Metallocene-based catalyst composition with an alcohol compound and olefin polymerization process

Description

"Metallocene-based catalyst composition with an alcohol compound and olefin polymerization process" FIELD OF THE INVENTION

[001] This disclosure relates to metallocene-based catalyst systems and, more particularly, to the use of an alcohol compound during the preparation of metallocene-based catalyst systems. FUNDAMENTALS OF THE INVENTION

[002] There are several methods used to prepare metallocene-based catalytic systems containing an activator-support. These catalytic systems can be used to polymerize olefins to produce olefin-based polymers, such as ethylene / α-olefin copolymers. Using the same metallocene, activator-support, and organoaluminum components of the catalytic system, it would be beneficial for these catalytic systems to have higher catalytic activities for the production of olefin-based polymers. Consequently, the present invention relates generally to these purposes. SUMMARY OF THE INVENTION

[003] This summary is provided to present a selection of concepts that are better described below in the detailed description. This summary is not intended to identify necessary or essential features of the claimed subject matter. Nor is it intended to be used to limit the scope of the claimed subject matter.

[004] The present invention relates generally to novel catalyst compositions, methods for preparing catalyst compositions, methods for using catalyst compositions to polymerize olefins, polymeric resins produced using such catalyst compositions, and articles produced using these polymeric resins. In particular, the present invention relates to methods for preparing metallocene-based catalyst compositions and to the resulting catalyst compositions. The catalyst compositions of the present invention can be used to produce, for example, ethylene-based homopolymers and copolymers.

[005] Several processes related to the preparation of metallocene-based catalyst compositions are disclosed in this document. In one aspect, a process is provided for producing a catalyst composition and, Petition 870260049981, dated 05 / 26 / 2026, p. 10 / 64 2 / 44 In this respect, the process may comprise (i) contacting an alcohol compound with an organoaluminum compound for a first period of time to form a pre-contacted mixture, and (ii) contacting the pre-contacted mixture with an activating support and a metallocene compound for a second period of time to form the catalyst composition. While we do not wish to be bound by the following theory, it is believed that the metallocene-based catalyst composition, prepared as described herein, may exhibit an unexpected increase in catalytic activity.

[006] Catalyst compositions are also covered by the present invention. In one aspect, the catalyst composition may comprise (A) an activating support, (B) a metallocene compound, (C) an organoaluminum compound, and (D) a dialkyl aluminum alkoxide. Optionally, the catalyst composition may further comprise an alkyl aluminum dialkoxide and / or an aluminum trialkoxide.

[007] The present invention also contemplates and encompasses olefin polymerization processes. Such processes may comprise contacting a catalyst composition with an olefin monomer and, optionally, an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer. Generally, the catalyst composition employed may comprise any of the metallocene-based catalyst systems disclosed herein or a metallocene-based catalyst system prepared by any of the processes disclosed in this document.

[008] Both the aforementioned summary and the following detailed description provide examples and are merely explanatory. Consequently, the preceding summary and the following detailed description should not be considered restrictive. Furthermore, features or variations may be provided beyond those set forth in this document. For example, certain aspects and modalities may be directed to various combinations and subcombinations of features described in the detailed description. DEFINITIONS

[009] To define more clearly the terms used in this document, the following definitions are provided. Unless otherwise indicated, the following Petition 870260049981, dated 05 / 26 / 2026, page 11 / 64 3 / 44 definitions are applicable to this disclosure. If a term is used in the disclosure but is not specifically defined in this document, the definition from the IUPAC Compendium of Chemical Terminology, 2nd Ed. (1997) may be applied, provided that such definition does not conflict with any other disclosure or definition applied in this document, render indefinite, or make impossible any claim for that definition to apply. To the extent that any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein shall prevail.

[0010] In this document, material features are described in such a way that, within particular aspects, a combination of different features can be anticipated. For any and all aspects and / or features disclosed in this document, all combinations that do not adversely affect the designs, compositions, processes and / or methods described in this document are contemplated with or without explicit description of the particular combination. Furthermore, unless explicitly indicated otherwise, any aspect and / or feature disclosed herein may be combined to describe inventive features consistent with this disclosure.

[0011] Although compositions and methods are described in this document in terms of “comprising” various components or steps, compositions and methods may also “consist essentially of” or “consist of” various components or steps, unless stated otherwise.

[0012] The terms “a”, “an”, “the” and “the” are intended to include plural alternatives, for example, at least one. For example, the disclosure of “an activating support” and “a metallocene compound” is intended to cover one, or mixtures or combinations of more than one, activating support and metallocene compound, respectively, unless otherwise specified.

[0013] For any particular compound or group disclosed herein, any name or structure (general or specific) presented is also intended to encompass all conformational isomers, regioisomers, stereoisomers, and mixtures thereof that may arise from a particular set of substituents, unless otherwise indicated. The name or structure (general or specific) also encompasses all enantiomers, diastereomers, and other optical isomers (if any), whether in enantiomeric or racemic forms, as well as mixtures thereof. Petition 870260049981, dated 05 / 26 / 2026, p. 12 / 64 4 / 44 stereoisomers, as would be recognized by one skilled in the art, unless otherwise indicated. Thus, a general reference to a pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane, while a general reference to a butyl group includes an n-butyl group, a sec-butyl group, an iso-butyl group, and a t-butyl group.

[0014] The term polymer is used generically in this document to include homopolymers, copolymers, olefin terpolymers, and so forth. The term polymer as used in this document also includes impact, block, graft, random, and alternating copolymers. A copolymer is derived from an olefin monomer and an olefin comonomer, while a terpolymer is derived from an olefin monomer and two olefin comonomers. Thus, polymer encompasses both copolymers and terpolymers. Similarly, the scope of the term polymerization includes homopolymerization, copolymerization, terpolymerization, etc. Therefore, an ethylene polymer includes ethylene homopolymers, ethylene copolymers (e.g., ethylene / α-olefin copolymers), ethylene terpolymers and the like, as well as blends or mixtures thereof. Thus, an ethylene polymer encompasses polymers frequently referred to in the art as LLDPE (linear low-density polyethylene) and HDPE (high-density polyethylene).For example, an olefin copolymer, such as an ethylene copolymer, can be derived from ethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. If the monomer and comonomer were ethylene and 1-hexene, respectively, the resulting polymer can be categorized as an ethylene / 1-hexene copolymer. The term "polymer" also includes all possible geometric configurations unless otherwise stated, and such configurations may include isotactic, syndiotactic, and random symmetries. The term polymer is also intended to include all polymers of molecular mass.

[0015] The terms “catalyst composition”, “catalyst mixture”, “catalyst system” and the like are independent of the actual product or composition resulting from the contact or reaction of the initial components of the disclosed or claimed catalyst composition / mixture / system, the nature of the active catalytic site, or the fate of the alcohol compound(s), organoaluminum compound(s), metallocene compound(s), or activator support(s)(s) after the combination of these components. Therefore, the terms “catalyst composition”, “mixture of Petition 870260049981, dated 05 / 26 / 2026, page 13 / 64 The terms “catalyst,” “catalyst system,” and the like encompass the initial starting components of the composition, as well as any product(s) that may result from the contact of these initial starting components, and this is inclusive of both heterogeneous and homogeneous catalyst systems or compositions. The expressions catalyst composition, catalyst mixture, catalyst system, and the like may be used interchangeably throughout this disclosure.

[0016] The term contact product is used in this document to describe compositions in which the components are brought into contact in any order, in any manner, and for any period of time, unless otherwise specified. For example, the components may be combined by blending or mixing, or by using any suitable technique. The contact or combination of two or more components may form a reaction product or a reaction mixture.

[0017] A “pre-contacted mixture” describes a mixture of catalyst components that are combined or brought into contact for a period of time before coming into contact with other catalyst components. According to this description, it is possible that the components of the pre-contacted mixture, once contacted, have reacted to form at least one chemical compound, formulation, species, or structure different from the distinct initial compounds or components used to prepare the pre-contacted mixture.

[0018] The term “hydrocarbon” refers to a compound containing only carbon and hydrogen. The term “hydrocarbyl group” is used in this document in accordance with the definition specified by IUPAC: a univalent group formed by the removal of a hydrogen atom from a hydrocarbon (i.e., a group containing only carbon and hydrogen). Non-limiting examples of hydrocarbyl groups include alkyl, alkenyl, aryl, and aralkyl groups, among others.

[0019] Several numerical ranges are disclosed in this document. When a range of any kind is disclosed or claimed, the intention is to disclose or claim individually every possible number that such range could reasonably encompass, including range endpoints, as well as any subranges and combinations of subranges encompassed therein. As a representative example, this disclosure cites that the weight ratio of the metallocene compound to the support Petition 870260049981, dated 05 / 26 / 2026, p. 14 / 64 The 6 / 44 activator in a catalyst composition may be in certain ranges. By disclosing that the weight ratio may be in a range of 1:1 to 1:1,000,000, the intention is to state that the weight ratio may be any ratio in the range and, for example, may include any range or combination of ranges from 1:1 to 1:1,000,000, such as 1:10 to 1:10,000, 1:20 to 1:1,000, or 1:50 to 1:500, and so forth. Similarly, all other ranges disclosed herein should be interpreted in a manner similar to these examples.

[0020] In general, a quantity, size, formulation, parameter, range, or other quantity or characteristic is "about" or "approximate," whether or not expressly stated as such. Whether or not modified by the term about, the claims include equivalents to the quantities.

[0021] Although any methods, devices and materials similar or equivalent to those described in this document may be used in the practice or testing of the invention, the typical methods, devices and materials are described in this document.

[0022] All publications and patents mentioned herein are incorporated herein by reference in their entirety for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications and patents, which may be used in connection with the invention presently described. DETAILED DESCRIPTION OF THE INVENTION

[0023] Methods for preparing metallocene-based catalyst compositions using a metallocene compound, an activating support, an organoaluminum compound, and a controlled amount of an alcohol compound are disclosed in this document. Polymerization processes using these catalytic compositions are also disclosed.

[0024] Alcoholic compounds are normally poisons that can deactivate metallocene-based catalyst systems and are therefore avoided. However, by using a controlled amount of the alcohol compound, the catalyst methods and compositions disclosed in this document show an unexpected increase in catalytic activity. PROCESSES FOR PREPARING CATALYST COMPOSITIONS

[0025] Various processes for preparing a catalyst composition that Petition 870260049981, dated 05 / 26 / 2026, page 15 / 64 7 / 44 containing a metallocene compound, an activating support, and an organoaluminum compound are disclosed and described. One or more of a metallocene compound, one or more of an activating support, and one or more of an organoaluminum compounds may be employed in the disclosed processes and compositions. A process for producing a catalytic composition consistent with aspects of this invention may comprise (or essentially consist of, or consist of): (i) contacting an alcohol compound with an organoaluminum compound for a first period of time to form a pre-contacted mixture (alternatively, and equivalently, a first mixture); and (ii) contacting the pre-contacted mixture with an activating support and a metallocene compound for a second period of time to form the catalyst composition.

[0026] Generally, the characteristics of any of the processes disclosed in this document (e.g., the activating support, the organoaluminum compound, the metallocene compound, the alcohol compound, the first time period and the second time period, among others) are described independently herein, and these characteristics may be combined in any combination to better describe the disclosed processes. Furthermore, other process steps may be conducted before, during, and / or after any of the steps listed in the disclosed processes, unless otherwise indicated. In addition, catalyst compositions produced according to the disclosed processes are within the scope of this disclosure and are covered herein.

[0027] In step (i), there is a molar excess of the organoaluminum compound (or compounds) compared to the alcohol compound (or compounds). As one skilled in the art readily recognizes, an excess of the alcohol compound compared to certain components of the catalyst system can drastically reduce catalyst activity and polymer production rate and may eventually “stop” the reaction. Thus, the practical maximum amount of alcohol compound added to the catalyst system is limited. Typically, the molar ratio of hydroxyl groups (—OH) of the alcohol compound to aluminum of the organoaluminum compound (OH:Al) is within a range of 0.05:1 to 0.9:1. Representative and non-limiting ranges include, for example, an OH:Al molar ratio of 0.05:1 to 0.7:1, 0.05:1 to 0.5:1, 0.07:1 to 0.65:1, 0.1:1 to 0.8:1, 0.1:1 Petition 870260049981, dated 05 / 26 / 2026, page 16 / 64 8 / 44 to 0.7:1, or 0.2:1 to 0.6:1, and similar ratios.

[0028] Although not limited to this, the molar ratio of the alcohol compound (before the formation of the pre-contacted mixture in step (i)) to the metallocene compound (or compounds) (before the formation of the catalyst composition in step (ii)) can often vary from as low as 1:1 up to and including 1000:1. In one aspect, the molar ratio of the alcohol compound to the metallocene compound can vary from 10:1 to 500:1, while in another aspect, the molar ratio can vary from 50:1 to 750:1, and in yet another aspect, the molar ratio can vary from 100:1 to 400:1.

[0029] Similarly, and not limited to this, the weight ratio of the alcohol compound (before the formation of the pre-contacted mixture in step (i)) to the activating support (or supports) (before the formation of the catalyst composition in step (ii)) can often vary from 1:1 to 1:500. In one aspect, the weight ratio of the alcohol compound to the activating support can vary from 1:2 to 1:250, while in another aspect, the weight ratio can vary from 1:5 to 1:150, and in yet another aspect, the weight ratio can vary from 1:10 to 1:100.

[0030] Step (i) of the process can generally be referred to as the pre-contact step, and in the pre-contact step, an alcohol compound is brought into contact with an organoaluminum compound for an initial period of time to form a pre-contacted mixture. The pre-contact step can be conducted at a variety of temperatures and time periods. For example, the pre-contact step can be conducted at a pre-contact temperature in a range of 0 °C to 100 °C; alternatively, from 0°C to 75°C; alternatively, from 10°C to 75°C; alternatively, from 20 °C to 60 °C; alternatively, from 20°C to 50°C; Alternatively, from 15 °C to 45 °C; or alternatively, from 20 °C to 40 °C. In these and other respects, these temperature ranges should also cover circumstances where the pre-contact step is conducted at a series of different temperatures, rather than a single fixed temperature, being within the respective ranges, where at least one temperature is within the respective ranges.

[0031] The duration of the pre-contact stage (the first time period) is not limited to any specific time period, as long as the first time period is sufficient for any reaction to occur between the alcohol compound and the organoaluminum compound, thus forming the pre-contacted mixture. Therefore, the first time period can be, for example, a time period ranging from Petition 870260049981, dated 05 / 26 / 2026, page 17 / 64 9 / 44 to 10 seconds to 48 hours or more. The first appropriate time period may depend, for example, on the pre-contact temperature, the amounts of alcohol compound and organoaluminum compound in the pre-contacted mixture, the presence of diluents or solvents in the pre-contact step, and the degree of mixing, among other variables. Generally, however, the first time period may be at least 5 seconds, at least 15 seconds, at least 30 seconds, at least 1 minute, at least 5 minutes, at least 10 minutes, and so on. Typical ranges for the first time period may include, but are not limited to, 1 second to 15 seconds, 1 second to 10 minutes, 1 second to 48 hours, 10 seconds to 12 hours, 30 seconds to 24 hours, 30 seconds to 6 hours, 30 seconds to 5 minutes, 1 minute to 12 hours, 5 minutes to 24 hours, or 10 minutes to 8 hours, as well as ranges within these exemplary ranges.

[0032] Frequently, the pre-contact step can be carried out by combining (e.g., mixing) the alcohol compound with a solution of the organoaluminum compound in any suitable hydrocarbon solvent. The alcohol compound can be used pure or can also be diluted in any suitable hydrocarbon solvent, which may be the same as or different from that used with the organoaluminum compound.

[0033] In step (ii) of the process, the pre-contacted mixture (usually a solution) may be brought into contact with an activating support and a metallocene compound for a second period of time to form the catalyst composition. Step (ii) may likewise be conducted at a variety of temperatures and periods of time. For example, step (ii) may be conducted at a temperature in the range of 0 °C to 100 °C; alternatively, from 10 °C to 75 °C; alternatively, from 20 °C to 60 °C; alternatively, from 15 °C to 45 °C; or alternatively, from 20 °C to 40 °C. In these and other respects, these temperature ranges must also encompass circumstances in which step (ii) is conducted at a series of different temperatures, rather than a single fixed temperature, being within the respective ranges, where at least one temperature is within the respective ranges.As an example, the pre-contacted mixture, the activating support, and the metallocene compound can be contacted at an elevated temperature, followed by cooling to a lower temperature for long-term storage of the finished catalyst composition. Petition 870260049981, dated 05 / 26 / 2026, page 18 / 64 10 / 44

[0034] The second time period is not limited to any specific time period. Thus, the second time period can vary from 1 to 10 seconds up to 48 hours or more. The appropriate second time period may depend, for example, on the temperature, the quantities of the pre-contacted mixture and activating support and metallocene compound, the presence of diluents or solvents in step (ii), the degree of mixing, and considerations for long-term storage, among other variables. Generally, however, the second time period can be at least 5 seconds, at least 15 seconds, at least 30 seconds, at least 1 minute, at least 5 minutes, at least 10 minutes, and so on.Assuming the catalyst composition is not intended for long-term storage, which may extend over days or weeks, typical intervals for the second time period may include, but are not limited to, 1 second to 15 seconds, 1 second to 10 minutes, 1 second to 48 hours, 10 seconds to 12 hours, 30 seconds to 24 hours, 30 seconds to 6 hours, 30 seconds to 5 minutes, 1 minute to 6 hours, 5 minutes to 24 hours, or 10 minutes to 8 hours.

[0035] In one aspect, the pre-contacted mixture is contacted in step (ii) with the activating support before the metallocene compound, while in another aspect, the pre-contacted mixture is contacted with the metallocene compound before the activating support, and in yet another aspect, the pre-contacted mixture is contacted substantially contemporaneously with the activating support and the metallocene compound, which in this context means that the pre-contacted mixture, the activating support and the metallocene compound are contacted together as soon as commercially practicable, such as within 10 min, within 5 min, within 1 min or within 30 s, of two of the components being contacted (e.g., the metallocene compound and the activating support).

[0036] Frequently, step (ii) can be carried out by combining (e.g., mixing) the pre-contacted mixture with a flowable paste of the activating support in any suitable hydrocarbon solvent and a solution of the metallocene compound in any suitable hydrocarbon solvent (same or different). Alternatively, the activating support in dry solid form can be combined with the pre-contacted mixture and the metallocene compound. Generally, any suitable procedure known to those of common skill in the art to thoroughly combine the activating support, the metallocene compound Petition 870260049981, dated 05 / 26 / 2026, page 19 / 64 11 / 44 and the pre-contacted mixture can be used.

[0037] Non-limiting examples of suitable hydrocarbon solvents that may be used independently in step (i) or step (ii) include, but are not limited to, cyclohexane, cyclohexene, isobutane, n-butane, n-pentane, isopentane, neopentane, hexane, 1-hexene, heptane, toluene and the like, or combinations thereof. For example, the solvent used for the organoaluminum compound may be the same as or different from the solvent used for the activator-support paste and the same as or different from the solvent used for the metallocene compound.

[0038] In one aspect, the catalyst composition may comprise (A) an activating support, (B) a metallocene compound, (C) an organoaluminum compound, and (D) a dialkyl aluminum alkoxide. In a further aspect, the catalyst composition may comprise (A) an activating support, (B) a metallocene compound, (C) an organoaluminum compound, (D) a dialkyl aluminum alkoxide, and (E) an alkyl aluminum dialkoxide and / or an aluminum trialkoxide.

[0039] With regard to the organoaluminum compound in catalyst compositions and methods of its preparation, one or more organoaluminum compounds may be used. Similarly, there may be one or more alcohol compounds used to react with the organoaluminum compound to form the pre-contacted mixture (and to form one or more of a dialkyl aluminum alkoxide, an alkyl aluminum dialkoxide and / or an aluminum trialkoxide).

[0040] Referring first to organoaluminum compounds, suitable organoaluminum compounds may have the formula (RZ)3Al, wherein each RZ independently may be an aliphatic group having from 1 to 10 carbon atoms. For example, each RZ may independently be methyl, ethyl, propyl, butyl, hexyl or isobutyl. Examples of suitable organoaluminum compounds for use according to the present invention may include, but are not limited to, trialkylaluminum compounds, dialkylaluminum halide compounds, dialkylaluminum hydride compounds and combinations thereof. Specific, non-limiting examples of suitable organoaluminum compounds may include trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum chloride and the like, or combinations thereof. Petition 870260049981, dated 05 / 26 / 2026, p. 20 / 64 12 / 44 same. In one aspect, an organoaluminum compound used in the processes and catalyst systems disclosed herein may comprise (or consist essentially of, or consist of) triethylaluminum (TEA), while in another aspect, an organoaluminum compound used in the processes and catalyst systems disclosed herein may comprise (or consist essentially of, or consist of) triisobutylaluminum (TIBA). Still, in another aspect, a mixture of TEA and TIBA may be used as the organoaluminum component in the processes described herein (or as the organoaluminum component in the catalyst systems disclosed herein).

[0041] Suitable alcohol compounds for use in this document may include, for example, mono-ols (monoalcohols), diols, triols or polyols, as well as combinations thereof. In addition, suitable alcohol compounds may be linear or branched and may be a primary alcohol, a secondary alcohol or a tertiary alcohol. Typically, the alcohol compound may comprise a hydrocarbyl alcohol, although this is not a requirement. For example, the alcohol compound may comprise an alkyl alcohol, a cycloalkyl alcohol, an aryl alcohol, an arylalkyl alcohol and the like, as well as combinations thereof.

[0042] The number of carbon atoms in the alcohol compound is not particularly limited, although in some respects the alcohol compound may comprise a C1 to C32 alcohol; alternatively, a C1 to C18 alcohol; alternatively, a C1 to C12 alcohol; alternatively, a C1 to C8 alcohol; alternatively, a C1 to C4 alcohol; alternatively, a C2 to C12 alcohol; or alternatively, a C2 to C6 alcohol. Representative and non-limiting examples of suitable alcohol compounds (e.g., mono-ol compounds) may include the following: methanol, ethanol, propanol (e.g., isopropanol, n-propanol), butanol (e.g., n-butanol, isobutanol), pentanol, hexanol, heptanol, octanol, decanol, hexadecanol, cyclohexanol, phenol, benzyl alcohol and the like, as well as combinations thereof.In one aspect, the alcohol compound may comprise methanol, ethanol, propanol (e.g., isopropanol, n-propanol), butanol (e.g., n-butanol, isobutanol), pentanol, hexanol, heptanol, octanol, decanol, hexadecanol and the like, or a combination thereof. In another aspect, the alcohol compound may comprise cyclohexanol, phenol, benzyl alcohol and the like, or a combination thereof. In yet another aspect, the compound... Petition 870260049981, dated 05 / 26 / 2026, page 21 / 64 13 / 44 of alcohol may comprise methanol, ethanol, propanol (e.g., isopropanol, n-propanol), butanol (e.g., n-butanol, isobutanol), pentanol, hexanol, heptanol, octanol and the like, or a combination thereof. In another aspect, the alcohol compound may comprise methanol, ethanol, propanol (e.g., isopropanol, n-propanol), butanol (e.g., n-butanol, isobutanol) and the like, or a combination thereof, or alternatively, ethanol, propanol (e.g., isopropanol, n-propanol), butanol (e.g., n-butanol, isobutanol) and the like, or a combination thereof.

[0043] In certain respects, the alcohol compound may comprise a diol, illustrative examples of which may include, but are not limited to, methanediol, ethylene glycol, propylene glycol, butanediol (e.g., 1,4-butanediol), pentanediol, octanediol, bisphenol A and the like, as well as any combination thereof. Consequently, the alcohol compound may comprise ethylene glycol, propylene glycol or both, in some respects; alternatively, methanediol; alternatively, ethylene glycol; alternatively, propylene glycol; alternatively, butanediol (e.g., 1,4-butanediol); alternatively, pentanediol; alternatively, octanediol; or alternatively, bisphenol A.

[0044] In other respects, the alcohol compound may comprise a triol, a polyol, or combinations thereof, illustrative examples of which may include, but are not limited to, glycerol, benzenetriol, erythritol, xylitol, mannitol, and the like, as well as combinations thereof. Consequently, the alcohol compound may comprise glycerol in some respects; alternatively, benzenetriol; alternatively, erythritol; alternatively, xylitol; or alternatively, mannitol.

[0045] Beneficially, the alcohol compound, in certain respects, may be a liquid (under atmospheric pressure) at a temperature in a range of 20 °C to 400 °C; alternatively, in a range of 20 °C to 100 °C; or alternatively, in a range of 20 °C to 75 °C. For convenience, the alcohol compound used herein frequently comprises (or essentially consists of, or consists of) one or a mixture of two or more of methanol, ethanol, propanol (e.g., isopropanol, n-propanol) and / or butanol (e.g., n-butanol, isobutanol).

[0046] Dialkyl aluminum alkoxide, alkyl aluminum dialkoxide and / or aluminum trialkoxide compounds formed in the pre-contacted mixture and catalyst composition from the contact and reaction of the compound Petition 870260049981, dated 05 / 26 / 2026, p. 22 / 64 14 / 44 organoaluminum compounds with the alcohol compound may have the following formulas: dialkyl aluminum alkoxide compounds may have the formula (RZ)2Al(ORA), alkyl aluminum dialkoxide compounds may have the formula (RZ)Al(ORA)2, and aluminum trialkoxide compounds may have the formula Al(ORA%). In these formulas, each RZ and each RA may independently be a C1 to C18 alkyl group; alternatively, a C1 to C10 alkyl group; alternatively, a C1 to C6 alkyl group; or alternatively, a C1 to C4 alkyl group.

[0047] For example, if the organoaluminum compound is TEA and the alcohol compound is ethanol, then a typical dialkyl aluminum alkoxide compound formed from it is diethylaluminum ethoxide. Furthermore, a typical alkyl aluminum dialkoxide compound that can be formed from it is ethyl aluminum dioxide, and a typical aluminum trialkoxide compound that can be formed from it is aluminum triethoxide.

[0048] Unexpectedly, these catalyst compositions and methods of their preparation can result in improvements in catalytic activity. For example, the activity of the catalyst composition may be greater (e.g., by at least 10%, at least 15%, at least 20%, at least 30%, or at least 35%, and often up to 50%, 60%, 75%, or 100%) than that of an otherwise identical catalyst system obtained without the alcohol compound (or without the aluminum dialkyl alkoxide and without the aluminum alkyl dialkyl oxide and / or aluminum trialkoxide, if present), under the same catalyst preparation and polymerization conditions. The same polymerization conditions refer to flow paste polymerization conditions, using isobutane as a diluent, with a polymerization temperature of 80 °C and a reactor pressure of 320 psig.Furthermore, all components used to prepare the catalyst systems are kept constant (e.g., same quantity / type of metallocene compound, same quantity / type of organoaluminum, same quantity / type of activator support, such as fluorinated silica-alumina or sulfated alumina) and all polymerization conditions are kept constant (e.g., same polymerization temperature and same polymerization pressure). Therefore, the only difference is the method used to produce the catalyst system, i.e., the use of an alcohol compound to contact / react with the organoaluminum compound to form a pre-contacted mixture as part of the composition. Petition 870260049981, dated 05 / 26 / 2026, page 23 / 64 15 / 44 catalyst.

[0049] Generally, in the catalyst compositions and methods of their preparation disclosed in this document, the weight ratio between the activating support (or activating supports) and the organoaluminum compound (or compounds) may be in the range of 1:2 to 500:1, or 1:2 to 200:1. If more than one organoaluminum compound and / or more than one activating support are employed, this ratio will be based on the total weight of each respective component. In one aspect, the weight ratio of activating support to organoaluminum compound may be in the range of 1:1 to 100:1, 1:1 to 50:1, or 2:1 to 20:1.

[0050] Similarly, the weight ratio of the metallocene compound(s) to the activating support(s) may be in a range of 1:1 to 1:1000000, or 1:10 to 1:10000. If more than one metallocene compound and / or more than one activating support are employed, this ratio will be based on the total weight of each respective component. In one aspect, the weight ratio between the metallocene compound and the activating support may be in a range of 1:20 to 1:1000, or 1:50 to 1:500, and the like.

[0051] In some respects, catalyst compositions and methods of their preparation are substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds and / or other similar materials; alternatively, substantially free of aluminoxanes; alternatively, substantially free of organoboron or organoborate compounds; or alternatively, substantially free of ionizing ionic compounds. For example, the catalyst composition may contain less than 500 ppm, less than 100 ppm, less than 10 ppm or less than 1 ppm (by weight), regardless of aluminoxanes, organoboron or organoborate compounds and ionizing ionic compounds. In these respects, the catalyst composition has catalytic activity, as discussed in this document, in the absence of these additional materials.For example, a catalyst composition of the present invention may consist essentially of an activating support, a metallocene compound, an organoaluminum compound, a dialkyl aluminum alkoxide and an alkyl aluminum dialkoxide and / or an aluminum trialkoxide, wherein no other material is present in the catalyst composition that increases / decreases the activity of the catalyst composition by more than about 10% of the catalyst activity. Petition 870260049981, dated 05 / 26 / 2026, page 24 / 64 16 / 44 of the catalyst composition in the absence of said materials. metallocene compounds

[0052] Metallocene-based catalyst compositions consistent with this invention may contain a bridged metallocene compound and / or an unbridged metallocene compound. Metallocene-based catalyst compositions consistent with this invention may also contain two or more bridged metallocene compounds and / or two or more unbridged metallocene compounds. The metallocene compound may comprise, for example, a transition metal (one or more) from Groups IIIB-VIIIB of the Periodic Table of Elements. In one aspect, the metallocene compound may comprise a transition metal from Group III, IV, V or VI, or a combination of two or more transition metals. The metallocene compound comprises chromium, titanium, zirconium, hafnium, vanadium or a combination thereof, or may comprise titanium, zirconium, hafnium or a combination thereof, in other aspects.In other respects, the metallocene compound may comprise titanium, or zirconium, or hafnium, alone or in combination.

[0053] In some aspects of this invention, the metallocene compound may comprise a bridged metallocene compound, for example, with titanium, zirconium or hafnium, such as a zirconium or hafnium-based bridged metallocene compound with a fluorenyl group and without aryl groups in the bridged group, or a zirconium or hafnium-based bridged metallocene compound with a cyclopentadienyl group and a fluorenyl group and without aryl groups in the bridged group. These bridged metallocenes, in some aspects, may contain an alkenyl substituent (e.g., a terminal alkenyl) in the bridged group and / or in a cyclopentadienyl type group (e.g., a cyclopentadienyl group or a fluorenyl group).In another aspect, the metallocene compound may comprise a zirconium- or hafnium-based metallocene compound bridged with a fluorenyl group and an aryl group in the linking group; alternatively, a zirconium- or hafnium-based metallocene compound bridged with a cyclopentadienyl group and a fluorenyl group and an aryl group in the linking group; alternatively, a zirconium-based metallocene compound bridged with a fluorenyl group and an aryl group in the linking group; or alternatively, a hafnium-based metallocene compound bridged with a fluorenyl group and an aryl group in the linking group. In these and other aspects, the... Petition 870260049981, dated 05 / 26 / 2026, p. 25 / 64 17 / 44 The aryl group in the bridging group can be a phenyl group. Optionally, these bridging metallocenes may contain an alkenyl substituent (e.g., a terminal alkenyl) in the bridging group and / or in a cyclopentadienyl type group.

[0054] In some respects, the metallocene compound may comprise a zirconium- or hafnium-based metallocene compound bridged with two indenyl groups (e.g., a bis-indenyl metallocene compound). Therefore, the metallocene compound may comprise a zirconium-based metallocene compound bridged with two indenyl groups or, alternatively, a hafnium-based metallocene compound bridged with two indenyl groups. In some respects, an aryl group may be present in the bridged group, while in other respects there are no aryl groups present in the bridged group. Optionally, these bridged indenyl metallocenes may contain an alkenyl substituent (e.g., a terminal alkenyl) in the bridged group and / or in the indenyl group (one or both indenyl groups).The bonding atom of the linking group can be, for example, a carbon atom or a silicon atom; alternatively, the bridge can contain a chain of two carbon atoms, a chain of two silicon atoms, and so on.

[0055] Illustrative and non-limiting examples of bridged metallocene compounds (e.g., with zirconium or hafnium) that can be employed in catalyst systems consistent with aspects of the present invention are described in U.S. Patents Nos. 7,026,494, 7,041,617, 7,226,886, 7,312,283, 7,517,939 and 7,619,047.

[0056] In some aspects of this invention, the metallocene compound may comprise an unbridged metallocene; alternatively, an unbridged zirconium- or hafnium-based metallocene compound and / or an unbridged dinuclear zirconium- and / or hafnium-based metallocene compound; alternatively, an unbridged zirconium- or hafnium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or one cyclopentadienyl group and one indenyl group; alternatively, an unbridged zirconium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or one cyclopentadienyl group and one indenyl group. Illustrative and non-limiting examples of unbound metallocene compounds (e.g., with zirconium or hafnium) that can be employed in catalytic systems consistent with aspects of the present invention are described in U.S. Patents Nos. 7,199,073, 7,226,886, 7,312,283, and 7,619,047. Petition 870260049981, dated 05 / 26 / 2026, page 26 / 64 18 / 44

[0057] In addition, the metallocene compound may comprise an unbridged dinuclear metallocene, such as those described in U.S. Patents Nos. 7,919,639 and 8,080,681. The metallocene compound may comprise an unbridged zirconium- and / or hafnium-based dinuclear metallocene compound. For example, the metallocene compound may comprise an unbridged zirconium-based homodinuclear metallocene compound, or an unbridged hafnium-based homodinuclear metallocene compound, or an unbridged zirconium- and / or hafnium-based heterodinuclear metallocene compound (i.e., a dinuclear compound with two hafniums, or two zirconium compounds, or a zirconium and a hafnium).

[0058] Aspects of this invention are also directed to catalytic compositions and methods of preparing catalytic compositions in which two or more metallocene compounds are employed, for example, a double metallocene catalytic composition. Independently, each respective metallocene compound may be any bridged metallocene compound disclosed in this document or any unbridged metallocene compound disclosed in this document.

[0059] Thus, in certain aspects of this invention, the catalyst composition and the method of preparing the catalyst composition may comprise more than one metallocene compound, for example, a bridged metallocene compound and an unbridged metallocene compound, or two or more bridged metallocene compounds, or two or more unbridged metallocene compounds. In such cases, the weight ratio of the first metallocene compound to the second metallocene compound may generally be in a range of 1:100 to 100:1, such as 1:50 to 50:1, 1:10 to 10:1, 1:5 to 5:1, 1:3 to 3:1, 1:2 to 2:1, 1:1.5 to 1.5:1, or 1:1.2 to 1.2:1, and the like. ACTIVATING SUPPORTS

[0060] The present invention encompasses various catalyst compositions containing an activator support and various methods of preparing catalyst compositions using an activator support. In one aspect, the activator support may comprise a solid oxide treated with an electron-withdrawing anion. Alternatively, in another aspect, the activator support may comprise a solid oxide treated with an electron-withdrawing anion, the solid oxide containing an ion Petition 870260049981, dated 05 / 26 / 2026, p. 27 / 64 19 / 44 Lewis metallic acid. Non-limiting examples of suitable activating supports are disclosed, for example, in US Patents Nos. 7,294,599, 7,601,665, 7,884,163 and 8,309,485.

[0061] The solid oxide of this invention encompasses oxide materials such as alumina, mixed oxide compounds thereof, such as silica-alumina, and combinations and mixtures thereof. Mixed oxide compounds, such as silica-alumina, may be single or multiple chemical phases with more than one metal combined with oxygen to form a solid oxide compound. Examples of mixed oxides that may be used in the activator-support of the present invention include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, zeolites, various clay minerals, alumina-titania, alumina-zirconia, zinc-aluminate, aluminaboria, silica-boria, aluminophosphate-silica, titania-zirconia, and the like. The solid oxide used herein may also include oxide materials, such as coated silica-alumina, as described in U.S. Patent No. 7,884,163.

[0062] For example, the solid oxide may comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boron, zinc oxide, mixed oxides thereof, or any combination thereof. For example, the solid oxide may comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boron, zinc oxide, mixed oxides thereof, or any combination thereof. In another aspect, the solid oxide may comprise silica, alumina, titania, thorium, stannia, zirconia, magnesia, boron, zinc oxide, a mixed oxide thereof, or any mixture thereof. In yet another aspect, the solid oxide may comprise silica-alumina, coated silica-alumina, silica-titania, silica-zirconia, alumina-boria, or any combination thereof.In yet another aspect, the solid oxide may comprise alumina, silica-alumina, coated silica-alumina, or any mixture thereof; alternatively, alumina; alternatively, silica-alumina; or alternatively, coated silica-alumina.

[0063] Solid silica-alumina or silica-coated alumina oxide materials that may be used may have a silica content of 5% to 95% by weight. In one aspect, the silica content of these solid oxides may be 10% to 80%, or 20% to 70%, by weight. In another aspect, such materials may have contents of Petition 870260049981, dated 05 / 26 / 2026, p. 28 / 64 20 / 44 silica ranging from 15% to 60%, or from 25% to 50%, by weight. The solid oxides contemplated herein may have any suitable surface area, pore volume, and particle size, as would be recognized by those skilled in the art.

[0064] The electron-withdrawing component used to treat the solid oxide can be any component that increases the Lewis or Bronsted acidity of the solid oxide in the treatment (when compared to the solid oxide that is not treated with at least one electron-withdrawing anion). According to one aspect of the present invention, the electron-withdrawing component is an electron-withdrawing anion derived from a salt, an acid, or another compound, such as a volatile organic compound, that serves as a source or precursor for that anion. Examples of electron-withdrawing anions include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phosphotungstate, tungstate, molybdate, and the like, including mixtures and combinations thereof.Additionally, other ionic or non-ionic compounds that serve as sources for these electron-withdrawing anions may also be employed. It is contemplated that the electron-withdrawing anion may be, or may comprise, fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate and the like, or any combination thereof, in some aspects of this invention. In other aspects, the electron-withdrawing anion may comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate and the like, or any combination thereof. Still, in other aspects, the electron-withdrawing anion may comprise fluoride and / or sulfate.

[0065] The activator support may generally contain from 1 to 25% by weight of the electron-withdrawing anion, based on the weight of the activator support. In particular aspects provided in this document, the activator support may contain from 1 to 20% by weight, from 2 to 20% by weight, from 3 to 20% by weight, from 2 to 15% by weight, from 3 to 15% by weight, from 3 to 12% by weight, or from 4 to 10% by weight of the electron-withdrawing anion, based on the total weight of the activator support.

[0066] In one aspect, the activating support may comprise fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, phosphated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, silica Petition 870260049981, dated 05 / 26 / 2026, page 29 / 64 21 / 44 sulfated alumina, phosphated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated coated silica-alumina, chlorinated coated silica-alumina, sulfated coated silica-alumina, phosphated coated silica-alumina and the like, as well as any mixture or combination thereof.In another aspect, the activating support employed in the catalyst processes and systems described herein may be, or may comprise, a fluorinated solid oxide and / or a sulfated solid oxide and / or a phosphated solid oxide, non-limiting examples of which may include fluorinated alumina, sulfated alumina, phosphated alumina, fluorinated silica-alumina, sulfated silica-alumina, phosphated silica-alumina, fluorinated zirconia silica, fluorinated coated silica-alumina, chloride coated silica-alumina, sulfate coated silica-alumina, phosphate coated silica-alumina and the like, as well as combinations thereof.In another aspect, the activator support may comprise fluorinated alumina; alternatively, chlorinated alumina; alternatively, sulfated alumina; alternatively, phosphated alumina; alternatively, fluorinated silica-alumina; alternatively, sulfated silica-alumina; alternatively, phosphated silica-alumina; alternatively, fluorinated silica-zirconia; alternatively, chlorinated silica-zirconia; alternatively, sulfated coated silica-alumina; alternatively, phosphated coated silica-alumina; alternatively, fluorinated-chlorinated coated silica-alumina; or alternatively, fluorinated coated silica-alumina.

[0067] Various processes can be used to form activator supports useful in the present invention. Methods of contacting the solid oxide with the electron-withdrawing component, suitable electron-withdrawing components and amounts of addition, impregnation with metals or metal ions (for example, zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium and the like, or combinations thereof) and various calcination procedures and conditions are disclosed, for example, in US Patents Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666, 6,524,987, 6,548,441, 6,548,442, 6,576,583 6,613,712, 6,632,894, 6,667,274, 6,750,302, 7,294,599, 7,601,665, 7,884,163 and 8,309,485. Other suitable processes and procedures for preparing activating supports (e.g., fluorinated solid oxides, sulfated solid oxides, or phosphated solid oxides) are well known to those of common skill in Petition 870260049981, dated 05 / 26 / 2026, page 30 / 64 22 / 44 technique. Olefin Monomers and Olefin Polymers

[0068] The olefin monomers contemplated here typically include olefin compounds having from 2 to 30 carbon atoms per molecule and having at least one olefinic double bond. Homopolymerization processes using a single olefin, such as ethylene, propylene, butene, hexene, octene, and the like, are covered, as well as copolymerization and terpolymerization, reactions using an olefin monomer with at least one different olefinic compound. For example, the resulting ethylene copolymers, or terpolymers, may generally contain a higher amount of ethylene (> 50 molar percent) and a lower amount of comonomer (< 50 molar percent), although this is not a requirement. Comonomers that can be copolymerized with ethylene generally have 3 to 20 carbon atoms, or 3 to 10 carbon atoms, in their molecular chain.

[0069] Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched, substituted, unsubstituted, functionalized and non-functionalized olefins may be used. For example, typical unsaturated compounds that can be polymerized to produce olefin polymers may include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, the four normal octenes (e.g., 1-octene), the four normal nonenes, the five normal decenes and the like, or mixtures of two or more of these compounds. Cyclic and bicyclic olefins, including, but not limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene and the like, may also be polymerized as described herein. Styrene can also be used as a monomer or as a comonomer.In one aspect, the olefin monomer may comprise a C2-C20 olefin; alternatively, a C2-C20 α-olefin; alternatively, a C2-C12 olefin; alternatively, a C2-C10 α-olefin; alternatively, ethylene, propylene, 1-butene, 1-hexene or 1-octene; alternatively, ethylene or propylene; alternatively, ethylene; or alternatively, propylene.

[0070] When a copolymer (or alternatively, a terpolymer) is desired, the olefin monomer can be, for example, ethylene or propylene, which is Petition 870260049981, dated 05 / 26 / 2026, page 31 / 64 23 / 44 copolymerized with at least one comonomer (for example, a C2-C20 α-olefin, a C3-C20 α-olefin). In one aspect, the olefin monomer in the polymerization process may be ethylene. In this aspect, examples of suitable olefin comonomers may include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene and the like, or combinations thereof. According to another aspect, the comonomer may comprise an α-olefin (e.g., a C3-C10 α-olefin), while in another aspect, the comonomer may comprise 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof. For example, the comonomer may comprise 1-butene, 1-hexene, 1-octene, or a combination thereof.

[0071] Generally, the amount of comonomer introduced into a polymerization reactor to produce the copolymer can be from 0.01 to 50 percent by weight of the comonomer based on the total weight of the monomer and comonomer. According to another aspect, the amount of comonomer introduced into a polymerization reactor can be from 0.01 to 40 percent by weight of the comonomer based on the total weight of the monomer and comonomer. In another aspect, the amount of comonomer introduced into a polymerization reactor can be from 0.1 to 35 percent by weight of the comonomer based on the total weight of the monomer and comonomer. Still, in another aspect, the amount of comonomer introduced into a polymerization reactor can be from 0.5 to 20 percent by weight of the comonomer based on the total weight of the monomer and comonomer.

[0072] Although we do not intend to be bound by this theory, when branched, substituted or functionalized olefins are used as reagents, it is believed that steric hindrance can prevent and / or retard the polymerization reaction. Thus, branched and / or cyclic portions of the olefin removed slightly from the carbon-carbon double bond are not expected to impede the reaction in the same way that the same olefin substituents located closer to the carbon-carbon double bond might.

[0073] According to one aspect, at least one monomer / reagent can be ethylene (or propylene), so the polymerization reaction can be a homopolymerization involving only ethylene (or propylene) or a Petition 870260049981, dated 05 / 26 / 2026, page 32 / 64 24 / 44 copolymerization with a different acyclic, cyclic, terminal, internal, linear, branched, substituted or unsubstituted olefin. Furthermore, the methods disclosed in this document are intended to also encompass diolefin compounds which include, but are not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene and the like.

[0074] The olefin polymers covered herein may include any polymer produced from any olefin monomer and optional comonomer(s) described herein. For example, the olefin polymer may comprise an ethylene homopolymer, a propylene homopolymer, an ethylene copolymer (e.g., ethylene / α-olefin, ethylene / 1-butene, ethylene / 1-hexene or ethylene / 1-octene), a propylene copolymer, an ethylene terpolymer, a propylene terpolymer and the like, including combinations thereof. In one aspect, the olefin polymer may be (or may comprise) an ethylene homopolymer, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer or an ethylene / 1-octene copolymer, or a combination thereof; or, alternatively, an ethylene / 1-hexene copolymer.In another aspect, the olefin polymer may be (or may comprise) a polypropylene homopolymer and / or a propylene-based copolymer. In some aspects, the olefin polymer may have a bimodal molecular weight distribution, while in other aspects, the olefin polymer may have a multimodal molecular weight distribution. However, in other aspects, the olefinic polymer may have a unimodal molecular weight distribution. POLYMERIZATION REACTOR SYSTEMS AND PROCESSES

[0075] The disclosed catalyst systems and methods of their preparation are intended for any olefin polymerization process using various types of polymerization reactors, polymerization reactor systems, and polymerization reaction conditions. As used in this document, “polymerization reactor” includes any polymerization reactor capable of polymerizing olefin monomers and comonomers (one or more of a comonomer) to produce homopolymers, copolymers, terpolymers, and the like. The various types of polymerization reactors include, but are not limited to, those that may be termed batch reactor, fluidized paste reactor, gas-phase reactor, solution reactor, high-pressure reactor, tubular reactor, autoclave reactor, and the like. Petition 870260049981, dated 05 / 26 / 2026, page 33 / 64 25 / 44 or combinations thereof. Suitable polymerization conditions are used for the various reactor types. Gas-phase reactors may comprise fluidized bed reactors or horizontal staged reactors. Fluid slurry reactors comprise vertical and / or horizontal circuits. High-pressure reactors may comprise autoclave reactors, tubular reactors, or combinations thereof, in parallel or in series. Reactor types may include batch or continuous processes. Continuous processes could use intermittent or continuous product discharge. Processes may also include partial or complete direct recycling of unreacted monomer, unreacted comonomer, and / or diluent.

[0076] A polymerization reactor system may comprise a single reactor or multiple reactors (e.g., 2 reactors or more than 2 reactors) of the same type or of different types. For example, the polymerization reactor system may comprise a fluidized paste reactor, a gas-phase reactor, a solution reactor, or a combination of two or more of these reactors. Polymer production in multiple reactors may include several stages in at least two separate polymerization reactors interconnected by at least one transfer device, enabling the transfer of the resulting polymers from the first polymerization reactor to the second reactor. The desired polymerization conditions in one of the reactors may be different from the operating conditions of another reactor (or reactors).Alternatively, polymerization in multiple reactors may involve the manual transfer of polymer from one reactor to subsequent continuous polymerization reactors. Multiple reactor systems may include any combination, including but not limited to, multiple circuit reactors, multiple gas-phase reactors, a combination of circuit and gas-phase reactors, multiple high-pressure reactors, or a combination of high-pressure with circuit and / or gas-phase reactors. Multiple reactors may be operated in series, in parallel, or in both.

[0077] According to one aspect of the invention, the polymerization reactor system may comprise at least one circuit-based fluid paste reactor comprising vertical or horizontal circuits. The monomer, diluent, catalyst, and comonomer may be continuously fed into a circuit reactor where polymerization occurs. Generally, continuous processes may comprise the continuous introduction of monomer / comonomer, a catalyst, and a diluent into a Petition 870260049981, dated 05 / 26 / 2026, page 34 / 64 26 / 44 polymerization reactor and the continuous removal from this reactor of a suspension comprising polymer particles and the diluent. The reactor effluent can be instantaneously evaporated to remove the continuous polymer from the liquids comprising the diluent, monomer and / or comonomer. Several technologies can be used for this separation step, including, but not limited to, flashing which may include any combination of heat addition and pressure reduction, cyclonic action separation in a cyclone or hydrocyclone, or centrifugal separation.

[0078] A typical fluid paste polymerization process (also known as a particle-forming process) is disclosed, for example, in U.S. Patents Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, 6,833,415 and 8,822,608. Suitable diluents used in fluid polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane and n-hexane. Some polymerization cycle reactions can occur under bulk conditions, where no diluent is used.

[0079] According to another aspect, the polymerization reactor system may comprise at least one gas-phase reactor (e.g., a fluidized bed reactor). These reactor systems may employ a continuous recycle stream containing one or more monomers continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions. A recycle stream may be withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, the polymeric product may be withdrawn from the reactor and a new or fresh monomer may be added to replace the polymerized monomer.Such gas-phase reactors may comprise a process for a multi-stage gas-phase polymerization of olefins, in which olefins are polymerized in the gas phase in at least two independent gas-phase polymerization zones, while feeding a catalyst-containing polymer formed in a first polymerization zone to a second polymerization zone. Representative gas-phase reactors are disclosed in U.S. Patents Nos. 5,352,749, 4,588,790, 5,436,304, 7,531,606 and 7,598,327.

[0080] According to another aspect, the polymerization reactor system Petition 870260049981, dated 05 / 26 / 2026, page 35 / 64 27 / 44 may comprise a high-pressure polymerization reactor, for example, it may comprise a tubular reactor and / or an autoclave reactor. Tubular reactors may have several zones where new monomers, initiators or catalysts are added. The monomer may be entrained in an inert gas stream and introduced into one zone of the reactor. Initiators, catalysts and / or catalyst components may be entrained in a gas stream and introduced into another zone of the reactor. The gas streams may be intermixed for polymerization. Heat and pressure may be appropriately employed to obtain ideal polymerization reaction conditions.

[0081] According to another aspect, the polymerization reactor system may comprise a solution polymerization reactor in which the monomer / comonomer is brought into contact with the catalyst composition by suitable stirring or other means. A carrier comprising an inert organic diluent or excess monomer may be employed. If desired, the monomer / comonomer may be brought into contact with the product of the catalytic reaction in the presence or absence of liquid material in the vapor phase. The polymerization zone may be maintained at temperatures and pressures that will result in the formation of a polymer solution in a reaction medium. Stirring may be employed to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization.

[0082] Polymerization reactors suitable for the present invention may further comprise any combination of at least one raw material feeding system, at least one feeding system for the catalyst or catalyst components, and / or at least one polymer recovery system. Reactor systems suitable for the present invention may further comprise systems for raw material purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, discharge, laboratory analysis, and process control. Depending on the desired properties of the olefin polymer, hydrogen may be added to the polymerization reactor as needed (e.g., continuously or pulsed). Petition 870260049981, dated 05 / 26 / 2026, page 36 / 64 28 / 44

[0083] The polymerization conditions that are controlled for efficiency and to provide the desired polymer properties may include temperature, pressure, and the concentrations of various reagents. The polymerization temperature can affect catalyst productivity, polymer molecular weight, and molecular weight distribution. A suitable polymerization temperature can be any temperature below the depolymerization temperature, according to the Gibbs free energy equation. Typically, this includes 60 °C to 280 °C, for example, 60 °C to 120 °C, depending on the type of reactor polymerization. In some reactor systems, the polymerization temperature may generally be within a range of 65 °C to 110 °C, 70 °C to 100 °C, or 75 °C to 95 °C.

[0084] Suitable pressures will also vary depending on the type of reactor and polymerization. The pressure for liquid-phase polymerizations in a circuit reactor can typically be less than 1000 psig. The pressure for gas-phase polymerization can be in the range of 200 to 500 psig. High-pressure polymerization in tubular reactors or autoclaves can generally be conducted at 20,000 to 75,000 psig. Polymerization reactors can also be operated in a supercritical region, which generally occurs at higher temperatures and pressures. Operation above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages to the polymerization reaction process.

[0085] Also covered here are olefin polymerization processes using any of the catalyst compositions described herein. One such process may comprise contacting a catalyst composition with an olefin monomer and, optionally, an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer. Generally, the polymerization process may utilize any olefin monomer and optional comonomer disclosed in this document, and the catalyst composition employed may be a single (or double) metallocene catalyst system using, for example, any of the metallocene compounds, any of the activating supports and any of the organoaluminum compounds disclosed herein, and the catalyst system may be prepared by any of the processes disclosed herein.This invention also relates to, and includes, polymers produced by some of the polymerization processes disclosed herein. Petition 870260049981, dated 05 / 26 / 2026, page 37 / 64 29 / 44

[0086] As another example, an olefin polymerization process covered herein may comprise (or essentially consist of, or consist of) contacting an alcohol compound with an organoaluminum compound for a first period of time to form a pre-contacted mixture, contacting the pre-contacted mixture with an activating support and a metallocene compound for a second period of time to form a catalyst composition, and contacting the catalyst composition with an olefin monomer and, optionally, an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

[0087] In a particular aspect, polymerization processes consistent with this invention may comprise contacting such catalyst compositions (for example, as described herein or prepared as described herein) with ethylene and, optionally, an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer.

[0088] As described in this document, the catalytic activities of these catalytic compositions may unexpectedly be greater than those of otherwise identical catalytic systems obtained without the use of the alcohol compound during catalyst preparation (under otherwise identical catalyst preparation conditions) or without the aluminum dialkyl alkoxide (and any aluminum alkyl dialkoxides and / or aluminum trialkoxides, if present), when tested and compared under the same polymerization conditions.Thus, the disclosed olefin polymer processes (or catalyst compositions) can be characterized by a catalyst composition activity that is higher (e.g., by at least 10%, at least 20%, at least 25%, at least 30%, or at least 35%, and often up to and including 50%, 60%, 75%, or 100%) than that of an otherwise identical catalyst system obtained without the alcohol compound (or without the aluminum dialkyl alkoxide and without the aluminum alkyl dialkyl oxide and / or aluminum trialkoxide, if present), under the same catalyst preparation and polymerization conditions. EXAMPLES

[0089] This invention is further illustrated by the following examples, which do not Petition 870260049981, dated 05 / 26 / 2026, p. 38 / 64 30 / 44 should be interpreted in a way that imposes limitations on the scope of the invention in any manner. Various other aspects, embodiments, modifications and equivalents thereof, after reading the description in this document, may be suggested to a person of ordinary skill in the art without departing from the spirit of the present invention or the scope of the appended claims.

[0090] The activating support (AS) was prepared as follows. A paste was made by mixing 400 ml of water and 100 g of coated silica-alumina (40 wt% alumina, a surface area of ​​450 m² / g, a pore volume of 1.3 ml / g and an average particle size of 35 microns). A solution of concentrated hydrofluoric acid (5 g HF) was mixed into the paste and the resulting paste was then spray-dried to a dry, free-flowing powder. Calcination was carried out at 600 °C by fluidizing the fluorinated coated silica-alumina (4.75 wt% fluorine) in dry nitrogen for 3 hours, followed by cooling to room temperature while still fluidized under nitrogen.

[0091] The metallocene (MET) compound used in the examples was methyl(buten-3-yl)methylidene(n5-cyclopentadienyl)(n5-2,7-di-tert-butylfluoren-9-ylidene)zirconium dichloride. The organoaluminum (OA) compound was triisobutylaluminum (TIBA) or triethylaluminum (TEA). The alcoholic compound was methanol (MeOH) or isopropanol (IPA).

[0092] Molecular weights and molecular weight distributions were obtained using a PL-GPC 220 system (Polymer Labs, an Agilent® Company) equipped with an IR4 detector (Polymer Char, Spain) and three (3) Styragel®HMW-6E GPC columns (Waters, MA) running at 145 °C. The flow rate of the 1,2,4-trichlorobenzene (TCB) mobile phase containing 0.5 g / l of 2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 ml / min, and polymer solution concentrations were approximately 1 mg / ml, depending on the molecular weight. Sample preparation was conducted at 150 °C for approximately 4 h with occasional gentle stirring before the solutions were transferred to sample vials for injection. An injection volume of approximately 400 μL was used. The integral calibration method was used to deduce the molecular weights and molecular weight distributions using a Chevron Phillips Chemical Company HDPE polyethylene resin, MARLEX®BHB5003, as the standard.The complete standard table was predetermined in a separate experiment with SEC-MALS. Mn is the number-average molecular weight, Mw is the weight-average molecular weight, Mz is the z-average molecular weight, and Mp. Petition 870260049981, dated 05 / 26 / 2026, page 39 / 64 31 / 44 is the peak molecular weight (the molecular weight location of the highest point on the molecular weight distribution curve).

[0093] Rheological characterizations of the casting were performed as follows. Small deformation (10%) oscillatory shear measurements were performed on an Anton Paar® MCR 501 rheometer using parallel plate geometry. All rheological tests were performed at 190 °C. The complex viscosity data | η* versus frequency (ω) were then fitted to the curve using the three modified parameters, the Carreau-Yasuda (CY) empirical model to obtain the zero shear viscosity - ηο, the characteristic viscous relaxation time - τη and the amplitude parameter - a (CY-a parameter). The simplified Carreau-Yasuda (CY) empirical model is as follows. I η*(®) I =Γ1Zη0 a ,(1-n) / a , [1 + (τηω)a](1 n) / a, where: | η*(ω) | = magnitude of complex shear viscosity; ηο = zero shear viscosity; τη = viscous relaxation time (Tau(n) in s); a = “width” parameter (CY-a parameter); n = corrects the final slope of the power law, corrected by 2 / 11; and ω = angular frequency of oscillating shear strain.

[0094] Details of the meaning and interpretation of the CY model and derived parameters can be found in: CA Hieber and HH Chiang, Rheol. Acta, 28, 321 (1989); CA Hieber and HH Chiang, Polym. Eng. Sci., 32, 931 (1992); and RB Bird, RC Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987).

[0095] Table I summarizes the catalyst compositions and polymerization experiments using a one-gallon stainless steel autoclave reactor containing isobutane as diluent. First, the reactor was charged at room temperature with a mixture of the organoaluminum compound (OA, 1 M in hexanes) with the alcohol compound, which were mixed / reacted for a period of 30 seconds to 5 minutes. Then, the activator support (AS, dry powder) was charged, followed by a toluene solution (1 mg / ml) of the metallocene compound (MET). The reactor was sealed and charged with 2 L of isobutane, and the contents Petition 870260049981, dated 05 / 26 / 2026, p. 40 / 64 32 / 44 of the reactor was heated to the target polymerization temperature of 80 °C with stirring (for approximately 5 min). When the reactor contents reached the target temperature, 1-hexene was added while the reactor was charged with ethylene to the target pressure (320 psig, 15 wt% 1-hexene based on ethylene). No hydrogen was added. Ethylene and 1-hexene were supplied on demand to maintain the target pressure. The reactor was maintained at the target temperature throughout the experiment by an automated heating and cooling system. After reactor venting, purging, and cooling, the resulting polymer product was dried under reduced pressure.

[0096] As shown in Table I, Examples A1-A9 used a pre-contacted mixture of TIBA and IPA during catalyst preparation, and Examples B1-B8 used a pre-contacted mixture of TIBA and MeOH during catalyst preparation – the OH:Al molar ratio ranged from approximately 0.07:1 to 2:1. Examples C1-C3 were duplicate comparative examples using TIBA and no alcohol addition; the average catalyst activity of Examples C1-C3 was used for comparison with the examples in which an alcohol was used. Examples C4-C5 were comparative examples that used TIBA and IPA or MeOH during catalyst preparation, but no activating support. No polymer was produced in these experiments.

[0097] Similarly, Examples D1-D4 used a pre-contacted mixture of TEA and IPA during catalyst preparation, and Examples E1-E5 used a pre-contacted mixture of TEA and MeOH during catalyst preparation – the OH:Al molar ratio ranged from approximately 0.07:1 to 0.8:1. Examples C6-C7 were duplicate comparative examples using TEA and no alcohol addition; the average catalyst activity of Examples C6-C7 was used for comparison with the examples in which an alcohol was used.

[0098] Table I summarizes the catalyst activities for the examples based on the amount of metallocene compound (g of polymer per g of MET per hour) and based on the amount of activating support (g of polymer per g of AS per hour). The molecular weight and rheological properties of the ethylene polymer produced in the examples are also summarized in Table I.

[0099] Unexpectedly, for the combination of TIBA and IPA in OH:Al molar ratios of approximately 0.15:1 to 0.5:1, the increase in catalyst activity Petition 870260049981, dated 05 / 26 / 2026, page 41 / 64 For the combination of TIBA and MeOH in molar ratios of approximately 0.07:1 to 0.5:1, the increase in catalyst activity was 40 to 60%; for the combination of TEA and IPA in molar ratios of approximately 0.08:1 to 0.65:1, the increase in catalyst activity was 15 to 55%; and for the combination of TEA and MeOH in molar ratios of approximately 0.15:1 to 0.65:1, the increase in catalyst activity was 10 to 35%. Notably, at higher OH:Al molar ratios, such as approximately 0.8:1 and above (and depending on the particular combination of organoaluminum compounds and alcohol), catalyst activity often decreased significantly.

[00100] For the examples observed above, in which the catalyst activity increased from 10 to 70%, the molecular weight properties of the produced polymer were not significantly affected. However, compared to the respective comparative examples, the inventive examples showed slight reductions in molecular weight (Mn, Mw, and Mz). Similarly, and consistent with the lower molecular weight, there were increases in the high-load melt index (HLMI, ASTM D1238 at 190 °C with a weight of 21600 grams) and decreases in the zero-shear viscosity of the inventive polymers. Surprisingly, the CY-a parameters for polymers of the inventive examples with catalytic activity increases of 10 to 70%, compared to the respective comparative examples, increased on average 6% for the TIBA and IPA combination, on average 15% for the TIBA and MeOH combination, on average 18% for the TEA and IPA combination, and on average 8% for the TEA and MeOH combination. Table I. Summary of Examples. Example MET (mg) AS (mg) Type OA OA (mmol) Type of Alcohol Alcohol (mmol) C-1 1.0 150 TIBA 0.4 - 0 C-2 1.0 150 TIBA 0.4 - 0 C-3 1.0 150 TIBA 0.4 - 0 C-4 1.0 0 TIBA 0.4 IPA 0.130 C-5 1.0 0 TIBA 0.4 MeOH 0.154 A-1 1.0 150 TIBA 0.4 IPA 0.033 A-2 1.0 150 TIBA 0.4 IPA 0.065 Petition 870260049981, dated 05 / 26 / 2026, p. 42 / 64 34 / 44 A-3 1.0 150 TIBA 0.4 IPA 0.130 A-4 1.0 150 TIBA 0.4 IPA 0.130 A-5 1.0 150 TIBA 0.4 IPA 0.195 A-6 1.0 150 TIBA 0.4 IPA 0.260 A-7 1.0 150 TIBA 0.4 IPA 0.326 A-8 1.0 150 TIBA 0.4 IPA 0.391 A-9 1.0 150 TIBA 0.4 IPA 0.781 B-1 1.0 150 TIBA 0.4 MeOH 0.031 B-2 1.0 150 TIBA 0.4 MeOH 0.062 B-3 1.0 150 TIBA 0.4 MeOH 0.154 B-4 1.0 150 TIBA 0.4 MeOH 0.185 B-5 1.0 150 TIBA 0.4 MeOH 0.246 B-6 1.0 150 TIBA 0.4 MeOH 0.246 B-7 1.0 150 TIBA 0.4 MeOH 0.308 B-8 1.0 150 TIBA 0.4 MeOH 0.308 C-6 1.0 150 TEA 0.4 - 0 C-7 1.0 150 TEA 0.4 - 0 D-1 1.0 150 TEA 0.4 IPA 0.033 D-2 1.0 150 TEA 0.4 IPA 0.195 D-3 1.0 150 TEA 0.4 IPA 0.260 D-4 1.0 150 TEA 0.4 IPA 0.326 E-1 1.0 150 TEA 0.4 MeOH 0.031 E-2 1.0 150 TEA 0.4 MeOH 0.062 E-3 1.0 150 TEA 0.4 MeOH 0.185 E-4 1.0 150 TEA 0.4 MeOH 0.246 E-5 1.0 150 TEA 0.4 MeOH 0.308 Table I. Summary of Examples (continued) Example OH / Al (molar) Alcohol / MET (molar) Alcohol / AS (wt) MET Activity (g / g / h) AS Activity (g / g / h) Activity Increase (%) Petition 870260049981, dated 05 / 26 / 2026, pp. 43 / 64 35 / 44 C-1 0 0 0 480400 3203 — C-2 0 0 0 491600 3277 — C-3 0 0 0 520800 3472 — C-4 0,326 76 — 0 0 — C-5 0,385 90 — 0 0 — A-1 0,081 19 0,013 541400 3609 8,8 A-2 0,163 38 0,026 600600 4004 20,7 A-3 0,326 76 0,052 826333 5509 66,1 A-4 0,326 76 0,052 814154 5428 63,6 A-5 0,488 114 0,078 726231 4842 46,0 A-6 0,651 152 0,104 537600 3584 8,0 A-7 0,814 190 0,130 540600 3604 8,7 A-8 0,976 228 0,156 413400 2756 -16,9 A-9 1,953 456 0,312 1000 7 -99,8 B-1 0,077 18 0,007 734160 4894 47,6 B-2 0,154 36 0,013 715710 4771 43,8 B-3 0,385 90 0,033 793714 5291 59,5 B-4 0,462 108 0,039 742200 4948 49,2 B-5 0,616 144 0,053 338600 2257 -31,9 B-6 0,616 144 0,053 326000 2173 -34,5 B-7 0,770 180 0,066 1000 7 -99,8 B-8 0,770 180 0,066 1000 7 -99,8 C-6 0 0 0 416600 2777 — C-7 0 0 0 416200 2775 — D-1 0,081 19 0,013 480800 3205 15,5 D-2 0,488 114 0,078 633000 4220 52,0 D-3 0,651 152 0,104 530200 3535 27,3 D-4 0,814 190 0,130 95600 637 -77,0 E-1 0,077 18 0,007 443800 2959 6,6 E-2 0,154 36 0,013 556400 3709 33,6 E-3 0,462 108 0.039 471800 3145 13.3 Petition 870260049981, dated 05 / 26 / 2026, pp. 44 / 64 36 / 44 E-4 0.616 144 0.053 477200 3181 14.6 E-5 0.770 180 0.066 345400 2303 -17.1 Table I. Summary of Examples (continued) Example Mn (kg / mol) Mw (kg / mol) Mz (kg / mol) Mw / Mn Mz / Mw C-1 63.0 189 412 3.0 2.2 C-2 72.5 195 401 2.7 2.1 C-3 70.5 184 392 2.6 2.1 C-4 - - - - - C-5 - - - - - A-1 64.6 181 376 2.8 2.1 A-2 66.1 180 372 2.7 2.1 A-3 62.6 161 326 2.6 2.0 A-4 61.9 170 343 2.7 2.0 A-5 72.4 170 323 2.3 1.9 A-6 69.8 189 394 2.7 2.1 A-7 72.9 190 368 2.6 1.9 A-8 87.2 208 389 2.4 1.9 A-9 - - - - - B-1 68.1 173 347 2.5 2.0 B-2 - - - - - B-3 61.8 163 348 2.6 2.1 B-4 63.0 167 354 2.7 2.1 B-5 89.6 220 426 2.5 1.9 B-6 89.8 227 430 2.5 1.9 B-7 - - - - - B-8 - - - - - C-6 80.7 213 413 2.6 1.9 C-7 83.7 215 412 2.6 1.9 D-1 62.5 193 380 3.1 2.0 D-2 58.1 182 367 3.1 2.0 Petition 870260049981, dated 05 / 26 / 2026, pp. 45 / 64 37 / 44 D-3 81.0 204 405 2.5 2.0 D-4 138.6 311 566 2.2 1.8 E-1 84.6 202 383 2.4 1.9 E-2 83.1 195 374 2.4 1.9 E-3 81.7 196 373 2.4 1.9 E-4 80.2 194 369 2.4 1.9 E-5 - - - - - Table I. Summary of Examples (continued) Example HLMI (g / 10 min) Zero Shear (ηο, Pa-s) CY-a C-1 3.7 5.59E+04 0.348 C-2 3.4 5.04E+04 0.375 C-3 4.3 4.19E+04 0.365 C-4 - - - C-5 - - - A-1 4.3 3.64E+04 0.380 A-2 4.7 3.68E+04 0.375 A-3 7.3 2.39E+04 0.375 A-4 2.3 3.12E+04 0.373 A-5 6.0 2.50E+04 0.423 A-6 4.3 3.96E+04 0.397 A-7 3.4 4.03E+04 0.434 A-8 2.5 4.92E+04 0.459 A-9 - - - B-1 5.7 2.82E+04 0.400 B-2 - - - B-3 7.9 1.87E+04 0.433 B-4 6.8 2.32E+04 0.416 B-5 1.9 7.83E+04 0.416 B-6 2.6 7.60E+04 0.432 B-7 - - - B-8 - - - Petition 870260049981, dated 05 / 26 / 2026, pp. 46 / 64 38 / 44 C-6 2.3 7.17E+04 0.376 C-7 3.5 8.57E+04 0.363 D-1 3.1 4.94E+04 0.404 D-2 4.2 4.87E+04 0.405 D-3 2.9 3.06E+05 0.498 D-4 0.0 3.46E+04 0.407 E-1 2.6 6.29E+04 0.388 E-2 3.4 4.55E+04 0.402 E-3 3.4 4.91E+04 0.409 E-4 3.0 4.81E+04 0.392 E-5 1.4 - -

[00101] The invention is described above with reference to various specific aspects and examples. Many variations will be suggested to those skilled in the art in light of the detailed description above. All such obvious variations are encompassed by the complete intended scope of the appended claims. Other aspects of the invention may include, but are not limited to, the following (aspects are described as “comprising”, but alternatively may “essentially consist of” or “consist of”): Aspect 1. Process for producing a catalytic composition, the process comprising: (i) bringing an alcohol compound into contact with an organoaluminum compound for a first period of time to form a precontacted mixture; and (ii) bringing the precontacted mixture into contact with an activating support and a metallocene compound for a second period of time to form the catalyst composition.

[00102] Aspect 2. The process, as defined in aspect 1, in which the pre-contacted mixture is brought into contact with the activating support before the metallocene compound.

[00103] Aspect 3. The process, as defined in aspect 1, in which the pre-contacted mixture is brought into contact with the metallocene compound before the activating support.

[00104] Aspect 4. The process, as defined in any of the Petition 870260049981, dated 05 / 26 / 2026, page 47 / 64 39 / 44 aspects 1 to 3, where the organoaluminum compound is present as a solution in any suitable hydrocarbon solvent.

[00105] Aspect 5. The process, as defined in any one of aspects 1 to 4, in which the metallocene compound is present as a solution in any suitable hydrocarbon solvent.

[00106] Aspect 6. The process, as defined in any one of aspects 1 to 5, wherein the activating support compound is present as a fluid paste in any suitable hydrocarbon solvent.

[00107] Aspect 7. The process, as defined in any one of aspects 4 to 6, wherein the hydrocarbon solvent comprises cyclohexane, cyclohexene, isobutane, n-butane, n-pentane, isopentane, neopentane, hexane, 1-hexene, heptane, toluene or combinations thereof.

[00108] Aspect 8. The process, as defined in any one of aspects 1 to 5, in which the activating support is introduced as a dry solid.

[00109] Aspect 9. The process, as defined in any one of aspects 1 to 8, wherein a molar ratio of hydroxyl groups (—OH) of the alcohol compound to aluminum of the organoaluminum compound (OH:Al) is in any suitable range, for example, from 0.05:1 to 0.9:1, from 0.05:1 to 0.7:1, from 0.05:1 to 0.5:1, from 0.07:1 to 0.65:1, from 0.1:1 to 0.8:1, from 0.1:1 to 0.7:1 or from 0.2:1 to 0.6:1.

[00110] Aspect 10. The process, as defined in any one of aspects 1 to 9, in which a molar ratio of the alcohol compound to the metallocene compound is in any suitable range, for example, from 1:1 to 1000:1, from 10:1 to 500:1 or from 100:1 to 400:1.

[00111] Aspect 11. The process, as defined in any one of aspects 1 to 10, wherein a weight ratio of the alcohol compound to the activating support is in any suitable range, for example, from 1:1 to 1:500, from 1:2 to 1:250 or from 1:5 to 1:150.

[00112] Aspect 12. The process, as defined in any of aspects 1 to 11, wherein the first time period is any time period sufficient to form the pre-contacted mixture, for example, from 1 second to 15 seconds, from 1 second to 10 minutes, from 1 second to 48 hours, from 10 seconds to 12 hours, from 30 seconds to 6 hours, from 30 seconds to 5 minutes, at least 5 seconds, at least 15 seconds or at least 1 minute. Petition 870260049981, dated 05 / 26 / 2026, pp. 48 / 64 40 / 44

[00113] Aspect 13. The process, as defined in any of aspects 1 to 12, wherein the second time period is any time period sufficient to form the catalyst composition, for example, from 1 second to 15 seconds, from 1 second to 10 minutes, from 1 second to 48 hours, from 10 seconds to 12 hours, from 30 seconds to 6 hours, from 30 seconds to 5 minutes, at least 5 seconds, at least 15 seconds or at least 1 minute.

[00114] Aspect 14. The catalyst composition produced by the process, as defined in any of the aspects above.

[00115] Aspect 15. A catalyst composition comprising (A) an activating support, (B) a metallocene compound, (C) an organoaluminum compound and (D) a dialkyl aluminum alkoxide (and optionally, an alkyl aluminum dialkoxide and / or an aluminum trialkoxide),

[00116] Aspect 16. The process or composition, as defined in any of aspects 1 to 15, in which the activity of the catalyst composition is greater (by any amount disclosed herein, for example, by at least 10%, at least 15%, at least 20%, at least 30% or at least 35%, up to 50%, 60%, 75% or 100%) than that of an otherwise identical catalyst system obtained without the alcohol compound (or without the aluminum dialkyl alkoxide and without the aluminum alkyl dialkyl oxide and / or aluminum trialkoxide, if present), under the same catalyst preparation and polymerization conditions.

[00117] Aspect 17. The process or composition, as defined in any one of aspects 1 to 16, wherein a weight ratio of the metallocene compound to the activating support is in any suitable range, for example, from 1:1 to 1:1000000, from 1:10 to 1:10000 or from 1:20 to 1:1000.

[00118] Aspect 18. The process or composition, as defined in any of aspects 1 to 17, wherein the weight ratio between the activating carrier and the organoaluminum compound is in any suitable range, for example, from 1:1 to 100:1, from 1:1 to 50:1, or from 2:1 to 20:1.

[00119] Aspect 19. The process or composition, as defined in any one of aspects 1 to 18, wherein the activating support comprises a solid oxide treated with an electron-withdrawing anion.

[00120] Aspect 20. The process or composition, as defined in Petition 870260049981, dated 05 / 26 / 2026, p. 49 / 64 41 / 44 any of aspects 1 to 19, wherein the activating support comprises a fluorinated solid oxide, a sulfated solid oxide, a phosphated solid oxide or a combination thereof.

[00121] Aspect 21. The process or composition, as defined in any of aspects 1 to 19, wherein the activating support comprises fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, phosphated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, phosphated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated coated silica-alumina, chlorinated coated silica-alumina, sulfated coated silica-alumina, phosphated coated silica-alumina or any combination thereof.

[00122] Aspect 22. The process or composition, as defined in any of aspects 1 to 21, in which the organoaluminum compound comprises any organoaluminum compound disclosed in this document.

[00123] Aspect 23. The process or composition, as defined in any one of aspects 1 to 22, wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum chloride or any combination thereof.

[00124] Aspect 24. The process or composition, as defined in aspect 22 or 23, in which the organoaluminum compound comprises triethylaluminum.

[00125] Aspect 25. The process or composition, as defined in aspect 22 or 23, in which the organoaluminum compound comprises triisobutylaluminum.

[00126] Aspect 26. The process or composition, as defined in any one of aspects 1 to 25, in which the catalyst composition is substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds or combinations thereof.

[00127] Aspect 27. The process or composition, as defined in any of aspects 1 to 26, in which the alcohol compound comprises any alcohol compound disclosed in this document, for example, a mono-ol, a diol, a triol or a polyol, as well as combinations thereof. Petition 870260049981, dated 05 / 26 / 2026, pp. 50 / 64 42 / 44

[00128] Aspect 28. The process or composition, as defined in any of aspects 1 to 27, wherein the alcohol compound comprises a hydrocarbyl alcohol, for example, an alkyl alcohol, a cycloalkyl alcohol, an aryl alcohol or an arylalkyl alcohol, as well as combinations thereof.

[00129] Aspect 29. The process or composition, as defined in any one of aspects 1 to 28, wherein the alcohol compound comprises a C1 to C32 alcohol, for example, a C1 to C18 alcohol, a C1 to C8 alcohol or a C1 to C4 alcohol.

[00130] Aspect 30. The process or composition, as defined in any of aspects 1 to 29, wherein the alcohol compound comprises any mono-ol disclosed in this document, for example, methanol, ethanol, propanol (e.g., isopropanol, n-propanol), butanol (e.g., n-butanol, isobutanol), pentanol, hexanol, heptanol, octanol, decanol, hexadecanol, cyclohexanol, phenol or benzyl alcohol, as well as combinations thereof.

[00131] Aspect 31. The process or composition, as defined in any of aspects 1 to 30, wherein the metallocene compound comprises a bridging metallocene compound, for example, any bridging metallocene compound disclosed herein.

[00132] Aspect 32. The process or composition defined in any of aspects 1 to 31, wherein the metallocene compound comprises an unbridged metallocene compound, for example, any unbridged metallocene compound disclosed herein.

[00133] Aspect 33. The process or composition, as defined in any one of aspects 1 to 32, wherein the catalyst composition comprises a single metallocene compound, two metallocene compounds or more than two metallocene compounds.

[00134] Aspect 34. An olefin polymerization process, wherein the process comprises placing the catalyst composition, as defined in any one of aspects 1 to 33, in contact with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

[00135] Aspect 35. The process, as defined in aspect 34, in which the olefin monomer comprises any olefin monomer disclosed herein, for example, any C2-C20 olefin. Petition 870260049981, dated 05 / 26 / 2026, pages 51 / 64 43 / 44

[00136] Aspect 36. The process, as defined in aspect 34, wherein the olefin monomer and the optional olefin comonomer independently comprise a C2-C20 alpha-olefin.

[00137] Aspect 37. The process, as defined in any one of aspects 34 to 36, wherein the olefin monomer comprises ethylene.

[00138] Aspect 38. The process, as defined in any one of aspects 34 to 37, in which the catalyst composition is brought into contact with ethylene and an olefin comonomer comprising a C3-C10 alpha-olefin.

[00139] Aspect 39. The process, as defined in any one of aspects 34 to 38, in which the catalyst composition is brought into contact with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene or a mixture thereof.

[00140] Aspect 40. The process, as defined in any one of aspects 34 to 39, wherein the polymerization reactor system comprises a batch reactor, a fluid paste reactor, a gas phase reactor, a solution reactor, a high-pressure reactor, a tubular reactor, an autoclave reactor or a combination thereof.

[00141] Aspect 41. The process, as defined in any one of aspects 34 to 40, wherein the polymerization reactor system comprises a paste reactor, a gas phase reactor, a solution reactor or a combination thereof.

[00142] Aspect 42. The process, as defined in any one of aspects 34 to 41, wherein the polymerization reactor system comprises a flow-through reactor in a circuit.

[00143] Aspect 43. The process, as defined in any one of aspects 34 to 42, wherein the polymerization reactor system comprises a single reactor.

[00144] Aspect 44. The process, as defined in any one of aspects 34 to 42, wherein the polymerization reactor system comprises two reactors.

[00145] Aspect 45. The process, as defined in any one of aspects 34 to 42, in which the polymerization reactor system comprises more than two reactors. Petition 870260049981, dated 05 / 26 / 2026, pages 52 / 64 44 / 44

[00146] Aspect 46. The process, as defined in any of aspects 34 to 45, in which the olefin polymer comprises any olefin polymer disclosed in this document.

[00147] Aspect 47. The process, as defined in any one of aspects 34 to 46, wherein the olefin polymer comprises an ethylene homopolymer, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer and / or an ethylene / 1-octene copolymer.

[00148] Aspect 48. The process, as defined in any one of aspects 34 to 47, wherein the olefin polymer comprises an ethylene / 1-hexene copolymer.

[00149] Aspect 49. The process, as defined in any one of aspects 34 to 48, wherein the polymerization conditions comprise a polymerization temperature in a range of 60 °C to 120 °C, 65 °C to 110 °C, 70 °C to 100 °C, or 75 °C to 95 °C.

[00150] Aspect 50. The process, as defined in any of aspects 34 to 49, wherein an activity of the catalyst composition is greater (by any amount disclosed herein, for example, by at least 10%, at least 20%, at least 25%, at least 30% or at least 35%, up to 50%, 60%, 75% or 100%) than that of an otherwise identical catalyst system obtained without the alcohol compound (or without the aluminum dialkyl alkoxide and without the aluminum alkyl dialkyl oxide and / or aluminum trialkoxide, if present), under the same catalyst preparation and polymerization conditions.

[00151] Aspect 51. The olefin polymer produced by the olefin polymerization process, as defined in any one of aspects 34 to 50.

Claims

1. Catalyst composition, characterized in that it comprises: (A) an activating support; (B) a metallocene compound; (C) a trialkylaluminum compound; (D) a dialkyl aluminum alkoxide; and (E) an alkyl aluminum dialkoxide and / or a trialkyl aluminum oxide.

2. Composition according to claim 1, characterized in that the activity of the catalyst composition is greater than that of an otherwise identical catalyst system without the aluminum dialkyl alkoxide, under the same catalyst preparation and polymerization conditions.

3. Composition according to claim 1, characterized in that the activity of the catalyst composition is greater than that of an otherwise identical catalyst system without the aluminum dialkyl alkoxide and the aluminum alkyl dialkyl oxide and / or the aluminum trialkoxide, under the same catalyst preparation and polymerization conditions.

4. Composition according to claim 1, characterized in that: the weight ratio of the metallocene compound to the activating support is in a range of 1:10 to 1:10000; the weight ratio of the activating support to the trialkylaluminum compound is in a range of 1:1 to 100:1; or the catalyst composition is substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, or combinations thereof.

5. Composition according to claim 1, characterized in that: the trialkylaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trinoctylaluminum or any combination thereof; and the activating support comprises a fluorinated solid oxide, a sulfated solid oxide, a phosphated solid oxide or any combination thereof. Petition 870260049981, dated 05 / 26 / 2026, p. 54 / 64 2 / 3 6. Olefin polymerization process, characterized in that it comprises contacting the catalyst composition, as defined in claim 1, with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

7. Process according to claim 6, characterized in that: the activating support comprises fluorinated alumina-silica, fluorinated coated alumina-silica, fluorinated-chlorinated coated alumina-silica, sulfated alumina, phosphated alumina or a combination thereof; the polymerization reactor system comprises a fluid paste reactor, a gas phase reactor, a solution reactor or a combination thereof; and the olefin monomer comprises ethylene and the olefin comonomer comprises 1-butene, 1-hexene, 1-octene or a mixture thereof.

8. Process according to claim 7, characterized in that the activity of the catalyst composition is greater than that of an otherwise identical catalyst system without the aluminum dialkyl alkoxide, under the same catalyst preparation and polymerization conditions.

9. Process according to claim 6, characterized in that: the polymerization conditions comprise a polymerization temperature in the range of 60 °C to 120 °C; the polymerization reactor system comprises a circuit suspension reactor; and the olefin polymer comprises an ethylene homopolymer, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer and / or an ethylene / 1-octene copolymer.

10. Process according to claim 6, characterized in that: the activating support comprises a fluorinated solid oxide, a sulfated solid oxide, a phosphated solid oxide or any combination thereof.

11. Process according to claim 10, characterized in that the metallocene compound comprises a bridged metallocene compound.

12. Process, according to claim 10, characterized by the fact that the metallocene compound comprises a non-bridged metallocene compound.

13. Composition according to claim 1, characterized in that the activating support comprises fluorinated alumina silica, fluorinated coated alumina silica, fluorinated-chlorinated coated alumina silica, sulfated alumina, phosphated alumina, or a combination thereof.

14. Composition according to claim 13, characterized in that the catalyst composition is substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds or combinations thereof.

15. Composition according to claim 1, characterized in that the metallocene compound comprises a bridged metallocene compound.

16. Composition according to claim 1, characterized in that the metallocene compound comprises an unbridged metallocene compound.

17. Composition according to claim 1, characterized in that the metallocene compound comprises two metallocene compounds.

18. Composition according to claim 1, characterized in that the catalyst composition comprises aluminum alkyl dialkoxide.

19. Composition according to claim 1, characterized in that the catalyst composition comprises aluminum trialkoxide.

20. Composition according to claim 5, characterized in that the catalyst composition comprises aluminum alkyl dialkoxide.

21. Composition according to claim 5, characterized in that the catalyst composition comprises aluminum trialkoxide.

22. Composition according to claim 13, characterized in that the catalyst composition comprises aluminum alkyl dialkoxide.

23. Composition according to claim 13, characterized in that the catalyst composition comprises aluminum trialkoxide.