oligomerization catalyst system and olefin oligomerization process

专利摘要:
oligomerization catalyst system and olefin oligomerization process among other things, the present invention relates to an olefin oligomerization process and system, the system comprising: a) a transition metal compound; b) a pyrrole compound having a 5 or 2-position hydrogen atom and 5-position of a pyrrole compound and having a bulky substituent located on each carbon atom adjacent to the carbon atom with a 5 or 5-position hydrogen atom. position 2 and 5 of a pyrrole compound. These catalyst systems have significantly improved productivity, selectivity for 1-hexene, and provide higher purity of 1-hexene within the C-6 ~ fraction than catalyst systems using 2,4-dimethyl pyrrol.
公开号:BR112012027892B1
申请号:R112012027892-4
申请日:2011-04-21
公开日:2018-12-04
发明作者:Orson L. Sydora
申请人:Chevron Phillips Chemical Company Lp；
IPC主号:

专利说明:

(54) Title: OLIGOMERIZATION CATALYST SYSTEM AND OLEFINE OLIGOMERIZATION PROCESS (73) Holder: CHEVRON PHILLIPS CHEMICAL COMPANY LP, Sociedade Norte Americana. Address: 10001 Six Pines Drive The Woodlands, TX 77380, UNITED STATES OF AMERICA (US) (72) Inventor: ORSON L. SYDORA.
Validity Period: 20 (twenty) years from 04/21/2011, subject to legal conditions
Issued on: 12/04/2018
Digitally signed by:
Liane Elizabeth Caldeira Lage
Director of Patents, Computer Programs and Topographies of Integrated Circuits
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OLIGOMERIZATION CATALYST SYSTEM AND OLEFINES OLIGOMERIZATION PROCESS
CROSS REFERENCE TO RELATED ORDERS
This Application is a Partly Continuation of US Patent Application No. 12/609272, filed on October 30, 2009 which in turn claims priority for and benefit from US Provisional Patent Application No. 61 / 110,396 , filed October 31, 2008, US Provisional Patent Application No. 61 / 110,407, filed on October 31, 2008, and US Provisional Patent Application No. 61 / 110,476, filed on October 31, 2008, each of these provisional patent applications is incorporated in this document by references in their entirety.
TECHNICAL FIELD OF THE INVENTION
This disclosure relates to an oligomerization catalyst system, methods for preparing the oligomerization catalyst system, and methods for using the oligomerization catalyst system for the preparation of an oligomerization product.
FUNDAMENTALS
The synthesis of catalyzed chromium from ethylene 1-hexene constitutes a commercially significant process for the selective preparation of this alpha olefin, which in turn is useful for the preparation of a variety of polyolefins when used as a comonomer with ethylene. A widely reported chromium catalyst system for the selective production of 1-hexene comprises chromium (III) carboxylates (for example, chromium (III) tris (2-ethylhexanoate) (Cr (EH) ₃ )), a composed of pyrrole and an alkyl metal.
Many 1-hexene selective oligomerization catalyst systems contain a chromium compound, a pyrrole compound, at least one alkyl metal, optionally a solvent and optionally additional component, which can be combined in different ways and in different ratios to provide the catalyst system. Some preparative methods of the catalyst system seem to rely on the presence of a special solvent to stabilize the catalyst system. Typically, any method of preparation, activation and use of a catalyst system can present challenges in relation to its particular preparation, activation and stability, as well as to the activity and selectivity provided by the catalyst system.
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Consequently, it would be useful to discover and develop new oligomerization catalyst systems, new methods for preparing oligomerization catalyst systems and new methods for using oligomerization systems to prepare an oligomerization product that can provide greater efficiency and cost-effectiveness. New catalyst oligomerization systems and methods to prepare the oligomerization catalyst systems that could provide greater activity, increased efficiency, lower costs, greater selectivity for Cq (or 1hexene) products, and / or increased 1-hexene in the fraction of C ₆ product would be desirable.
SUMMARY OF THE INVENTION
Among other things, the present disclosure provides for olefin oligomerization catalyst systems, methods for the preparation of olefin oligomerization catalyst systems, and methods for using the olefin oligomerization catalyst system for the preparation of an olefin product. oligomerization. In one aspect, the oligomerization catalyst systems described in this document and prepared according to the various described modalities can allow to achieve good catalyst activity and selectivity.
In one aspect, the present disclosure provides for a catalyst system comprising: a) a transition metal compound, b) a compound having pyrrole i) a hydrogen atom located on at least one atom of the carbon pyrrole ring adjacent to the nitrogen atom of the pyrrole ring, and ii) a bulky C ₃ to C ₈ organyl group or a C ₃ to C ₆ bulky silyl group located on a pyrrole ring carbon atom adjacent to any pyrrole ring carbon atom having the hydrogen atom adjacent to the nitrogen atom of the pyrrole ring, and c) an alkyl metal. In one embodiment, the bulky substituent located on the carbon atom of the pyrrole ring adjacent to any carbon atom of the pyrrole ring having the hydrogen atom adjacent to the nitrogen atom of the pyrrole ring may have a structure such that i) the carbon atom of the bulky C ₃ to Ci ₈ organyl group attached to the carbon atom of the pyrrole ring is attached to three or four carbon atoms, ii) the carbon atom of the C ₃ to Ci ₈ bulky organila group adjacent to the carbon atom attached to the carbon atom of the pyrrole ring is attached to three or four carbon atoms or iii) the silicon atom of the bulky silyl group C ₃ to C ₆ the attached to the carbon atom of the pyrrole ring is attached to four atoms carbon.
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In another aspect, the present disclosure provides for catalyst systems comprising a pyrrole compound having Formula P2, P3, or P4:
r33p ^ ^H
Γ / ΗΗ
R ^34p Λ
H
on what
P2
i) R ^12p
P4 r ²² P of Formula P3 independently are a hydrocarbyl group C-ι to Ci ₅ ; and ii) R ^14p in Formula P2,
R ^24p in Formula P3, and R ^33p and R ^34p in Formula P4 independently are bulky hydrocarbyl group C3 to C15 or a bulky silyl group C ₃ to C45. In one embodiment, the group R ^14p in Formula P2, group R ^24p in Formula P3, and groups
R ^33p and R ^34p in Formula P4 are linked so that i) the carbon atom attached to the pyrrole ring is attached to three or four carbon atoms, ii) the carbon atom adjacent to the carbon atom attached to the pyrrole ring is attached to three or four carbon atoms, or iii) The C ₃ to C 45 silyl group has the Formula Si 1: d1s
r2s_ _yes - * r ^{3s /}
Si1 where R ^s1 , R ^s2 , and R ^s3 independently are a C1 to C15 hydrocarbyl group.
In one aspect, the present disclosure provides a process for oligomerization, comprising: A) coming into contact with an olefin feedstock with a catalyst system comprising i) a transition metal compound and ii) a pyrrole compound having (a) a hydrogen atom located on at least one pyrrole ring carbon atom adjacent to the pyrrole ring nitrogen atom, and (b) a bulky C ₃ organyl group a
Cys or a bulky C ₃ to aθο silyl group located on a pyrrole ring carbon atom adjacent to any pyrrole ring carbon atom having 0 hydrogen atom adjacent to the pyrrole ring nitrogen atom, and iii) a metal alkyl and B) oligomerization of olefins under the condition of oligomerization to form an oligomerization product. In one embodiment, a bulky substituent located on the carbon atom of the pyrrole ring adjacent to any carbon atom of the pyrrole ring having 0 hydrogen atom adjacent to the
4/74 nitrogen atom of the pyrrole ring may have a structure such that i) the carbon atom of a bulky C3 to Cie organyl group attached to the carbon atom of the pyrrole ring is attached to three or four carbon atoms, ii) The carbon atom of the bulky C ₃ to Cw organyl group adjacent to the carbon atom attached to the carbon atom of the pyrrole ring is attached to three or four carbon atoms or iii) The silicon atom of the bulky C 3 a sily group Οθο attached to the carbon atom of the pyrrole ring is attached to four carbon atoms.
In one aspect, the present invention provides for a trimerization process comprising: A) coming into contact with an olefin feedstock comprising i) a transition metal compound comprising a chromium (II) or chromium (III) carboxylate that each carboxylate is a C ₄ to C19 carboxylate, ii) a pyrrole compound having Formula P2, P3, or P4:
where (a) R ^12p and R ^13p of Formula P2 and R ^22p of Formula P3 independently are a hydrocarbyl group C1 to C15 and (b) R ^14p in Formula P2, R ^24p in Formula P3, and R ^33p and R ^34p in Formula P4 independently are a bulky C ₃ to C 15 hydrocarbyl group or a C ₃ to C 45 bulky silyl group, θ iii) an alkyl metal comprising a mixture of triethyl aluminum chloride and diethyl aluminum; and B) trimerizing the olefin feedstock under trimerization conditions to form a trimerization product comprising 1-hexene. In one embodiment, the R ^14p group in Formula P2, R ^24p group in Formula P3, and R ^33p and R ^{34p groups} in Formula P4 are linked so that i) the carbon atom attached to the pyrrole ring is linked to three to four carbon atoms, ii) The carbon atom adjacent to the carbon atom attached to the pyrrole ring is attached to three or four carbon atoms, or iii) The silyl group C3 to C45 has the Formula Si1:
1s
R ^2s -Si— * r ^{3s /}
Si1
5/74 where R ^s1 , R ^s2 , and R ^s3 independently are a C 1 to C ₁₅ hydrocarbyl group. In other embodiments, the trimerization process may have a productivity (g C ₆ / g transition metal - for example, Cr) than the 2,4-dimethylpyrrole process such as the pyrrole compound, provides a high selectivity for C6 products than the process using 2,4-dimethylpyrrole as the pyrrole compound, and / or provides a higher purity of the 1-hexene product than the process using 2,4-dimethylpyrrole as the pyrrole compound.
In yet another aspect, the present disclosure provides a process for preparing a catalyst system, comprising contacting, a) a transition metal compound, b) a compound having pyrrole i) a hydrogen atom located in at least a pyrrole ring carbon atom adjacent to the pyrrole ring nitrogen atom, and ii) a C3 to C18 bulky organyl group or a C3 to C60 bulky silyl group located on a pyrrole ring carbon atom adjacent to any atom carbon of the pyrrole ring having the hydrogen atom adjacent to the nitrogen atom of the pyrrole ring, and c) an alkyl metal.
In another aspect, this disclosure provides a process for preparing a catalyst system, comprising contacting, a) a transition metal compound comprising a chromium (II) or chromium (III) carboxylate in which each carboxylate is a C ₄ to C19 carboxylate, b) a pyrrole compound having Formula P2, P3 or P4:

P3
where i) R ^12p and R ^13p of Formula P2 and R ^22p of Formula P3 independently are a hydrocarbyl group C1 to C15 and ii) R ^14p in Formula P2, R ^24p in Formula P3, and R ^33p and R ^34p in Formula P4 independently they are a C ₃ to C 15 bulky hydrocarbyl group or a C ₃ to C 45 bulky silyl group; and c) an alkyl metal comprising a mixture of triethyl aluminum chloride and diethyl aluminum.
DETAILED DESCRIPTION OF THE INVENTION
General description
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According to various aspects and modalities of the present description, olefin oligomerization catalyst systems, methods for their preparation, and methods for their use for the preparation of an olefin oligomerization product are provided. In one aspect, the oligomerization catalyst systems described in this document and prepared according to the various described modalities can allow to achieve the good activity of the catalyst system, productivity of the catalyst system, the selectivity of the product, and / or the purity of the product by selecting the pyrrole compound used in the catalyst system.
Definitions
In order to define more clearly the terms used in this document, the following definitions are provided. Unless otherwise indicated, the following definitions apply to this disclosure. If a term is used in this disclosure, but is not specifically defined in this document, from the definition from IUPAC Compendium of Chemical Terminology, 2 ^nd Ed (1997) can be applied, as long as this definition does not conflict with any other disclosure or definition applied in this document, or sue for an indefinite or unqualified period for any claim for that definition to apply. Insofar as any definition or use of any document incorporated in this document by reference conflicts with the definition or use provided herein, the definition or use provided herein controls.
As for the transition terms or phrases of the claim, the transition term comprising, which is synonymous with inclusive, contains or characterized by the fact that it is inclusive or open and does not exclude additional, unreported elements or steps in the method. The transition phrase “consisting of excludes any element, stage or ingredient not specified in the order. The transition phrase consisting essentially of limits the scope of an order to the specified materials or steps and those that do not significantly affect the basic and new feature (s) of the claimed invention. The claim essentially consists of occupying an intermediate position between closed claims that are written in a format consisting of and fully open claims, which are written in the format comprising. Unless otherwise indicated, when describing a compound or composition from consisting essentially of it it should not be understood as comprising, but is intended to describe the
7/74 recited component that includes materials that do not significantly change the composition or method to which the term is applied. For example, the raw material consisting of material A may include impurities normally present in a sample produced commercially or commercially available from the recited compound or composition. When an order includes different and / or classes of different characteristics (for example, a method step, the characteristics of the raw material and / or characteristics of the product, among other possibilities), the transition conditions comprising, consisting essentially of, and consisting of only apply the class of characteristic for which it is used, and it is possible to have different transition terms or phrases used with different characteristics in a claim. For example, a possible method comprises several recited steps (and other non-recited steps), but uses a catalyst system preparation that consists of specific steps, but uses a catalyst system comprising the recited components and other non-recited components.
Although the compositions and methods are described in terms of comprising several components or steps, the compositions and methods can also consist essentially of or consist of the various components or steps.
The term essentially consists of, or variations thereof, whenever used in this specification and claims in relation to a commercial product (for example, an olefin feedstock, such as ethylene) refers to a commercially available product. The commercially available product may contain impurities that are not the specific product that are not removed during the product process of the commercial product. One skilled in the art will recognize that the identity and amount of specific impurities present in the commercial product will depend on the source of, and / or manufacturing process used to produce the commercial product. Consequently, the term essentially consisting of and its variants, when used in conjunction with a commercial, is not intended to limit the equivalence / quantity of non-specific impurities in products more strictly than the equivalences / quantities present in a given commercial product.
The terms one, one, and o are intended, unless specifically stated otherwise, to include plural alternatives, for example, at least one. For example, the disclosure of a chromium carboxylate is intended
8/74 includes chromium carboxylate, or mixtures or combinations of more than one chromium carboxylate unless otherwise specified.
In one aspect, a chemical group can be defined or described according to how that group is formally derived from a reference or main compound, for example, by the number of hydrogen atoms that are formally removed from the main compound to generate the group, even that this group is not literally synthesized in this way. These groups can be used as substituents or coordinated or attached to metal atoms. As an example, an alkyl group can be formally derived by removing a hydrogen atom from an alkane, while an alkylene group can be formally derived by removing two hydrogen atoms from an alkane. In addition, a more general term can be used to encompass a variety of groups that are formally derived, removing any number (one or more) of hydrogen atoms from a main compound, which in this example can be described as an alkane group, and which includes an alkyl group, an alkylene group and materials with three or more hydrogen atoms, as needed for the situation, taken from an alkane. Everywhere, the disclosure that a substituent, linker or other chemical moiety may constitute a particular group implies that the known rules of chemical structure and bonding are followed when that group is employed as described. By way of example, if a subject compound is disclosed in which the substituent X may be an alkyl group, an alkylene group, or an alkane group, the normal rules of valence or bonding are followed. When describing a group as being derived from, derived from, formed by or formed from, such terms are used in a formal sense and are not intended to reflect any specific synthetic methods or procedures, unless otherwise specified or the context require otherwise.
In addition, unless otherwise specified, any carbon-containing group for which the number of carbon atoms is not specified may have, according to appropriate chemical practice, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, or 30 atoms carbon, or any interval or combination of intervals between these values. For example, unless otherwise specified, any group containing carbon may have from 1 to 30 carbon atoms, from 1 to 25 carbon atoms, from 1 to 20 carbon atoms, from 1 to 15 carbon atoms
9/74 carbon, from 1 to 10 carbon atoms, or 1 to 5 carbon atoms, and the like. In addition, other qualifying identifiers or conditions may be used to indicate the presence of, or the absence of, a specific substituent, the specific regiochemistry, and / or stereochemistry or the presence or absence of a branched or underlying main structure or structure. Any group containing specific carbon is limited according to the chemical and structural requirements for that specific group, as understood by one skilled in the art. For example, unless otherwise specified, an aryl group may have 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 20 carbon atoms, 6 to 15 carbon atoms, or 6 to 10 carbon atoms, and the like. Thus, according to proper chemical practice and, unless otherwise specified, an aryl group may have 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 , 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, or 30 carbon atoms, or any range or combination of ranges between these values.
The term substituted when used to describe a group, for example, when referring to a substituted analog of a specific group, is intended to describe the compound or group in which any portion of non-hydrogen formally replaces the hydrogen in that group or compound and is intended to be non-limiting. A compound or group may also be referred to in this document as unsubstituted or in equivalent terms, such as unsubstituted, which refers to the original group or compound. Substituted is intended not to limit and include inorganic substituents or organic substituents as specified and as understood by one skilled in the art.
A halide has its usual meaning. Examples of halides include flouride, chloride, bromide and iodide.
The term hydrocarbon when used in this specification and in the claims refers to a compound that contains only carbon and hydrogen. Other identifiers can be used to indicate the presence of specific groups in the hydrocarbon (for example, halogenated hydrocarbon indicates that the presence of one or more halogen atoms that replace an equivalent number of hydrogen atoms in the hydrocarbon). The term hydrocarbyl group is used in this document according to the definition specified by IUPAC: a monovalent group formed by the removal of a hydrogen atom from a hydrocarbon (that is, a group containing only carbon and hydrogen). Likewise, a hydrocarbilene group refers to a group
10/74 formed by the removal of two hydrogen atoms from a hydrocarbon, or two hydrogen atoms from one carbon atom or one hydrogen atom from each of the two different carbon atoms. Thus, according to the terminology used here, a hydrocarbon group refers to a group formed by the generalized removal of one or more hydrogen atoms (as needed for the specific group) from a hydrocarbon. A hydrocarbyl group, hydrocarbilene group and hydrocarbon group can be acyclic or cyclic groups, and / or they can be linear or branched. A hydrocarbyl group, hydrocarbene group and hydrocarbon group can include rings, ring systems, aromatic rings, and aromatic ring systems, which contain only carbon and hydrogen. Hydrocarbyl groups, ”hydrocarbene groups and hydrocarbon groups include, by way of example, aryl, ariiene, arene, alkyl, alkylene groups, alkane, cycloalkyl, cycloalkylene groups, cycloalkane, aralkyl, aralkylene groups, and aralkane groups, respectively, between other groups as elements.
An aliphatic compound is a non-aromatic organic compound. An aliphatic group is a generalized group formed by removing one or more hydrogen atoms (as needed for the specific group) of carbon atoms in an aliphatic compound. An aliphatic compound can be acyclic or cyclic, saturated or unsaturated, and / or linear or branched organic compound. Aliphatic compounds and aliphatic groups may contain organic functional group (s) and / or atom (s) other than carbon and hydrogen.
The term alkane whenever used in this specification and claims refers to a saturated hydrocarbon compound. Other identifiers can be used to indicate the presence of certain groups in the alkane (for example, halogenated alkane indicates the presence of one or more halogen atoms, replacing an equivalent number of hydrogen atoms in the alkane). The term alkyl group is used in this document according to the definition specified by IUPAC: a univalent group formed by removing a hydrogen atom from an alkane. Similarly, an alkylene group refers to a group formed by the removal of two hydrogen atoms from an alkane (two hydrogen atoms from a carbon atom) or an atom from two different carbon atoms. An alkane group is a general term that refers to a group formed by the removal of one or more hydrogen atoms (as necessary for the special group) an alkane. An alkyl group, alkylene group and alkane group can be linear or
11/74 branched, unless otherwise specified. Primary, secondary and tertiary alkyl groups are derived by removing a hydrogen atom from a primary, secondary, tertiary carbon atom, respectively, from an alkane. The n-alkyl group derived by removing a hydrogen atom from a terminal carbon atom of a linear alkane. The groups RCH2 (R Ψ H), R2CH (R Ψ H), and R3C (R # H) are alkyl groups are primary, secondary, and tertiary, respectively. The carbon atom to which the indicated portion is attached is a secondary, tertiary, and quaternary carbon atom, respectively.
The term organyl group is used in this document according to the definition specified by IUPAC: an organic substituent group, regardless of the functional type, having a free valence on a carbon atom. Likewise, an organylene group refers to an organic group, regardless of the functional type, derived by the removal of two hydrogen atoms from an organic compound (or two hydrogen atoms from a carbon atom or an atom hydrogen from each of the two different carbon atoms). An organic group refers to a group formed by the generalized removal of one or more hydrogen atoms from carbon atoms in an organic compound. Thus, an organyl group, an organylene group, and an organic group can contain organic functional group (s) and / or different atom (s) of carbon and hydrogen, that is, a group organic which can comprise functional groups and / or atoms in addition to carbon and hydrogen. For example, non-limiting examples of other carbon and hydrogen atoms include halogens, oxygen, nitrogen, phosphorus, and the like. Non-limiting examples of functional groups include ethers, aldehydes, ketones, esters, sulfides, amines and phosphines, and the like. In one aspect, the hydrogen atom (s) removed to form the organyl group, organylene group, or organic group can be attached to a carbon atom belonging to a functional group, for example, an acyl group (-C (O) R), a formyl group -C (O) H), a carboxy group (-C (O) OH), a hydrocarboxycarbonyl group (-C (O) OR), a cyano group (-C = N), a carbamoyl group (C (O) NH ₂ ), a / V-hydrocarbilcarbamoyl (-C (O) NHR) group, or Λ /, Λ / '- dihydrocarbilcarbamoyl group (-C (O) NR ₂ ), among other possibilities. In another aspect, the hydrogen atom (s) removed to form the "organyl group", "organylene group", or "organic group" can be attached to a carbon atom not belonging to, and remote from , a functional group, for example, CH ₂ C (O) CH ₃ , -CH ₂ NR ₂ , and the like. An organila group, organylene group, or
12/74 organic group can be aliphatic or aromatic, cyclic or acyclic, and / or linear or branched. Organyl groups, organylene groups and organic groups also encompass rings containing heteroatom, ring systems containing heteroatom, heteroaromatic rings and heteroaromatic ring systems. Finally, it has been observed that the definitions of organyl group, organylene group, or organic group include hydrocarbyl group, hydrocarbene group, hydrocarbon group, respectively, and alkyl group, alkylene group, and alkane group, respectively, among others, as elements.
For the purposes of the present application, the term or variations of the term organyl group consisting of inert functional groups refers to a group in which organic organyl groups and / or atoms other than carbon and hydrogen present in the functional group are restricted to those functional groups and / or other carbon and hydrogen atoms, which are non-reactive under the conditions of the process defined herein. Thus, the term or variation of the term inert organila groups consisting of functional groups further defines the specific organila groups that may be present. In addition, the term organyl group consisting of inert functional groups can refer to the presence of one or more inert functional groups within the organyl group. The term or variation of the definition of an organyl group consisting of an inert functional group includes the hydrocarbyl group, among others, as an element.
For the purposes of this application, an inert functional group is a group that does not substantially interfere with any process described herein to which it belongs (for example, interfering with the oligomerization process). Non-limiting examples of inert functional groups that cannot substantially interfere with any process described herein may include halogens (fluorine, chlorine, bromine, and iodine), organoxy groups (eg, hydrocarbon group or alkoxy group, among others), sulfidyl groups, and / or hydrocarbyl groups.
A cycloalkane is a saturated cyclic hydrocarbon, with or without side chains (for example, cyclobutane or methylcyclobutane). Unsaturated cyclic hydrocarbons, having an endocyclic double or a triple bond are called cycloalkenes and cycloalkines, respectively. Those who have more of such a multiple bond are cycloalkadienes, cycloalcatrienes, and the like.
A cycloalkyl group is a univalent group derived through the removal of a hydrogen atom from a ring carbon atom of a cycloalkane. For example, a 1-methylcyclopropyl group and a 2methylcyclopropyl group are illustrated as follows.
13/74 jwv
L-ch _{3 ch} / / h ₂ c — CH ₂ H ₃ C ^{CH CH2}
Similarly, a cycloalkylene group refers to a group derived by the removal of two hydrogen atoms from a cycloalkane, at least one of which is a ring carbon atom. Thus, a cycloalkylene group includes both a group derived from a cycloalkane in which two hydrogen atoms are formally removed from the carbon in the same ring, a group derived from a cycloalkane in which two hydrogen atoms are formally removed from two atoms. different ring carbon, and a group derived from a cycloalkane in which a first hydrogen atom is formally removed from a ring carbon and a second hydrogen atom is formally removed from a carbon atom that is not a ring carbon atom . A cycloalkane group refers to a group formed by the generalized removal of one or more hydrogen atoms (as needed for the specific group and at least one of which is a carbon ring) from a cycloalkane.
The term aicene whenever used in this specification and in the claims refers to a compound that has at least one non-aromatic carbon-carbon double bond. The term aicene includes aliphatic or aromatic, cyclic or acyclic, and / or linear and branched aicene, unless expressly stated otherwise. The term aicene, by itself, does not indicate the presence or absence of heteroatoms and / or the presence or absence of other carbon-carbon double bonds, unless explicitly indicated. The terms aicene hydrocarbon or aicene hydrocarbon refer only to alkenes containing hydrogen and carbon. Other identifiers can be used to indicate the presence or absence of specific groups in an aicene. Alkenes can also be identified through the position of the carbon-carbon double bond. Alkenes, having more than one such multiple bond are alkali, alkaline, and the like. Aiken can be further identified by the position of the carbon-carbon double bond (s).
An alkenyl group is a univalent group, derived from an aicene by removing a hydrogen atom from any carbon atom in the aicene. Thus, the aicene group includes groups in which the hydrogen atom is formally removed from a hybridized (olefinic) sp ² carbon atom and
14/74 groups in which the hydrogen atom is formally removed from any other carbon atom. For example, and unless otherwise specified, propen-1-yl groups (-CH = CHCH ₃ ), propen-2-yl [(CH ₃ ) C = CH ₂ ], and propen-3-yl (CH ₂ CH = CH ₂ ) are all included with the term "alkenyl group". Similarly, an "alkenylene group" refers to a group formed by formally removing two hydrogen atoms from an alkene, two hydrogen atoms from a carbon atom or a hydrogen atom from two different carbon atoms. An alkene group refers to a generalized group, formed by the removal of one or more hydrogen atoms (as needed for the specific group) from an alkene. When the hydrogen atom is removed from a carbon atom, participating in a carbon-carbon double bond, the carbon regiochemistry from which the hydrogen atom is removed and the regiochemistry of the double bond can also be specified. The terms alkenyl group, alkenylene group and alkene group alone do not indicate the presence or absence of heteroatoms and / or the presence or absence of other carbon-carbon double bonds unless explicitly indicated. The terms alkene hydrocarbon group, alkenylene hydrocarbon group and alkene hydrocarbon group refer to alkene groups containing only carbon and hydrogen. Other identifiers can be used to indicate the presence or absence of certain groups within an alkene group. Alken groups can also have more of such a multiple bond. The alkene group can also be identified further by the position of the carbon-carbon double bond (s).
The term alkaline is used in this specification and claims to refer to a compound that has at least one carbonocarbon triple bond. The term alkaline includes aliphatic or aromatic, cyclic or acyclic, linear and branched alkines, unless otherwise indicated. The term alkaline, by itself, does not indicate the presence or absence of heteroatoms and / or the presence or absence of other carbon-carbon triple bonds unless explicitly indicated. The terms alkaline hydrocarbons or alkaline hydrocarbons refer to alkaline compounds containing only carbon and hydrogen. Other identifiers can be used to indicate the presence or absence of specific groups in an alkyne. Alkynes, having more than such a multiple bond are alkali, alkaline, and the like. The alkaline group can also be further identified by the carbonocarbon triple bond position (s).
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An alkene group is a univalent group, derived from an alkaline by removing a hydrogen atom from any carbon atom in the alkaline. Thus, the alkene group includes groups in which the hydrogen atom is formally removed from a hybridized carbon atom sp (acetylenic) and in which the hydrogen atom is formally removed from any other carbon atom. For example, and unless otherwise specified, groups 1propyn-1-yl (-C = CCH ₃ ) and propin-3-yl (HC = CCH ₂ -) are all encompassed by the term "alkenyl group". Similarly, an alkynylene group refers to a group formed by formally removing two hydrogen atoms from an alkaline, two hydrogen atoms from a carbon atom if possible or an atom from two different carbon atoms. An alkaline group refers to a generalized group, formed by the removal of one or more hydrogen atoms (as needed for the special group) from an alkaline group. The terms alkene group, alkynylene group and alkaline group alone do not indicate the presence or absence of heteroatoms and / or the presence or absence of other carbon-carbon double bonds unless explicitly indicated. The terms alkene hydrocarbon group, alkaline hydrocarbon group and alkaline hydrocarbon group refer to groups of olefins containing only carbon and hydrogen. Other identifiers can be used to indicate the presence or absence of certain groups within an alkaline group. Alkyne groups can have more than one such multiple bond. More alkaline groups can also be identified by the position of the carbonocarbon triple bonds.
The term alpha olefin as used in this specification and claims refers to an olefin that has a double bond between the first and the second carbon atoms in the longest contiguous chain of carbon atoms. The term alpha olefin includes linear and branched alpha olefins, unless otherwise indicated. In the case of branched alpha olefins, a branch can be in position 2 (a vinylidene) and / or in position 3 or higher with respect to the olefin double bond. The term vinylidene whenever used in this specification and claims refers to an alpha olefin having a branch in position 2 with respect to the olefin double bond. By itself, the term alpha olefin does not indicate the presence or absence of heteroatoms and / or the presence or absence of other carbon-carbon double bonds unless explicitly indicated. The terms alpha olefin hydrocarbon or alpha hydrocarbon
16/74 olefin refers to alpha olefin compounds containing only carbon and hydrogen.
The term linear alpha olefin as used in this document refers to a linear olefin with a double bond between the first and the second carbon atoms. The term linear alpha olefin alone does not indicate the presence or absence of heteroatoms and / or the presence or absence of other carbon-carbon double bonds, unless explicitly indicated. The terms linear olefin hydrocarbon alpha or linear hydrocarbon alpha olefin refer to linear alpha olefin compounds containing only carbon and hydrogen.
The term normal alpha olefin whenever used in this specification and claims refers to a linear hydrocarbon monoolefin having a double bond between the first and the second carbon atoms. It should be noted that normal alpha olefin is not synonymous with linear alpha olefin as the term linear alpha olefin can include linear olefinic compounds having a double bond between the first and second carbon atoms and having additional heteroatoms and / or double bonds.
An aromatic group refers to a generalized group, formed by removing one or more hydrogen atoms (as needed for the specific group and at least one that is a carbon atom in the aromatic ring) from an aromatic compound. Thus, an aromatic group as used in this document refers to a derivative group, removing one or more hydrogen atoms from an aromatic compound, that is, a compound containing a cyclically conjugated hydrocarbon that follows Huckel's rule (4n + 2) and containing pi-electrons (4n + 2), where n is an integer from 1 to about 5, aromatic compounds and, therefore, aromatic groups can be monocyclic or polycyclic, unless otherwise indicated. Aromatic compounds include arenes (aromatic hydrocarbon compounds) and heteroarenes, also called hetarenes (heteroaromatic compounds formally derived from arenes by replacing one or more methyl carbon atoms (-C =) with bivalent or trivalent heteroatoms, in order to maintain the continuous pi-electron system characteristic of aromatic systems and a number of out-of-plane pyelectrons corresponding to Huckel's rule (4n + 2). Although arenes and heteroarenes are mutually exclusive elements of a group of aromatic compounds, a compound which has an arene group and a heteroarene group which the compound is generally considered to be a heteroarene compound. Aromatic, arene and heteroarene compounds can be mono- or
17/74 polycyclic, unless otherwise stated. Examples of arenes include, but are not limited to, benzene, naphthalene and toluene, among others. Examples of heteroarenes include, but are not limited to, furan, pyridine and methylpyridine, among others. As disclosed in this document, the term substituted can be used to describe an aromatic group in which any portion of non-hydrogen formally replaces a hydrogen in that group, and is intended to be non-limiting.
An aryl group refers to a generalized group, formed by removing a hydrogen atom from a carbon atom from the aromatic hydrocarbon ring of an arene. An example of an aryl group is ortho-tolyl (o-tolyl), the structure that is shown in this document.
CH
Similarly, an arylene group refers to a group formed by the removal of two hydrogen atoms (at least one of which is an aromatic hydrocarbon ring carbon) from an arene. An arene group refers to a generalized group, formed by the removal of one or more hydrogen atoms (as needed for the special group and at least one of which is an aromatic hydrocarbon ring carbon) from an arene. However, if a group contains different and separate arene and heteroarene rings or ring systems (for example, the phenyl and benzofuran moieties in 7phenylbenzofuran) their classification depends on the specific ring or ring system from which the hydrogen atom has been removed. , that is, an arene group if the hydrogen removed comes from the aromatic hydrocarbon ring or carbon atom of the ring system (for example, carbon atom 2 in the 6-phenylbenzofuran phenyl group) and a heteroarene group if the carbon removed of the hydrogen comes from a heteroaromatic ring or the carbon atom of the ring system (for example, carbon atom 2 or 7 of the benzofuran group 6phenylbenzofuran).
An aralkyl group is an aryl-substituted alkyl group with a free valence on a non-aromatic carbon atom, for example, a benzyl group is an aralkyl group. Similarly, an aralkylene group is an
18/74 aryl-substituted alkylene group with two free valences on a single non-aromatic carbon atom or a free valence on two non-aromatic carbon atoms while an aralkane group is a generalized one is an arane-substituted alkane group having one or more valences free in non-aromatic carbon atoms. A heteroaralkyl group is an alkyl group substituted by heteroaryl having a free valence on a non-heteroaromatic ring or the carbon atom of the ring system. Similarly, a heteroaralkylene group is a heteroaryl-substituted alkylene group having two free valences on a single non-heteroaromatic ring or ring atom carbon or a free valence on two ring carbon atoms or ring system as a group heteroaralkane is a generalized aryl-substituted alkane group having one or more free valences in a non-heteroaromatic ring or ring system carbon atoms.
If a compound or group contains more than one portion it is formally an element of the group having the highest nomination priority as stipulated by IUPAC. For example, 4-phenylpyridine is a heteroaromatic compound and a 4- (phen-2-ylene) pyridin-2-yl group is a heteroaromatic group, as the most common nomenclature groups are the pyridine group and the pyridin-2- group ila, respectively.
A silane is a compound containing a silicone atom. A silyl group is a group formed by the general removal of a hydrogen atom from the silicon atom of a silane.
An organoaluminium compound, is used to describe any compound that contains an aluminum-carbon bond. Thus, organoaluminium compounds include hydrocarbyl aluminum compounds, such as trialkyl-, dialkyl-, or monoalkyl aluminum compounds; hydrocarbyl alumoxane compounds; and aluminate compounds that contain an aluminum-organyl bond such as tetrakis (p-tolyl) aluminate salts.
The term reactor effluent, and its derivatives (for example, oligomerization reactor effluent) generally refers to all material that leaves the reactor. The term reactor effluent, and its derivatives, can also be preceded by other descriptors that limit the portion of the reactor effluent to be referenced. For example, while the term reactor effluent refers to all the material that leaves the reactor (for example, product and solvent or diluent, among others), the olefin reactor effluent refers to the reactor effluent that
19/74 contains an olefin double bond (ie carbon-carbon).
The term oligomerization, and its derivatives, refers to processes that produce a mixture of products that contain at least 70 weight percent of products containing from 2 to 30 monomer units. Similarly, an oligomer is a product that contains 2 to 30 units of monomer, while an oligomerization product includes all products made by the oligomerization process including oligomers and products produced by the process that are not oligomers (for example, the product containing more than 30 monomer units. It should be noted that the monomer units in the oligomer or oligomerization product do not have to be the same. For example, an oligomer or oligomerization product from the oligomerization process using ethylene and propylene as the monomers can contain both ethylene and / or propylene units.
The term trimerization and its derivatives, refers to a process that produces a product that contains at least 70 percent by weight of products containing three and only three monomer units. A trimer is a product that contains three and only three units of the monomer, while a trimerization product includes all products manufactured by the trimerization process including trimer and non-trimer products (for example, dimers or tetramers). Generally, an olefin trimerization reduces the number of olefinic bonds, that is, carbon-carbon double bonds, by two when considering the number of olefin bonds in monomer units and the number of olefin bonds in the trimer. Note that the monomer units in the trimer or trimer product are not the same. For example, a trimer from a trimerization process using ethylene and butene as monomers can contain monomer units of ethylene and / or butene. That is, the trimer can include products C6, Cs, C ₁₀ and C12. In another example, a trimer from a trimerization process using ethylene as the monomer may contain monomer units of ethylene. It should also be noted that a single molecule can contain two monomer units. For example, dienes such as 1,3-butadiene and 1,4-pentadiene have two monomeric units in a molecule.
Oligomerization catalyst system
The minimally oligomerization catalyst system comprises a transition metal compound, a pyrrole compound and an alkyl metal. In
In another aspect, the oligomerization catalyst system may additionally include a halogen-containing compound. The transition metal compounds, alkyl metal, pyrrole compound and optional halogen-containing compounds are independent elements of the oligomerization catalyst system. These elements of the oligomerization catalyst system are independently described in this document and the catalyst system can be further described using any combination of transition metal described in this document, the pyrrole compound described herein, the alkyl metal described herein, and compound containing optional halogen described here.
Transition Metal Compound
Generally, the transition metal compound for the oligomerization catalyst system may include, essentially consist of or consist of a group 5, 6, 7, 8, 9, 10 or 11 transition metal. In some embodiments, the compound transition metal comprises, consists essentially of or consists of, chromium, nickel, cobalt, iron, molybdenum or copper. In other embodiments, the transition metal compound comprises, consists essentially of or consists of chromium.
In some respects, the transition metal compound for the oligomerization catalyst system can be an inorganic transition metal compound. In other respects, transition metal compounds may contain binders formally derived from an organic compound or fraction (for example, carboxylate, alkoxide, or beta-dionate, among others). In one embodiment, suitable inorganic transition metal compounds include, but are not limited to, a transition metal halide, transition metal sulfate, transition metal sulfite, transition metal bisulfate, a metal oxide transition, a transition metal nitrate, a transition metal nitrite, a transition metal hydroxide, transition metal chlorate or any combination thereof; alternatively, transition metal halide, transition metal sulfate, transition metal oxide or transition metal nitrate. In one embodiment, the transition metal halide can be a transition metal chloride, a transition metal bromide or a transition metal iodide. In one embodiment, the transition metal compound can be a transition metal alkoxide, a transition metal aryloxide, a transition metal carboxylate, a transition metal beta-dionate (such as an acetylacetonate) or a transition metal amide; alternatively, a transition metal alkoxide or
21/74 transition metal; alternatively, a transition metal carboxylate, a transition metal beta-dionate; or, alternatively, a transition metal amide. In addition, in another aspect, suitable transition metal compounds can contain combinations of these recited binders. Some embodiments, the transition metal compound comprises, consists essentially of or consists of a transition metal carboxylate.
Alternatively and in any aspect and embodiment, suitable transition metal compounds may include, essentially consist of or consist of a transition metal halide; alternatively, a transition metal sulfate; alternatively, a transition metal sulfite; alternatively, a transition metal bisulfate; alternatively, a transition metal oxide; alternatively, a transition metal nitrate; alternatively, a transition metal nitrite; alternatively, a transition metal hydroxide; alternatively, a transition metal alkoxide; alternatively, a transition metal aryloxide; alternatively, a transition metal carboxylate; alternatively, a transition metal beta-dionate; alternatively, a transition metal chlorate; or, alternatively, a transition metal amide. In one embodiment, the transition metal halide can be a transition metal chloride; alternatively, a transition metal bromide; or, alternatively, a transition metal iodide.
According to another aspect of disclosure and in any embodiment, each hydrocarbon group (alkoxy or aryloxy), carboxylate group, beta-dionate group, or amide group of the transition metal compound can be a C1 to C24 hydrocarbon group, a C ₄ to C ₁₉ or a C ₅ to C ₁₂ (alkoxy or aryloxy), carboxylate group, beta-dionate group or amide group. In one embodiment, each carboxylate group of the transition metal compound can be a C ₂ to C ₂₄ carboxylate group; alternatively, a C ₄ to C ₁₉ carboxylate group; or, alternatively, a Ci to C5 carboxylate group _2. In some embodiments, each alkoxy group of the transition metal compound may be a C1 to _C24 group; alternatively, a C ₄ to C ₉ alkoxy group; or, alternatively, a C ₅ to C ₂ alkoxy group. In other embodiments, each aryloxy group of the transition metal compound can be a Ce to C ₂₄ alkoxy group; alternatively, a C ₆ to C ₉ alkoxy group; or, alternatively, a Ce to Ci ₂ alkoxy group. In still other embodiments, each beta-dionate group of the transition metal compound can be a C5 to C ₂₄ beta-dionate group; alternatively, a C5 beta-dionate group at
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C ₁₉ ; or, alternatively, a C ₅ to C ₁₂ beta-dionate group - In other embodiments, the amide group of the transition metal compound can be a C 1 to C 24 amide group; alternatively, a C ₃ to Ci® amide group; or, alternatively, a C ₄ to C 12 amide group. In some embodiments, the transition metal carboxylate carboxylate may be monocarboxylate.
In accordance with a further aspect of the present disclosure and, in any embodiment, the transition metal of the transition metal compound can have an oxidation state of 0, +1 (or 1), +2 (or 2), +3 (or 3), +4 (or 4), +5 (or 5), or +6 (or 6), respectively. In another aspect, and in other embodiments, the transition metal compound may have an oxidation state of +2 or +3, or alternatively, the transition metal compound may have an oxidation state of +3, in addition to this aspect, and in any embodiment, the transition metal compound may have an oxidation state of 0, alternatively, +1, alternatively, +2, alternatively, +3, alternatively, +4, alternatively, +5, or alternatively , +6.
In yet another aspect of the present disclosure, the transition metal compound of the oligomerization catalyst system may comprise, consist essentially of, or consist of, a chromium compound. In this respect, the chromium compound may have a chromium oxidation state of 0 to 6, in some embodiments, the chromium in the chromium compound may have an oxidation state of 2 or 3 (ie, a chromium (II ) or chromium (III) compound). In other embodiments, the chromium in the chromium compound can have an oxidation state of 2 (i.e., a chromium compound (II)), or, alternatively, have an oxidation state of 3 (i.e., a chromium compound) (lll)). For example, chromium (II) compounds, compounds that can be used as the transition metal compound for the oligomerization catalyst system may comprise, consist essentially of, or consist of, chromium nitrate (II), chromium sulfate (II), flouride (II), chromium (II) chloride, chromium (II) bromide, or chromium (II) iodide. In addition, by way of example, the chromium (lll) compounds that can be used as the transition metal compound for the oligomerization catalyst system can comprise, consist essentially of, or consist of, chromium nitrate (lll) ), chromium sulfate (lll), chromium flouride (lll), chromium chloride (lll), chromium bromide (lll), or chromium (III) iodide. Alternatively, the chromium compounds that can be used as the transition metal compound for the oligomerization catalyst system can comprise, essentially consist of,
23/74 or consist of chromium (II) nitrate, alternatively, chromium (II) sulfate, alternatively, chromium (li) fluoride, alternatively, chromium (II) chloride, alternatively, chromium (II) bromide , alternatively, chromium (II) iodide, alternatively, chromium (III) nitrate, alternatively, chromium (III) sulphate, alternatively, chromium (III) flouride; alternatively, chromium (III) chloride, alternatively, chromium (III) bromide, or, alternatively, chromium (III) iodide.
In a still further aspect of the present disclosure, and in any event, the transition metal compound for the oligomerization catalyst system comprises, consists essentially of, or consists of, a chromium (II) alkoxide, an ethyl carboxylate of chromium (II), chromium (II) beta-dionate, chromium (III) alkoxide, chromium (III) ethyl carboxylate, or chromium (III) beta-dionate, alternatively, chromium alkoxide (II) or a chromium (III) alkoxide, alternatively, a chromium (II) ethyl carboxylate or a chromium (III) ethyl carboxylate, alternatively, a chromium (II) beta-dionate or a beta-dionate chromium (III), alternatively, a chromium (II) alkoxide, alternatively, a chromium (II) methyl carboxylate; alternatively, chromium (II) betadionate, alternatively, a chromium (III) alkoxide, alternatively, a chromium (III) ethyl carboxylate, or alternatively, a chromium (III) beta-dionate. In one embodiment, each of the carboxylate groups of the chromium compound can be a C ₂ to C ₂ 4 carboxylate group, alternatively, a C ₄ to C19 carboxylate group, or alternatively, a C5 to C ₂ carboxylate group. In some embodiments, each of the alkoxy groups with the chromium compound can be a C1 to C _24, alternatively C ₄ alkoxy group to C19, or, alternatively, an alkoxy group C ₅ to C _2. In other embodiments, each of the aryloxy groups of the chromium compound can be a C ₆ to C ₂₄ aryloxy, alternatively, a C ₆ to C19 aryloxy group, or, alternatively, a C ₆ to C ₁₂ aryloxy group. In yet other embodiments, each of the beta-dionate groups of the chromium compound can be a C ₅ to C ₂₄ beta-dionate group, alternatively, a C ₅ to C19 beta-dionate group, or, alternatively, a beta-dionate group C ₅ to Ci ₂ . In other embodiments, the 0 amide group chromium compound may be an amide group C 1 to C _24, alternatively, a C3 to C19 amide group, or alternatively an amide group C ₂ to C _4.
Chromium carboxylates are the transition metal compounds particularly useful for the oligomerization catalyst system. Thus, in one aspect, the catalyst system and process according to
The present disclosure provides for the use of chromium carboxylate compositions, including, but not limited to, chromium carboxylate compositions in which the carboxylate is a C2 to C ₂ 4 monocarboxylate, alternatively, a C ₄ to C monocarboxylate ₁₉ , or alternatively, a C ₅ to C ₁₂ monocarboxylate. Some widely used chromium carboxylate composition catalysts are those of chromium (III), for example, chromium (III) compositions comprising catalyst components of 2-ethylhexanoate are effective catalyst system components for the synthesis of 1-hexene selective.
In one aspect, the carboxylate group of the chromium carboxylate can be a C2 to C24 monocarboxylate. In one embodiment, the carboxylate group of the chromium carboxylate can be an acetate, a propionate, a butyrate, a pentanoate, a hexanoate, a heptanoate, an octanoate, a nonanoate, a decanoate, an undecanoate, a dodecanoate, a tridecanoate, a tetradecanoate, pentadecanoate, hexadecanoate, heptadecanoate, or octadecanoate, or alternatively, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, or dodecanoate. In some embodiments, the carboxylate group of chromium carboxylate can be 0 acetate, propionate, n-butyrate, isobutyrate, (npentanoate) valerate, neo-pentanoate, capronate (n-hexanoate), n-heptanoate, caprylate (n-octanoate) ), 2-ethylhexanoate, n-nonanoate, caprate (n-decanoate), nundecanoate, laurate (n-dodecanoate), or (n-octadecanoate) stearate, alternatively, (n-pentanoate) valerate, neo- pentanoate, capronate (nhexanoate), n-heptanoate, caprylate (n-octanoate), 2-ethylhexanoate, n-nonanoate, caprate (n-decanoate), n-undecanoate, or laurate (n-dodecanoate); alternatively, acetate, alternatively, ethyl propionate; alternatively, n-butyrate, alternatively, isobutyrate, alternatively, (npentanoate) valerate, alternatively, neo-pentanoate, alternatively, capronate (nhexanoate), alternatively, n-heptanoate, alternatively, caprylate (noctanoate), alternatively, 2-ethyl- hexanoate, alternatively, n-nonanoate, alternatively, caprate (n-decanoate), alternatively, n-undecanoate, alternatively, laurate (n-dodecanoate), or alternatively, (noctadecanoate) stearate.
In one aspect and in any embodiment, the transition metal compound for the oligomerization catalyst system may comprise, essentially consist of or consist of a chromium (II) carboxylate; or,
25/74 alternatively, a chromium carboxylate. Exemplary chromium (ll) carboxylates may include, but are not limited to, chromium acetate (lll), chromium propionate (lll), chromium butyrate (lll), chromium (ll) isobutyrate, chromium (ll) neopentanoate , chromium (ll) oxalate, chromium (ll) octanoate, chromium (ll) ethyl (2-ethylhexanoate), chromium laurate (ll) or chromium stearate (ll); or alternatively, chromium acetate (lll), chromium propionate (lll), chromium butyrate (lll), chromium isobutyrate (ll), chromium neopentanoate (ll), chromium octanoate (ll), (2-ethylhexanoate) of chromium (ll), chromium laurate (ll) or chromium stearate (ll). In one aspect and in any embodiment, the transition metal compound used in the catalyst system may comprise, essentially consist of or consist of, chromium acetate (lll), chromium propionate (lll), chromium butyrate (lll), isobutyrate chromium, chromium neopentanoate (lll), chromium oxalate (lll), chromium octanoate (lll), chromium 2-ethylhexanoate (lll), 2,2,6,6, chromium (III) -tetramethylheptanedionate , chromium (III) naphthenate, chromium laurate (ll) or chromium stearate (ll); or alternatively, chromium acetate (lll), chromium propionate (lll), chromium butyrate (lll), chromium isobutyrate, chromium neopentanoate (lll), chromium octanoate (lll), chromium 2-ethylhexanoate ( III). In a further aspect and in any number of embodiments, the transition metal compound for the oligomerization catalyst system may comprise, consist essentially of, or consist of, chromium acetate (III); alternatively, chromium propionate (ll); alternatively, chromium butyrate (ll); alternatively, chromium (ll) isobutyrate; alternatively, chromium (ll) neopentanoate; alternatively, chromium (ll) oxalate; alternatively, chromium (ll) octanoate; alternatively, chromium (11) (2-ethylhexanoate); alternatively, chromium (ll) laurate; alternatively, chromium (ll) stearate; alternatively, chromium acetate (ll); alternatively, chromium propionate (ll); alternatively, chromium butyrate (ll); alternatively, chromium isobutyrate; alternatively, chromium (lll) neopentanoate; alternatively, chromium oxalate (ll); alternatively, chromium octanoate (ll); alternatively, chromium 2-ethylhexanoate (ll); alternatively, 2,2,6,6, chromium tionramethylheptane (IIli); alternatively, chromium naphthenate (ll); alternatively, chromium laurate (ll); or alternatively, chromium stearate (ll). In some embodiments, the transition metal compound for the oligomerization catalyst system may comprise, consist essentially of or consist of chromium (11) 2-ethylhexanoate or chromium (11) 2-ethylhexanote; or alternatively chromium 2-ethylhexanoate (III).
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Pitrol Compound
In one aspect, the pyrrole compound (also called pyrrole) of the oligomerization catalyst system can comprise, essentially consist of or consist of any pyrrole compound that will react with a chromium source to form a metal pyrrolide complex. transition (eg, chromium pyrrolide complex). As used in the disclosure, the term pyrrole compound refers to pyrrole (C5H5N), pyrrole derivatives (for example, indole), substituted pyrroles, as well as metal pyrrolide complexes. A pyrrole compound is defined as a compound comprising a nitrogen-containing heterocyclyl, of 5 elements such as, for example, pyrrole, pyrrole derivatives and mixtures thereof. Generally speaking, the pyrrole compound can be pyrrole or any heteroleptic or homoleptic metal complex or salt containing a pyrrolide radical or binder.
Generally, the pyrrole compound can be a C4 to C20 pyrrole, or C4 to C10. Exemplary pyrrole compounds that can be used in the oligomerization catalyst system include, but are not limited to, pyrrole-2-carboxylic acid, 2-acetylpyrrole, pyrrole-2-carboxaldehyde, tetrahydroindole, 2,5-dimethylpyrrole, 2,4- dimethyl-3-ethylpyrrole, 3-acetyl-2,4-dimethylpyrrole, ethyl-2,4-dimethyl-5- (ethoxycarbonyl) -3pyrrol-propionate, ethyl-3,5-dimethyl-2-pyrrolecarboxylate, pyrrole, 2, 5-dimethylpyrrole, 3,4-dimethylpyrrole, 3,4-dichloropyrrole, 2,5-diethylpyrrole, 2-methyl-5-ethylpyrrole, 2-methyl-5propylpyrrole, 2,3,4,5-tetrachloropyrrole, 2-acetylpyrrole, pyrazole, pyrrolidine, indole, and dipyrrolmethane, and mixtures thereof, among others. Pyrrolides that can be used as a nitrogen compound include 2,5-dimethylpyrrolide diethyl aluminum; di (2,5-dimethylpyrrolid) ethyl aluminum; and tri (2,5-dimethylpyrrolid) aluminum; among others.
In one aspect, the pyrrole compound may have Formula P1 or Formula 11. In one embodiment, the pyrrole compound may have Formula P1; or alternatively Formula 11.

In one aspect, R ^2p , R ^3p , R ^4p , and R ^5p of Formula P1 and R ²ⁱ , R ³ⁱ , R ⁴ⁱ , R ⁵ⁱ , R ⁶ⁱ , and R ⁷ 'of Formula 11 can independently be a hydrogen, a group organyl Ci to C ₁₈ , or silyl group C3 to C6ol alternatively, hydrogen, an organyl group
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Ci to Ci ₅ , or a C3 to C45 silyl group; alternatively, hydrogen, a C1 to C10 organyl group, or a C ₃ to C30 silyl group; alternatively, hydrogen, a C5 organyl group, or C ₃ to C ₁₅ silyl group; alternatively, hydrogen or an organyl group C1 to C ₁₈ ; alternatively, hydrogen or an organyl group C1 to C ₁₅ ; alternatively, hydrogen or an organyl group C-ι to Cw; or alternatively, hydrogen or an organyl group C1 to C ₅ . In one embodiment, R ^2p , R ^3p , R ^4p , and R ^5p of Formula P1 and R ²ⁱ , R ³ⁱ , R ⁴ⁱ , R ⁵ⁱ , R ⁶ⁱ , and R ⁷ⁱ of Formula 11 can be independently a hydrogen, a hydrocarbyl group C1 to C ₁₈ , or a C ₃ to Ceo silyl group! alternatively, hydrogen, a C1 to C ₁₅ hydrocarbyl group, or a C ₃ to C ₄₅ silyl group; alternatively, hydrogen, a C1 to C10 hydrocarbyl group, or a C ₃ to C ₃₅ silyl group; alternatively, hydrogen, a C1 to C5 hydrocarbyl group, or a C ₃ to C15 silyl group; alternatively, hydrogen or a C1 to Ci ₈ hydrocarbyl group; alternatively, hydrogen or a C1 to C ₁₅ hydrocarbyl group; alternatively, hydrogen or a C1 to C10 hydrocarbyl group; or alternatively, hydrogen or a C ₅ hydrocarbyl group.
In an embodiment where the pyrrole compound has the formula P1, R ^3p and R ^4p can be hydrogen and R ^2p and R ^5p can be any non-hydrogen pyrrole substituent described herein; alternatively, R ^2p and R ^5p can be hydrogen and R ^3p and R ^4p can be any non-hydrogen pyrrole substituent described herein; or, alternatively, R ^2p and R ^4p can be hydrogen and R ^3p and R ^5p can be any non-hydrogen pyrrole substituent described herein. In some embodiments, R ^2p , R ^3p and R ^5p can be hydrogen and R ^4p can be any non-hydrogen pyrrole substituent described here; alternatively, R ^2p , R ^3p and R ^4p can be hydrogen and R ^5p can be any non-hydrogen pyrrole substituent described herein; or alternatively, R ^2p can be hydrogen and R ^3p , R4p, and R ^5p can be any non-hydrogen substituent described. In other embodiments, R ^2p , R ^3p , R ^4p and R ^5p can be any non-hydrogen pyrrole substituent described herein.
In one embodiment, each non-hydrogen group, which can be used as R ^2p , R ^3p , R ^4p , and / or R ^5p of the formula P1 and R ²ⁱ , R ³ⁱ , R ⁴ⁱ , R ⁵ⁱ , R ⁶ⁱ , and / or R ⁷ⁱ of formula 11 independently can be an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aromatic group, a substituted aromatic group, an aryl group, a substituted aryl group, an aralkyl group , a substituted aralkyl group, or a silyl group. In other modalities, each non-hydrogen group, which can be used as R ^2p , R ^3p , R ^4p , and / or R ^5p of the formula P1 and R ²ⁱ , R ³ⁱ , R ⁴ⁱ , R ⁵ⁱ , R ⁶ⁱ , and / or R ⁷ⁱ of
Formula 11 may independently be an alkyl group; alternatively, a substituted alkyl group; alternatively, a cycloalkyl group; alternatively, a substituted cycloalkyl group; alternatively, an aromatic group; alternatively, a substituted aromatic group; alternatively, an aryl group; alternatively, a substituted aryl group; alternatively, an aralkyl group; alternatively, a substituted aralkyl group; or, alternatively, a silyl group. Generally, alkyl group, substituted alkyl group, cycloalkyl group, substituted cycloalkyl group, aromatic group, substituted aromatic group, aryl group, substituted aryl group, aralkyl group, substituted aralkyl group, and / or silyl group, which can be used as non-hydrogen R ^2p , R ^3p , R ^4p , and / or R ^5p group of formula P1 or non-hydrogen group R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula 11 can have the same number of carbons as their respective organyl group, hydrocarbyl group, or silyl group that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or non-hydrocarbonyl group R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula 11 disclosed herein.
In one embodiment, each alkyl group, which can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a non-hydrogen group R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula 11 can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group , an octyl group, a nonyl group, a decila group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group or a nonadecyl group; or, alternatively, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group or a decyl group. In some embodiments, each alkyl group that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a non-hydrogen group R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula 11 can be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso group -butyl, a sec-butyl group, a tert-butyl group, an n-pentyl group, an iso-pentyl group, a sec-pentyl group or a neopentyl group; alternatively, a methyl group, an ethyl group, an iso-propyl group, a tert-butyl group or a neopentyl group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, an n-propyl group; alternatively, an isopropyl group; alternatively, a tert-butyl group; or, alternatively, a group
29/74 neopentilla. In one embodiment, any of these alkyl groups can be substituted with a halide, or hydrocarbon group to form the substituted alkyl group that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a non-hydrogen group R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula 11. Halides and substituted hydrocarbon groups are disclosed herein and may be used without limitation to better describe the substituted alkyl group that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a non-hydrogen group R ² ', R ³ ', R ⁴ ', R ⁵ⁱ , R ⁶ⁱ , and / or R ⁷ 'of Formula 11.
In one embodiment, the substituted cycloalkyl or cycloalkyl group that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a group of non-hydrogen R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ 'of Formula 11 can be a chloroform group, a substituted chloroform group, a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, a substituted cyclohexyl group, a cycloheptyl group, a substituted cycloheptyl group, a cyclooctyl group or a substituted cyclooctyl group. In some embodiments, the cycloalkyl group, substituted cycloalkyl group that can be used as a non-hydrogen group R2 _P , R3p, R4p, and / or Rs _p of Formula P1 or non-hydrogen group R ² ', R ³ ' , R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula 11 can be a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group or a substituted cyclohexyl group. In other embodiments, the cycloalkyl or substituted cycloalkyl group that can be used a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or non-hydrogen group R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷¹ of Formula 11 can be a chloroform group or a substituted chloroform group; alternatively, a cyclopentyl group or a substituted cyclopentyl group; alternatively, a cyclohexyl group or a substituted cyclohexyl group; alternatively, a cycloheptyl group or a substituted cycloheptyl group; or, alternatively, a cyclooctyl group, or a substituted cyclooctyl group. In additional embodiments, the cycloalkyl group or substituted cycloalkyl group that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or non-hydrogen group R ² ', R ³ ' , R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula 11 can be a cyclopentyl group; alternatively, a substituted cyclopentyl group; a cyclohexyl group; or, alternatively, a substituted cyclohexyl group. Substituents that can be used for independently substituted cycloalkyl groups are disclosed in this document and can be used without limitation to describe
30/74 better substituted cycloalkyl group that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or non-hydrogen group R ² ', R ³ ', R ⁴ ' , R ⁵ ', R ⁶ ', and / or R ⁷ 'of Formula 11. In one aspect, the aryl group (s) that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a non-hydrogen group R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula can be a phenyl group, a substituted phenyl group, a naphthyl group, or a substituted naphthyl group. In one embodiment, the aryl group (s) that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a group of non-hydrogen R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ 'of Formula 11 can be a phenyl group, a substituted phenyl group, alternatively a naphthyl group or substituted naphthyl group; alternatively, a phenyl or naphthyl group; or alternatively, a substituted phenyl group or a substituted naphthyl group. Substituents that can be used for substituted phenyl groups or independent substituted naphthyl groups are disclosed here and can be used without limitation to describe substituted phenyl groups or substituted naphthyl groups that can be used as non-hydrogen groups R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or non-hydrogen group R ²ⁱ , R ^3í , R ^4í , R ^5í , R ^6í , and / or R ⁷ⁱ of Formula 11.
In one embodiment, the substituted phenyl group that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a group of non-hydrogen R ² ', R ³ ' , R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula 11 can be a substituted phenyl group 2, a substituted phenyl group 3, a substituted phenyl group 4, a disubstituted phenyl group 2,4, a disubstituted phenyl group 2,6, a disubstituted phenyl group 3,5, or a tri-substituted phenyl group 2,4,6. In other embodiments, the substituted phenyl group, which can be used with a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a group of non-hydrogen R ² ', R ³ ' , R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula 11 can be a substituted phenyl group 2, a substituted phenyl group 4, a disubstituted phenyl group 2,4 or a disubstituted phenyl group 2, 6; alternatively, a substituted phenyl group 3 or disubstituted phenyl group 3,5; alternatively, a substituted phenyl group or a substituted phenyl group 4; alternatively, a disubstituted phenyl group 2,4 or disubstituted phenyl group 2,6; alternatively, a substituted phenyl group 2; alternatively, a substituted phenyl group 3; alternatively, a substituted phenyl group 4; alternatively, a disubstituted phenyl group 2,4; alternatively, a disubstituted phenyl group 2,6; alternatively, disubstituted phenyl group 3,5; or, alternatively, a group
31/74 trisubstituted phenyl 2,4,6. Substituents that can be used for these specific substituted phenyl groups independently are disclosed in this document and can be used without limitation to describe these substituted phenyl groups, which can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or non-hydrogen group R ² ', R ³ ', R ⁴ ', R5i, R ⁶ ', and / or R ⁷ 'of Formula 11.
In one respect, the aralkyl group that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a non-hydrogen group R ² ', R ³ ', R ⁴ ' , R ⁵ ', R ⁶ ', and / or R ⁷ 'of Formula 11 can be a substituted benzyl group. In one embodiment, the aralkyl group that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a non-hydrogen group R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula 11 can be a benzyl group; or, alternatively, a substituted benzyl group. Substituents that can be used for independently substituted aralkyl groups are disclosed in this document and can be used without limitation to describe substituted aralkyl groups that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or non-hydrogen group R ²ⁱ , R ^3í , R ^4í , R ^5í , R ^6í , and / or R ⁷ⁱ of Formula 11.
In one aspect, the trimethylsilyl groups that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a group of non-hydrogen R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula 11 can have Formula Si1.
Generally, R ^s1 , R ^s2 and R ^s3 of the silyl group having Formula S ' ¹ p1s
_R 2s_s— * r ^{3s /}
Si1 can independently be an organyl group or a hydrocarbyl group; alternatively, an organila group; or alternatively, a hydrocarbyl group. Generally, the organyl group and / or the hydrocarbyl groups that can be used as R ^s1 and R ^s2 R ^s3 of the silyl group having Formula Si1 can have any number of carbon such as the organyl groups and hydrocarbyl groups that can be used as substituents for non-hydrogen pyrrole described herein. In one embodiment, R ^s1 and R ^s2 R ^s3 of the silyl group having Formula Si1 can independently be an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aromatic group, a substituted aromatic group, a group arila, a substituted arila group, a group
32/74 aralkyl or a substituted aralkyl group; alternatively, an alkyl group; alternatively, a substituted alkyl group; alternatively, a cycloalkyl group; alternatively, a substituted cycloalkyl group; alternatively, an aromatic group; alternatively, a substituted aromatic group; alternatively, an aryl group; alternatively, a substituted aryl group; alternatively, an aralkyl group; or, alternatively, a substituted aralkyl group. Alkyl groups, substituted alkyl groups, cycloalkyl groups, substituted cycloalkyl groups, aromatic groups, substituted aromatic groups, aryl groups, substituted aryl groups, aralkyl groups and substituted aralkyl groups have been independently described herein as potential non-hydrogen pyrrole substituents and can be used, without limitation, as the silyl group R ^s1 and R ^s2 R ^s3 having Formula Si1.
In one embodiment, each non-hydrogen substitute (s) for the substituted cycloalkyl group, substituted aromatic group, substituted aryl group or substituted aralkyl group that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a non-hydrogen group R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula 11 independently can be a halide, a hydrocarbyl group Ci to C10, or a Ci to Cw hydrocarbon group; alternatively, a halide or a hydrocarbyl group C1 to Cw; alternatively, a C1 to C10 halide or hydrocarbon group; alternatively, a Ci to Cw hydrocarbyl group or a Ci to Cw hydrocarbon group! alternatively, a halide; alternatively, a C1 to C10 hydrocarbyl group; or, alternatively, a Ci to Cw hydrocarbon group - In some embodiments, each non-hydrogen substituent (s) for the substituted cycloalkyl group, substituted aromatic group, substituted aryl group, or substituted aralkyl group that can be used as a non-group -hydrogen R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a group of non-hydrogen R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ 'of Formula 11 independently may be a halide, a Ct to C5 hydrocarbyl group, or a C1 to C5 hydrocarbon group; alternatively, a C1 to C5 halide or hydrocarbyl group;
alternatively, a C1 to C5 halide or hydrocarbon group; alternatively, a hydrocarbyl group _C1-C5 or hydrocarboxy group C1 to C5;
alternatively, a halide; alternatively, a C1 to C5 hydrocarbyl group; or, alternatively, a C1 to C5 hydrocarbon group. Specific substituent halides, hydrocarbyl groups, and hydrocarbon groups independently are disclosed in this document and can be used without limitation to better describe the substituents on the substituted cycloalkyl groups, aromatic groups
33/74 substituted, substituted aryl groups or substituted aralkyl groups that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a group of non-hydrogen R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ 'of Formula 11.
In one embodiment, any halide substituent of a substituted alkyl group (general or specific), substituted cycloalkyl group (general or specific), substituted aromatic group (general or specific), substituted aryl group (general or specific) or substituted aralkyl group can be a flouride, chloride, bromide, or iodide; alternatively, a fluorine or a chloride. In some embodiments, any halide substituent of a substituted alkyl group (general or specific), substituted cycloalkyl group (general or specific), substituted aromatic group (general or specific), substituted aryl group (general or specific), or substituted aralkyl group it can be a floureto; alternatively, a chloride; alternatively, a bromide; or alternatively, an iodide.
In one embodiment, any hydrocarbyl substituent of a substituted cycloalkyl group (general or specific), substituted aromatic group (general of specific), substituted aryl group (general or specific), or substituted aralkyl group, can be an alkyl group, a group aryl or an aralkyl group; alternatively, an alkyl group; alternatively, an aryl group; or alternatively, an aralkyl group. Generally, the alkyl, aryl and aralkyl substituent groups may have the same number of carbon atoms as the hydrocarbyl substituent group disclosed herein. In one embodiment, any alkyl substituent of a substituted cycloalkyl group (general or specific), substituted aromatic group (general or specific), substituted aryl group (general or specific), or substituted aralkyl group can be a methyl group, an ethyl group , an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group , a 2-methyl-1-butyl group, a terpentyl group, a 3-methyl-1-butyl group, a 3-methyl-2-butyl group or a neopentyl group; alternatively, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or a neo-pentyl group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, an isopropyl group; alternatively, a tert-butyl group; or, alternatively, a neopentyl group. In one embodiment, any aryl substituent from a substituted cycloalkyl group (general or specific), substituted aromatic group (general or specific), substituted aryl group (general or specific) or aralkyl group
34/74 be a phenyl group, a tolyl group, a xylyl group or a 2,4,6-trimethylphenyl group; alternatively, a phenyl group; alternatively, a tolyl group, alternatively, a xylyl group; or, alternatively, a 2,4,6-trimethylphenyl group. In one embodiment, any aralkyl substituent of a substituted cycloalkyl group (general or specific), substituted aromatic group (general or specific), substituted aryl group (general or specific), or substituted aralkyl group can be benzyl group.
In one embodiment, any hydrocarbon substituent of a substituted alkyl group (general or specific), substituted cycloalkyl group (general or specific), substituted aromatic group (general or specific), substituted aryl group (general or specific) or substituted aralkyl group can be an alkoxy group, an aryloxy group or an aralkoxy group; alternatively, an alkoxy group; alternatively, an aryloxy group; or, alternatively, an aralkoxy group. Generally, the alkoxy, aryloxy and aralkoxy substituent groups may have the same number of carbon atoms as the hydrocarbon substituent group disclosed in this document. In one embodiment, any substituent on a substituted alkyl group (general or specific), substituted cycloalkyl group (general or specific), the substituted aromatic group (general or specific), the substituted aryl group (general or specific) or substituted aralkyl group can be a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentoxy group, a 2-pentoxy group , a 3-pentoxy group, a 2-methyl-1-butoxy group, a tert-pentoxy group, a 3-methyl-1-butoxy group, a 3-methyl-2-butoxy group or a neo-pentoxy group; alternatively, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group or a neo-pentoxy group; alternatively, a methoxy group; alternatively, an ethoxy group; alternatively, an isopropoxy group; alternatively, a tert-butoxy group; or alternatively, a neopentoxy. In one embodiment, any aroxy substituent of a substituted alkyl group (general or specific), substituted cycloalkyl group (general or specific), substituted aromatic group (general or specific), substituted aryl group (general or specific) or substituted aralkyl group can be a phenoxy group, a toloxy group, a xyloxy group, or a 2,4,6-trimethylphenoxy group; alternatively, a phenoxy group; alternatively, a toloxy group, alternatively, a xyloxy group; or, alternatively, a 2,4,6-trimethylphenoxy group. In one embodiment, any aralkoxy substituent of a substituted alkyl group (general or specific), substituted cycloalkyl group (general or
35/74 specific), the substituted aromatic group (general or specific), substituted aryl group (general or specific) or substituted aralkyl group can be benzoxy group.
In one embodiment, each silyl group, which can be used as a group of non-hydrogen R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a group of non-hydrogen R ² ', R ³ ' , R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula 11 can be a trihydrocarbylsilyl group. In some embodiments, each silyl group that can be used as a non-hydrogen group R ^2p , R ^3p , R ^4p , and / or R ^5p of Formula P1 or a non-hydrogen group R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', and / or R ⁷ ' of Formula 11 can be a trialkylsilyl group, a triphenylsilyl group, or a tri (substituted phenyl) silyl group; alternatively, a trialkylsilyl group; alternatively, a triphenylsilyl group; or, alternatively, a tri (substituted phenyl) silyl group. Hydrocarbyl groups, alkyl groups, and substituted phenyl groups have been described independently in this document as non-hydrogen pyrrole substituents and can be used, without limitation, as R ^s1 , R ^s2 , and R ^s3 of the silyl group having the silyl group.
In one embodiment, the pyrrole compound can comprise, essentially consist of, or consist of, a pyrrole compound having a C1 to C1 group attached to positions 2 and 5 of the pyrrole. Unless otherwise specified, the pyrrole compound having a Ci to Ci _{8 group} attached to positions 2 and 5, and, may have groups attached to positions 1, 3, and / or 4. In one embodiment, the pyrrole compound of the oligomerization catalyst system can be a 2,5-disubstituted pyrrole compound, that is, the pyrrole compound has substituents only at positions 2 and 5. Regardless of whether or not the pyrrole compound has substituents present at positions 1, 3, and / or 4, the groups attached to positions 2 and 5 and the pyrrole compound can be the same or different. For example, 2,5-dimethyl pyrrole, 2-ethyl-5-methyl pyrrole and 2-ethyl-5-propyl pyrrole are among the 2,5-disubstituted pyrrole suitable for use in the catalyst system and methods of this disclosure. In other aspects and embodiments, the groups attached to positions 2 and 5 of the pyrrole compound can be the same. Generally, the groups attached to positions 2 and 5 of the pyrrole compound can be any substituent pyrrole group disclosed herein.
In a certain non-limiting embodiment, the pyrrole compound may have C ₂ to C ₈ organyl groups linked at positions 2 and 5 of the pyrrole ring. In other embodiments, the groups linked at positions 2 and 5 of the pyrrole ring independently may be C ₂ to C- | ₂ , or alternatively, C ₂ to C ₈ organyl groups. In other specific, non-limiting modalities,
36/74 groups linked positions at 2 and 5 of the pyrrole ring independently can be hydrocarbyl groups C ₂ to C- | ₈ ; alternatively, hydrocarbyl groups C ₂ to C ₁₂ ; or, alternatively, C ₂ to C ₈ hydrocarbyl groups. In yet other specific non-limiting embodiments, the groups linked at positions 2 and 5 of the pyrrole ring independently can be C ₂ to C ₈ alkyl groups; alternatively, C ₂ to C ₁₂ alkyl groups; or, alternatively, C ₂ to C ₈ alkyl groups.
In one aspect, the groups attached at positions 2 and 5 of the pyrrole ring are attached to the pyrrole ring in such a way that at least one carbon atom attached to positions 2 and 5 of the pyrrole ring is a secondary carbon atom; alternatively, the groups attached to positions 2 and 5 of the pyrrole ring are attached to the pyrrole ring in such a way that both carbon atoms attached to positions 2 and 5 of the pyrrole ring are secondary carbon atoms. That is, when the carbon atom of the group attached to the pyrrole ring is a secondary carbon atom, that secondary carbon is attached to one and only one, another carbon atom in addition to the carbon atom of the pyrrole ring. In some embodiments, the groups attached to positions 2 and 5 are linked in such a way that the carbon atoms attached to positions 2 and 5 of the pyrrole ring are secondary carbon atoms, and the groups are branched. In other embodiments, the groups attached to positions 2 and 5 of the pyrrole ring can be linear. In one embodiment, an ethylene trimerization process using a catalyst system using a pyrrole compound or comprising groups attached to positions 2 and 5 of the pyrrole ring, and in which groups attached to positions 2 and 5 are attached to the ring pyrrole such that at least one carbon atom attached to positions 2 and 5 of the pyrrole ring is a secondary carbon atom that can provide greater selectivity for 1-hexene than the process using 2,5-dimethylpyrrole as the compound of pyrrole provides a higher purity 1hexene product than the process using 2,5-dimethylpyrrole as the pyrrole compound. In another embodiment, an ethylene trimerization process using a catalyst system using a pyrrole compound, or comprising groups attached to positions 2 and 5 of the pyrrole ring, and in which groups attached to positions 2 and 5 are attached to the ring of pyrrole such that at least one carbon atom attached to positions 2 and 5 of the pyrrole ring is a secondary carbon atom that can provide greater selectivity for 1-hexene than the process using 2,5-dimethylpyrrole as the compound pyrrole and / or provide a higher purity 1-hexene product than the process using 2,5-dimethylpyrrole as the pyrrole compound.
37/74
In an embodiment where the carbon atom of one of the groups attached to positions 2 and 5 of the pyrrole ring is a secondary carbon atom, the groups attached to position 2 and / or position 5 independently can be an ethyl group, a group n-propyl, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group or an n-octyl group; alternatively, an ethyl group, an n-propyl group, an n-butyl group or an n-pentyl group; alternatively, an ethyl group; alternatively, an n-propyl group; alternatively, an n-butyl group; alternatively, an n-pentyl group; alternatively, an n-hexyl group; alternatively, a non-heptyl group; or, alternatively, a non-octyl group. For example, the pyrrole compound can be a 2,5-disubstituted pyrrole, such as 2,5-diethyl pyrrole.
In one aspect, the pyrrole may have the formula P1, in which R ^2p and R ^5p independently are any group disclosed in this document and in which at least one of the groups attached to positions 2 and 5 is attached in a form in which the atom of carbon attached to the pyrrole ring is a secondary carbon atom and R ^3p and R ^4p independently are hydrogen and any non-hydrogen pyrrole substituent disclosed here; alternatively, R ^2p and R ^5p independently are any group disclosed herein and in which at least one of the groups attached to positions 2 and 5 is attached in a form in which the carbon atom attached to the pyrrole ring is a secondary carbon atom and R ^3p and R ^4p are hydrogen. In another aspect, R ^2p and R ^5p independently are any group disclosed here each of the groups attached to positions 2 and 5 is attached in a way in which the carbon atom attached to the pyrrole ring is a secondary carbon atom and R ^3p and R ^4p independently are hydrogen and any non-hydrogen pyrrole substituent disclosed here; alternatively, R ^2p and R ^5p independently are any group disclosed here in which the groups attached to positions 2 and 5 are linked in a way in which the carbon atom attached to the pyrrole ring are secondary carbon atoms and R ^3p and R ^4p are hydrogen.
In some non-limiting modalities where the groups attached to positions 2 and 5 are linked in such a way that at least one (or alternatively both) of the carbon atoms attached to the pyrrole ring are secondary carbons, the pyrrole compound can be a 2, 5-dialkylpyrrole, a
2,3,5-trialkylpyrrole, 2,4,5-trialkylpyrrole, 2,3,4,5-tetraalkylpyrrole, or any combination thereof; alternatively, a 2,5-dialkylpyrrole;
38/74 alternatively, a 2,3,5-trialkylpyrrole; alternatively, a 2,4,5-trialkylpyrrole; or, alternatively, a 2,3,4,5-tetraalkylpyrrole.
In some non-limiting embodiments in which the groups attached to positions 2 and 5 are linked in such a way that at least one (or alternatively both) of the carbon atoms attached to the pyrrole ring are secondary carbons, the compound of may be 2-methyl -5-ethylpyrrole, 2,5-diethylpyrrole,
2.5- di-n-propylpyrrole, 2,5-di-n-butylpyrrole, 2,5-di-n-pentylpyrrole, 2,5-di-n-hexylpyrrole, 2,5di-n-heptylpyrrole, 2,5- di-n-octylpyrrole, 2,3,5-triethylpyrrole, 2,3,5-tri-n-butylpyrrole, 2,3,5-trin-pentylpyrrole, 2,3,5-tri-n-hexylpyrrole, 2, 3,5-tri-n-heptylpyrrole, 2,3,5-tri-n-octylpyrrole,
2.3.4.5- tetraethylpyrrole, 2,3,4,5-tetra-n-butylpyrrole, 2,3,4,5-tetra-n-hexylpyrrole, 2,5bis (2 ', 2', 2 ^l -triflouroethyl) pyrrole , 2,5-bis (2'-methoxymethyl) pyrrole or any combination thereof; alternatively, 2-methyl-5-ethylpyrrole, 2,5-diethylpyrrole, 2,5-di-n-propylpyrrole, 2,5-di-n-butylpyrrole, 2,5-di-n-pentylpyrrole, 2,5-di- n-hexylpyrrole, 2,5-di-nheptylpyrrole, 2,5-di-n-octylpyrrole or any combination thereof; alternatively, 2-methyl-5-ethylpyrrole; alternatively, 2,5-diethylpyrrole; alternatively, 2,5-di-n-propylpyrrole; alternatively, 2,5-di-n-butylpyrrole; alternatively, 2,5-di-n-pentylpyrrole; alternatively, 2,5-n-hexylpyrrole; alternatively, 2,5-di-n-heptylpyrrole; or, alternatively, 2,5-di-n-octylpyrrole.
In one aspect, the pyrrole compound may have a hydrogen atom located on at least one pyrrole ring carbon atom adjacent to the pyrrole ring nitrogen atom and a bulky group located on an adjacent pyrrole ring carbon atom to any carbon atom of the pyrrole ring having the hydrogen atom adjacent to the nitrogen atom of the pyrrole ring; alternatively, it has a hydrogen atom located on each carbon atom of the pyrrole ring adjacent to the nitrogen atom of the pyrrole ring and a bulky group located on each carbon atom of the pyrrole ring adjacent to the carbon atoms of the pyrrole ring having the hydrogen atom adjacent to the nitrogen atom of the pyrrole ring. Generally, each group in this regard can be any group described in this document and have any number of carbons described that meets the requirements of the pyrrole compound. For example, any non-hydrogen pyrrole group located on a pyrrole ring carbon atom adjacent to the pyrrole ring nitrogen atom and any non-hydrogen pyrrole group located on a pyrrole ring carbon atom adjacent to a carbon atom of the pyrrole ring having a non-hydrogen pyrrole group on a carbon atom of the pyrrole ring adjacent to the nitrogen atom of the pyrrole ring can be any organyl group Ci a Cis, Ci a
39/74
C ₁₅ , Ci to Cio or Ci to C5 (alternatively any hydrocarbyl group) described herein, while the group located on a pyrrole ring carbon atom adjacent to a pyrrole ring carbon atom having 0 hydrogen atom which is adjacent the nitrogen atom of the pyrrole ring may be any bulky C3 to Cw, C3 to C15, C3 to Cw, or C3 to C5 (alternatively any hydrocarbyl) group described herein. In one aspect, each bulky substituent may be a triorganylsilyl group, or, alternatively, a trihydrocarbylsilyl group. Generally, the triorganylsilyl group and / or the trihydrocarbylsilyl group can have the same number of carbon atoms as the silyl group 0 which can be used as a pyrrole substituent described herein. In one embodiment, each bulky substituent may be a trialkylsilyl group, a triphenylsilyl group or a tri (substituted phenyl) silyl group, alternatively a trialkylsilyl group, alternatively a triphenylsilyl group, or alternatively, a tri (substituted phenyl) group.
In one aspect, the pyrrole compound can be a pyrrole compound having Formula P2, Formula P3, Formula P4, or a combination thereof, alternatively, Formula P2; alternatively Formula P3; alternatively Formula P4. In one mode, R ^12p and R ^13p of

Formula P2 and R ^22p of Formula P3 can be any pyrrole substituting group disclosed herein while R ^14p of Formula P2, R ^24p of Formula P3, and R ^33p and R ^34p of Formula P4 can be any bulky pyrrole substituent disclosed here. For example, R ^12p and R ^13p of Formula P2 and R ^23p of Formula P3 can be any C1 to Cw, C1 to C15, θι θ Cio, or C1 to C5 (alternatively, any hydrocarbyl) group described herein as R ^14P of Formula P2, R ^22p of Formula P3, and R ^33P and R ^34p of Formula P4 can be any bulky C ₃ to Cw, C ₃ to Cw, C ₃ to C ₁₀ , or C ₃ to C ₅ (alternatively, any hydrocarbyl group) described herein. In one aspect, each bulky substituent may be a triorganylsilyl group, or, alternatively, a trihydrocarbylsilyl group.
40/74
In one embodiment, the bulky pyrrole substituent can be defined as one in which the carbon atom of the bulky group that is attached to the carbon atom of the pyrrole ring is a tertiary or quaternary carbon atom or one in which the carbon atom the bulky group that is adjacent to the carbon atom attached to the carbon atom of the pyrrole ring is a tertiary or quaternary carbon atom; alternatively one in which the carbon atom of the bulky group which is attached to the carbon atom of the pyrrole ring is a tertiary or quaternary carbon atom, or alternatively one in which the carbon atom of the bulky group which is adjacent to the atom of carbon attached to the carbon atom of the pyrrole ring is a tertiary or quaternary carbon atom. In some embodiments, the bulky pyrrole substituent can be defined as one in which the carbon atom in the bulky group that is attached to the carbon atom in the pyrrole ring is a tertiary carbon atom or one in which the carbon atom in the group bulky which is adjacent to the carbon atom attached to the carbon atom of the pyrrole ring is a tertiary carbon atom, alternatively, in which a carbon atom of the bulky group that is attached to the carbon atom of the pyrrole ring is an atom of tertiary carbon, or, alternatively, one in which the carbon atom of the bulky group that is adjacent to the carbon atom attached to the carbon atom of the pyrrole ring is a tertiary carbon atom. In other embodiments, the bulky pyrrole substituent can be defined as one in which the carbon atom of the bulky group that is attached to the carbon atom of the pyrrole ring is a quaternary carbon atom or one in which the carbon atom of the group roughage which is adjacent to the carbon atom attached to the carbon atom of the pyrrole ring is a quaternary carbon atom, alternatively, in which a carbon atom of the bulky group which is attached to the carbon atom of the pyrrole ring is a carbon atom quaternary, or, alternatively, one in which the carbon atom of the bulky group that is adjacent to the carbon atom attached to the carbon atom of the pyrrole ring is a quaternary carbon atom.
In another embodiment, the bulky pyrrole substituent can be defined as one in which the carbon atom of the bulky group that is attached to the carbon atom in the pyrrole ring is attached to 3 or 4 carbon atoms or one in which the carbon of the bulky group which is adjacent to the carbon atom attached to the carbon atom of the pyrrole ring is bonded to 3 or 4 carbon atoms, alternatively, where one carbon atom of the bulky group
41/74 which is attached to the carbon atom of the pyrrole ring is attached to 3 or 4 carbon atoms, or alternatively, one in which the carbon atom of the bulky group which is adjacent to the carbon atom attached to the carbon atom of the pyrrole ring is attached to 3 or 4 carbon atoms. In some embodiments, the bulky pyrrole substituent can be defined as one in which the carbon atom of the bulky group that is attached to the carbon atom of the pyrrole ring is attached to 3 carbon atoms or one in which the carbon atom of the bulky group that is adjacent to the carbon atom attached to the carbon atom of the pyrrole ring is linked to 3 carbon atoms, alternatively, where a carbon atom of the bulky group that is attached to the carbon atom of the pyrrole ring is attached to 3 carbon atoms, or, alternatively, one in which the carbon atom of the bulky group which is adjacent to the carbon atom attached to the carbon atom of the pyrrole ring is attached to 3 carbon atoms. In other embodiments, the bulky pyrrole substituent can be defined as one in which the carbon atom of the bulky group that is attached to the carbon atom of the pyrrole ring is attached to 4 carbon atoms or one in which the carbon atom of the bulky group that is adjacent to the carbon atom attached to the carbon atom of the pyrrole ring is linked to 4 carbon atoms, alternatively, where a carbon atom of the bulky group that is attached to the carbon atom of the pyrrole ring is attached to 4 carbon atoms, or, alternatively, one in which the carbon atom of the bulky group that is adjacent to the carbon atom attached to the carbon atom of the pyrrole ring is attached to 4 carbon atoms.
For purposes of illustration, Formula E1 is used to illustrate the carbon atom attached to the pyrrole ring and the carbon atom adjacent to the carbon atom attached to the carbon atom of the pyrrole ring.
Using Formula E1, the carbon atom marked 1 in the group attached to the pyrrole ring represents the carbon atom attached to the carbon atom in the pyrrole ring, while the carbon atom 2 marked in the group attached to the pyrrole ring represents the atom of carbon adjacent to the carbon atom attached to the
42/74 carbon atom of the pyrrole ring. In one embodiment, a bulky silyl group is one in which the silicon atom of the bulky silyl group attached to the carbon of the pyrrole ring is attached to four carbon atoms.
In one embodiment, the bulky substituent may independently be an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aromatic group, a substituted aromatic group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, or a silyl group. In general, the alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aromatic group, a substituted aromatic group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, and an silyl group that can be used as a bulky substituent can have the same number of carbon atoms as the bulky (or hydrocarbyl) pyrrole substituent described herein. Alkyl groups, substituted alkyl groups, substituted cycloalkyl groups, cycloalkyl groups, aromatic groups, substituted aromatic groups, aryl groups, substituted aryl groups, aralkyl groups, substituted aralkyl groups, and silyl groups are generally those described here that meet the criteria for that a bulky substituent can be used, without limitation, to further describe the pyrrole compound that can be used in some aspects and embodiments described herein.
In one embodiment, each bulky substituent may independently be a propan-2-yl group, a butan-2-yl group, a 2-methylpropan-1-yl group, a 2-methylpropan-2-yl group, a pentan-2-yl group , a pentan-3-yl group, a 2-methylbutan-1-yl group, a 2-methylbutan-2-yl group, a 3-methylbutan-2-yl group, a 2,2-dimethylpropan-1-yl group , a hexan-2-yl group, a hexan-3-yl group, a 2-methylpentan-1-yl group, a 2-ethylbutan-1-yl group, a 2-methylpentan-2-yl group, a group 2 , 3-dimethylbutan-1-yl, a 2,3-dimethylbutan-2-yl group, a heptan-2-yl group, a heptan-3-yl group, a heptan-4-yl group, a 2-methyl-hexan group -1-yl, a 2-ethylpentan-1-yl group, a 2-methylhexan-2-yl group, a 2,3-dimethylpentan-1-yl group, a 2,3-dimethylpentan2-yl group, a 2,3,3-trimethiipentan-1-yl group, 2,3,3-trimethylpentan-2-yl group, octan-2-yl group, octan-3-yl group, octan-4-yl group , a 2-methylheptan-1-yl group, a 2-ethylhexan-1-yl group, a 2-methyl-heptan-2-yl group, a nonan-2-yl group, a nonan-3-yl group, a nonan-4-yl group, a nonan-5-yl group, a decan-2-yl group, a decan-3-yl group, a decan group -4-yl, or a decan-5-yl group. In other embodiments, each bulky substituent can be
43/74 independently a propan-2-yl group, a butan-2-üa, a 2-methylpropan-1-yl group, a 2-methylpropan-2-yl group, a pentan-2-yl group, a pentan-3 group -yl, a 2-methylbutan-1-yl group, a 2-methylbutan-2-yl group, a 3-methylbutan-2-yl group, a 2,2-dimethylpropan-1-yl group; alternatively, a propan-2-yl group, a 2-methylpropan-2-yl group, or a 2,2-dimethylpropan-1-yl group. In other embodiments, each bulky substituent may independently be a propan-2-yl group; alternatively, a butan-2-yl; alternatively, a 2-methylpropan-1-yl group; alternatively, a 2-methylpropan-2-yl group; alternatively, a pentan-2-yl group; alternatively, a pentan-3-yl group; alternatively, a 2-methylbutan-1-yl group; alternatively, a 2methylbutan-2-yl group; alternatively, a 3-methylbutan-2-yl group; alternatively, a 2,2-dimethylpropan-1-yl group.
In one aspect, each bulky substituent can be independently a phenyl group or a substituted phenyl group; alternatively, a phenyl group; or alternatively, a substituted phenyl group. In one embodiment, the substituted phenyl group that can be used as a bulky substituent can be a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a group
2,3-dimethylphenyl, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, or a group 2 , 4,6-triphenyl. In some embodiments, the substituted phenyl group that can be used as a bulky substituent can be a 2-methylphenyl group, a 2,4-dimethylphenyl group, a 2,6-dimethylphenyl group, a 3,5-dimethylphenyl group, or a 2,4 group , 6-triphenyl. In other embodiments, the substituted phenyl group that can be used as a bulky substituent can be a 2-methylphenyl group; alternatively, a 3-methylphenyl group; alternatively, a 4-methylphenyl group; alternatively, a 2,3-dimethylphenyl group; alternatively, a 2,4-dimethylphenyl group; alternatively, a 2,5-dimethylphenyl group; alternatively, a 2,6-dimethylphenyl group; alternatively, a 3,4dimethylphenyl group; alternatively, a 3,5-dimethylphenyl group; or alternatively, a 2,4,6-triphenyl group.
In another aspect, each bulky substituent may independently be a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tri-tert-butylsilyl group, or a triphenylsilyl group; alternatively, a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, or a tri-tert-butylsilyl group. In one embodiment, each bulky substituent can be a trimethylsilyl group; alternatively, a group
44/74 triethylsilyl; alternatively, a triisopropylsilyl group; alternatively, a tri-tert-butylsilyl group; or alternatively, a triphenylsilyl group.
In a non-limiting example, the pyrrole compound can be 2-methyl-4isopropylpyrrole, 2-ethyl-4-isopropylpyrrole, 2-methyl-4-sec-butylpyrrole, 2-ethyl-4-secbutylpyrrole, 2-methyl-4- isobutylpyrrole, 2-ethyl-4-isobutylpyrrole, 2-methyl-4-t-butylpyrrole, 2-ethyl4-t-butylpyrrole, 2-methyl-4-neopentylpyrrole, or 2-ethyl-4-neopentylpyrrole. In some non-limiting examples, the pyrrole compound can be 2-methyl-4-isopropylpyrrole, 2-ethyl-4-isopropylpyrrole, 2-methyl-4-t-butylpyrrole, 2-ethyl-4-t-butylpyrrole, 2-methyl- 4neopentylpyrrole, or 2-ethyl-4-neopentylpyrrole. In other non-limiting examples the pyrrole compound can be 2-methyl-4-isopropylpyrrole; alternatively, 2-ethyl-4isopropylpyrrole; alternatively, 2-methyl-4-sec-butylpyrrole; alternatively, 2-ethyl-4sec-butylpyrrole; alternatively, 2-methyl-4-isobutylpyrrole; alternatively, 2-ethyl-4isobutylpyrrole; alternatively, 2-methyl-4-t-butylpyrrole; alternatively, 2-ethyl-4-tbutylpyrrole; alternatively, 2-methyl-4-neopentylpyrrole; or alternatively, 2-ethyl-4neopentylpyrrole. In other non-limiting examples, the pyrrole compound can be
3.4- diisopropylpyrrole, 3,4-di-sec-butylpyrrole, 3,4-diisobutylpyrrole, 3,4-di-t-butylpyrrole, or
3.4- di-neo-pentylpropylpyrrole. In yet another embodiment, the pyrrole compound can be 3,4-diisopropylpyrrole: alternatively, 3,4-di-sec-butylpyrrole; alternatively, 3,4-diisobutylpyrrole; alternatively, 3,4-di-t-butylpyrrole; or alternatively, 3,4-di-neo-pentylpropylpyrrole.
Metal Alkylate
Generally, and according to one aspect of the present disclosure, the alkyl metal can be any homoleptic or heteroleptic compound of the alkyl metal. For example, the metal of the alkyl metal may comprise, consist essentially of, or consist of, Metal group 1, 2, 11, 12, 13, or 14; or alternatively, a metal Group 13 or 14; or alternatively, a Metal Group 13. In some embodiments and aspects, the alkyl metal may comprise, essentially consist of, or consist of, an alkyl lithium, alkyl sodium, alkyl magnesium, alkyl boron, alkyl zinc, or alkyl aluminum group. In this regard, for example, suitable alkyl metals include, but are not limited to, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, diethyl magnesium, or diethyl zinc. In one embodiment, the alkyl metals may comprise, essentially consist of, or consist of, an alkyl aluminum.
According to a further aspect and in any embodiment of the present description, the alkyl metal can comprise an alkyl metal halide. Metal alkyl halides are described in this document and can be used
45/74 as the alkyl metal component of the oligomerization catalyst system. The halide portion of the alkyl metal halide may be chloride, alternatively bromide; or alternatively iodide.
In some aspects and embodiments in accordance with this disclosure, the alkyl metal may be a non-hydrolyzed alkyl aluminum compound. In one embodiment, the non-hydrolyzed alkyl-aluminum compound can be a trialkyl-aluminum compound, an alkyl-aluminum halide, and / or alkyl-aluminum alkoxide.
Generally, each alkyl group of an alkyl metal described herein (for example, alkyl aluminum compound or alkyl aluminum halide, among others), if there is more than one, can independently be a C1 to C20 alkyl group; alternatively, a C1 to C10 alkyl group; or alternatively, a C1 to C6 alkyl group. In one embodiment, each alkyl group can, independently, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group or; alternatively, a methyl, an ethyl group, a butyl group, a hexyl group, or an octyl group. In some embodiments, each of the alkyl groups of any alkyl metal described herein can be independently a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-butyl group, a nhexyl group, an or n-octyl group; alternatively, a methyl group, an ethyl group, an n-butyl group, or an iso-butyl group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, an n-propyl group; alternatively, an n-butyl group; alternatively, an iso-butyl group; alternatively, an n-hexyl group; or alternatively, a non-octyl group.
According to another aspect of the present disclosure, the alkyl metal may comprise, essentially consist of, or consist of, a trialkyl aluminum compound, a dialkyl aluminum halide compound, an alkyl aluminum di halide compound , an alkyl-aluminum hydride compound, an alkyl-aluminum dihydride compound, a dialkyl-aluminum hydrocarbon compound, an alkyl-aluminum dihydrocarbon compound, an alkyl-aluminum sesqui-halide compound aluminum, an alkyl aluminum aluminum sesquihydrocarbon compound, an aluminoxane, or any combination thereof. In some embodiments, the alkyl metal may comprise, consist essentially of, or consist of, a trialkyl aluminum compound, the dialkyl aluminum halide compound, an alkyl aluminum di halide compound, or any combination thereof; alternatively, a trialkyl aluminum compound, alternatively, a dialkyl46 / 74 aluminum halide compound; alternatively, an alkyl aluminum aluminum halide compound, alternatively, a dialkyl aluminum hydride compound; alternatively, an alkyl aluminum aluminum hydride compound; alternatively, a dialkyl aluminum hydrocarbon compound; alternatively, an alkyl aluminum aluminum dihydrocarbon compound; alternatively, an alkyl aluminum aluminum sesquihalide compound; alternatively, an alkyl aluminum aluminum sesquihidrocarbonoxide compound; or alternatively, an aluminoxane. Applicable alkyl groups and halides for alkyl metal, alkyl metal halides and / or alkyl metal hydrocarbons are described herein and can be used to describe suitable alkyl metals.
Examples of trialkyl aluminum compounds include, but are not limited to, trimethyl aluminum (TMA), triethyl aluminum (TEA), tripropyl aluminum, tri-n-butyl aluminum, or tri-isobutyl-aluminum, or a combination thereof . Exemplary alkyl aluminum halide compounds may include, but are not limited to, diethyl aluminum chloride (DEAC), diethyl aluminum bromide, ethyl aluminum dichloride, ethyl aluminum sesquichloride, and combinations thereof. In several embodiments, the trialkyl aluminum compound can be triethyl aluminum.
According to another aspect, the alkyl metal compound may comprise, essentially consist of, or consist of, a mixture of a trialkyl aluminum compound and an alkyl aluminum halide. Generally, the trialkyl aluminum compound of the mixture may comprise, essentially consist of, or consist of, any trialkyl aluminum compound described herein. The alkyl aluminum halide compound of the mixture can be any alkyl aluminum compound described herein. In some embodiments, the mixture of the trialkyl aluminum compound and the alkyl aluminum halide may comprise, essentially consist of, or consist of a mixture of triethyl aluminum chloride and diethyl aluminum, a mixture of triethyl aluminum dichloride and ethyl - aluminum, or a mixture of trieyl aluminum sesquichloride and ethyl aluminum. In one embodiment, the alkyl metal oligomerization catalyst system component may comprise, consist essentially of, or consist of a mixture of triethyl aluminum chloride and diethyl aluminum.
In another aspect and in any embodiment, specific examples of metal alkyl that are useful for this disclosure may include, consist essentially of, or consist of, but are not limited to, trimethyl aluminum (TMA), triethyl aluminum (TEA), ethyl aluminum dichloride, tripropyl aluminum, diethyl aluminum ethoxide, tributyl aluminum, diisobutyl aluminum hydride, tri isobutyl aluminum,
47/74 diethyl aluminum chloride (DEAC), and combinations thereof. In other respects and in any manner, specific examples of alkyl metals that are useful in this disclosure may comprise or may include, but are not limited to, triethyl aluminum (TEA), diethyl aluminum chloride (DEAC), or any combination of the themselves.
In a non-limiting modality, useful aluminoxanes may have a Formula I repeat unit:
R '
Formula I where R 'is straight or branched alkyl. Alkyl to metal alkyl groups have been independently described here and can be used without limitation to better describe aluminoxanes having Formula I. Generally, n of Formula I is greater than 1; or alternatively greater than 2, in one embodiment, it may not vary from 2 to 15; or alternatively, vary from 3 to 10.
In a non-limiting embodiment, useful aluminoxanes that can be used in the catalyst system may comprise, consist essentially of, or consist of, methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propylaluminoxane, iso-propylaluminoxane, n- butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, tert-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane,
3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof. In some non-limiting embodiments, aluminoxanes may comprise, consist essentially of, or consist of, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutyl aluminoxane, tertbutylaluminoxane, or mixtures thereof. In some non-limiting embodiments, useful aluminoxanes may be methylaluminoxane (MAO); alternatively, ethylaluminoxane; alternatively, modified methylaluminoxane (MMAO); alternatively, n-propylaluminoxane; alternatively, iso-propylaluminoxane; alternatively, n-butylaluminoxane; alternatively, secbutylaluminoxane; alternatively, iso-butylaluminoxane; alternatively, tertbutylaluminoxane; alternatively, 1-pentylaluminoxane; alternatively, 2 pentylaluminoxane; alternatively, 3-pentylaluminoxane; alternatively, isopentylaluminoxane; or alternatively, neopentylaluminoxane.
Halogen-containing compound
48/74
Although not claiming to be limited by theory, it is thought that a halogen-containing compound can improve the purity of the product and / or the selectivity of the oligomerization process. In some aspects and embodiments, the halogen-containing compound may be a chloride-containing compound, a bromide-containing compound, or an iodide-containing compound. In one embodiment, the halogen-containing compound can be a chloride-containing compound.
In one aspect, the halogen-containing compound, regardless of whether it is a chloride, bromide, or iodide-containing compound, can be a metal halide, alkyl metal halide, or organic halide. In several aspects and modalities, the halogen-containing compound can be a metal chloride; alternatively, a metal bromide; or alternatively, a metal iodide. In one embodiment, the halogen-containing compound may be an alkyl metal chloride; alternatively, an alkyl metal bromide; or alternatively, a metal iodide. In one embodiment, the halogen-containing compound can be an organic chloride, alternatively, an organic bromide; or alternatively, an organic iodide.
On the other hand, and in another aspect, the halogen-containing compound comprises a group 3 metal halide, a group 4 metal halide, a group 5 metal halide, a group 13 metal halide, a metal halide group 14, a group 15 metal halide, or any combination thereof. For example, the halogen-containing compound may be the halogen-containing compound may comprise scandium chloride, yttrium chloride, lanthanum chloride, titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, boron trichloride, aluminum chloride, chloride gallium, silicon tetrachloride, trimethylchlorosilane, germanium tetrachloride, tin tetrachloride, phosphorus trichloride, antimony trichloride, antimony pentachloride, bismuth, trichloride, boron tribromide, aluminum trichloride, silicon tetrachloride, flour tetrachloride, flour tetrachloride aluminum, molybdenum pentachloride, tungsten hexachloride, tilyl hexachloroantimonate, or any combination thereof.
According to another aspect, the halogen-containing compound may comprise, consist essentially of, or consist of a Group 1, 2, 12, 13 or alkyl metal halide; alternatively, a Group 12 or 13 alkyl metal halide; or alternatively, an alkyl aluminum halide or an alkylthine halide. According to another aspect, the halogen-containing compound can
49/74 comprise, consist essentially of, or consist of an alkyl aluminum halide. In some embodiment, the alkyl aluminum halide can be an alkyl aluminum chloride; alternatively, an alkyl aluminum bromide; or alternatively and alkyl aluminum aluminum iodide. In other embodiments, the alkylthine halide can be an alkylthine chloride; alternatively, an alkylthine bromide; or alternatively, an alkylthine iodide. In one embodiment, the alkyl metal halide may be an alkyl aluminum halide. In another embodiment, the alkyl metal halide may be an alkylthine halide.
In various embodiments and according to another aspect, the halogen containing compounds may comprise, consist essentially of, or consist of a dialkyl aluminum halide, alkyl aluminum dihalide, or an alkyl aluminum sesqui-halide, or any combination thereof; alternatively, a dialkyl aluminum halide; alternatively, an alkyl aluminum dihalide; or alternatively, an alkyl aluminum aluminum sesqui-halide. In this respect, the alkyl aluminum alkyl halide group, the alkyliltine halide, the dialkyl aluminum halide, an alkyl aluminum dihalide, or alkyl aluminum sesquihalide can be a C 1 to C 6 alkyl group . In addition, and in this regard, the halogen-containing compound may comprise, essentially consist of, or consist of, diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, tributyltin chloride, dibutyl dichloride tin, or any combination thereof; alternatively, diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, or any combination thereof; or alternatively, diethyl aluminum chloride; alternatively, ethyl aluminum sesquichloride; or alternatively, ethyl aluminum dichloride.
According to a further aspect and, in any embodiment, the halogen-containing compound can comprise an organic halide C1 to C15; alternatively, a C1 to C10 organic halide; or alternatively, a C1 to C8 organic halide. By way of example, according to this aspect, the halogen-containing compound may comprise, consist essentially of, or consist of, carbon tetrachloride, carbon tetrabromide, chloroform, bromoform, dichloromethane, dibromoethane, diiodine, chloromethane, bromomethane, iodomethane, dichloroethane, tetrachloroethane, trichloroacetone, hexachloroacetone, hexachlorocyclohexane, 1,3,5-trichlorobenzene, chloride, trityl hexachlorobenzene, benzyl chloride, benzyl bromide, benzyl iodide, chlorobenzene, any bromobenzene, combination thereof.
50/74
In one aspect, the catalyst system can have a molar ratio in the metal of the transition metal compound in which the alkyl metal ranges from 1: 1 to 1: 150; alternatively, from 1: 1 to 1: 100; or alternatively, 1: 9 to 1:21. In one embodiment, when the transition metal compound is a chromium compound (for example, a chromium (III) ethyl carboxylate composition) and the alkyl metal is an alkyl aluminum compound (for example, trietii aluminum, diethyl aluminum chloride, or a mixture thereof), the catalyst system can have an aluminum to chromium molar ratio ranging from 1: 1 to 1: 150; alternatively, from 1: 1 to 1: 100; or alternatively, 01: 09-01: 21.
In one aspect, the catalyst system may have a molar ratio of nitrogen from the pyrrole compound to the metal, from the transition metal compound ranging from 1: 0: 1 to 4, 0: 1; alternatively 1, 5: 1,3, 7: 1; alternatively 1, 5: 1,2, 5: 1; alternatively 2, 0: 1, 3, 7: 1; alternatively 2, 5: 1, 3, 5: 1; or alternatively 2, 3, 1: 1, 9: 1 in one embodiment when the transition metal compound is a chromium compound (e.g., a chromium carboxylate composition) the molar ratio of pyrrole chromium may vary from 1.0: 1 to 4.0: 1; alternatively from 1.5: 1 to 3.7: 1; alternatively from 1.5: 1 to 2.5: 1; alternatively from 2.0: 1 to 3.7: 1; alternatively from 2.5: 1 to 3.5: 1; or alternatively from 2.9: 1 to 3.1: 1.
Oligomerization Process
The oligomerization catalyst system described herein can be used within an oligomerization process or a process for preparing an oligomerization product. Generally, the oligomerization process or process for preparing an olefin oligomerization product comprises oligomerization of a raw material with the oligomerization catalyst, as described herein.
In various embodiments and according to one aspect, the olefin feedstock may comprise, consist essentially of, or consist of, an alpha-olefin and the oligomerization process can be an oligomerization process for the preparation of an oligomerization product alpha olefins, alternatively, the olefin feedstock may comprise, consist essentially of, or consist of, a linear alpha olefin and the oligomerization process may be an oligomerization process for the preparation of a linear alpha olefin oligomerization product ; or alternatively, the olefin feedstock may comprise, consist essentially of, consist of, a normal alpha-olefin and the oligomerization process may be a
51/74 oligomerization process for the preparation of a normal alpha-olefin oligomerization product.
In one aspect, the oligomerization process for the preparation of an olefin oligomerization product can be an olefin trimerization process for the preparation of an olefin trimer product. In one embodiment, the trimerization of olefin feedstock may comprise, consist essentially of, consist of an alpha olefin and the oligomerization process may be a trimerization process for the preparation of an alpha olefin trimerization product; alternatively, the trimerization of olefin feedstock may comprise, consist essentially of, or consist of a linear alpha olefin and the oligomerization process may be a trimerization process for the preparation of a linear alpha olefin trimerization product; or alternatively, trimerization of the olefin feedstock may comprise, consist essentially of, or consist of a normal alpha olefin and the oligomerization process may be a trimerization process for the preparation of a normal alpha olefin trimerization product.
Generally, the raw material of olefin (s), alpha olefin (s), alpha linear olefin (s), or normal alpha olefin (s) can be C ₂ to C30, C ₂ to Cw, or C ₂ to Cw olefin (s), linear alpha olefin (s), normal alpha olefin (s), or normal alpha olefin (s). In one embodiment, the olefin may comprise, consist essentially of, or consist of ethylene. When it comprises the olefin feedstock, it consists essentially of, or consists of ethylene, the oligomerization process can be an ethylene trimerization process, the trimer product can be 1hexene and the trimerization product comprises 1-hexene.
A composite catalyst system that can be used in the invention is the combination of chromium (III) ethylhexanoate, 2,5-diethylpyrrole, triethyl aluminum and diethyl aluminum chloride. This composite catalyst system can be used, for example, to trimerize ethylene to form 1-hexene. Other applicable catalyst catalyst systems can be readily discerned from the present disclosure.
In one aspect, contact and / or reaction of the chromium compound, pyrrole compound, and alkyl metal is carried out in the presence of an unsaturated hydrocarbon. The unsaturated hydrocarbon can be any aliphatic or aromatic hydrocarbon, in a gas, solid or liquid state. In some embodiments, the unsaturated compound can be an aromatic hydrocarbon; alternatively,
52/74 an unsaturated aliphatic compound. For the effect through the contact of chromium compound, pyrrole compound, and alkyl metal, unsaturated hydrocarbon can be in liquid state. It should be understood, however, that some embodiments can be used in suitable catalyst systems, regardless of the production method of the catalyst system. In one aspect, the unsaturated hydrocarbon can be 1-hexene. Alternatively, the contact and / or reaction of chromium compound, pyrrole compound, and alkyl metal can be carried out in the absence of 1-hexene.
The unsaturated hydrocarbon can have any number of carbon atoms per molecule. Generally, the unsaturated hydrocarbon will comprise less than 70 carbon atoms per molecule, or less than 20 carbon atoms per molecule. Exemplary aliphatic, unsaturated hydrocarbon compounds include, but are not limited to, ethylene, 1-hexene, 1,3-butadiene, and mixtures thereof. In one aspect of the invention, the unsaturated aliphatic hydrocarbon compound is 1-hexene. If 1-hexene is the target oligomer to be formed, this may lessen the need for subsequent purification steps. Aromatic hydrocarbons that can be used as the unsaturated hydrocarbon in the preparation of the catalyst system may include, but are not limited to, aromatic compounds C6 to C50; alternatively, aromatic compounds C6 to C30; alternatively, aromatic compounds C6 to C18; or alternatively, aromatic compounds C6 to C10. Exemplary aromatic hydrocarbons include, but are not limited to, benzene, toluene, ethylbenzene, xylene, mesitylene, hexamethylbenzene and mixtures thereof. In one embodiment, the aromatic compound can be toluene; alternatively ethylbenzene, or alternatively xylene. Without being limited by theory, it is believed that the use of an unsaturated hydrocarbon during the preparation of the catalyst system has improved the stability of the catalyst system.
It should be recognized that the reaction mixture, comprising a chromium compound, the pyrrole compound, alkyl metal and unsaturated hydrocarbon, may contain additional components that do not harm and may improve the resulting catalyst system, such as, for example, transitions and / or halides.
The amount of aromatic compound that can be used in the preparation of the oligomerization catalyst system can be on a scale of up to 15 weight percent, based on the amount of solvent in the reactor, varies from 0.001
53/74 to 10 percent, or in the range of 0.01 to 5 percent by weight. The excess of aromatic compound can inhibit the activity of the catalyst system and insufficient aromatic compound cannot stabilize the catalyst system. Generally, the amounts of the aromatic compound per mol of metal of the transition metal compound (for example, chromium compound) in the catalyst system can be in the range of up to 6,000, range of 10 to 3,000, or range of 20 to 1,000 ols of aromatic compound per mol of metal (e.g., chromium compound) in the catalyst system.
The contact of the aromatic compound and catalyst system can occur under any conditions sufficient to stabilize the catalyst system in the presence of heat. Generally, the temperatures to contact may vary from -50 ° C to 70 ° C, vary from -10 ° C to 70 ° C, or vary from 5 ° C to 30 ° C. Generally, contacting periods can be less than 5 hours, vary from 0.01 seconds to 4 hours, or range from 0.1 seconds to 3 hours. Contact periods cannot additionally improve the stability of the catalyst system and shorter contact time may be insufficient to allow complete contact of the aromatic compound and catalyst system and therefore may not be sufficient to stabilize the catalyst system. Any type of pressure that allows complete contact of the aromatic compound and catalyst system can be used. Generally, any type of pressure can be used that can keep the aromatic compound and catalyst system in liquid form. The preparation of the catalyst system is usually carried out under an inert atmosphere, such as nitrogen or argon, to decrease the amount of water vapor and oxygen present. Nitrogen is often used due to cost and availability. In addition to the discussion here, other applicable examples of oligomerization catalyst systems and transition metal compounds and their exemplary preparation are provided in US Patent No. 6,133,495 and US Patent No. 7,384,886, which are incorporated into this document by reference in its entirety for all purposes.
Oligomerization reaction products, for example, olefin trimers, can be prepared from the catalyst system of this invention by solution, suspension, and / or gas phase reaction techniques using conventional equipment and coming into contact with processes. The contact with monomers or monomer with a catalyst system can be done in any way known in the art. It is a convenient method to suspend the catalyst system in organic medium to stir the mixture to maintain the
54/74 catalyst system in solution throughout the trimerization process. Other known contact methods can also be employed.
For example, a continuous feed autoclave reactor with a fluid coating or internal heat transfer coil and any suitable mixing mechanism, such as mechanical stirring or spraying with an inert gas, usually nitrogen, can be used. In another embodiment, a circuit reactor with mechanical agitation, such as a circulation pump, can be used. Alternatively, tubular reactions for carrying out the oligomerization can also be used in connection with the invention.
The trimerization or oligomerization process can be carried out in a solvent, which is used as a process medium. If used, any number of hydrocarbon solvent can be used as a process medium for the trimerization or oligomerization reaction.
In the embodiment, the solvent that can be used as a process medium can be hydrocarbon or halogenated hydrocarbon; alternatively, a hydrocarbon; or alternatively a halogenated hydrocarbon. Hydrocarbons and halogenated hydrocarbons may include, for example, aliphatic hydrocarbons, aromatic hydrocarbons, petroleum distillates, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, or combinations thereof; alternatively aliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons and combinations thereof; alternatively, aliphatic hydrocarbons; alternatively, aromatic hydrocarbons; alternatively, halogenated aliphatic hydrocarbons; or alternatively, halogenated aromatic hydrocarbons. Aliphatic hydrocarbons, which may be useful as a solvent include aliphatic hydrocarbons Ci to C20; alternatively aliphatic hydrocarbons C ₄ to C 15; or alternatively, aliphatic hydrocarbons C5 to C10. Aliphatic hydrocarbons may be cyclic or acyclic and / or may be linear or branched, unless otherwise stated. Non-limiting examples of suitable acyclic aliphatic hydrocarbon solvents that can be used alone or in any combination include propane, iso-butane, n-butane, butane (n-butane or a mixture of linear or branched C ₄ aliphatic hydrocarbons), pentane (n-pentane or a mixture of linear or branched C ₅ acyclic aliphatic hydrocarbons), hexane (n-hexane or mixture of
55/74 linear or branched C ₆ acyclic aliphatic hydrocarbons, heptane (nheptane or a mixture of linear or branched C ₇ acyclic hydrocarbons), octane (n-octane or Οβ linear or branched aliphatic hydrocarbon mixture), and combinations thereof ; alternatively, isobutane, n-butane, butane (n-butane or a mixture of straight or branched C ₄ acyclic hydrocarbons), pentane (n-pentane or a mixture of straight or branched C ₅ acyclic hydrocarbons), hexane (n- hexane or mixture of linear or branched acθ acyclic hydrocarbons), heptane (n-heptane or mixture of linear or branched C ₇ acyclic hydrocarbons), octane (n-octane or a mixture of straight or branched C8 acyclic hydrocarbons), and combinations thereof; alternatively, iso-butane, n-butane, butane (n-butane or a mixture of linear or branched C ₄ acyclic hydrocarbons), pentane (npentane or a mixture of linear or branched C ₅ acyclic hydrocarbons), heptane (n- heptane or a mixture of linear or branched C ₇ acyclic hydrocarbons), octane (n-octane or a mixture of linear or branched Cs acyclic hydrocarbons), and combinations thereof; alternatively, propane, alternatively, iso-butane, alternatively, n-butane, alternatively, butane (n-butane or a mixture of linear or branched C ₄ acyclic hydrocarbons); alternatively, pentane (n-pentane or a mixture of linear or branched C ₅ acyclic hydrocarbons); alternatively, hexane (nhexane or a mixture of linear or branched C ₆ acyclic hydrocarbons); alternatively, heptane (n-heptane or mixture of linear or branched C ₇ acyclic hydrocarbons); or alternatively, octane (noctane or a mixture of linear or branched Cs acyclic hydrocarbons). Non-limiting examples of suitable solvents of cyclic aliphatic hydrocarbons include cyclohexane, methylcyclohexane, alternatively cyclohexane; or alternatively, methylcyclohexane. Aromatic hydrocarbons that may be useful as a solvent include aromatic hydrocarbons Οθ to C20; or alternatively, aromatic hydrocarbons C6 to C10. Non-limiting examples of suitable aromatic hydrocarbons that can be used alone or in any combination include benzene, toluene, xylene (including ortho-xylene, meta-xylene, para-xylene, mixtures thereof) or, and ethylbenzene, or combinations thereof; alternatively benzene, alternatively toluene, alternatively xylene
56/74 (including ortho-xylene, meta-xylene, para-xylene and / or mixtures thereof); or alternatively, ethylbenzene. Halogenated aliphatic hydrocarbons that may be useful as a solvent include C ₁₅ aliphatic halogenated hydrocarbons; alternatively, aliphatic halogenated hydrocarbons Ci to C-io! or alternatively, halogenated aliphatic hydrocarbons Ci to C ₅ . Aliphatic halogenated hydrocarbons may be acyclic or cyclic and / or may be linear or branched, unless otherwise specified. Non-limiting examples of suitable aliphatic halogenated hydrocarbons that can be used include methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, and combinations thereof; alternatively, methylene chloride, chloroform, dichloroethane, trichloroethane, and combinations thereof; alternatively, methylene chloride; alternatively, chloroform; alternatively, carbon tetrachloride; alternatively, dichloroethane; or alternatively, trichloroethane. Halogenated aromatic hydrocarbons that may be useful as a solvent include halogenated aromatic hydrocarbons C ₆ to C ₂₀ ; or alternatively, halogenated aromatic hydrocarbons C ₆ to C ₁₀ . Non-limiting examples of suitable aromatic halogenated hydrocarbons include dichlorobenzene, chlorobenzene, and combinations thereof; alternatively chlorobenzene and dichlorobenzene.
The choice of the oligomerization solvent can be made based on processing convenience. For example, isobutane can be chosen to be compatible with diluents used for the formation of polyolefins in a subsequent processing step. In some embodiments, a reaction product or reaction olefin feedstock can be used as the process / solvent medium. For example, since 0 1-hexene can be the reaction product of an ethylene trimerization process, it can be chosen as the solvent oligomerization to decrease the need for separation.
According to another embodiment of the present invention, a suspension process can be carried out in a diluent (medium), which is a product of the olefin oligomerization process. Therefore, the choice of reactor diluent, or medium, can be based on the selection of the initial olefin reagent and / or oligomerization product. For example, if the oligomerization catalyst is used to trimerize 0 ethylene to 1-hexene, the solvent for the oligomerization reaction may be 1-hexene. If ethylene and hexene are trimerized, the solvent for the oligomerization reaction may be 1-hexene, and / or a trimerization product.
57/74
If ο 1,3-butadiene has been trimerized to 1,5-cyclooctadiene, the trimerization reactor solvent may be 1,3-butadiene or 1,5-cyclooctadiene.
The reaction temperatures and pressures can be any temperature and pressure that are suitable for trimming the olefin reagents using the catalyst system. Reaction temperatures are generally within the range of -20 ° C to 250 ° C. In another aspect of the invention, the reaction temperatures are within the range of 60 ° C to 200 ° C. In yet another aspect, the reaction temperatures are within the range of 80 ° C to 150 ° C. Reaction pressures are generally within the atmospheric range at 2500 psig. In another aspect of the invention, the reaction pressures can be within an atmospheric range at 2500 psig; or alternatively, within a 1600 psig atmospheric range. Yet another aspect of the invention, the reaction pressure varies between 300psig and 900 psig. When the olefinic compound is ethylene, the reaction can be carried out at a partial pressure of ethylene ranging from 20 psi to 2500 psi; alternatively, from 100 psi to 2000; alternatively, from 200 psi to 1500 psi; or alternatively, from 300 psi to 1000 psi.
If the reaction temperature is too low, it can produce a lot of undesirable insoluble product, such as, for example, the polymer, and if the reaction temperature is too high, it can cause the catalyst system to be deactivated and the reaction products isomerized. A reaction pressure that is too low can result in low catalyst system activity.
Optionally, hydrogen can be added to the reactor to accelerate the reaction and / or increase the activity of the catalyst system. If desired, hydrogen can also be added to the reactor to suppress polymer production. When hydrogen is used, the partial pressure of hydrogen can vary from 2 psi to 100 psi; alternatively, 5 psi to 75 psi; or alternatively, 10 psi to 50 psi.
The reactor contents can be agitated or stirred by an inert gas purge (for example, nitrogen), introducing the reagent, hydrogen, fluid medium, or catalyst or pouring the effluent in a way that causes agitation, by mechanical or magnetic agitation, of properly.
The reaction is usually carried out continuously below the 1-olefin reagent (s), catalyst system, and process medium and removing the liquid content from the reactor. For example, a continuously agitated tank reactor system that includes
58/74 supply for catalyst system, reagent and medium and a discharge system for the effluent. Alternatively, a batch process can also be employed.
The trimerization reaction is an exothermic process, so the reaction temperature can generally be regulated by the circulation of cooled water, through a heat transfer coil or coating, thus transferring the heat out of the reactor. The transfer of heat out of the effective reactor allows effective maintenance of the desired reaction temperature. Another advantage of more effective heat transfer is that the trimerization reaction can be performed with a higher yield for a given temperature, which can improve production efficiency.
In one aspect, the effluent from the reactor is treated to deactivate the active catalyst system, and in addition it can be treated to separate products, recycle residual reagents, medium and other components suitable for recycling, and eliminate all components that are not recycled.
In one aspect, the effluent from the reactor is treated to deactivate the active catalyst system, and in addition it can be treated to separate products, recycle residual reagents, medium and other components suitable for recycling, and eliminate all components that are not recycled.
When the trimerization or oligomerization process is considered complete, the reactor effluent flow comprising solvent, olefin (s), catalyst system and some oligomer and / or polymer, can come in contact with an alcohol to deactivate the active catalyst system. . Any alcohol that is soluble in the reactor effluent stream can be used. As used here, the term alcohol includes mono-alcohols, diols and polyols. The alcohol can be selected by the boiling point, molecular weight, or that the alcohol will not be azeotropic with the olefin monomer product. In some embodiments, alcohol has a different boiling point than the olefin product in the reactor effluent stream. In an exemplary process, in which the catalyst system is used to trimerize ethylene in 1-hexene, an alcohol with six or more carbon atoms per molecule can be used. In an alcohol modality it can be a C ₄ to C ₃₀ , C ₄ to C ₂₀ , or C ₄ to C 12 alcohol. In some embodiments, the alcohol is selected to be easily removable from the oligomerization product (for example, the 1-hexene trimerization product). Exemplary alcohols include, but are not limited to, 1-hexanol, 2-hexanoi, 3-hexanol, 2-ethylhexanol, 1heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-methyl-3-heptanol, 1-octanol, 259/74 octanol, 3-octanol, 4-octanol, 7-methyl-2-decanol, 1-decanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-ethyl-1 -decanol, and mixtures thereof. In one embodiment, the alcohol may be 2-ethyl-1-hexanol.
Alternatively, a low molecular weight polyol or diol, for example ethylene glycol, for example, can be used as a catalyst deactivating agent. Diols and polyols usually have much more high boiling points than monoalcohols of comparable molecular weight and thus can be easily separated in some oligomerization products (for example, the 1-hexene trimerization product).
The alcohol is added to the reactor effluent flow in an amount sufficient to extinguish and / or end the catalyst system to inhibit, or stop: (1) production of undesirable solids, that is, polymer; and / or (2) oligomerization (or alternatively, trimerization) degradation of the purity product due to isomerization, in the product separation process.
After the catalyst system has been deactivated, oligomerization products, such as, for example, 1-hexene, can be removed. Any removal process can be used, for example, including distillation.
In one aspect, the process oligomerization or the process for preparing an oligomerization product comprising contacting the olefin feedstock with the oligomerization catalyst system using a compound having the substituent attached at positions 2 and 5, and in which at least one of the groups, the carbon atoms attached to positions 2 and 5 of the pyrrole ring is a secondary carbon atom (or alternatively both carbon atoms in the groups attached to positions 2 and 5 of the pyrrole ring is a carbon atom described) produces less polymer than the process using an oligomerization catalyst system using 2,5-dimethyl pyrrole as the pyrrole compound. In an aspect where oligomerization is an ethylene trimerization process, the catalyst system using a pyrrole compound having the substituent attached to positions 2 and 5, and in which at least one of the groups, the carbon atoms attached to the positions 2 and 5 of the pyrrole ring is a secondary carbon atom (or alternatively, both carbon atoms of the groups attached to positions 2 and 5 of the pyrrole ring is a secondary carbon atom) produces an oligomerization product having a greater selectivity for 1-hexene that an oligomerization catalyst system using 2,5dimethyl pyrrole as the pyrrole compound. Another aspect in which oligomerization is
60/74 an ethylene trimerization process, the catalyst system using a pyrrole compound having the substituent attached to positions 2 and 5, and in which at least one of the groups, the carbon atoms attached to positions 2 and 5 of the ring pyrrole is a secondary carbon atom (or alternatively, both carbon atoms in the groups attached to positions 2 and 5 of the pyrrole ring is a secondary carbon atom) produces a 1-hexene product, having a greater purity than an oligomerization catalyst system using 2,5dimethyl pyrrole as the pyrrole compound. In one embodiment, the catalyst system using a pyrrole compound having the substituent attached to positions 2 and 5, and in which at least one of the groups, the carbon atoms attached to positions 2 and 5 of the pyrrole ring is an atom of Secondary carbon (or alternatively, both carbon atoms of the groups attached to positions 2 and 5 of the pyrrole ring is a secondary carbon atom) produces an oligomerization selectivity to C6 products by at least 0.5, 1.0, 1 , 5, 2.0 (absolute) of greater oligomerization selectivity to C6 products produced by an oligomerization catalyst system using 2,5-dimethyl pyrrole as the pyrrole compound.
In another aspect, an ethylene trimerization process or the process for preparing an ethylene trimerization product comprising contacting the raw material with the oligomerization catalyst system using a pyrrole compound having a hydrogen atom located in at least one carbon atom of the pyrrole ring adjacent to the nitrogen atom of the pyrrole ring and a bulky group located on a carbon atom of the pyrrole ring adjacent to any pyrrole carbon atom having the hydrogen atom adjacent to the nitrogen atom of the ring of pyrrole (or alternatively, has a hydrogen atom located on each carbon atom of the pyrrole ring adjacent to the nitrogen atom of the pyrrole ring and a bulky group located on carbon atoms of the pyrrole ring adjacent to the ring carbon atom of pyrrole having the hydrogen atom adjacent to the nitrogen atom of the pyrrole ring) can have a higher productivity (transition metal g C ₆ g - po example, Cr) than the process using 2,4-dimethylpyrrole as the pyrrole compound, provides greater selectivity for C ₆ products than the process using 2,4-dimethylpyrrole as the pyrrole compound, and / or provides a 1-hexene product of higher purity than the process using 2,4-dimethylpyrrole as the pyrrole compound; alternatively, it has a higher productivity (transition metal g Côg - for example, Cr) than the process
61/74 using 2,4-dimethylpyrrole as the pyrrole compound; alternatively, it provides greater selectivity for C ₆ products than the process using 2,4-dimethylpyrrole as the pyrrole compound; or alternatively, it provides a higher purity 1-hexene product than the process using 2,4-dimethylpyrrole as the pyrrole compound. In one embodiment, the productivity (transition metal g C ₆ g - for example, Cr) of the catalyst system using any pyrrole compound described herein, having a hydrogen atom located on at least one carbon atom of the adjacent pyrrole ring to the nitrogen atom of the pyrrole ring and a bulky group located on a carbon atom of the pyrrole ring adjacent to any pyrrole carbon atom having the hydrogen atom adjacent to the nitrogen atom of the pyrrole ring, (or alternatively, has a hydrogen atom located on each carbon atom of the pyrrole ring adjacent to the nitrogen atom of the pyrrole ring and a bulky group located on carbon atoms of the pyrrole ring adjacent to the carbon atom of the pyrrole ring having the hydrogen atom adjacent to the nitrogen atom of the pyrrole ring) can be 50%, 75%, or 100% (relative) greater than the productivity of the process using 2,4-dimethylpyrrole as the pyrrole compound. In some embodiments, the trimerization selectivity of a trimerization process using the catalyst system using any compound with a hydrogen atom located on at least one carbon atom of the pyrrole ring adjacent to the nitrogen atom of the pyrrole ring and a group roughage located on a pyrrole ring carbon atom adjacent to any pyrrole carbon atom having the hydrogen atom adjacent to the pyrrole ring nitrogen atom (or alternatively pyrrole described here has a hydrogen atom located on each atom of pyrrole ring carbon adjacent to the pyrrole ring nitrogen atom and a bulky group located on pyrrole ring carbon atoms adjacent to the pyrrole ring carbon atom having the hydrogen atom adjacent to the pyrrole ring nitrogen atom ) can be 1.0, 1.5, 2.0, 2.5 (absolute) greater than the oligomerization selectivity of C ₆ products produced by a catalyst system oligomerization agent using 2,5-dimethyl pyrrole as the pyrrole compound.
In other embodiments, the purity of 1-hexene produced by the trimerization process, using the catalyst system using any compound described herein, pyrrole having a hydrogen atom located on at least one carbon atom of the pyrrole ring adjacent to the nitrogen atom of the pyrrole ring and a bulky group located on a carbon atom of the ring
62/74 pyrrole adjacent to any pyrrole carbon atom having the hydrogen atom adjacent to the nitrogen atom of the pyrrole ring (or alternatively, has a hydrogen atom located on each carbon atom of the pyrrole ring adjacent to the nitrogen atom of the pyrrole ring and a bulky group located on pyrrole ring carbon atoms adjacent to the pyrrole ring carbon atom having the hydrogen atom adjacent to the pyrrole ring nitrogen atom), can be 0.5%, 1.0%, 1.5%, or 2.0 (absolute) greater than the purity of the 1-hexene oligomerization product produced by an oligomerization catalyst system using 2,5-dimethylpyrrole as the pyrrole compound.
In yet another aspect, an ethylene trimerization process or the process for preparing an ethylene trimerization product comprising contacting the olefin feedstock with the oligomerization catalyst system using any compound described herein the pyrrole compound having Formula P2 , Formula P3, or Formula P4 where R ^12p and R ^13p of Formula P2 and R ^22p of Formula P3 can be any pyrrole substituting group disclosed herein while R ^14P of Formula P2, R ^24p of Formula P3, and R ^33P and R ^34p of Formula P4 can be any bulky pyrrole substituent disclosed herein may have an increase in productivity (g C / g transition metal - for example Cr) than the process using 2,4-dimethyl-pyrrole as the pyrrole compound, provides greater selectivity for C6 products than the process using 2,4-dimethyl-pyrrole as the pyrrole compound, and / or provides a higher purity of the 1-hexene product than the process using 2,4-dimethylpyrrole with pyrrole compound hand; alternatively, it has an increase in productivity (transition metal g Cô / g - for example Cr) than the process using 2,4-dimethyl-pyrrole as the pyrrole compound; alternatively, it provides greater selectivity for C ₆ products than the process using 2,4-dimethyl-pyrrole as the pyrrole compound; or alternatively, it provides a higher purity of the 1-hexene product than the process using 2,4-dimethyl-pyrrole as the pyrrole compound. In one embodiment, the productivity (transition metal g Ce / g - for example Cr) of the catalyst system, using the catalyst system using any pyrrole compound described herein having Formula P2, Formula P3, or Formula P4 in which R ^12p and R ^13p from Formula P2 and R ^22p from Formula P3 can be any pyrrole substituting group disclosed herein while R ^14P from Formula P2, R ^24p from Formula P3 and R ^33P and R ^34p from Formula P4 can be any pyrrole substituent described herein
63/74 roughage can be 50%, 75%, or 100% (relative) greater than the productivity of the process using 2,4-dimethyl-pyrrole as the pyrrole compound. In some embodiments, the trimerization selectivity of a trimerization process, using the catalyst system using any pyrrole compound described herein having Formula P2, Formula P3, or Formula P4 in which R ^12p and R ^13p of Formula P2 and R ^22p of Formula P3 can be any pyrrole substituting group disclosed herein while R ^up of Formula P2, R ^24p of Formula P3 and R ^33p and R ^34p of Formula P4 can be any bulky pyrrole substituent described herein may be 1.0%, 1 , 5%, 2.0%, or 2.5% (absolute) greater than the selectivity for C ₆ oligomerization products produced by an oligomerization catalyst system using 2,5-dimethyl-pyrrole as the pyrrole compound . In other embodiments, the purity of 1-hexene produced by the trimerization process, using the catalyst system using any compound described herein the pyrrole compound having Formula P2, Formula P3, or Formula P4 in which R ^12p and R ^13p of Formula P2 and R ^22p of Formula P3 can be any pyrrole substituting group disclosed herein while R ^14p of Formula P2, R ^24p of Formula P3 and R ^33p and R ^34p of Formula P4 can be any bulky pyrrole substituent described herein can be 0, 5%, 1.0%, 1.5%, or 2.0 (absolute) greater than the purity of the 1-hexene oligomerization product produced by an oligomerization catalyst system using 2,5-dimethyl-pyrrole as the pyrrole compound.
Articles prepared in accordance with this Disclosure
In accordance with yet another aspect of the present description and in various embodiments, this description includes several articles prepared from the olefinic oligomers produced by the described process. For example, and not as a limitation, this disclosure encompasses an article prepared from the product produced from the oligomerization process as described herein. For example, the article can be produced using the oligomerization product in which the oligomerization product is a copolymer. In addition, as an example, the article can be produced using the oligomerization product in which the oligomerization product is a polyethylene copolymer and the oligomerization product is 1-hexene.
In an additional aspect, and also by way of example, the article can be produced using the oligomerization product in which the oligomerization product is a high density polyethylene, a low density polyethylene, a medium density polyethylene, a polyethylene of low density
64/74 linear. In these aspects, the oligomerization product can be subjected to mixing, heating, melting, composition, extrusion, injection molding, precision molding, blow molding, film formation, coating formation, or any combination thereof, for form the article.
Comparative Results
Referring to figures 1 and 2 and tables 1 and 2, oligomerization studies were performed to compare the catalytic behavior of pyrroles under different standard selective 1-hexene oligomerization reaction conditions to identify active pyrrole compounds that provide catalyst systems ethylene trimerization, determine the relative levels of oligomerization activity, determine the productivity of the catalyst system, determine the selectivity of the catalyst system for C ₆ products ₎ and / or determine the purity of the C ₆ fraction (that is,% in weight of 1-hexene found in products β produced in oligomerization.
Figure 1 illustrates a graphical representation of C ₆ productivity (g Cq / g Cr) as a function of temperature (° C), for chromium-based catalyst systems prepared using the following pyrroles: 2,5-dimethyl- pyrrole (2.5DMP); 2,5-dibenzylpyrrole (2,5-PD); 2,4-dimethyl-pyrrole (2,4-DMP), 2-methyl-4isopropypyrrole (2-M-4-IPP and 2,5-diethylpyrrole (2,5-DEP) over the tested temperatures. seen in figure 1, each pyrrole has a unique temperature profile in the oligomerization catalyst system and can be optimized under optimal or desired operating conditions for the catalyst system with a specific pyrrole compound. that the productivity of catalyst systems using 2,5-disubstituted and 2,4-disubstituted pyrrole with a bulky substituent at position 4 of the pyrrole ring was more acutely affected by temperature variations than other catalyst systems. 1 are provided in detail in Table 1.
The data in Table 2 provide the purity of 1-hexene (% 1-hexene of product C ₆ produced in oligomerization), as shown in figure 2, and the selectivity of C ₆ , shown as in figure 2, to indicate pyrrole. These data are reported at the temperature (° C) of the highest observed productivity (g C ₆ / g Cr), which is shown in Table 2, using the catalyst prepared according to the Examples. Among other things, this data illustrates that 2,5-substituted pyrroles provide catalytic systems with more productivity
65/74 higher than those containing 2,5-unsubstituted pyrroles. In addition, these data show that 2,4-substituted pyrroles with a bulky substituent at position 4 of the pyrrole ring to provide catalytic systems that have increased C ₆ productivity, increased Ce selectivity and / or produce a Ü6 product having a higher purity of 1-hexene than the catalyst system than a 2,4-substituted pyrrole, which lacks a bulky substituent at position 4 of the pyrrole ring (for example, 2,4-dimethyl-pyrrole. Generally , catalytic productivity was observed to increase in the change from unsubstituted pyrrole, to 2,4-disubstituted pyrrole, to 2- or 5-substituted pyrrole, to the 2,5-dimethyl-pyrrole prototype.
The data in Figure 2 and Table 2 further illustrate higher purities of 1-hexene and C ₆ selectivities are generally obtained with the 2,5-disubstituted pyrrole compound or 2,4-disubstituted pyrrole compounds having a bulky substituent on position 4 of the pyrrole ring have their catalytic productivity temperatures measured higher. As shown in Figure 2, 2,5-DMP, 2,5-DEP, 2,5-DIP, 2,5-PAD, 2-M-4-IPP, as well as others, such as 2-Melnd, appear offer a good combination of selectivity and purity.
In other comparisons, 2-methyl-3-ethyl-5-methylpyrrole (productivity - 21,700 g C ₆ / g Cr) and 2-methyl-indole (productivity - 3,500 g C ₆ / g Cr) - two compounds characterized by a pattern similar substitution and similar steric congestion - provide very different productivity. Although not intended to be limited by theory, it is possible that the electron receptor phenyl group fused to the pyrrole ring, in 2-methylindole produces a catalyst with low activity. As an additional illustration, indole (productivity - 800 g Ce / g Cr), which also has a fused electron receptor group for the pyrrole ring, produces a catalyst with an order of magnitude lower than the catalyst productivity pyrrole (yield - 6,400 g C ₆ / g Cr). Again, while intending to be bound by theory, it is possible that the effects of electrons may reduce the productivity of 2,5-dibenzylpyrrole (productivity - 23,400 g C ₆ / g Cr), compared to 2,5-diethylpyrrole (productivity - 75800 g Ce / g Cr), although increased steric effects can play a significant role.
General Disclosure Information
All publications and patents mentioned in this description are incorporated into this document by reference in their entirety, for the purpose of
66/74 to describe and disclose the constructions and methods described in these publications, which can be used in connection with the methods of the present disclosure. Any publications and patents discussed above and throughout the text are provided solely for their disclosure before the date of filing this application. Nothing here should be construed as an admission that inventors are not entitled to predate such disclosure by virtue of a preceding invention.
Unless otherwise stated, when a variety of any kind is disclosed or claimed, for example, a range of carbon atoms number, molar proportions, temperature, and the like, it is intended to individually disclose or claim each possible number that a range could so reasonably cover, including any sub-ranges covered in this document. For example, when describing a range of number of carbon atoms, each possible individual integer and ranges between the whole numbers of atoms that the range includes are included in this document. Thus, when disclosing a C 1 to C-ιο alkyl group or an alkyl group having 1 to 10 carbon atoms or up to 10 carbon atoms, the applicants' intention is to recite that the alkyl group may have 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms, and these methods for describing such a group are interchangeable. When describing a series of measures, such as molar ratios, each possible number that such a range can reasonably cover, for example, refers to values within the range with a significant figure more than is present at the end points of a range. In this example, a molar ratio between 1.03: 1 and 1.12: 1 individually includes molar ratios of 1.03: 1, 1.04: 1, 1.05: 1, 1.06: 1, 1, 07 : 01, 1.08: 1, 1.09: 1, 1.10: 1, 1.11: 1 and 1.12: 1, the applicant's intention is that these two methods for describing the range are interchangeable. In addition, when a range of values is disclosed or claimed, the claimants' intention is to individually reflect each possible number that a range could so reasonably cover, claimants intend to disclose a range to reflect, and be interchangeable with, the entire disclosure and any sub-bands and sub-band combinations covered in this document. In this regard, disclosure of applicants for a C 1 to C 6 alkyl group is intended to literally cover a C ₁ to C ₆ alkyl group, a C ₄ to C ₆ alkyl group, a C ₂ to C ₇ alkyl group, a combination of an alkyl group Ci to _C3 and an alkyl group C5 to _C7, and so on. When describing a range where the end points of the range have different numbers of significant digits, for example, a
67/74 molar ratio from 1: 1 to 1.2: 1, for every possible number that such a range can reasonably cover, for example, it refers to values within the range with a significant digit more than is present at the end point of a range that has the largest number of significant digits, in this case 1.2: 1. In this example, the 1: 1 to 1.2: 1 molar ratio individually includes 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1 molar ratios , 08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, and 1, 20, all in relation to 1, and any and all sub-bands and sub-combinations of bands included in this report. Accordingly, claimants reserve the right to save or exclude any individual elements from any of these groups, including any sub-bands or combinations of sub-bands within the group, if for any reason the claimants choose to claim less than the full measure of disclosure, for example, to account for a reference that applicants are not aware of when submitting the application.
In any Order prior to the United States Patent and Trademark Office, the Summary of this Order is provided for the purpose of meeting the requirements of 37 CFR § 1.72 and the purposes stated in 37 C.F.R. § 1.72 (b) to allow the United States Patent and Trademark Office and the general public to quickly determine from a quick inspection the nature and content of technical information. Therefore, the summary of this request is not intended to be used to interpret the scope of the claims or to limit the scope of the matter that is disclosed in this document. In addition, any titles that may be employed here are also not intended to be used to interpret the scope of the claims or to limit the scope of the matter that is disclosed in this document. Any use of the verb in the past to describe an example that is indicated as prophetic or constructive is not intended to reflect that the prophetic or constructive example has actually been realized.
For any specific compound described in this document, the general name or structure presented in this document is also intended to cover all structural isomers, conformational isomers and stereoisomers, which may arise from a given set of substituents, unless otherwise indicated. . Thus, a general reference to a compound includes all structural isomers, unless explicitly stated otherwise; for example, a general reference to butane includes n-pentane, 2-methyl-butane and 2,2-dimethylpropane. In addition
68/74 reference to a general name or structure covers all enantiomers, diastereomers and other optical isomers either in racemic or enantiomeric forms, as well as mixtures of stereoisomers, as the context allows or requires. For any specific name or formula that is presented, any name or general formula presented also covers all conformational isomers, regioisomers and stereoisomers, which may arise from a given set of substituents.
The present description is further illustrated by the following examples, which are not to be interpreted in any way as imposing limitations on the scope of the same. On the contrary, it is to be clearly understood that they may have to resort to several other aspects, modalities, modifications and their equivalents that, after reading the present description, can be suggested to a person skilled in the art without departing from the spirit of the invention or the scope of the attached claims.
In the following examples, unless otherwise specified, the syntheses and preparations described in this document were carried out under an inert atmosphere such as nitrogen and / or argon. The solvents were purchased from commercial sources and were normally dried before use. Unless otherwise specified, the reagents were obtained from commercial sources.
EXAMPLES
General Experimental Procedures and Starting Materials
Unless otherwise specified, all reactions were carried out under an inert atmosphere. All glass products were oven dried at 100 ° C for 4 hours and brought in an inert atmosphere glove box (dry box) while hot. All solvents were purchased from Aldrich as anhydrous grade and were stored on newly activated 5Â molecular sieves.
A. Pirróis.
The following abbreviations are used for the pyrrole and indole binders used in this document: 2,4-dimethyl-pyrrole (2,4-DMP), 2-methyl-4-isopropylpyrrole (2-M-4-IPP); 2,5-dimethyl-pyrrole (2,5-DMP or DMP); 2,5-diethylpyrrole (2,5-DEP or DEP); 2,5-dibenzylpyrrole (2,5-PAD or PAD), 2,5-diisopropylpyrrole (2,5-DIP or DIP); indole (Ind), 2-methyl-indole (2-Melnd) and pyrrole (Pyr).
The compounds 2,4-dimethyl-pyrrole (2,4-DMP), indole, and 2-methyl-indole were purchased from Aldrich. Both indole (RP> 99%) and 2-methyl-indole (RP 98%)
69/74 were dried under vacuum at 110 ° C for several hours, without further purification (RP is the reported purity in% by weight; MP is the purity measured in% by weight). 2,4-dimethyl-pyrrole (2,4-DMP, RP 97%) was purified by distillation under a nitrogen atmosphere (bp = 165 to 167 ° C), producing a colorless liquid (99.5% MP).
Other binders, such as 2,5-diethylpyrrole (2,5-DEP), 2,5-dibenzylpyrrole (2,5PD), 2,5-diisopropylpyrrole (2,5-DIP), and 2-methyl-4 -isopropypyrrole (2-M-4-IPP) were obtained from Chemstep (Carbon-Blanc, France). 2,5-DIP (RP> 95%) was received as a colorless liquid (MP 96.8%) and was used without further purification. 2,5-DEP (RP%> 97) was distilled (98.5% MP) before use. 2,5-PAD (RP 82%), was received as an orange waxy material (MP 82.2%) and was used without further purification. 2-M-4-IPP was distilled (98.1% MP) before use. The identity of these four pyrroles was confirmed by GC-MS.
B. Preparation of Catalyst
A catalyst solution was prepared using the standard procedure described in this document, in which the molar ratios of TEA (triethyl aluminum) to DEAC (diethyl aluminum chloride) of pyrrole compound to Cr were standardized for TEA: DEAC: pyrrole: Cr = 11: 08: 03: 1. Degassed anhydrous ethylbenzene was added to a dry bottle from a dry box. Pure triethyl aluminum (TEA) and pure diethyl aluminum chloride (DEAC) were added to this flask. The contents were mixed and left to stand for 15 minutes. The selected pyrrole was then added slowly, as the evolution of the gas was observed in most cases. Chromium 2-ethylhexanoate (11) (7.25% by weight of Cr in ethylbenzene) was used as the transition metal compound, and was added slowly to the alkyl aluminum / pyrrole solution with stirring. The catalyst solution was diluted to a concentration of 5.6 mg Cr / ml by adding an appropriate amount of ethylbenzene to constitute the active catalyst that was used as prepared. Orange solutions were observed for 2,4-DMP, 2-methyl-indole and 2,5-DEP based on catalyst, which are typical. 2,5-PAD initially produced an orange solution, but gradually precipitated a considerable amount of solid gray over 24 hours. Both indole and pyrrole produced an orange colored solution with a fluffy white solid that was removed by filtration. The abundant amounts of
2,5-DIP produced from the black precipitate suggested that the catalyst solution was relatively unstable.
EXAMPLE 1
Oligomerization reactions
70/74
Oligomerization reaction studies were carried out comparing the catalytic behavior of different pyrroles under standard selective 1-hexene oligomerization reaction conditions, as follows. The standard reactor was a 1L batch reactor, and the oligomerization reactions were carried out at the temperature indicated under 50 psig H ₂ , and ethylene under 850 psig with ethylene capture on demand, plus 30 minutes of run time, using 2.5 mg of Cr in 450 mL of cyclohexane. This methodology was useful to identify several substituted pyrroles that provided reactive catalysts.
Catalyst System Productivity as a Function of
Temperature
The activity of selected pyrroles and their catalyst systems was investigated. Particularly, catalyst systems that employed 2,5dimethylpyrrole (2,5-DMP), 2,5-dibenzylpyrrole (2,5-DBP), 2,4-dimethylpyrrole (2,4-DMP), pyrrole, 2,5- diethylpyrrole (2,5-DEP), and 2-methyl-4-isopropylpyrrole (2-M-4-IPP) were investigated for their catalytic temperature profile, in which their activity and productivity were examined as a function of temperature. Figure 1 illustrates a portion of productivity (g Ce / g Cr) as a function of temperature (° C), for chromium-based catalyst systems prepared using the following pyrroles:
2.5-dimethylpyrrole (2,5-DMP); 2,5-dibenzylpyrrole (2,5-DMP); 2,4-dimethylpyrrole (2,4DMP); pyrrole; 2,5-diethylpyrrole (2,5-DEP) and 2-ethanolamine-4-isopropylpyrrole (2-M-4IPP). The productivity of figure 1 versus the temperature data are listed in table 1, among other things, these studies indicated that each pyrrole is typically characterized by its own unique temperature profile, which can be easily verified, and which can be used to establish ideal or desirable operating conditions.
As illustrated in figure 1 and the data in table 1, a consequence of comparing the productivity of different catalyst systems at a single standard temperature is that an incomplete comparative table may result. For example, at higher temperatures (130 to 135 ° C) the 2.5-DMP and 2.5-DEP catalyst systems provide some comparable results (25,900 g C ₆ / g Cr and 22,828 g C ₆ / g Cr , respectively), but when compared to their respective higher productivity at about 92 to 95 ° C, this difference in productivity was exaggerated. At these lower temperatures, the
2.5- DMP (99.460 g C ₆ / g Cr, 95 ° C) is approximately 31% more productive than the corresponding 2.5-DEP catalyst system (75.757 g Cq / g Cr, 92 ° C).
71/74
Catalyst System Productivity as a Function of
Pirrol replacement
The oligomerization data, data provided in Table 1 and figure 1, illustrate that 2,5-disubstituted pyrroles provide catalysts generally with higher productivity than those that do not contain 2,5-disubstituted pyrroles. Generally, catalytic productivity has been observed to increase in the movement of unsubstituted pyrrole to 2,4-dimethyl pyrrole, to 2,4-disubstituted pyrrole having a bulky substituent in position 4, to 2,5-disubstituted pyrrole (2,5dimethylpyrrole prototypical pyrrole being 2.5-disubstituted).
Table 1. Productivity (g CqI g Cr) versus temperature for a variety of pyrrole compounds. These data are illustrated in figure 1.
Pyrrole Compound Temperature (° C) Productivity(g C6 / g Cr) HDEP 92 75,757 98 74,478 105 66,443 115 39,233 130 22,828 NH2,5-DMP 95 99,460 105 87,300 115 60,660 125 43,000 135 25,900 HDBP 45 2,792 70 15,021 85 23,411 115 9,325 NH 100 11,882 115 14,278 130 13,523
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2,4-DMP 145 13.404 ryHH2-methyl-4-isopropyl pyrrole 100 30,300 115 43,900 ONHpyrrole 90 6.427 115 6.138 125 2.977
1-Hexene Purity and Selectivity as a Pyrrole Replacement Function
Table 2 and Figure 2 provide a comparison between C ₆ selectivity (C ₆ of the total oligomerized product) and 1-hexene (% by weight) of the C ₆ product (1-hexene purity) for catalyst systems using pyrroles. indicated in the highest observed productivity of the catalyst system. The data in Figure 2 and Table 2 illustrate the purities of 1-hexene and higher C selectivities are generally obtained with compounds of 2,5-disubstituted pyrrole and 2,4-disubstituted pyrrole having a bulky substituent at position 4 at their temperatures of higher catalyst productivity measures. As shown in figure 2, 2,5-DMP, 2,5-DEP, 2,5-DIP and 2,5-DBP, 2-M-4-IPP, as well as others such as 2-Melnd, appear to offer a good combination of Οθ selectivity and 1-hexene purity.
Productivity of 1-Hexene as a Function of Systems
Indole Based or Pyrrole Based Catalyst
Additional experiments were carried out to evaluate the potential effect of using fused ring compounds such as indole or substituted indole as the nitrogen-containing compound in the catalyst systems. 2-Methyl-3-ethyl-5methylpyrrole (21,700 g Ce / g Cr) and 2-methylindol (3,500 g Cei g Cr) have a similar substitution pattern, with similar steric congestion. However, the productivity of the catalyst systems produced using these frozen compounds differed by more than 600%. In addition, indole (800 g Cei g Cr) produced a catalyst with almost an order of lower productivity of magnitude than the pyrrole catalyst (6,400 g C ₆ / g Cr). These data can be compared with the productivity of 2,5-dibenzylpyrrole (23,400 g C ₆ / g Cr) compared to
73/74 a of 2,5-diethylpyrrole (75,800 g Q, qI g Cr), while the increased steric effects may play a role in this observed productivity.
Table 2. Purity of 1-Hexene (% of total C6 product) and selectivity of C6 (% of total oligomerized product) for a variety of pyrrole compounds, reported at the highest observed temperature (° C) (g Cg / g Cr), using the catalyst prepared according to the examples.
Compound Productivity (g C ₆ / g Cr) Temperature(° C) Purity of 1-Hexene Cg selectivity € 0NHindole 789 115 95.21 93.1 XDNH2-methylindole 3.508 115 98.48 94.93 vÇv2.5-DIP 3,631 115 98.89 94.57 ONHpyrrole 6.427 90 96.54 95.39 NH2,4-DMP 14,284 115 96.46 92.89 ΓΛH2-methyl-4-isopropyl pyrrole 43,900 100 98.90 95.95 HDBP 23,411 85 99.38 96.13
74/74
Λ,ΝΗ2,5-DMP 99,456 95 99.02 91.72 ΗDEP 75,757 92 99.20 94.21
1/6

权利要求:
Claims (6)
[1]
1. Catalytic system characterized by comprising:
a) a transition metal compound in which the transition metal in the transition metal compound is chromium;
b) a pyrrole compound having
i) a hydrogen atom located on at least one pyrrole ring carbon atom adjacent to the pyrrole ring nitrogen atom, and ii) a bulky C3 to Cie hydrocarbyl group or a bulky C3 to Ceo trihydrocarbyl group located in a bulky Ceo pyrrole ring carbon atom adjacent to any pyrrole ring carbon atom having the hydrogen atom adjacent to the pyrrole ring nitrogen atom; and
c) an alkyl metal comprising an alkyl aluminum compound.
[2]
2. Catalytic system, according to claim 1, characterized by the fact that
i) the carbon atom of the bulky C3 hydrocarbyl group attached to the carbon atom of the pyrrole ring is bonded to three or four carbon atoms, ii) the carbon atom of the bulky C3 hydrocarbyl group adjacent to the carbon atom attached to the carbon atom of the pyrrole ring is attached to three or four carbon atoms, or iii) the silicon atom of the bulky C3a trihydrocarbyl Ceo sily group attached to the carbon atom of the pyrrole ring is attached to four carbon atoms.
[3]
3. Catalytic system, according to claim 1, characterized by the fact that
b) the pyrrole compound has the Formula P2, P3 or P4:
on what
i) R ^12p and R ^13p of Formula P2 and R ^22p of Formula P3 independently are a hydrocarbyl group C1 to C15; and
Petition 870180071904, of 16/08/2018, p. 9/14
2/6 ii) R ^14p in Formula P2, R ^24p in Formula P3, and R ^33p and R ³⁴¹³ in Formula P4 are, independently, a bulky C3 to C15 hydrocarbyl group or a bulky C3 to C45 trihydrocarbyl group.
[4]
4. Catalytic system according to claim 3, characterized by the fact that the group R ^14p in Formula P2, group R ^24p in Formula P3 and groups R ^33p and R ³⁴¹³ in Formula P4 are linked so that
i) the carbon atom attached to the pyrrole ring is attached to three or four carbon atoms,
II) the carbon atom adjacent to the carbon atom attached to the 10 pyrrole ring is attached to three or four carbon atoms, or
III) the C3a C45 trihydrocarbyl silyl group has Formula Si1 p1s
R ^2s -Si— *
R ³ ® ⁷
Si1 where R ^1s , R ^2s and R ^3s are independently a C1 to C15 hydrocarbyl group.
5. Catalytic system according to claim 3, characterized by the fact that R ^14p in Formula P2, R ^24p in Formula P3, and R ^33p and R ³⁴¹³ in Formula P4 are, independently, a propan-2-yl group , a butan-2-yl, a 2-methylpropan-1-yl group, a 2-methylpropan-2-yl group, a pentan-2-yl group, a pentan-3-yl group, a 2-methylbutan-1- group ila, a 2-methylbutan-2-yl group, a group
20 3-methylbutan-2-yl, a 2,2-dimethylpropan-1-yl group, a hexan-2-yl group, a hexan-3-yl group, a 2-methylpentan-1-yl group, a group 2 -ethylbutan-1-yl, a 2-methylpentan-2-yl group, a 2,3-dimethylbutan-1-yl group, a 2,3-dimethylbutan-2-yl group, a heptan-2-yl group, a heptan group -3-yl, a heptan-4-yl group, a 2-methylhexan-1-yl group, a 2-ethylpentan-1-yl group, a group
25 2-methyl-hexan-2-yl, a 2,3-dimethylpentan-1-yl group, a 2,3-dimethylpentan2-yl group, a 2,3,3-trimethylpentan-1-yl group, a group 2 , 3,3-trimethylpentan-2-yl, an octan-2-yl group, an octan-3-yl group, an octan-4-yl group, a 2-methylheptan-1-yl group, a 2-ethyl group -hexan-1-yl, a 2-methyl-heptan-2-yl group, a nonan-2-yl group, a nonan-3-yl group, a nonan-4-yl group, a nonan-5-yl group ,
30 is a decan-2-yl group, a decan-3-yl group, a decan-4-yl group, or a decan-5-yl group.
Petition 870180071904, of 16/08/2018, p. 10/14
3/6
6. Catalytic system according to claim 3, characterized by the fact that the pyrrole compound is 2-methyl-4-isopropylpyrrole, 2-ethyl-4-isopropylpyrrole, 2-methyl-4-t-butylpyrrole or 2- ethyl-4-t-butylpyrrole.
7. Catalytic system according to claim 3, characterized by the fact that the chromium compound comprises a chromium (II) or chromium (II) halide, 1,3-diketonate or carboxylate.
8. Catalytic system according to claim 3, characterized by the fact that the chromium compound comprises a chromium (ll) or chromium (lll) carboxylate in which each carboxylate is a C4 to C19 carboxylate,
10. Catalytic system according to claim 3, characterized by the fact that the chromium compound is chromium 2-ethylhexanoate (lll), chromium octanoate (lll), 2,2,6,6, - chromium tetramethylheptanedionate (lll), chromium naphthenate (lll), chromium acetate (lll), chromium propionate (lll), chromium butyrate (lll), chromium neopentanoate (lll), chromium laurate (lll) , chromium stearate (lll),
15 chromium oxalate (ll), chromium bis (2-ethylhexanoate) (ll), chromium acetate (ll), chromium propionate (ll), chromium butyrate (ll), chromium neopentanoate (ll), chromium laurate (ll), chromium stearate (ll), chromium oxalate (ll) or any combination thereof.
10. Catalytic system according to claim 1, characterized by the
20 the fact that the alkyl aluminum compound comprises a trialkyl aluminum compound, a dialkyl aluminum halide compound, an alkyl aluminum dihalide compound, a dialkyl aluminum hydride compound, an alkyl aluminum dihydride compound, a dialkyl aluminum hydrocarbon compound, a dihydrocarbon dioxide compound of alkyl aluminum, a compound
25 of alkyl aluminum sesqui-halide, an alkyl aluminum sesquihydrocarbon compound, an aluminoxane or any combination thereof.
11. Catalytic system according to claim 1, characterized in that it further comprises a halogen containing compound which is a metal halide and alkyl metal halide or an organic halide.
12. Catalytic system according to claim 3, characterized in that the transition metal compound comprises a chromium (ll) or chromium (lll) carboxylate, in which each carboxylate is a C4 to C19 carboxylate and the alkyl metal comprises a mixture of triethyl aluminum chloride and diethyl aluminum.
13. Oligomerization process characterized by comprising:
A) contacting a raw material olefin with the catalyst system as defined in claim 1; and
Petition 870180071904, of 16/08/2018, p. 11/14
4/6
b) oligomerize the olefin under oligomerization conditions to form an oligomerization product.
14. Oligomerization process, according to claim 13, characterized by the fact that
a) the raw material olefin comprises ethylene and the oligomerization product comprises 1-hexene,
b) the transition metal compound is a chromium (II) or chromium (II) carboxylate, wherein each carboxylate is a C4 to C19 carboxylate;
c) the pyrrole compound has the Formula P2, P3 or P4:
on what
i) R ^12p and R ^13p of Formula P2 and R ^22p of Formula P3 are, independently, a hydrocarbyl group C1 to C15; and ii) R ^14p in Formula P2, R ^24p in Formula P3, and R ^33p and R ³⁴¹³ in Formula P4 are, independently, a bulky C3 to C15 hydrocarbyl group or a bulky C3 to C45 trihydrocarbyl group; and
d) the alkyl metal comprises a mixture of triethyl aluminum chloride and diethyl aluminum.
15. Process for preparing a catalytic system characterized by understanding contact with:
a) a transition metal compound in which the transition metal in the transition metal compound is chromium;
b) a pyrrole compound having
i) a hydrogen atom located on at least one pyrrole ring carbon atom adjacent to the pyrrole ring nitrogen atom, and ii) a bulky C3 to Cie hydrocarbyl group or a bulky C3 to Ceo trihydrocarbyl group located in a bulky Ceo pyrrole ring carbon atom adjacent to any pyrrole ring carbon atom having the hydrogen atom adjacent to the pyrrole ring nitrogen atom; and
c) an alkyl metal comprising an alkyl aluminum compound.
Petition 870180071904, of 16/08/2018, p. 12/14
[5]
5/6
16. Process, according to claim 15, characterized by the fact that
a) the transition metal compound is a chromium (II) or chromium (II) carboxylate, wherein each carboxylate is a C4 to C19 carboxylate;
5 b) the pyrrole compound has Formula P2, P3 and P4:
on what
i) R ^12p and R ^13p of Formula P2 and R ^22p of Formula P3 are, independently, a hydrocarbyl group C1 to C15; and ii) R ^14p in Formula P2, R ^24p in Formula P3, and R ^33p and R ³⁴¹³ in Formula P4 are, independently, a bulky C3 to C15 hydrocarbyl group or a bulky C3 to C45 trihydrocarbyl group; and
c) the alkyl metal comprises a mixture of triethyl aluminum chloride and diethyl aluminum.
17. Process according to claim 16, characterized in that the transition metal compound, pyrrole and alkyl metal are bonded in the presence of an unsaturated compound.
18. Process according to claim 17, characterized by the fact that the unsaturated compound comprises an aromatic compound Οβ a Cie.
19. Process according to claim 16, characterized by the fact that R ^14p in Formula P2, R ^24p in Formula P3, and R ^33p and R ³⁴¹³ in Formula P4 are, independently, a propan-2-yl group, a butan-2-yl, a 2methylpropan-1-yl group, a 2-methylpropan-2-yl group, a pentan-2-yl group, a pentan-3-yl group, a 2-methylbutan-1-yl group, a 2-methylbutan-2-yl group, a 3-methylbutan-2-yl group, a 2,2-dimethylpropan-1-yl group, a hexan-2-yl group, a hexan-3-yl group, a group 2-methylpentan-1-yl, a 2-ethylbutan-1-yl group, a 2-methylpentan-2-yl group, a 2,3-dimethylbutan-1-yl group, a 2,3dimethylbutan-2-yl group, a heptan-2-yl group, a heptan-3-yl group, a heptan-4-yl group, a 2-methylhexan-1-yl group, a 2-ethylpentan-1-yl group, a 2- group methyl-hexan-2-yl, a 2,3-dimethylpentan-1-yl group, a 2,3-dimethylpentan groupPetition 870180071904, of 16/08/2018, p. 13/14
[6]
6/6
2-yl, a 2,3,3-trimethylpentan-1-yl group, a 2,3,3-trimethylpentan-2-yl group, an octan-2-yl group, an octan-3-yl group, a group octan-4-yl, a 2-methylheptan-1-yl group, a 2-ethylhexan-1-yl group, a 2-methyl-heptan-2-yl group, a nonan-2-yl group, a group nonan-3-ila, a nonan-4-ila group, a nonan-5-ila group,
5 is a decan-2-yl group, a decan-3-yl group, a decan-4-yl group, or a decan-5-yl group.
20. Process according to claim 16, characterized in that the pyrrole compound is 2-methyl-4-isopropylpyrrole, 2-ethyl-4-isopropylpyrrole, 2methyl-4-t-butylpyrrol or 2-ethyl-4 -t-butylpyrrole.
Petition 870180071904, of 16/08/2018, p. 14/14
120,000 (jq § / 93 soinpoid §) aphptApnpoij
Oligomerization temperature (° C)

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法律状态:
2018-05-22| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2018-10-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2018-12-04| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/04/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US12/771,122|2010-04-30|

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US12/771,122|US8471085B2|2008-10-31|2010-04-30|Oligomerization catalyst system and process for oligomerizing olefins|

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PCT/US2011/033431|WO2011137027A1|2010-04-30|2011-04-21|Oligomerization catalyst system and process for oligomerizing olefins|

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