron (II) acetylacetonate, iron (III) acetylacetonate, cobalt (II) octoate, cobalt (III) acetylacetonate, nickel (II) octoate or nickel (II) acetylacetonate.

[0098] When hydrogen is utilized, the reaction zone may have any hydrogen to ethylene ratio that provides any desired effect described herein. In one aspect, the minimum hydrogen to ethylene ratio may be (0.05 g hydrogen) / (kg ethylene), (0.1 g hydrogen) / (kg ethylene), (0.25 g hydrogen) / (kg ethylene), (0.4 g hydrogen) / (kg ethylene), or (0.5 g hydrogen) / (kg ethylene); additionally or alternatively, the maximum hydrogen to ethylene ratio may 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 may have a hydrogen to ethylene ratio that may be within the range of any minimum hydrogen to ethylene ratio described herein to any maximum hydrogen to ethylene ratio described herein. Thus, suitable reaction zone hydrogen to ethylene ratios may range from (0.05 g hydrogen) / (kg ethylene) to (5 g hydrogen) / (kg ethylene), from (0.25 g hydrogen) / (kg ethylene) to (5 g hydrogen) / (kg ethylene), from (0.25 g hydrogen) / (kg ethylene) to (4 g hydrogen) / (kg ethylene), from (0.4 g hydrogen) / (kg ethylene) to (3 g hydrogen) / (kg ethylene), from (0.4 g hydrogen) / (kg ethylene) to (2.5 g hydrogen) / (kg ethylene), from (0.4 g hydrogen) / (kg ethylene) to (2 g hydrogen) / (kg ethylene), or from (0.5 g hydrogen) / (kg ethylene) to (2 g hydrogen) / (kg ethylene). Other suitable reaction zone hydrogen to ethylene ratio ranges will be apparent from this disclosure.

[0099] The organic reaction medium that can be used in the methods described herein can be, for example, a hydrocarbon, a halogenated hydrocarbon, or a combination thereof. The hydrocarbons and halogenated hydrocarbons that can be used as organic reaction media can include aliphatic hydrocarbons, aromatic hydrocarbons, petroleum distillates, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, or any combination thereof. The aliphatic hydrocarbons that can be used as organic reaction media include C 3 To C 20 Aliphatic hydrocarbons; or C 4 To C 15 Aliphatic hydrocarbons; or C 5 To C 10 Aliphatic hydrocarbons. Aliphatic hydrocarbons useful as organic reaction media may be cyclic or acyclic and / or may be 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, isobutane, n-butane, butane (n-butane, or straight and branched C 4 mixture of acyclic aliphatic hydrocarbons), pentane (n-pentane, or straight-chain and branched C 5 mixture of acyclic aliphatic hydrocarbons), hexane (n-hexane, or straight-chain and branched C 6mixture of acyclic aliphatic hydrocarbons), heptane (n-heptane, or straight-chain and branched C 7 mixture of acyclic aliphatic hydrocarbons) and octane (n-octane, or straight-chain and branched C 8 Aromatic hydrocarbons that can be used as organic reaction medium include aromatic hydrocarbons or C 6 To C 10 Aromatic hydrocarbons. Non-limiting examples of suitable aromatic hydrocarbons that can be used as organic reaction media, either alone or in any combination, include benzene, toluene, xylene (including o-xylene, m-xylene, p-xylene or mixtures thereof), and ethylbenzene. Halogenated aliphatic hydrocarbons that can be used as organic reaction media include C 1 To C 15 Halogenated aliphatic hydrocarbons or C 1 To C 10 Halogenated aliphatic hydrocarbons or C 1 To C 5 Halogenated aliphatic hydrocarbons. Halogenated aliphatic hydrocarbons useful as organic reaction media may be cyclic or acyclic and / or may be linear or branched, unless otherwise specified. Non-limiting examples of suitable halogenated aliphatic hydrocarbons useful as organic reaction media include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, or any combination thereof. Halogenated aromatic hydrocarbons useful as organic reaction media include C 6 To C 20 Halogenated aromatic hydrocarbons or 6 To C 10 Halogenated Aromatic Hydrocarbons. Non-limiting examples of suitable halogenated aromatic hydrocarbons that may be used as the organic reaction medium include chlorobenzene, dichlorobenzene, or any combination thereof.

[0100] In general, the oligomer product can be formed under any conditions capable of forming the oligomer product. The conditions that can be used to form the oligomer product can include the reaction zone pressure, the reaction zone ethylene partial pressure, the reaction zone temperature, the molar ratio of zirconium to ethylene of the reaction zone zirconium compound, the mass ratio of ethylene to 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 oligomer product Schultz-Flory K value, and the selectivity of the oligomer product to normal alpha olefins, alone or in any combination. 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 organic reaction medium in the reaction zone, the reaction zone residence time (or average residence time), the ethylene conversion rate (or single-pass ethylene conversion rate), the Schultz-Flory K value of the oligomer product, and the selectivity of the oligomer product to normal α-olefins are independently described herein, 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 organic reaction medium in the reaction zone, the reaction zone residence time (or average residence time), the ethylene conversion rate (or single-pass ethylene conversion rate), the Schultz-Flory K value of the oligomer product, and the selectivity of the oligomer product to normal α-olefins can be used without limitation and in any combination to further describe the process disclosed herein.

[0101] The oligomer product may be formed at a reaction zone minimum pressure of (or the reaction zone may have 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); alternatively or additionally, may be formed at (or the reaction zone may have a maximum 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, may be formed at a maximum pressure of (or the reaction zone may have a maximum pressure of) In some embodiments, the oligomer product may be formed at a reaction zone pressure ranging from any minimum pressure disclosed herein to any maximum pressure disclosed herein (or the reaction zone may have a pressure ranging from any minimum pressure disclosed herein to any maximum pressure disclosed herein). In some non-limiting aspects, the oligomer product can be formed at a reaction zone pressure (or the reaction zone can have a pressure) of from 100 psi (689 kPa) to 5000 psi (34.5 MPa), 100 psi (689 kPa) to 2,500 psi (17.2 MPa), 100 psi (689 kPa) to 1000 psi (6.89 MPa), 500 psi (3.45 MPa) to 4500 psi (31 MPa), 500 psi (3.45 MPa) to 2,500 psi (17.2 MPa), 500 psi (3.45 MPa) to 1000 psi (6.89 MPa), 750 psi (5.17 MPa) to 4500 psi (31 MPa), 900 psi (6.21 MPa) to 4,000 psi (27.6 MPa), or 1000 psi (6.89 MPa) to 3500 psi (24.1 MPa). Other pressure ranges that may be utilized will be readily apparent to those skilled in the art with the benefit of this disclosure.

[0102] The oligomer product may be formed at a minimum ethylene partial pressure in the reaction zone (or the reaction zone may have 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); alternatively or additionally, the oligomer product may be formed at a maximum pressure (or the reaction zone may have a maximum 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); (500 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). In general, the oligomer product can be formed at a reaction zone ethylene partial pressure ranging from any minimum ethylene partial pressure disclosed herein to any maximum ethylene partial pressure disclosed herein (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 aspects, the oligomer product can be formed at (or the reaction zone can have) an ethylene partial pressure of from 100 psi (689 kPa) to 5000 psi (34.5 MPa), from 100 psi (689 kPa) to 2,500 psi (17.2 MPa), from 100 psi (689 kPa) to 1000 psi (6.89 MPa), from 500 psi (3.45 MPa) to 4500 psi ( psi (27.6 MPa), 1000 psi (6.89 MPa) to 3500 psi (24.1 MPa). Other ethylene partial pressure ranges will be readily apparent to those skilled in the art with the benefit of this disclosure.

[0103] The oligomer product may be formed at a reaction zone minimum temperature of (or the reaction zone may have a minimum temperature of) 0° C., 25° C., 40° C., 50° C., 75° C., 100° C., or 125° C.; alternatively or additionally, may be formed at a maximum temperature of (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 oligomer product is formed at a reaction zone temperature ranging from any minimum temperature disclosed herein to any maximum temperature disclosed herein (or the reaction zone may have a temperature ranging from any minimum temperature disclosed herein to any maximum temperature disclosed herein). In some non-limiting aspects, the oligomer product can be formed at a reaction zone temperature (or the reaction zone can have a temperature) of from 0° C. to 250° C., from 25° C. to 200° C., from 40° C. to 150° C., from 40° C. to 100° C., from 50° C. to 100° C., from 50° C. to 150° C., from 75° C. to 125° C., from 75° C. to 250° C., from 100° C. to 200° C., or from 100° C. to 200° C. Other temperature ranges that may be utilized will be readily apparent to those skilled in the art with the benefit of this disclosure.

[0104] The oligomer product may be formed at a minimum reaction zone zirconium compound molar ratio of zirconium to ethylene in the reaction zone (or the reaction zone has a minimum reaction zone zirconium compound molar ratio of zirconium to ethylene): 5 x 10 -7 :1, 1x10 -6 :1, 5x10 -5 :1 or 2.5x10 -5 :1; Additionally or alternatively, it may be formed at a maximum reaction zone zirconium compound zirconium to ethylene molar ratio (or the reaction zone has a maximum reaction zone zirconium compound zirconium to ethylene molar ratio): 7.5x10 -4 :1, 5x10 -4 :1, 2.5x10 -4 :1 or 1x10 -4 :1. Generally, the molar ratio of zirconium to ethylene of the reaction zone zirconium compound can range from any minimum molar ratio of zirconium to ethylene of the reaction zone zirconium compound disclosed herein to any maximum molar ratio of zirconium to ethylene of the reaction zone zirconium compound disclosed herein. In non-limiting aspects, the molar ratio of zirconium to ethylene of the reaction zone zirconium compound can range from 5x10 -7 :1 to 1x10 -4 :1, 1x10 -6 :1 to 2.5x10 -4 :1, 5x10 -5 :1 to 5x10 -4 :1 or 2.5x10 -5 :1 to 7.5x10 -4In the range of : 1. With the help of this disclosure, those skilled in the art will readily appreciate other molar ratio ranges of zirconium to ethylene that can be utilized for the zirconium compounds in the reaction zone.

[0105] The oligomer product may be formed at a reaction zone minimum ethylene:organic reaction medium mass ratio (or the reaction zone may have a minimum ethylene:organic reaction medium mass ratio) of 0.5:1, 0.75:1, 1:1, 1.25:1, or 1.5:1; additionally or alternatively, may be formed at a maximum ethylene:organic reaction medium mass ratio (or the reaction zone may have 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. Generally speaking, the oligomer product may be formed at a reaction zone ethylene:organic reaction medium mass ratio ranging from any minimum ethylene:organic reaction medium mass ratio disclosed herein to any maximum ethylene:organic reaction medium mass ratio disclosed herein (or the reaction zone may have an ethylene:organic reaction medium mass ratio 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 aspects, oligomer products can be formed at a reaction zone ethylene: organic reaction medium mass ratio in the following ranges (or the reaction zone can have an ethylene: organic reaction medium mass ratio in the following ranges): 0.5: 1 to 4.5: 1, 0.75: 1 to 4: 1, 0.75: 1 to 2: 1, 1: 1 to 3: 1, or 1.5: 1 to 2.5: 1. Other ethylene to organic reaction medium mass ratio ranges that may be utilized will be readily apparent to those skilled in the art in light of this disclosure.

[0106] The oligomer product may be formed at any desired reaction zone residence time (or average reaction zone residence time) (or the reaction zone may have any desired reaction zone residence time (or average reaction zone residence time)). In one aspect, the oligomer product may be formed at a reaction zone residence time (or average reaction zone residence time) for producing a desired amount of oligomer product, a desired catalyst system productivity, providing a desired ethylene conversion, or any combination thereof; alternatively, for producing a desired amount of oligomer product; alternatively, a desired catalyst system productivity; or alternatively, providing a desired ethylene conversion. The oligomer product may be formed at (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, may be formed at (or the reaction zone may have a maximum reaction zone residence time (or average reaction zone residence time) of 3 hours, 2.5 hours, 2 hours, or 1.5 hours. In general, 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 aspects, the oligomer product can be formed at a reaction zone residence time (or average reaction zone residence time) of 10 minutes to 2.5 hours, 20 minutes to 2 hours, 30 minutes to 2 hours, or from 30 minutes to 1.5 hours. With the aid of this disclosure, those skilled in the art will readily appreciate other reaction zone residence time (or average reaction zone residence time) ranges that can be utilized.

[0107] The oligomer product may have (or may be formed with) a minimum Schultz-Flory K value of 0.4, 0.45, 0.5; or 0.55; alternatively or additionally, a maximum Schultz-Flory K value of 0.9, 0.85, 0.8, 0.75, 0.7, or 0.65. The oligomer product may have (or may 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 aspects, the oligomer product may have (or may be formed with) a Schultz-Flory K value ranging from 0.4 to 0.9, from 0.4 to 0.8, from 0.5 to 0.8, from 0.5 to 0.7, or from 0.55 to 0.7. Other ranges of Schulz-Flory K values ​​for the oligomer product will be apparent in the present disclosure. In any aspect, the Schultz-Flory K value can be determined using adjacent pairs of oligomeric products, where both adjacent oligomeric products are selected from C 8 , C 10 , C 12 , C 14 or C 16 In embodiments, the Schultz-Flory K value can be the average of any two or more Schultz-Flory K values ​​of the oligomers described herein produced using different adjacent pairs. In some aspects, the Schultz-Flory K value can be calculated using C 8 and C 10 Oligomer products, C 10 and C 12 Oligomer products, C 12 and C 14 Oligomer products, C 14 and C 16低 Polymer product, C 8 , C 10 and C 12 oligomeric product, or the average of any two or more adjacent pairs of oligomeric products.

[0108] The oligomer product may be formed at any desired ethylene conversion (or single pass ethylene conversion). The oligomer product may be formed at 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%. In general, the oligomer product may be formed at an ethylene conversion (or single pass ethylene conversion) that may be within the range of any minimum ethylene conversion (or single pass ethylene conversion) disclosed herein to any maximum ethylene conversion (or single pass ethylene conversion) disclosed herein. In some non-limiting aspects, oligomer products can be formed under the ethylene conversion (or single pass ethylene conversion) of the range from 30% to 90%, from 35% to 90%, from 40% to 87.5%, from 45% to 87.5%, from 50% to 85% or from 55% to 85%. With the help of the present disclosure, it is easy for those skilled in the art to understand other available ethylene conversion (or single pass ethylene conversion) scopes. In some aspects, oligomer products can be formed under the ethylene conversion of oligomer products for providing selectivity (e.g., with the percentage of the normal alpha olefin in the indicated oligomer product carbon number) to desired normal alpha olefins.

[0109] The methods described herein can produce oligomer products with high selectivity for normal α-olefins. In one aspect, the C 6 The olefin oligomer product may have a 1-hexene content of at least 98.5 wt.%, 98.75 wt.%, 99.0 wt.%, 99.25 wt.%. In one aspect, the C 8 The olefin oligomer product may have a 1-octene content of at least 98 wt.%, 98.25 wt.%, 98.5 wt.%, 98.75 wt.%, or 99.0 wt.% 1-octene content. 10 The olefin oligomer product may have a 1-decene content of at least 97.5 wt.%, 97.75 wt.%, 98 wt.%, 98.25 wt.%, or 98.5 wt.%. In one aspect, the C 12 The olefin oligomer product may have a 1-dodecene content of at least 96.5 wt.%, 97 wt.%, 97.5 wt.%, 97.75 wt.%, or 98.0 wt.%. In one aspect, the process described herein may produce an oligomer product having any combination of: any C 6 The 1-hexene content of the olefin oligomer product, any C 8 The 1-octene content of the olefin oligomer product, any C10 The 1-decene content of the olefin oligomer product and / or any C 8 The olefin oligomer product 1-octene content. In some non-limiting aspects, the oligomer product can have at least 99 wt.% C 6 The olefin oligomer product has a 1-hexene content and at least 97.5 wt.% C 12 1-dodecene content of the olefin oligomer product; alternatively, at least 98.5 wt.% of C 8 The olefin oligomer product has a 1-octene content and at least 97.5 wt.% C 12 1-dodecene octene content of the olefin oligomer product; or alternatively, at least 99 wt.% C 6 The olefin oligomer product has a 1-hexene content of at least 98.5 wt.% C 8 The olefin oligomer product has a 1-octene content of at least 98 wt.% C 10 The olefin oligomer product has a 1-decene content and at least 97.5 wt.% C 12 Olefin Oligomer Product 1-Dodecene Content. Other combinations of oligomer product normal alpha olefin content will be apparent from this disclosure.

[0110] In one aspect, the methods 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.% polymer, (b) less than 2.5 wt.%, 1 wt.%, 0.75 wt.%, 0.5 wt.%, or 0.25 wt.% of compounds having a weight average molecular weight greater than 1000 g / mol, or (c) any combination thereof, relative to the same method not using 1) a chain transfer agent comprising a compound having a hydrogen-silicon bond, a compound having a hydrogen-sulfide 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 wt.% of polymer and the weight average molecular weight of the oligomer product are based on the total weight of the oligomer product. In another separate or combinable aspect, the methods described herein can produce oligomer products having the following: (a) an oligomer product comprising a polymer with a lower Mw, (b) an oligomer product in which the polymer has a lower Mw maximum peak, (c) an oligomer product with a reduced amount of polymer, (d) an oligomer product with a reduced % of polymer with a molecular weight greater than 100,000 molecular weight, or (e) any combination thereof, relative to the same method not using 1) a chain transfer agent comprising a compound having a hydrogen-silicon bond, a compound having a hydrogen-sulfide 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 aspect, the amount of polymer present in the oligomer product per gram of oligomer product produced can be reduced by at least 10%, 25%, 40%, 50%, 60%, 70%, or 80% relative to polymer produced by the same process without using 1) a chain transfer agent comprising a compound having a hydrogen-silicon bond, a compound having a hydrogen-sulfide 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 aspect, the amount of polymer having a molecular weight greater than 100,000 molecular weight can be reduced by at least 10%, 25%, 40%, 50%, 60%, 70%, or 80% relative to polymer produced by the same process without using 1) a chain transfer agent comprising a compound having a hydrogen-silicon bond, a compound having a hydrogen-sulfide bond, a compound having a hydrogen-phosphorus bond, or any combination thereof, 2) hydrogen, and / or 3) a transition metal compound chain transfer agent.

[0111] The reaction zone for forming the oligomer product 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 ring slurry reactor, a solution reactor, a tubular reactor, a recirculation reactor, or any combination thereof; alternatively, a continuous stirred tank reactor; alternatively, a ring slurry reactor; alternatively, a solution reactor; alternatively, a tubular reactor; or alternatively, a recirculation reactor. In one aspect, the reaction zone may have more than one reactor, which are connected in series and / or in parallel and include any combination of reactor types and arrangements. In addition, the oligomerization process for forming the oligomer product may be a continuous process, a semi-continuous process, or a batch process, or any reactor or container within the oligomerization reaction system may be operated continuously, semi-continuously, or batchwise.

[0112] Additional information regarding zirconium-based catalyst systems for oligomerizing ethylene, including specific examples, and methods for producing oligomer products using the zirconium-based catalyst systems can be found in, but is not necessarily limited to, the following references: U.S. Pat. Nos. 4,361,714, 4,377,720, 4,396,788, 4,409,414, 4,410,750, 4,434,312, 4,434,313, 4,442,309, 4,486,615, 4,783,573, 4,855,525, 4,886,933, 4,966,874, 5,260,500, 6,576,721, 7,897,826, 8,914,983,978, 9,101,113,114,123,136,137,148,150, 114,115,139,151,161,170,181,191,203,213,223,234,243,257,261, 2003 / 0153798, US 7,169,961, US 7,291,685, US 7,566,679, US 8,269,055, US 2009 / 0216057, US 2009 / 0306312, US2010 / 0191029, US 2010 / 0292423, US 2011 / 0046429, US 2011 / 0054130, US 2011 / 0054233, US 2012 / 0184692, US2020 / 0055799, US2020 / 0062672, US2020 / 0055800, US2020 / 0062673, EP 320,571 A2, EP 444,505 A2, EP 1,749,807 A1, EP 1,752,434 A1, EP 1,780,189, EP2,258,674 A1, WO 91 / 02707, Sekiyu Gakkaishi, Vol. 37, No. 4, 1994, pp. 337-346, Sekiyu Gakkaishi, Vol. 42, No. 4, 1999, pp. 235-245, Sekiyu Gakkaishi, Vol. 43, No. 5,200o, pp. 328-338, Sekiyu Gakkaishi, Vol. 44, No. 1, 2001, pp. 25-35, and Sekiyu Gakkaishi, Vol. 44, No. 2, 2001, pp. 109-119.

[0113] Example

[0114] The present disclosure is further illustrated by the following examples, which should not be construed as limiting the scope of the present disclosure in any way. After reading the description herein, a person of ordinary skill in the art may think of various other aspects, modifications and their equivalents without departing from the spirit of the present disclosure or the scope of the appended claims.

[0115] Ethylene oligomerization unit

[0116] Figure 1 Provide a diagram of a continuous ethylene oligomerization device. The continuous ethylene oligomerization device includes a 0.5-liter autoclave (used as a reactor), a 5-gallon high-pressure product tank, a primary catalyst system pump, a secondary catalyst system pump, an organic reaction medium pump, a hydrogen feed line, a chain transfer agent feed line, and related equipment (such as other related equipment such as valves and pipelines). The autoclave effluent sample port is located on the autoclave effluent line running between the autoclave and the high-pressure product tank. The reactor effluent pipeline connecting the reactor and the high-pressure product tank is heat traced, and the skin temperature is maintained at the reaction temperature. The 0.5-liter autoclave includes an overhead magnetic mechanical stirrer for mixing the reaction mixture, as well as an internal cooling coil (for flowing the heat exchange fluid) and an external heating jacket, which is used to maintain the required temperature when necessary. The continuous ethylene oligomerization device also includes a high-pressure nitrogen feed line leading to the 0.5-liter autoclave reactor and the product tank to provide an inert atmosphere to these two containers. The hydrogen feed line is connected to the ethylene feed line and is metered to provide the required hydrogen:ethylene ratio (when utilized), while the chain transfer agent feed line is connected to the organic reaction medium feed line on the suction side of the diluent pump and is metered to provide the required amount of chain transfer agent to the reactor. The catalyst system is fed to the reactor via one or two ISCO syringe pumps (catalyst system feed pumps), while the organic reaction medium is fed from the organic reaction feed tank via an organic reaction medium pump. When the prepared catalyst system is fed into the reactor, the continuous ethylene oligomerization unit utilizes a primary catalyst system solution feed pump, and when two solutions containing one or more components of the catalyst system are fed separately to the feed line leading to the reactor, the continuous ethylene oligomerization unit utilizes primary and secondary catalyst system feed pumps.

[0117] During continuous ethylene oligomerization, one or more catalyst system pumps (ISCO syringe pumps) continuously feed one or more catalyst system solutions to the reactor at one or more desired rates, an organic reaction medium pump continuously feeds an organic reaction medium to the autoclave at a desired rate, and ethylene is continuously fed to the reactor at a desired rate via a connected mass flow meter. The catalyst system and ethylene are introduced into the autoclave via a dip tube so that the catalyst system solution and ethylene enter the liquid contents of the autoclave at approximately the midpoint of the vertical height of the autoclave.

[0118] Example 1

[0119] In an argon atmosphere drying oven, 20mmol of dry zirconium tetrachloride (ZrCl4) and 250mL of dry cyclohexane were loaded into a 500mL flask equipped with a stirrer. The mixture was then stirred at room temperature for 10 minutes. Triethylaluminum (TEA) was added to the stirred mixture, followed by ethylaluminum sesquichloride (EASC) to obtain a mixture having a molar ratio of EASC:TEA of 3.5:1 and a molar ratio of aluminum to zirconium of 7:1. The resulting mixture was then heated at 70°C for 2 hours. The mixture was then cooled to room temperature. A 50mL portion of the cooled mixture was transferred to a one-liter volumetric flask together with a certain amount of thiophene to achieve a molar ratio of thiophene to zirconium of 3:1. Sufficient dry cyclohexane was then loaded into the one-liter volumetric flask to provide a one-liter catalyst system mixture. The catalyst system mixture thus prepared has a zirconium concentration / liter of cyclohexane and has an aluminum: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 catalyst system mixture volumetric flask was then capped and removed from the argon atmosphere dry box.

[0120] Run 1-1 (Compare)

[0121] The oligomerization unit as previously described was utilized using only one catalyst system solution pump. 2 The filling line fills the high pressure product tank to the required pressure to prepare the oligomerization reactor for ethylene oligomerization. The reactor is isolated from the primary catalyst system solution pump and is circulated through three high pressure N 2Fill (to 800psig-5.5MPa) and exhaust cycle. Each nitrogen purge is performed by closing the valve to the product tank, filling the autoclave with nitrogen to reach a pressure of 800psig (5.5MPa) through the spare inlet, maintaining the nitrogen pressure on the autoclave for 5 minutes and then releasing the nitrogen pressure on the autoclave by opening the valve to the product tank. After the nitrogen release of the last nitrogen purge, the autoclave is maintained with a slight residual nitrogen pressure. Then 200mL of the catalyst system mixture is transferred to the catalyst system ISCO injection pump of the prepared ethylene oligomerization unit. Then the organic reaction medium (cyclohexane) is quickly injected into the reactor. Then the diluent pump is turned on at a rate of 335mL per hour to make the reactor reach a reaction pressure of 925psi (6.37MPa). When the reactor reaches the reaction pressure, the overhead magnetic stirrer is started and set to about 1200rpm, and the heating jacket is turned on and set to 120°C. When the reactor reached a stable temperature of 120°C, the catalyst system ISCO pump was turned on and set to feed the catalyst system mixture into the reactor at a rate of 15 mL / hr. After 30 minutes, ethylene was introduced into the reactor at an initial rate of 50 g / hr and gradually increased to a final rate of 175 g / hr over a period of 30 minutes. Internal cooling coils and external heating jackets were used to maintain the oligomerization temperature as required. After 6 hours, the oligomerization was terminated by reducing the catalyst system flow rate to zero, reducing the ethylene flow rate to zero and turning off the heating jacket. When the reactor reached room temperature, the flow rate of the organic reaction medium was reduced to zero and a high pressure N 2 The liquid contents of the reactor are pressurized into a high pressure product tank.

[0122] The reactor is then opened, and the solids inside the reactor and covering the internal reactor surfaces are collected and added to the reactor effluent collected in the high-pressure product tank. A 250-gram liquid sample is collected from the product tank, and a known amount of an internal standard (e.g., nonane) is added to the sample. The 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 to determine the oligomer product distribution, Schulz-Flory K value, carbon number purity, and catalyst system productivity. The remaining product tank contents are then homogenized, and a second 250-gram sample is taken from the product tank. The second sample is then rotary evaporated at 100°C at -30 inches of mercury 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) to calculate the fraction of the solid sample that is a polymer, using the following cutoff values ​​for calculation: A) liquid (≤175°C); B) wax (175°C to 420°C; C) polymer ≥420°C. The second wax and polymer were analyzed by HPLC to determine the molecular weight distribution of the polymer produced in the oligomerization reaction, including Mw, Mn and Mp. The liquid and polymer analysis results were 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.

[0123] Run 1-2 .

[0124] In an argon atmosphere dry box, 0.1 mole of triethylsilane (chain transfer agent) was charged to a 250 mL volumetric flask, followed by sufficient dry cyclohexane to provide 250 mL of chain transfer agent mixture. The chain transfer agent mixture volumetric flask was then capped and removed from the argon atmosphere dry box.

[0125] The chain transfer agent feed line was connected to the organic reaction medium feed line on the suction side of the organic reaction medium pump. The procedure of run 1-1 was repeated, but the amount of triethylsilane solution added to the suction side of the diluent pump was metered to provide 1x10 -3 :1 triethylsilane:ethylene molar ratio (when the ethylene flow rate is 175 g / hour, the addition amount is about 15 ml / hour).

[0126] Run 1-3

[0127] In an argon atmosphere drying box, 0.1mmol iron (III) octoate (transition metal compound chain transfer agent) was charged into a 250mL volumetric flask, and then sufficient dry cyclohexane was charged to provide 250mL of transition metal compound chain transfer agent mixture. The chain transfer agent mixture volumetric flask was then capped and removed from the argon atmosphere drying box.

[0128] The transition metal compound chain transfer agent feed line was connected to the organic reaction medium feed line on the suction side of the organic reaction medium pump. The procedure of run 1-1 was repeated, but the amount of iron (III) octoate solution added to the suction side of the diluent pump during the entire ethylene oligomerization reaction was metered to provide 1×10 -6 :1 iron (III) octoate: ethylene molar ratio (when the ethylene flow rate is 175 g / h, the addition amount is about 15 ml / h).

[0129] Run 1-4

[0130] The hydrogen feed line was connected to the ethylene feed line of the ethylene oligomerization unit. The procedure of run 1-1 was repeated, but with hydrogen being metered into ethylene at a rate throughout the ethylene oligomerization reaction to provide a hydrogen:ethylene mass ratio of (1 g hydrogen) / (kg ethylene).

[0131] Gas chromatography analysis and HPLC analysis of ethylene oligomerization runs 1-2, 1-3, and 1-4 using chain transfer agents were reviewed and compared to the gas chromatography analysis and HPLC analysis of ethylene oligomerization run 1-1. The analysis showed that the oligomer products produced in ethylene oligomerization runs 1-2, 1-3, and 1-4 using chain transfer agents had less than 1 wt.% polymer and / or less than 1 wt.% of compounds with a weight average molecular weight greater than 1000 g / mol compared to ethylene oligomerization run 1-1 without chain transfer agents. The analysis also showed that the oligomer products produced in ethylene oligomerization runs 1-2, 1-3, and 1-4 using chain transfer agents produced oligomer products containing polymers with lower Mw, polymers with lower Mw maximum peaks, reduced percentages of polymers, and / or polymers with reduced percentages of Mw greater than 100,000 when compared to ethylene oligomerization run 1-1 without chain transfer agents. Gas chromatographic analysis of the oligomer products of Runs 1-1, 1-2, 1-3, and 1-4 indicated that there was no significant effect on the Schulz-Flory K value, carbon number purity, and catalyst system productivity when a chain transfer agent was utilized in the ethylene oligomerization reaction.

[0132] Example 2

[0133] In an argon atmosphere drying oven, isopropyl carboxylic acid zirconium (IV) (60mmol), anisole (45mmol) and dry toluene (200mL) were loaded into a first 500mL flask equipped with a stirrer. The first mixture was then stirred at room temperature for 10 minutes. In an argon drying oven, 2-pyrrolidone (43mmol) and dry toluene (200mL) were loaded into a second 500mL flask equipped with a stirrer. Pure diethylaluminum chloride (1.2mol) was added to the second mixture over a period of 30 minutes. The second mixture was then stirred for another 10 minutes. The first mixture was then transferred to a one-liter volumetric flask. The second mixture was then added to the first mixture in the volumetric flask, and then enough dry toluene was loaded into the volumetric flask to provide a one-liter first catalyst system mixture solution. After sufficient mixing, a 200mL portion of the first catalyst system mixture was transferred to a second one-liter volumetric flask together with enough dry toluene to provide a one-liter second catalyst system mixture. The second catalyst system mixture thus prepared had a zirconium concentration of 12 mmol / L and had an anisole:zirconium molar ratio of 0.75:1, an aluminum:zirconium molar ratio of 20:1, and a 2-pyrrolidone:aluminum ratio of 0.15:1. The second catalyst system mixture volumetric flask was then capped and removed from the argon atmosphere dry box.

[0134] Run 2-1 (Comparison)

[0135] The oligomerization unit as previously described was utilized using only one catalyst system solution pump. 2 The filling line fills the high pressure product tank to the required pressure to prepare the oligomerization reactor for ethylene oligomerization. The reactor is isolated from the primary catalyst system solution pump and is circulated through three high pressure N 2Fill (to 800psig-5.5MPa) and exhaust cycle. Each nitrogen purge is performed by closing the valve to the product tank, filling the autoclave with nitrogen to reach a pressure of 800psig (5.5MPa) through the spare inlet, maintaining the nitrogen pressure on the autoclave for 5 minutes and then releasing the nitrogen pressure on the autoclave by opening the valve to the product tank. After the nitrogen release of the last nitrogen purge, the autoclave is maintained with a slight residual nitrogen pressure. Then 200mL of the second catalyst system mixture is transferred to the catalyst system ISCO injection pump of the prepared ethylene oligomerization unit. Then the organic reaction medium (cyclohexane) is quickly injected into the reactor. Then the diluent pump is turned on at a rate of 485mL per hour to allow the reactor to reach a reaction pressure of 450psi (3.1MPa). When the reactor reaches the reaction pressure, the overhead magnetic stirrer is started and set to about 1200rpm, and the heating jacket is turned on and set to 70°C. When the reactor reached a stable temperature of 70°C, the catalyst system ISCO pump was turned on and set to feed the catalyst system mixture into the reactor at a rate of 15 mL / hr. After 30 minutes, ethylene was introduced into the reactor at an initial rate of 50 g / hr and gradually increased to a final rate of 175 g / hr over a period of 30 minutes. Internal cooling coils and external heating jackets were used to maintain the oligomerization temperature as required. After 6 hours, the oligomerization was terminated by reducing the catalyst system flow rate to zero, reducing the ethylene flow rate to zero and turning off the heating jacket. When the reactor reached room temperature, the flow rate of the organic reaction medium was reduced to zero and a high pressure N 2 The liquid contents of the reactor are pressurized into a high pressure product tank.

[0136] The reactor is then opened, and the solids inside the reactor and covering the internal reactor surfaces are collected and added to the reactor effluent collected in the high-pressure product tank. A 250-gram liquid sample is collected from the product tank, and a known amount of an internal standard (e.g., nonane) is added to the sample. The 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 to determine the oligomer product distribution, Schulz-Flory K value, carbon number purity, and catalyst system productivity. The remaining product tank contents are then homogenized, and a second 250-gram sample is taken from the product tank. The second sample is then rotary evaporated at 100°C at -30 inches of mercury 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) to calculate the fraction of the solid sample that is a polymer, using the following cutoff values ​​for calculation: A) liquid (≤175°C); B) wax (175°C to 420°C; C) polymer ≥420°C. The second wax and polymer are analyzed by HPLC to determine the molecular weight distribution of the polymer produced in the oligomerization reaction, including Mw, Mn and Mp. The liquid and polymer analysis results 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, and percentage of polymer with.

[0137] Run 2-2 .

[0138] In an argon atmosphere dry box, 0.1 mole of triethylsilane (chain transfer agent) was charged to a 250 mL volumetric flask, followed by sufficient dry cyclohexane to provide 250 mL of chain transfer agent mixture. The chain transfer agent mixture volumetric flask was then capped and removed from the argon atmosphere dry box.

[0139] The chain transfer agent feed line was connected to the organic reaction medium feed line on the suction side of the organic reaction medium pump. The procedure of run 2-1 was repeated, but the amount of triethylsilane solution added to the suction side of the diluent pump was metered to provide 1×10 -3 :1 triethylsilane:ethylene molar ratio (when the ethylene flow rate is 175 g / hour, the addition amount is about 15 ml / hour).

[0140] Run 2-3

[0141] In an argon atmosphere drying box, 0.1mmol iron (III) octoate (transition metal compound chain transfer agent) was charged into a 250mL volumetric flask, and then sufficient dry cyclohexane was charged to provide 250mL of transition metal compound chain transfer agent mixture. The chain transfer agent mixture volumetric flask was then capped and removed from the argon atmosphere drying box.

[0142] The transition metal compound chain transfer agent feed line was connected to the organic reaction medium feed line on the suction side of the organic reaction medium pump. The procedure of run 2-1 was repeated, but the amount of iron (III) octoate solution added to the suction side of the diluent pump during the entire ethylene oligomerization reaction was metered to provide 1×10 -6 :1 iron (III) octoate: ethylene molar ratio (when the ethylene flow rate is 175 g / h, the addition amount is about 15 ml / h).

[0143] Run 2-4

[0144] The hydrogen feed line was connected to the ethylene feed line of the ethylene oligomerization unit. The procedure of run 2-1 was repeated, but with hydrogen being metered into ethylene at a rate throughout the ethylene oligomerization reaction to provide a hydrogen:ethylene mass ratio of (1 g hydrogen) / (kg ethylene).

[0145] Gas chromatography analysis and HPLC analysis of ethylene oligomerization runs 2-2, 2-3, and 2-4 using chain transfer agents were reviewed and compared to gas chromatography analysis and HPLC analysis of ethylene oligomerization run 2-1. The analysis showed that the oligomer products produced in ethylene oligomerization runs 2-2, 2-3, and 2-4 using chain transfer agents had less than 1 wt.% polymer and / or less than 1 wt.% of compounds with a weight average molecular weight greater than 1000 g / mol compared to ethylene oligomerization run 2-1 without chain transfer agents. The analysis also showed that the oligomer products produced in ethylene oligomerization runs 2-2, 2-3, and 2-4 using chain transfer agents produced oligomer products containing polymers with lower Mw, polymers with lower Mw maximum peaks, reduced percentages of polymers, and / or polymers with reduced percentages of Mw greater than 100,000 when compared to ethylene oligomerization run 1-1 without chain transfer agents. Gas chromatographic analysis of the oligomer products of Runs 2-1, 2-2, 2-3, and 2-4 indicated that there was no significant effect on the Schulz-Flory K value, carbon number purity, and catalyst system productivity when a chain transfer agent was utilized in the ethylene oligomerization reaction.

[0146] Example 3

[0147] In an argon atmosphere drying oven, zirconium tetrachloride (100 mmol), isodecyl acetate (105 mmol) and dry o-xylene (200 mL) were added to a first 500 mL flask equipped with a stirrer. The zirconium mixture was then stirred at room temperature for 10 minutes. The first zirconium mixture was then transferred to a one-liter volumetric flask, into which enough o-xylene was then loaded to provide a one-liter first zirconium solution. After thorough mixing, a 200 mL portion of the first zirconium solution was transferred to a second one-liter volumetric flask together with enough dry o-xylene to provide a one-liter second zirconium solution. The second zirconium solution had an isodecyl acetate: zirconium molar ratio of 1.05:1. The second zirconium solution volumetric flask was then covered with a lid and taken out from an argon atmosphere drying oven.

[0148] In an argon drying oven, dry o-Xylene (500mL) is loaded into a second 500mL flask equipped with agitator. Pure diethylaluminum chloride (1.2mol) is added to the o-Xylene through a 30-minute stirring period. The mixture is then stirred for another 10 minutes. The diethylaluminum chloride solution is then transferred to a one-liter volumetric flask, and then enough o-Xylenes are loaded into the one-liter volumetric flask to provide the first zirconium solution of one liter. After sufficient mixing, the 200mL portion of the first diethylaluminum chloride solution is transferred to a second one-liter volumetric flask together with enough dry o-Xylenes to provide the second diethylaluminum chloride solution of one liter. The second diethylaluminum chloride solution volumetric flask is then covered with a lid and taken out from an argon atmosphere drying oven.

[0149] Run 3-1 (Comparison)

[0150] The oligomerization apparatus was used as previously described with the following modifications: the 500 mL autoclave was replaced with a 200 mL autoclave (which was also equipped with an overhead magnetic mechanical stirrer for mixing the reaction mixture, as well as an internal cooling coil and an external heating mantle), and both the primary and secondary catalyst system pumps were utilized. 2 The filling line fills the high pressure product tank to the required pressure to prepare the oligomerization reactor for ethylene oligomerization. The reactor is isolated from the primary and secondary catalyst system solution pumps while circulating through three high pressure N 2Fill (to 800psig-5.5MPa) and exhaust cycle. Each nitrogen purge is performed in the following manner: close the valve leading to the product tank, fill the autoclave with nitrogen to reach a pressure of 800psig (5.5MPa) via the alternate inlet, keep the nitrogen pressure on the autoclave for 5 minutes and then release the nitrogen pressure on the autoclave by opening the valve leading to the product tank. After the nitrogen release of the last nitrogen purge, the autoclave is maintained to have a slight residual nitrogen pressure. 200mL of the second zirconium mixture is transferred to the ISCO injection pump of the primary catalyst system of the prepared ethylene oligomerization device. 200mL of the second diethylaluminum chloride solution is transferred to the ISCO injection pump of the secondary catalyst system of the prepared ethylene oligomerization device. Then quickly fill the dry organic reaction medium (o-xylene) in the reactor. Then open the diluent pump at a rate of 680mL per hour so that the reactor reaches a reaction pressure of 3000psi (20.7MPa). When the reactor reached the reaction pressure, the overhead magnetic stirrer was started and set to about 1200 rpm, and the heating jacket was turned on and set to 165°C. When the reactor reached a stable temperature of 70°C, the primary and secondary catalyst system ISCO pumps were turned on and set 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 provided an Al:Zr ratio of 12:1. After 30 minutes, ethylene was introduced into the reactor at an initial rate of 50 g / hour and gradually increased to a final rate of 600 g / hour over a period of 30 minutes. The oligomerization temperature was maintained using internal cooling coils and external heating jackets as needed. After 4 hours, the oligomerization reaction was terminated by reducing the feed flow rates of the zirconium solution and the diethylaluminum chloride solution to zero, reducing the ethylene flow rate to zero, and turning off the heating jacket. When the reactor reached room temperature, the flow rate of the organic reaction medium was reduced to zero, and a high pressure N 2 The liquid contents of the reactor are pressurized into a high pressure product tank.

[0151] The reactor is then opened, and the solids inside the reactor and covering the internal reactor surfaces are collected and added to the reactor effluent collected in the high-pressure product tank. A 250-gram liquid sample is collected from the product tank, and a known amount of an internal standard (e.g., nonane) is added to the sample. The 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 to determine the oligomer product distribution, Schulz-Flory K value, carbon number purity, and catalyst system productivity. The remaining product tank contents are then homogenized, and a second 250-gram sample is taken from the product tank. The second sample is then rotary evaporated at 100°C at -30 inches of mercury 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) to calculate the fraction of the solid sample that is a polymer, using the following cutoff values ​​for calculation: A) liquid (≤175°C); B) wax (175°C to 420°C; C) polymer ≥420°C. The second wax and polymer are analyzed by HPLC to determine the molecular weight distribution of the polymer produced in the oligomerization reaction, including Mw, Mn and Mp. The liquid and polymer analysis results 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, and percentage of polymer with.

[0152] Run 3-2 .

[0153] In an argon atmosphere dry box, 360 mmol triethylsilane (chain transfer agent) was charged into a 250 mL volumetric flask, followed by sufficient dry o-xylene to provide 250 mL of chain transfer agent mixture. The chain transfer agent mixture volumetric flask was then capped and removed from the argon atmosphere dry box.

[0154] The chain transfer agent feed line was connected to the organic reaction medium feed line on the suction side of the organic reaction medium pump. The procedure of run 3-1 was repeated, but the amount of triethylsilane solution added to the suction side of the diluent pump was metered to provide 1x10 -3 :1 triethylsilane:ethylene molar ratio (when the ethylene flow rate is 600 g / hour, the added amount is about 15 ml / hour).

[0155] Run 3-3

[0156] In an argon atmosphere drying box, 0.36mmol iron (III) octoate (transition metal compound chain transfer agent) was charged into a 250mL volumetric flask, and then sufficient dry cyclohexane was charged to provide 250mL of transition metal compound chain transfer agent mixture. The chain transfer agent mixture volumetric flask was then capped and removed from the argon atmosphere drying box.

[0157] The transition metal compound chain transfer agent feed line was connected to the organic reaction medium feed line on the suction side of the organic reaction medium pump. The procedure of 3-1 was repeated, but the amount of iron (III) octoate solution added to the suction side of the diluent pump during the entire ethylene oligomerization reaction was metered to provide 1×10 -6 :1 iron (III) octoate: ethylene molar ratio (when the ethylene flow rate is 175 g / h, the addition amount is about 15 ml / h).

[0158] Run 3-4

[0159] The hydrogen feed line was connected to the ethylene feed line of the ethylene oligomerization unit. The procedure of run 3-1 was repeated, but with hydrogen being metered into ethylene at a rate throughout the ethylene oligomerization reaction to provide a hydrogen:ethylene mass ratio of (1 g hydrogen) / (kg ethylene).

[0160] Gas chromatography analysis and HPLC analysis of ethylene oligomerization runs 3-2, 3-3, and 3-4 using chain transfer agents were reviewed and compared to gas chromatography analysis and HPLC analysis of ethylene oligomerization run 3-1. The analysis showed that the oligomer products produced in ethylene oligomerization runs 3-2, 3-3, and 3-4 using chain transfer agents had less than 1 wt.% polymer and / or less than 1 wt.% of compounds with a weight average molecular weight greater than 1000 g / mol compared to ethylene oligomerization run 3-1 without chain transfer agents. The analysis also showed that the oligomer products produced in ethylene oligomerization runs 3-2, 3-3, and 3-4 using chain transfer agents produced oligomer products containing polymers with lower Mw, polymers with lower Mw maximum peaks, reduced percentages of polymers, and / or polymers with reduced percentages of Mw greater than 100,000 when compared to ethylene oligomerization run 3-1 without chain transfer agents. Gas chromatography analysis of the oligomer products of Runs 3-1, 3-2, 3-3, and 3-4 indicated that there was no significant effect on the Schulz-Flory K value, carbon number purity, and catalyst system productivity when a chain transfer agent was utilized in the ethylene oligomerization reaction.

[0161] An illustrative statement of the subject matter claimed below will now be provided. For the sake of clarity, all features of the actual implementation are not described in this specification. It is understood that in the development of any such actual implementation scheme, a large number of implementation-specific decisions should be made to achieve the specific goals of the developer, such as meeting system-related constraints and business-related constraints, which may vary between different implementation schemes. In addition, it is understood that for those of ordinary skill in the art who benefit from this disclosure, such development work, even if complex and time-consuming, will also be routine work. In addition, various modifications can also be made within the scope of the present invention as intended herein, and embodiments of the present invention may include a combination of features other than the features explicitly required. In particular, fluid arrangements other than the fluid arrangements explicitly described herein are also within the scope of the present invention.

[0162] Statement 1. A process comprising a) contacting: i) ethylene, ii) a catalyst system (or catalyst system components) comprising 1) a catalyst having the formula ZrX 1 m Y 1 q A zirconium compound wherein each X 1 are independently halogen, each Y 1 are independently alkylene oxide, dialkylamino, alkyl carboxylate, alkyl 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) an alkyl metal compound, iii) a chain transfer agent, which chain transfer agent includes a compound having a hydrogen-silicon bond, a compound having a hydrogen-sulfur bond, a compound having a hydrogen-phosphorus bond, or any combination thereof, and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone.

[0163] Statement 2. A process comprising a) introducing into a reaction zone: i) ethylene, ii) a catalyst system (or catalyst system components) comprising 1) a catalyst having the formula ZrX 1 m Y 1 q A zirconium compound wherein each X 1 are independently halogen, each Y 1 are independently alkylene oxide, dialkylamino, alkyl carboxylate, alkyl 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) an alkyl metal compound, iii) a chain transfer agent, which chain transfer agent includes a compound having a hydrogen-silicon bond, a compound having a hydrogen-sulfur bond, a compound having a hydrogen-phosphorus bond, or any combination thereof, and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone.

[0164] Statement 3. The method of statement 1 or 2, wherein the chain transfer agent comprises a 31 S H 3 , (R 31 ) 2 S H 2 , (R 31 ) 3 SiH、R 31 OSiH3、(R 31 O) 2 S H 2 , (R 31 O) 3 SiH、R 32 SH, R 32 CO 2 CH 2 SH, R 32 CO 2 CH 2 CH 2 SH, R 33 PH 2 , (R 33 ) 2 PH, R 33 OPH 2 , (R 33 O) 2 PH or any combination thereof, wherein each R 31 , R 32 and R 33 are independently C 1 To C 15 Hydrocarbon.

[0165] Statement 4. The process of any of statements 1-3, wherein the reaction zone has any hydrogen to ethylene molar ratio of the chain transfer agent disclosed herein, for example (1 x 10 -5 :1, 5x10 -4 :1, 1x10 -4 :1 or 5x10 -3 :1 minimum value; 5x10 -1 :1, 1x10 -1 :1, 5x10 -2 :1, 1x10 -2 :1 maximum value; in the range from 1x10 -5 :1 to 5x10 -1 :1, 5x10 -4 :1 to 1x10 -1 :1, 1x10 -4 :1 to 5x10 -2 :1 or 5x10 -3:1 to 1x10 -2 :1; and other values ​​and ranges).

[0166] Statement 5. A process comprising a) contacting: i) ethylene, ii) a catalyst system (or catalyst system components) comprising 1) a catalyst having the formula ZrX 1 m Y 1 q A zirconium compound wherein each X 1 are independently halogen, each Y 1 are independently alkylene oxide, dialkylamino, alkyl carboxylate, alkyl 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) an alkyl metal compound, iii) hydrogen, and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone.

[0167] Statement 6. A process comprising a) introducing into a reaction zone: i) ethylene, ii) a catalyst system (or catalyst system components), said catalyst system (or catalyst system components) comprising 1) a ZrX 1 m Y 1 q A zirconium compound wherein each X 1 are independently halogen, each Y 1 are independently alkylene oxide, dialkylamino, alkyl carboxylate, alkyl 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) an alkyl metal compound, iii) hydrogen, and iv) an optional organic reaction medium; and b) forming an oligomer product in a reaction zone.

[0168] Statement 7. A method as described in statement 5 or 6, wherein the reaction zone has a minimum of any hydrogen to ethylene mass ratio disclosed herein (e.g., (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); and a maximum of (0.05 g hydrogen) / (kg ethylene). (g hydrogen) / (kg ethylene) to (5g hydrogen) / (kg ethylene), from (0.25g hydrogen) / (kg ethylene) to (5g hydrogen) / (kg ethylene), from (0.25g hydrogen) / (kg ethylene) to (4g hydrogen) / (kg ethylene), from (0.4g hydrogen) / (kg ethylene) to (3g hydrogen) / (kg ethylene), from (0.4g hydrogen) / (kg ethylene) to (2.5g hydrogen) / (kg ethylene), from (0.4g hydrogen) / (kg ethylene) to (2g hydrogen) / (kg ethylene), or from (0.5g hydrogen) / (kg ethylene) to (2g hydrogen) / (kg ethylene); and other values ​​and ranges).

[0169] Statement 8. A process comprising a) contacting: i) ethylene, ii) a catalyst system (or catalyst system components) comprising 1) a catalyst having the formula ZrX 1 m Y 1 q A zirconium compound wherein each X 1 are independently halogen, each Y 1 are independently alkylene oxide, dialkylamino, alkyl carboxylate, alkyl 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) an alkyl metal compound, iii) a transition metal compound chain transfer agent, and iv) an optional organic reaction medium; and b) forming an oligomeric product in a reaction zone.

[0170] Statement 9. A process comprising a) introducing into a reaction zone: i) ethylene, ii) a catalyst system (or catalyst system components) comprising 1) a catalyst having the formula ZrX 1 m Y 1 q A zirconium compound wherein each X 1 are independently halogen, each Y 1are independently alkylene oxide, dialkylamino, alkyl carboxylate, alkyl 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) an alkyl metal compound, iii) a transition metal compound chain transfer agent, and iv) an optional organic reaction medium; and b) forming an oligomeric product in a reaction zone.

[0171] Statement 10. The method of statement 8 or 9, wherein the transition metal compound chain transfer agent is any having the formula MX 4 p A transition metal compound chain transfer agent, wherein M is a transition metal, X 4 is a monoanion, and p is an integer from 2 to 4.

[0172] Statement 11. The method of statement 10, wherein the transition metal compound chain transfer agent is a transition metal compound having the formula MX 4 Any transition metal compound chain transfer agent of the formula p wherein M is iron, cobalt or nickel.

[0173] Statement 12. The method of statement 10 or 11, wherein the transition metal compound chain transfer agent is a compound having the formula MX 4 p Any transition metal compound chain transfer agent, wherein X 4 It is C 4 To C 19 Carboxylate.

[0174] Statement 13. The process of any one of statements 8 to 12, wherein the reaction zone has a molar ratio of any transition metal of the transition metal compound chain transfer agent disclosed herein to ethylene (1 x 10 -9 :1, 5x10 -8 :1, 1x10 -8 :1, 5x10 -7 :1 or 1x10 -7 :1 minimum value; 5x10 -3 :1, 1x10 -3 :1, 5x10 -4 :1, 1x10 -4 :1 or 5x10 -5 :1 maximum value; in the range from 1x10 -9 :1 to 5x10 -3 :1, 5x10 -8 :1 to 1x10 -3 :1, 1x10 -8 :1 to 5x10 -4 :1, 5x10 -7 :1 to 1x10 -4 :1 or 1x10-7 :1 to 5x10 -5 :1; and other values ​​and ranges).

[0175] Statement 14. The method of any of statements 1-13, wherein the hydrocarbyl metal compound is any hydrocarbyl metal compound disclosed herein (e.g., comprising any metal disclosed herein - a Group 1, 2, 11, 12, 13, or 14 metal as well as other Group metals disclosed herein - and any hydrocarbyl-C 1 To C 20 , C 1 To C 10 or C 1 To C 6 hydrocarbyl groups, as well as other more specific hydrocarbyl groups disclosed herein).

[0176] Statement 15. A method as described in any of Statements 1-14, wherein the metal of the hydrocarbon metal compound: the zirconium of the zirconium compound is any value disclosed herein (e.g., a minimum of 0.1:1, 0.2:1, 0.6:1, 1:1, 2:1 10:1; a maximum of 100:1 75:1, 50:1, 25:1, 15:1 or 10:1; or in the range of from 0.1:1 to 100:1, 0.2:1 to 75:1, 0.6:1 to 25:1, 1:1 to 50:1, 2:1 to 25:1, 1:1 to 15:1, 2:1 to 10:1, 10:1 to 50:1 or 10:1 to 25:1; and other values ​​and ranges).

[0177] Statement 16. The method of any of statements 1-15, wherein the catalyst system (or catalyst system components) further comprises a neutral nonionic organic modifier.

[0178] Statement 17. The method of statement 16 wherein the neutral nonionic organic modifier comprises any ether, ester, ketone, aldehyde, alcohol, anhydride, acid chloride, nitrile, thioether, disulfide, phosphine, amine, or amide described herein.

[0179] Statement 18. A method as described in statement 16 or 17, wherein the molar ratio of the neutral nonionic organic modifier to the zirconium of the zirconium compound can have 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 in the range of from 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; and other values ​​and ranges).

[0180] Statement 19. A method as described in any of Statements 16-18, wherein the molar ratio of the neutral nonionic organic modifier to the hydrocarbyl metal (or hydrocarbyl aluminum) compound can have any value described herein (e.g., a minimum value of 0.05:1, 0.1:1, 0.5:1, 0.75:1 0.8:1, 0.9:1, or 1:1; a maximum value of 5:1, 3:1, 2:1, 1.5:1, 1:1, 0.75:1, or 0.5:1; or in the range of from 0.05:1 to 5:1, 0.1 to 1:1, 0.1:1 to 0.5:1, 0.5:1 to 5:1, 0.5:1 to 3:1, 0.75:1 to 2:1, or 0.75:1 to 1.5:1; and other values ​​and ranges).

[0181] Statement 20. The method of any one of statements 1-19, wherein the zirconium compound has the formula ZrX 1 m Y 1 q , where each X 1 are independently chlorine or bromine, each Y 1 are independently C 1 To C 10 Oxygen (e.g., any described herein), C 1 To C 15 Hydrocarbyl carboxylate (e.g., any described herein) or C 1 To C 15 A hydrocarbyl sulfonate (eg, any described herein), m ranges from 0 to 4, q ranges from 0 to 4, and m+q is 4.

[0182] Statement 21. The method of any one of statements 1-20, wherein the hydrocarbyl metal compound comprises a compound having 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 C 1 To C 10 Alkyl, each X 2 are each independently chlorine, bromine or iodine, n is an integer from 0 to 3, and q is an integer from 0 to 6.

[0183] Statement 22. The method of any one of statements 20-22, wherein the neutral nonionic organic modifier comprises any C described herein. 2 To C 20 Ether, C 3 To C 20 Ester, C 3 To C 20 Ketone, C 2 To C 20 Nitrile, C 2 To C 20 Sulfide, C 2 To C 20 Disulfide, C 3 To C 20 Phosphine, C 1 To C 20 Amine or C 2 To C 20 Amide.

[0184] Statement 23. The method of any one of statements 1-19, wherein the zirconium compound has the formula ZrX 1 m , where each X 1 are independently chlorine or bromine and m is 4, the 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 are independently halogen and each R 1 are independently C 2 To C 4 An alkyl group, and a molar ratio of the metal of the hydrocarbylmetal compound (the aluminum of the hydrocarbylaluminum compound) to the zirconium of the zirconium compound is within any range disclosed herein (eg, within a range of 1:1 to 50:1).

[0185] Statement 24. The method of statement 23, wherein the catalyst system (or catalyst system components) further comprises a neutral nonionic organic modifier, wherein the neutral nonionic organic modifier comprises C 2 To C 20ester, and wherein the molar ratio of the neutral nonionic organic modifier to the zirconium of the zirconium compound is within any range 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 range disclosed herein (e.g., within the range of 10:1 to 25:1).

[0186] Statement 25. The method of statement 24 wherein the neutral nonionic organic modifier is contacted with the zirconium compound prior to the zirconium compound contacting ethylene and / or the hydrocarbyl metal compound (and / or being introduced into the reaction zone).

[0187] Statement 26. The method of statement 23 or 24, wherein the catalyst system (or catalyst system components) further comprises a neutral nonionic organic modifier, wherein the neutral nonionic organic modifier comprises C 2 To C 20 Ether, C 2 To C 20 Sulfide, C 1 To C 20 Amine, C 3 To C 20 phosphine, or any combination thereof, and wherein the molar ratio of the neutral nonionic organic modifier to the zirconium of the zirconium compound is within any range 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 range disclosed herein (e.g., within the range of 1:1 to 15:1).

[0188] Statement 27. The method of any one of statements 1-19, wherein the zirconium compound has the formula ZrX 1 m Y 1 q , where each X 1 are independently chlorine or bromine, each Y 1 are independently C 1 To C 10 Oxygen (e.g., any described herein), C 1 To C 10 Hydrocarbyl carboxylate (e.g., any described herein) or C 1 To 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, the hydrocarbyl metal compound comprising a compound having the formula AlX 2 n R 1 3-n 、Al2 X 2 3 R 1 3 or any combination thereof, wherein each X 2 are independently halogen and each R 1 are independently C 2 To C 4 An alkyl group, and a molar ratio of the metal of the hydrocarbyl metal compound (the aluminum of the hydrocarbyl aluminum compound) to the zirconium of the zirconium compound is in the range of 1:1 to 50:1.

[0189] Statement 28. The method of statement 27, wherein the zirconium compound can be at least partially hydrolyzed by contacting the zirconium compound with water using any molar ratio of water to zirconium disclosed herein (e.g., 0.01:1 to 3:1, 0.1: to 2:1, or 0.25:1 to 1.75:1).

[0190] Statement 29. The method of statement 27 or 28, wherein the catalyst system (or catalyst system components) further comprises a neutral nonionic organic modifier, wherein the neutral nonionic organic modifier comprises C 2 To C 15 Amide, and wherein the molar ratio of the neutral nonionic organic modifier to the metal of the metal hydrocarbyl compound (or the aluminum of the hydrocarbyl aluminum compound) is in the range of 0.1:1 to 1:1.

[0191] Statement 30. The method of statement 29 wherein the neutral nonionic organic modifier is contacted with the hydrocarbyl metal (or hydrocarbyl aluminum) compound before the hydrocarbyl metal (or hydrocarbyl aluminum) compound contacts ethylene (and / or is introduced into the reaction zone).

[0192] Statement 31. The method of any one of statements 27-30, wherein the catalyst system (or catalyst system components) further comprises a neutral nonionic organic modifier comprising C 2 To C 20 Ether, C 2 To C 20 Sulfide, C 1 To C 20 amines, or any combination thereof, and wherein the neutral nonionic organic modifier: zirconium of the zirconium compound is within any range disclosed herein (e.g., within a range of 0.1:1 to 10:1).

[0193] Statement 32. The method of statement 31 wherein the neutral nonionic organic modifier is contacted with the zirconium compound prior to the zirconium compound contacting ethylene and / or the hydrocarbyl metal compound (and / or being introduced into the reaction zone).

[0194] The method of any of Statements 1-32, wherein the oligomer product is formed at a reaction zone (or the reaction zone has) a zirconium to ethylene molar ratio (e.g., 5×10-10) of any reaction zone zirconium compound described herein. 7 :1, 1x10- 6 :1, 5x10 -5 :1 or 2.5x10- 5 :1 minimum reaction zone zirconium compound zirconium to ethylene molar ratio; 7.5x10- 4 :1, 5x10 -4 :1, 2.5x10 -4 :1 or 1x10 -4 :1 maximum reaction zone zirconium compound zirconium to ethylene molar ratio; range of 5x10- 7 :1 to 1x10 -4 :1, 1x10 -6 :1 to 2.5x10 -4 :1, 5x10 -5 :1 to 5x10 -4 :1 or 2.5x10 -5 :1 to 7.5x10 -4 :1; and other molar ratios and ranges of zirconium to ethylene in other reaction zones).

[0195] Statement 34. A method as described in any of statements 1-33, wherein the oligomer product is at any pressure described herein (e.g., a minimum pressure of 100 psi (689 kPa), 250 psi (1.72 MPa), 500 psi (3.45 MPa), 750 psi (5.17 MPa), 900 psi (6.21 MPa), or 1000 psi (6.89 MPa); a maximum pressure of 5000 psi (34.5 MPa), 4500 psi (31 MPa), 4,000 psi (27.6 MPa), 3500 psi (24.1 MPa), 3000 psi (20.7 MPa), 2,500 psi (17.2 MPa), 2,000 psi (13.8 MPa), 1,500 psi (10.3 MPa), 1250 psi (8.62 MPa), or 1000 psi (6.89 MPa); or at a maximum pressure of from 10 0psi(689kPa) to 5000psi(34.5MPa), 100psi(689kPa) to 2,500psi(17.2MPa), 100psi(689kPa) to 1000psi(6.89MPa), 500psi(3.45MPa) to 4500psi(31MPa), 500psi(3.45MPa) to 2,500psi(17.2MPa), 500psi(3.45MPa) to 4500psi(31MPa), 500psi(3.45MPa) to 2,500psi(17.2MPa), 500psi(3.45MPa) to 50 ... The reaction zone is formed at a pressure in the range of 1000psi (3.45MPa) to 1000psi (6.89MPa), 750psi (5.17MPa) to 4500psi (31MPa), 900psi (6.21MPa) to 4,000psi (27.6MPa), or 1000psi (6.89MPa) to 3500psi (24.1MPa); and other pressures and pressure ranges).

[0196] Statement 35. The method of any of statements 1-34, wherein the oligomer product is produced at any ethylene partial pressure described herein (e.g., a minimum ethylene partial pressure of 100 psi (689 kPa), 250 psi (1.72 MPa), 500 psi (3.45 MPa), 750 psi (5.17 MPa), 900 psi (6.21 MPa), or 1000 psi (6.89 MPa); 5000 psi (34.5 MPa), 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); 4500psi (31MPa), 4,000psi (27.6MPa), 3500psi (24.1MPa), 3000psi (20.7MPa), 2,500psi (17.2MPa), 2,000psi (13.8MPa), 1,500psi (10.3MPa), 1250psi (8.62MPa), or 1000psi (6.89MPa); or psi (689 kPa) to 5000 psi (34.5 MPa), 100 psi (689 kPa) to 2,500 psi (17.2 MPa), 100 psi (689 kPa) to 1000 psi (6.89 MPa), 500 psi (3.45 MPa) to 4500 psi (31 MPa), 500 psi (3.45 MPa) to 2,500 psi (17.2 MPa), 500 psi (3. The ethylene partial pressure is preferably formed at (or the reaction zone has) an ethylene partial pressure in the range of 45MPa) to 1000psi (6.89MPa), 750psi (5.17MPa) to 4500psi (31MPa), 900psi (6.21MPa) to 4,000psi (27.6MPa), or 1000psi (6.89MPa) to 3500psi (24.1MPa); or other ethylene partial pressures and ethylene partial pressure ranges).

[0197] Statement 36. A method as described in any of Statements 1-35, wherein the oligomer product is formed at any temperature described herein (e.g., a minimum temperature of 0°C, 25°C, 40°C, 50°C, 75°C, 100°C or 125°C; a maximum temperature of 250°C, 200°C, 150°C, 125°C, 100°C or 90°C; a temperature in the range of from 0°C to 250°C, from 25°C to 200°C, from 40°C to 150°C, from 40°C to 100°C, from 50°C to 100°C, from 50°C to 150°C, from 75°C to 125°C, from 75°C to 250°C, from 100°C to 200°C or from 100°C to 200°C; and other temperature values ​​and temperature ranges).

[0198] Statement 37. A method as described in any of Statements 1-36, wherein the oligomer product is formed at (or the reaction zone has) any ethylene:organic reaction medium mass ratio described herein (e.g., a minimum ethylene:organic reaction medium mass ratio of 0.5:1, 0.75:1, 1:1, 1.25:1, or 1.5:1; a maximum ethylene:organic reaction medium mass ratio of 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, or 2:1; an ethylene:organic reaction medium mass ratio ranging from 0.5:1 to 4.5:1, from 0.75:1 to 4:1, from 0.75:1 to 2:1, from 1:1 to 3:1, or from 1.5:1 to 2.5:1; and other ethylene:organic reaction medium mass ratio values ​​and ranges).

[0199] Statement 38. A method as described in any of Statements 1-37, wherein the oligomer product is formed at (or the reaction zone has) any reaction zone residence time (or average reaction zone residence time) described herein (e.g., a minimum reaction zone residence time (or average reaction zone residence time) of 10 minutes, 20 minutes, or 30 minutes; a maximum reaction zone residence time (or average reaction zone residence time) of 3 hours, 2.5 hours, 2 hours, or 1.5 hours; a reaction zone residence time (or average reaction zone residence time) in the range of from 10 minutes to 2.5 hours, from 20 minutes to 2 hours, from 30 minutes to 2 hours, or from 30 minutes to 1.5 hours; and other reaction zone residence time (or average reaction zone residence time) values ​​and ranges).

[0200] Statement 39. A method as described in any of Statements 1-38, wherein the oligomer product can be formed at any ethylene conversion (or single-pass ethylene conversion) described herein (e.g., a minimum ethylene conversion (or single-pass ethylene conversion) of 30%, 35%, 40%, 45%, 50% or 55%; additionally or alternatively, a maximum ethylene conversion (or single-pass ethylene conversion) of 95%, 90%, 87.5%, 85% or 80%; an ethylene conversion (or single-pass ethylene conversion) ranging from 30% to 90%, from 35% to 90%, from 40% to 87.5%, from 45% to 87.5%, from 50% to 85% or from 55% to 85%; and other ethylene conversion (or single-pass ethylene conversion) values ​​and ranges).

[0201] Statement 40. A method as described in any of statements 1-39, wherein the oligomer product can have any Schulz-Flory K value disclosed herein (e.g., a minimum Schulz-Flory K value of 0.4, 0.45, 0.5, or 0.55; a maximum Schulz-Flory K value of 0.9, 0.85, 0.8, 0.75, 0.7, or 0.65; a Schulz-Flory K value ranging from 0.4 to 0.9, from 0.4 to 0.8, from 0.5 to 0.8, from 0.5 to 0.7, or from 0.55 to 0.7; and other Schulz-Flory K values ​​and ranges).

[0202] Statement 41. A method as described in any of statements 1-40, wherein relative to the same method without using 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 as described in any of statements 1-4, 2) hydrogen as described in any of statements 5-7, and / or 3) a transition metal compound chain transfer agent as described in any of statements 8-13, the method produces an oligomer product comprising: (a) a polymer having a lower Mw, (b) a polymer having a lower Mw maximum peak, (c) a reduced percentage of polymers, (d) a polymer having a reduced percentage of polymers having a Mw greater than 100,000, or (e) any combination thereof.

[0203] Statement 42. A method as described in any of Statements 1-41, wherein the oligomer product contains (a) less than 1 wt% polymer, (b) less than 1 wt.% of compounds having a weight average molecular weight greater than 1000 g / mol, or (c) any combination thereof, wherein the wt.% is based on the total weight of the oligomer product.

[0204] All publications and patents mentioned herein are incorporated herein by reference.Publications and patents mentioned herein can be used to describe and disclose constructs and methods such as described in publications, which can be used in combination with the invention described at present.The publications discussed in the full text are provided only for the disclosures before the filing date of the present application.Nothing herein is interpreted as admitting that the inventor is not qualified to precede such disclosures of existing inventions.

Claims

1. A method comprising: a) contacting: i) ethylene, ii) a catalyst system, the catalyst system comprising 1) With the formula ZrX 1 m Y 1 q A zirconium compound wherein each X 1 are independently halogen, each Y 1 are independently alkoxy, dialkoxyamino, alkoxycarboxylate, alkoxysulfonate 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) Hydrocarbyl metal compounds, iii) a chain transfer agent comprising a compound having a hydrogen-silicon bond, and iv) optionally an organic reaction medium, and b) forming oligomeric products in a reaction zone; and The oligomer product has a Schulz-Flory K value of 0.4 to 0.

8.

2. The method of claim 1, wherein the chain transfer agent comprises a 31 SiH3、(R 31 )2SiH2、(R 31 )3SiH、R 31 OSiH3、(R 31 O)2SiH2、(R 31 O)3SiH or any combination thereof, wherein each R 31 are independently C1 to C 15 Hydrocarbon.

3. The process of claim 1, wherein the molar ratio of the chain transfer agent to ethylene in the reaction zone is from 1 x 10 -5 :1 to 5x10 -1 :

1.

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

5. The method of claim 1, wherein the method using a chain transfer agent comprising a compound having a hydridosilyl bond produces an oligomer product comprising: (a) a polymer having a lower Mw, (b) a polymer having a lower Mw maximum peak, (c) a reduced percentage of polymers, (d) a polymer having a reduced percentage of polymers having a Mw greater than 100,000 g / mol, or (e) any combination thereof, relative to the same method not using a chain transfer agent comprising a compound having a hydridosilyl bond.

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

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

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

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

10. The method of claim 9, wherein the catalyst system further comprises C2 to C 20 Esters, C2 to C 20 Ether or C2 to C 20 Thioethers are used as neutral nonionic organic modifiers.

11. The method of claim 1, wherein the zirconium compound has the formula ZrY 1 q , where each Y 1 All independently - OR 2 , where R 2 For C1 to C 10 Alkyl or - OC(=O)R 3 , where R 3 For C1 to C 10 alkyl, and q is an integer from 2 to 4, and wherein the hydrocarbyl metal compound has the formula AlX 2 n R 1 3-n 、Al2X 2 3R 1 3 or any combination thereof, where each X 2 are independently halogen, each R 1 are each independently a C2 to C4 alkyl group, and n is an integer from 1 to 3.

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