Process for preparation of metallocene-based catalyst systems for alcohol-containing compounds

Abstract

A method for preparing a metallocene-based catalyst composition includes the steps of contacting an alcohol compound with an organoaluminum compound for a first period of time to form a pre-contacting mixture, and contacting the pre-contacting mixture with an activator-support and a metallocene compound for a second period of time to form the catalyst composition. Such catalyst compositions may contain an activator-support, a metallocene compound, an organoaluminum compound, and a dialkylaluminium alkoxide, and these catalyst compositions have increased catalytic activity for olefin polymerization.

Description

Technical Field

[0001] The present disclosure relates to metallocene-based catalyst systems and, more particularly, to the use of alcohol compounds during the preparation of metallocene-based catalyst systems. Background Art

[0002] There are various methods for preparing metallocene-based catalyst systems containing activator-support and organoaluminum compounds. These catalyst systems can be used to polymerize olefins to produce olefin-based polymers, such as ethylene / alpha-olefin copolymers. Using catalyst systems with the same metallocene, activator-support and organoaluminum components will help these catalyst systems have higher catalytic activity for the production of olefin-based polymers. Therefore, the present disclosure is generally directed to this purpose. Summary of the invention

[0003] The present invention summary is provided to introduce a series of concepts that will be further described in the detailed description below in a simplified form. The present invention summary is not intended to identify the necessary or essential features of the claimed subject matter. The present invention summary is also not intended to be used to limit the scope of the claimed subject matter.

[0004] The present invention generally relates to novel catalyst compositions, methods for preparing catalyst compositions, methods for polymerizing olefins using the catalyst compositions, polymer resins produced using such catalyst compositions, and articles produced using these polymer resins. In particular, the present invention relates to methods for preparing metallocene-based catalyst compositions and the resulting catalyst compositions. The catalyst compositions of the present invention can be used to produce, for example, vinyl homopolymers and copolymers.

[0005] Various methods related to preparing metallocene-based catalyst compositions are disclosed herein. In one aspect, a method for producing a catalyst composition is provided, and in this aspect, the method may include (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 activator-support and a metallocene compound for a second period of time to form a catalyst composition. While not wishing to be bound by the following theory, it is believed that the metallocene-based catalyst composition prepared as described herein may have an unexpected increase in catalytic activity.

[0006] The present invention also encompasses a catalyst composition. In one aspect, the catalyst composition may comprise (A) an activator-support, (B) a metallocene compound, (C) an organoaluminum compound, and (D) a dialkylaluminum alkoxide. Optionally, the catalyst composition may further comprise an alkylaluminum dialkoxide and / or an aluminum trialkoxide.

[0007] The present invention also contemplates and encompasses olefin polymerization methods. Such methods may include contacting a catalyst composition with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer. In general, the catalyst composition employed may include any metallocene-based catalyst system disclosed herein or a metallocene-based catalyst system prepared by any method disclosed herein.

[0008] The foregoing summary of the invention and the following detailed description all provide examples and are merely illustrative. Therefore, the foregoing summary of the invention and the following detailed description should not be considered restrictive. Further, in addition to those features or variations set forth herein, features or variations may also be provided. For example, certain aspects may relate to various feature combinations and sub-combinations described in the detailed description.

[0009] definition

[0010] In order to more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to the present disclosure. If a term is used in the present disclosure, but is not specifically defined herein, the definition in IUPAC Compendium of Chemical Terminology, 2nd edition (1997) can be applied, as long as the definition does not conflict with any other disclosure or definition used in this article, or any claim to which the definition is applied is not uncertain or invalid. If any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, then the definition or usage provided herein shall prevail.

[0011] In this article, the features of the subject matter are described so that combinations of different features can be envisioned within a particular aspect. For each aspect and / or feature disclosed herein, with or without the explicit description of a particular combination, all combinations that do not adversely affect the compositions and methods described herein are considered. In addition, unless otherwise explicitly stated, any aspect and / or feature disclosed herein can be combined to describe features of the invention consistent with the present disclosure.

[0012] In the present disclosure, although compositions and methods are often described in terms of “comprising” various components or steps, the compositions and methods may also “consist essentially of” or “consist of” the various components or steps, unless otherwise specified.

[0013] The terms "a", "an", and "the" are intended to include plural alternatives, such as at least one. For example, unless otherwise indicated, disclosures of "activator-support" and "metallocene compound" are intended to encompass a mixture or combination of one activator-support and metallocene compound or more than one activator-support and metallocene compound, respectively.

[0014] For any particular compound or group disclosed herein, unless otherwise indicated, any name or structure (general or specific) presented is intended to encompass all conformational isomers, regioisomers, stereoisomers, and mixtures thereof that may result 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, in either enantiomeric or racemic form, as well as mixtures of stereoisomers, as known to those skilled in the art. For example, a general reference to pentane includes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane; and a general reference to butyl includes n-butyl, sec-butyl, isobutyl, and tert-butyl.

[0015] The term "polymer" is generally used herein to include olefin homopolymers, copolymers, terpolymers, etc. and alloys and blends thereof. The term "polymer" also includes impact, block, graft, random and alternating copolymers. Copolymers can be derived from olefin monomers and an olefin comonomer, and terpolymers can be derived from olefin monomers and two olefin comonomers. Therefore, "polymer" covers copolymers and terpolymers. Similarly, the scope of the term "polymerization" includes homopolymerization, copolymerization and terpolymerization. Therefore, ethylene polymers include ethylene homopolymers, ethylene copolymers (e.g., ethylene / α-olefin copolymers), ethylene terpolymers, etc., and blends or mixtures thereof. Therefore, ethylene polymers cover polymers commonly referred to in the art as LLDPE (linear low density polyethylene) and HDPE (high density polyethylene). As an example, ethylene copolymers can be derived from ethylene and comonomers, such as 1-butene, 1-hexene or 1-octene. If the monomer and comonomer are ethylene and 1-hexene, respectively, the resulting polymer can be classified as an ethylene / 1-hexene copolymer. If present and unless otherwise indicated, the term "polymer" also includes all possible geometric configurations, and such configurations may include isotactic, syndiotactic and random symmetries. The term "polymer" is also intended to include polymers of all molecular weights.

[0016] The terms "catalyst composition", "catalyst mixture", "catalyst system", etc. do not depend on the actual products or compositions produced by the contact or reaction of the initial components of the disclosed or claimed catalyst composition / mixture / system, the nature of the active catalytic sites, or the fate of the alcohol compound, organoaluminum compound, metallocene compound, or activator-support after combining these components. Therefore, the terms "catalyst composition", "catalyst mixture", "catalyst system", etc. can cover the initial starting components of the composition, as well as any products that can be produced by contacting these initial starting components, and this includes heterogeneous and homogeneous catalyst systems or compositions. The terms "catalyst composition", "catalyst mixture", "catalyst system", etc. can be used interchangeably throughout this disclosure.

[0017] Unless otherwise indicated, the term "contacting" is used herein to describe compositions and methods in which components are contacted or combined together in any order, in any manner, and for any length of time. For example, the components can be combined by blending or mixing or by using any suitable technique. The contact or combination of two or more components can form a reaction product or a reaction mixture.

[0018] "Precontacted mixture" describes a mixture of catalyst components that are combined or contacted for a period of time prior to contacting other catalyst components. According to this specification, the components of the precontacted mixture, once contacted, may react to form at least one chemical compound, formulation, species, or structure that is different from the different initial compounds or components used to prepare the precontacted mixture.

[0019] The term "hydrocarbon" refers to a compound containing only carbon and hydrogen. The term "hydrocarbyl" is used herein according to the definition specified by IUPAC: a monovalent group formed by removing one hydrogen atom from a hydrocarbon (i.e., a group containing only carbon and hydrogen). Non-limiting examples of hydrocarbyl groups include, among other groups, alkyl, alkenyl, aryl, and aralkyl.

[0020] Various numerical ranges are disclosed herein. When any type of range is disclosed or claimed, it is intended to disclose or claim each possible number individually so that such a range can be reasonably covered, including the endpoints of the range and any sub-ranges and combinations of sub-ranges covered therein, unless otherwise stated. As a representative example, the present disclosure states that the weight ratio of the metallocene compound to the activator-support in the catalyst composition can be within a certain range. It is disclosed that the weight ratio can be in the range of 1:1 to 1:1,000,000, and it is intended to state that the weight ratio can be any ratio within the range and, for example, can include any range or range combination of 1:1 to 1:1,000,000 (such as 1:10 to 1:10,000, 1:20 to 1:1000 or 1:50 to 1:500, etc.). Similarly, all other ranges disclosed herein should be interpreted in a manner similar to this example.

[0021] Generally, an amount, size, formulation, parameter, range, or other quantity or characteristic is "about" or "approximately", whether or not expressly stated as such. Whether or not modified by the term "about" or "approximately", the claims include equivalents to the quantities or characteristics.

[0022] Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the typical methods, devices, and materials are described herein.

[0023] 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 might be used in connection with the presently described invention. DETAILED DESCRIPTION

[0024] Disclosed herein are methods for preparing metallocene-based catalyst compositions using a metallocene compound, an activator-support, an organoaluminum compound, and a controlled amount of an alcohol compound. Also disclosed are polymerization processes utilizing these catalyst compositions.

[0025] Alcohol compounds are generally poisons that can deactivate metallocene-based catalyst systems and should therefore be avoided. However, by using controlled amounts of alcohol compounds, the methods and catalyst compositions disclosed herein exhibit unexpected increases in catalytic activity.

[0026] Method for preparing catalyst composition

[0027] Various methods for preparing catalyst compositions containing metallocene compounds, activator-supports, and organoaluminum compounds are disclosed and described. One or more metallocene compounds, one or more activator-supports, and one or more organoaluminum compounds may be employed in the disclosed processes and compositions. The method for producing a catalyst composition according to aspects of the invention may comprise (or consist essentially of, or consist of):

[0028] (i) contacting an alcohol compound with an organoaluminum compound for a first period of time to form a precontacted mixture (alternatively and equivalently, a first mixture); and

[0029] (ii) contacting the precontacted mixture with an activator-support and a metallocene compound for a second period of time to form a catalyst composition.

[0030] In general, the features of any process disclosed herein (e.g., activator-support, organoaluminum compound, metallocene compound, alcohol compound, first time period and second time period, etc.) are described independently herein, and these features can be combined in any combination to further describe the disclosed process. In addition, unless otherwise stated, other process steps can be performed before, during and / or after any step listed in the disclosed process. In addition, the catalyst composition produced according to the disclosed process is within the scope of the present disclosure and is included herein.

[0031] In step (i), the organoaluminum compound is in molar excess compared to the alcohol compound. As those skilled in the art will readily appreciate, an excess of alcohol compound can significantly reduce catalyst activity and polymer production rate compared to certain components of the catalyst system, and can ultimately "terminate" the reaction. Therefore, the actual maximum amount of alcohol compound added to the catalyst system is limited. Typically, the molar ratio of the hydroxyl group (-OH) of the alcohol compound to the aluminum of the organoaluminum compound (OH: A1) falls within the range of 0.05: 1 to 0.9: 1. Representative and non-limiting ranges include, for example, 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 to 0.7: 1, or 0.2: 1 to 0.6: 1, etc. OH: A1 molar ratio.

[0032] Although not limited thereto, the molar ratio of the alcohol compound (before forming the precontact mixture in step (i)) to the metallocene compound (before forming the catalyst composition in step (ii)) can generally range from as low as 1:1 to up to and including 1000:1. In one aspect, the molar ratio of the alcohol compound to the metallocene compound can range from 10:1 to 500:1, while in another aspect, the molar ratio can range from 50:1 to 750:1, and in another aspect, the molar ratio can range from 100:1 to 400:1.

[0033] Likewise, and also without limitation, the weight ratio of the alcohol compound (before forming the precontact mixture in step (i)) to the activator-support (before forming the catalyst composition in step (ii)) can generally be in the range of 1:1 to 1:500. In one aspect, the weight ratio of the alcohol compound to the activator-support can be in the range of 1:2 to 1:250, while in another aspect, the weight ratio can be in the range of 1:5 to 1:150, and in yet another aspect, the weight ratio can be in the range of 1:10 to 1:100.

[0034] Step (i) of the process may generally be referred to as a precontacting step, and in the precontacting step, the alcohol compound is contacted with the organoaluminum compound for a first period of time to form a precontacting mixture. The precontacting step may be conducted at a variety of temperatures and time periods. For example, the precontacting step may be conducted at a precontacting temperature in the range of 0°C to 100°C; alternatively, 0°C to 75°C; alternatively, 10°C to 75°C; alternatively, 20°C to 60°C; alternatively, 20°C to 50°C; alternatively, 15°C to 45°C; or alternatively, 20°C to 40°C. In these and other aspects, these temperature ranges are also intended to cover the case where the precontacting step is conducted at a series of different temperatures falling within the corresponding ranges rather than at a single fixed temperature, wherein at least one temperature falls within the corresponding ranges.

[0035] The duration of the pre-contact step (first time period) is not limited to any specific time period, as long as the first time period is sufficient to allow any reaction between the alcohol compound and the organoaluminum compound to form a pre-contact mixture. Therefore, the first time period can be, for example, a time period as short as 1-10 seconds to as long as 48 hours or more. The appropriate first time period may depend on, for example, the pre-contact temperature, the amount of the alcohol compound and the organoaluminum compound in the pre-contact mixture, the presence and degree of mixing of the diluent or solvent in the pre-contact step, and other variables. However, in general, the first 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, etc. The typical range of the first time period may include, but is 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, and ranges within these exemplary ranges.

[0036] Typically, the precontacting 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 directly or can be diluted in any suitable hydrocarbon solvent, which can be the same or different from the hydrocarbon solvent used for the organoaluminum compound.

[0037] In step (ii) of the process, the pre-contact mixture (typically a solution) may be contacted with the activator-support and the metallocene compound for a second period of time to form a catalyst composition. Step (ii) may also be carried out at a variety of temperatures and time periods. For example, step (ii) may be carried out at a temperature in the range of 0°C to 100°C; alternatively, 10°C to 75°C; alternatively, 20°C to 60°C; alternatively, 15°C to 45°C; or alternatively, 20°C to 40°C. In these and other aspects, these temperature ranges are also intended to cover the case where step (ii) is carried out at a series of different temperatures falling within the corresponding ranges rather than at a single fixed temperature, wherein at least one temperature falls within the corresponding ranges. As an example, the pre-contact mixture may be contacted with the activator-support and the metallocene compound at an elevated temperature and then cooled to a lower temperature for long-term storage of the final catalyst composition.

[0038] The second time period is not limited to any specific time period. Therefore, the scope of the second time period can be as short as 1-10 seconds to as long as 48 hours or longer. Suitable second time period can depend on the amount of diluent or solvent in step (ii), such as temperature, pre-contact mixture and activator-support and metallocene compound, mixing degree and long-term storage consideration and other variables. However, in general, 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, etc. Assuming that the catalyst composition is not intended for long-term storage (can be extended for several days or weeks), the typical range of the second time period can include but is 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.

[0039] In one aspect, the precontacted mixture is contacted with the activator-support prior to contacting with the metallocene compound in step (ii), while in another aspect, the precontacted mixture is contacted with the metallocene compound prior to contacting with the activator-support, and in yet another aspect, the precontacted mixture is contacted with the activator-support and the metallocene compound substantially simultaneously, which in this context means that the precontacted mixture, activator-support, and metallocene compound are contacted together as soon as commercially practicable, such as within 10 minutes, within 5 minutes, within 1 minute, or within 30 seconds after the two components (e.g., metallocene compound and activator-support) are contacted.

[0040] Typically, step (ii) can be performed by combining (e.g., mixing) the precontacted mixture with a slurry of the activator-support in any suitable hydrocarbon solvent and a solution of the metallocene compound in any (same or different) suitable hydrocarbon solvent. Alternatively, the activator-support can be combined with the precontacted mixture and the metallocene compound in dry solid form. In general, any suitable procedure known to those skilled in the art for thoroughly combining the activator-support, metallocene compound, and precontacted mixture can be employed.

[0041] Non-limiting examples of suitable hydrocarbon solvents that can 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 for the organoaluminum compound can be the same or different from the solvent for the activator-support slurry, and the same or different from the solvent for the metallocene compound.

[0042] In a related aspect, a catalyst composition according to the present invention may comprise (A) an activator-support, (B) a metallocene compound, (C) an organoaluminum compound, and (D) a dialkylaluminum alkoxide. In another aspect, the catalyst composition may comprise (A) an activator-support, (B) a metallocene compound, (C) an organoaluminum compound, (D) a dialkylaluminum alkoxide, and (E) an alkylaluminum dialkoxide and / or an aluminum trialkoxide.

[0043] When it comes to the organoaluminum compound in the catalyst composition and the method for preparing it, one or more than one organoaluminum compound can be utilized. Likewise, one or more than one alcohol compound can be used to react with the organoaluminum compound to form the precontacted mixture (and to form one or more of a dialkylaluminum alkoxide, an alkylaluminum dialkoxide, and / or an aluminum trialkoxide).

[0044] First, with reference to the organoaluminum compound, a suitable organoaluminum compound may have the formula (RZ) 3A1, wherein each RZ may independently be an aliphatic group having 1 to 10 carbon atoms. For example, each RZ may independently be methyl, ethyl, propyl, butyl, hexyl or isobutyl. Examples of organoaluminum compounds suitable for use in accordance with 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, etc. or combinations thereof. In one aspect, the organoaluminum compound used in the processes and catalyst systems disclosed herein can include (or consist essentially of, or consist of) triethylaluminum (TEA), while in another aspect, the organoaluminum compound used in the processes and catalyst systems disclosed herein can include (or consist essentially of, or consist of) triisobutylaluminum (TIBA). However, in another aspect, a mixture of TEA and TIBA can be used as the organoaluminum component in the processes described herein (or as the organoaluminum component in the catalyst systems disclosed herein).

[0045] Suitable alcohol compounds for use herein may include, for example, monoalcohols, diols, triols or polyols and combinations thereof. In addition, suitable alcohol compounds may be linear or branched, and may be primary, secondary or tertiary alcohols. Typically, the alcohol compound may include a hydrocarbyl alcohol, although this is not required. For example, the alcohol compound may include an alkyl alcohol, a cycloalkyl alcohol, an aryl alcohol, an arylalkyl alcohol, and the like and combinations thereof.

[0046] The number of carbon atoms in the alcohol compound is not particularly limited, although in some aspects, the alcohol compound may include C1 to C 32 Alcohol; alternatively, C1 to C 18 Alcohol; alternatively, C1 to C 12 Alcohol; alternatively, C1 to C8 alcohol; alternatively, C1 to C4 alcohol; alternatively, C2 to C 12Alcohol; or alternatively, C2 to C6 alcohol. Representative and non-limiting examples of suitable alcohol compounds (e.g., monohydric alcohol compounds) may include the following: methanol, ethanol, propanol (e.g., isopropanol, n-propanol), butanol (e.g., n-butanol, isobutanol), amyl alcohol, hexanol, heptanol, octanol, decanol, hexadecanol, cyclohexanol, phenol, benzyl alcohol, etc. and combinations thereof. In one aspect, the alcohol compound may include methanol, ethanol, propanol (e.g., isopropanol, n-propanol), butanol (e.g., n-butanol, isobutanol), amyl alcohol, hexanol, heptanol, octanol, decanol, hexadecanol, etc. or combinations thereof. In another aspect, the alcohol compound may include cyclohexanol, phenol, benzyl alcohol, etc. or combinations thereof. In another aspect, the alcohol compound may include methanol, ethanol, propanol (e.g., isopropanol, n-propanol), butanol (e.g., n-butanol, isobutanol), amyl alcohol, hexanol, heptanol, octanol, etc. or combinations thereof. In another aspect, the alcohol compound may include methanol, ethanol, propanol (e.g., isopropanol, n-propanol), butanol (e.g., n-butanol, isobutanol), the like, or a combination thereof, or alternatively, ethanol, propanol (e.g., isopropanol, n-propanol), butanol (e.g., n-butanol, isobutanol), the like, or a combination thereof.

[0047] In certain aspects, the alcohol compound may include a diol, illustrative examples of which may include, but are not limited to, methylene glycol, ethylene glycol, propylene glycol, butanediol (e.g., 1,4-butanediol), pentanediol, octanediol, bisphenol A, and the like, and any combination thereof. Thus, in certain aspects, the alcohol compound may include ethylene glycol, propylene glycol, or both; alternatively, methylene glycol; alternatively, ethylene glycol; alternatively, propylene glycol; alternatively, butanediol (e.g., 1,4-butanediol); alternatively, pentanediol; alternatively, octanediol; or alternatively, bisphenol A.

[0048] In other aspects, the alcohol compound may include a triol, a polyol, or a combination thereof, illustrative examples of which may include, but are not limited to, glycerol, pyrogallol, erythritol, xylitol, mannitol, and the like, and combinations thereof. Thus, in some aspects, the alcohol compound may include glycerol; alternatively, pyrogallol; alternatively, erythritol; alternatively, xylitol; or alternatively, mannitol.

[0049] Advantageously, in certain aspects, the alcohol compound may be liquid at a temperature (at atmospheric pressure) in the range of 20° C. to 400° C.; alternatively, in the range of 20° C. to 100° C.; or alternatively, in the range of 20° C. to 75° C. For convenience, the alcohol compound used herein generally comprises (or consists essentially 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).

[0050] The dialkylaluminum alkoxide, alkylaluminum dialkoxide, and / or aluminum trialkoxide compounds formed by contacting and reacting the organoaluminum compound with the alcohol compound in the precontacted mixture and in the catalyst composition can have the following formula: The dialkylaluminum alkoxide compound can have the formula (R Z )2Al(OR A ), the alkyl aluminum dialkoxide compound may have the formula (R Z )Al(OR A )2, and the aluminum trialkoxide compound may have the formula Al(OR A )3. In these formulas, each RZ and each R A Can be independently C1 to C 18 Alkyl; alternatively, C1 to C 10 Alkyl; alternatively, C1 to C6 alkyl; or alternatively, C1 to C4 alkyl.

[0051] As an example, if the organoaluminum compound is TEA and the alcohol compound is ethanol, a typical dialkylaluminum alkoxide compound formed therefrom is diethylaluminum ethoxide. In addition, a typical alkylaluminum dialkoxide compound that can be formed therefrom is ethylaluminum dialkoxide, and a typical aluminum trialkoxide compound that can be formed therefrom is aluminum triethoxide.

[0052] Unexpectedly, these catalyst compositions and methods for preparing the same catalyst compositions can result in an increase in catalytic activity. For example, under the same catalyst preparation and polymerization conditions, the activity of the catalyst composition can be higher (e.g., at least 10%, at least 15%, at least 20%, at least 30%, or at least 35%, and typically up to 50%, 60%, 75%, or 100%) than the activity of an otherwise identical catalyst system obtained without the alcohol compound (or without the dialkylaluminum alkoxide and without the alkylaluminum dialkoxide and / or aluminum trialkoxide, if present). The same polymerization conditions refer to slurry polymerization conditions, using isobutane as a diluent, and using a polymerization temperature of 80°C and a reactor pressure of 320 psig. In addition, all components used to prepare the catalyst system remain constant (e.g., the same amount / type of metallocene compound, the same amount / type of organoaluminum, the same amount / type of activator-support, such as fluorinated silica-coated alumina or sulfated alumina), and all polymerization conditions remain constant (e.g., the same polymerization temperature and the same polymerization pressure). Thus, the only difference is in the process used to produce the catalyst system, i.e., using an alcohol compound to contact / react with an organoaluminum compound to form a precontacted mixture as part of the catalyst composition.

[0053] In general, in the catalyst compositions and methods for preparing the same disclosed herein, the weight ratio of the activator-support to the organoaluminum compound 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 activator-support is employed, the ratio is based on the total weight of each respective component. In one aspect, the weight ratio of the activator-support to the organoaluminum compound may be in the range of 1:1 to 100:1, 1:1 to 50:1, or 2:1 to 20:1.

[0054] Likewise, the weight ratio of the metallocene compound to the activator-support may be in the range of 1:1 to 1:1,000,000 or 1:10 to 1:10,000. If more than one metallocene compound and / or more than one activator-support is employed, the ratio is based on the total weight of each respective component. In one aspect, the weight ratio of the metallocene compound to the activator-support may be in the range of 1:20 to 1:1000 or 1:50 to 1:500, etc.

[0055] In some aspects, the catalyst composition and its preparation method are substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds and / or other similar materials; alternatively, substantially free of aluminoxane; alternatively, substantially free of organoboron or organoborate compounds; or alternatively, substantially free of ionizing ionic compounds. For example, the catalyst composition may independently contain less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm (by weight) of aluminoxane, organoboron or organoborate compounds and ionizing ionic compounds. In these aspects, as discussed herein, in the absence of these additional materials, the catalyst composition has catalytic activity. For example, the catalyst composition of the present invention may be substantially composed of an activator-support, a metallocene compound, an organoaluminum compound, a dialkylaluminum alkoxide, and an alkylaluminum dialkoxide and / or an aluminum trialkoxide, wherein no other materials are present in the catalyst composition, and the other materials increase / decrease the activity of the catalyst composition by more than about 10% compared to the catalyst activity of the catalyst composition in the absence of the materials.

[0056] Metallocene compounds

[0057] The metallocene-based catalyst composition according to the present invention may contain bridged metallocene compounds and / or unbridged metallocene compounds. The metallocene-based catalyst composition according to the present invention may also contain two or more bridged metallocene compounds and / or two or more unbridged metallocene compounds. The metallocene compound may include, for example, a transition metal (one or more than one) of the IIIB-VIIIB group of the periodic table of the elements. In one aspect, the metallocene compound may include a transition metal of group III, IV, V or VI, or a combination of two or more transition metals. In other aspects, the metallocene compound may include chromium, titanium, zirconium, hafnium, vanadium or a combination thereof, or may include titanium, zirconium, hafnium or a combination thereof. In other aspects, the metallocene compound may include titanium or zirconium or hafnium alone or in combination.

[0058] In some aspects of the invention, the metallocene compound may include, for example, a bridged metallocene compound with titanium, zirconium or hafnium, such as a bridged zirconium or hafnium metallocene compound with a fluorenyl group and no aromatic group on the bridging group, or a bridged zirconium or hafnium metallocene compound with a cyclopentadienyl group and a fluorenyl group and no aromatic group on the bridging group. In some aspects, such bridged metallocenes may contain alkenyl substituents (e.g., terminal alkenyl groups) on the bridging group and / or on the cyclopentadienyl-type group (e.g., cyclopentadienyl or fluorenyl group). In another aspect, the metallocene compound may include a bridged zirconium or hafnium metallocene compound having a fluorenyl group and an aryl group on the bridging group; alternatively, a bridged zirconium or hafnium metallocene compound having a cyclopentadienyl group and a fluorenyl group and an aryl group on the bridging group; alternatively, a bridged zirconium metallocene compound having a fluorenyl group and an aryl group on the bridging group; or alternatively, a bridged hafnium metallocene compound having a fluorenyl group and an aryl group on the bridging group. In these and other aspects, the aryl group on the bridging group may be a phenyl group. Optionally, these bridged metallocenes may contain alkenyl substituents (e.g., terminal alkenyl groups) on the bridging group and / or on the cyclopentadienyl-type group.

[0059] In some aspects, the metallocene compound may include a bridged zirconium or hafnium metallocene compound (e.g., a bis-indenyl metallocene compound) having two indenyl groups. Thus, the metallocene compound may include a bridged zirconium metallocene compound having two indenyl groups, or alternatively, a bridged hafnium metallocene compound having two indenyl groups. In some aspects, an aryl group may be present on the bridging group, while in other aspects, an aryl group is not present on the bridging group. Optionally, these bridged indenyl metallocenes may contain an alkenyl substituent (e.g., a terminal alkenyl group) on the bridging group and / or on the indenyl group (one or two indenyl groups). The bridging atom of the bridging group may be, for example, a carbon atom or a silicon atom; alternatively, the bridge may contain a chain of two carbon atoms, a chain of two silicon atoms, etc.

[0060] Illustrative and non-limiting examples of bridged metallocene compounds (e.g., with zirconium or hafnium) that can be used in catalyst systems according to aspects of the present invention are described in U.S. Pat. Nos. 7,026,494, 7,041,617, 7,226,886, 7,312,283, 7,517,939, and 7,619,047.

[0061] In some aspects of the invention, the metallocene compound may include an unbridged metallocene; alternatively, an unbridged zirconium or hafnium-based metallocene compound and / or an unbridged zirconium and / or hafnium-based binuclear metallocene compound; alternatively, an unbridged zirconium or hafnium-based metallocene compound containing two cyclopentadienyls, two indenyls, or one cyclopentadienyl and one indenyl; alternatively, an unbridged zirconium-based metallocene compound containing two cyclopentadienyls, two indenyls, or one cyclopentadienyl and one indenyl. Illustrative and non-limiting examples of unbridged metallocene compounds (e.g., with zirconium or hafnium) that can be used in catalyst systems according to aspects of the invention are described in U.S. Patent Nos. 7,199,073, 7,226,886, 7,312,283 and 7,619,047.

[0062] In addition, the metallocene compound may include unbridged binuclear metallocenes, such as those described in U.S. Patent Nos. 7,919,639 and 8,080,681. The metallocene compound may include unbridged zirconium and / or hafnium-based binuclear metallocene compounds. For example, the metallocene compound may include unbridged zirconium-based homo-binuclear metallocene compounds or unbridged hafnium-based homo-binuclear metallocene compounds or unbridged zirconium and / or hafnium-based hetero-binuclear metallocene compounds (i.e., binuclear compounds with two hafnias or two zircons or one zirconium and one hafnium).

[0063] Aspects of the invention also relate to catalyst compositions and methods of preparing catalyst compositions, wherein two or more metallocene compounds are used, such as a dual metallocene catalyst composition. Independently, each corresponding metallocene compound can be any bridged metallocene compound disclosed herein or any unbridged metallocene compound disclosed herein.

[0064] Therefore, in certain aspects of the invention, the catalyst composition and the method for preparing the catalyst composition may include more than one metallocene compound, for example, one bridged metallocene compound and one 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 the 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, etc.

[0065] Activator-Carrier

[0066] The present invention encompasses various catalyst compositions containing activator-supports and various methods for preparing catalyst compositions using activator-supports. 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 a Lewis acidic metal ion. Non-limiting examples of suitable activator-supports are disclosed in, for example, U.S. Patent Nos. 7,294,599, 7,601,665, 7,884,163 and 8,309,485.

[0067] Solid oxides can encompass oxide materials such as alumina, "mixed oxides" thereof such as silica-alumina, coatings of one oxide on another oxide, and combinations and mixtures thereof. Mixed oxides such as silica-alumina can be single or multiple chemical phases in which more than one metal is combined with oxygen to form a solid oxide. Examples of mixed oxides that can be used to form activator-supports, either alone or in combination, can include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, alumina-titania, alumina-zirconia, zinc aluminate, alumina-boria, silica-boria, aluminum phosphate-silica, titania-zirconia, and the like. Solid oxides used herein can also encompass oxide materials such as silica-coated alumina as described in U.S. Pat. Nos. 7,884,163.

[0068] Thus, in one aspect, the solid oxide may comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstates, titania, silica-titania, zirconia, silica-zirconia, magnesia, boria, zinc oxide, any mixed oxides thereof, or any combination thereof. In another aspect, the solid oxide may comprise alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminum phosphate, heteropolytungstates, titania, silica-titania, zirconia, silica-zirconia, magnesia, boria, or zinc oxide, any mixed oxides thereof, or any mixture thereof. In another aspect, the solid oxide may comprise silica, alumina, titania, zirconia, magnesia, boria, or zinc oxide, any mixed oxides thereof, or any mixture thereof. In another aspect, the solid oxide can comprise silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, alumina-boria, or any combination thereof. In another aspect, the solid oxide can comprise alumina, silica-alumina, silica-coated alumina, or any mixture thereof; alternatively, alumina; alternatively, silica-alumina; or alternatively, silica-coated alumina.

[0069] Useful silica-alumina or silica-coated alumina solid oxide materials can have a silica content of 5% to 95% by weight. In one aspect, the silica content of these solid oxides can be 10% to 80% by weight, or 20% to 70% silica. In another aspect, such materials can have a silica content ranging from 15% to 60% by weight, or 25% to 50% silica. The solid oxides contemplated herein can have any suitable surface area, pore volume, and particle size, as will be appreciated by those skilled in the art.

[0070] The electron-withdrawing component used to treat the solid oxide can be an electron-withdrawing component that increases the Lewis or Bronsted acidity of the solid oxide after treatment (e.g., compared to a solid oxide not treated with at least one electron-withdrawing anion). Acidity). According to one aspect, the electron-withdrawing component can be an electron-withdrawing anion derived from: a salt, an acid, or other compounds (such as volatile organic compounds) that serve as the source or precursor of the anion. Examples of electron-withdrawing anions can include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, trifluoromethanesulfonate, fluorozirconate, fluorotitanate, phosphotungstate, tungstate, molybdate, etc., including mixtures and combinations thereof. In addition, other ions or nonionic compounds serving as the source of these electron-withdrawing anions can also be used. In some aspects provided herein, it is contemplated that the electron-withdrawing anion can be or may include fluoride, chloride, bromide, phosphate, trifluoromethanesulfonate, bisulfate or sulfate, etc., or any combination thereof. In other aspects, the electron-withdrawing anion can include sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, trifluoromethanesulfonate, fluorozirconate, fluorotitanate, etc. or combinations thereof. However, in other aspects, the electron-withdrawing anion can include fluoride and / or sulfate.

[0071] The activator-support can generally contain from 1 to 25 weight percent of the electron-withdrawing anion, based on the weight of the activator-support. In specific aspects provided herein, the activator-support can contain from 1 to 20 weight percent, 2 to 20 weight percent, 3 to 20 weight percent, 2 to 15 weight percent, 3 to 15 weight percent, 3 to 12 weight percent, or 4 to 10 weight percent of the electron-withdrawing anion, based on the total weight of the activator-support.

[0072] In one aspect, the activator-support can include fluorided alumina, chlorided alumina, brominated alumina, sulfated alumina, phosphated alumina, fluorided silica-alumina, chlorided silica-alumina, brominated silica-alumina, sulfated silica-alumina, phosphated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, fluorided-chlorinated silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, and the like, and any mixtures or combinations thereof. In another aspect, the activator-support employed in the processes and catalyst systems described herein can be or can include a fluorinated solid oxide and / or a sulfated solid oxide and / or a phosphated solid oxide, non-limiting examples of which can include fluorinated alumina, sulfated alumina, phosphated alumina, fluorinated silica-alumina, sulfated silica-alumina, phosphated silica-alumina, fluorinated silica-zirconia, fluorided silica-coated alumina, fluorided-chlorinated silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, the like and combinations thereof. In another aspect, the activator-support may comprise fluorided alumina; alternatively, chlorided alumina; alternatively, sulfated alumina; alternatively, phosphated alumina; alternatively, fluorided silica-alumina; alternatively, sulfated silica-alumina; alternatively, phosphated silica-alumina; alternatively, fluorided silica-zirconia; alternatively, chlorided silica-zirconia; alternatively, sulfated silica-coated alumina; alternatively, phosphated silica-coated alumina; alternatively, fluorided-chlorided silica-coated alumina; or alternatively, fluorided silica-coated alumina.

[0073] Various methods can be used to form the activator-support useful in the present invention. Methods for contacting the solid oxide with an electron-withdrawing component, suitable electron-withdrawing components and amounts thereof, impregnation with metals or metal ions (e.g., zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, etc., or combinations thereof), and various calcination procedures and conditions are disclosed, for example, in U.S. Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,356,630,631,632,633,634,636,637,638,639,640,641,643,644,645,646,647,648,649,650,661,670,671,671,672,673,674,675,676,677,678,679,680,690,691,701,693,714,723,694,734,695,736,737,738,696,813,739,747,750,764,778,779,819,820,839,830,831,831,839,851,861,870,871,871 Other suitable methods and procedures for preparing the activator-support (e.g., fluorided solid oxide, sulfated solid oxide, or phosphated solid oxide) are well known to those skilled in the art.

[0074] Olefin monomers and olefin polymers

[0075] The olefin monomers considered herein generally include olefin compounds with 2 to 30 carbon atoms and at least one olefinic double bond per molecule. The homopolymerization method using a single olefin (such as ethylene, propylene, butylene, hexene, octene etc.) is covered, as well as copolymerization and terpolymerization using olefin monomers and at least one different olefinic compound. For example, the gained ethylene copolymer or terpolymer generally can contain a large amount of ethylene (>50 mole percent) and a small amount of comonomer (<50 mole percent), although this is not essential. The comonomer that can be copolymerized with ethylene can generally have 3 to 20 carbon atoms or 3 to 10 carbon atoms in its molecular chain.

[0076] Acyclic, cyclic, polycyclic, terminal (α), internal, straight chain, branched, substituted, unsubstituted, functionalized and non-functionalized olefins can be used. For example, typical unsaturated compounds that can be polymerized to produce olefin polymers can 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, four kinds of n-octenes (e.g., 1-octene), four kinds of n-nonenes, five kinds of n-decenes, etc., or a mixture of two or more of these compounds. Cyclic and bicyclic olefins, including but not limited to cyclopentene, cyclohexene, norbornene, norbornadiene, etc., can also be polymerized as described herein. Styrene can also be used as a monomer or comonomer. In one aspect, olefin monomers can include C2-C 20 Olefins; alternatively, C2-C 20 α-olefins; alternatively, C2-C 12 Olefins; alternatively, C2-C 10 α-olefin; alternatively, ethylene, propylene, 1-butene, 1-hexene or 1-octene; alternatively, ethylene or propylene; alternatively, ethylene; or alternatively, propylene.

[0077] When a copolymer (or alternatively, a terpolymer) is desired, the olefin monomer may be, for example, ethylene or propylene, which is co-polymerized with at least one comonomer (e.g., C2-C 20 α-olefins, C3-C 20 α-olefin) copolymerization. According to one aspect, the olefin monomer in the polymerization method can be ethylene. In this regard, examples of suitable olefin comonomers can 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, etc. or combinations thereof. According to another aspect, the comonomer can include α-olefins (e.g., C3-C 10 In one aspect, the comonomer may include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof. For example, the comonomer may include 1-butene, 1-hexene, 1-octene, or a combination thereof.

[0078] In general, the amount of comonomer introduced into the polymerization reactor to produce the copolymer can be 0.01 to 50 weight percent comonomer based on the total weight of the monomer and the comonomer. According to another aspect, the amount of comonomer introduced into the polymerization reactor can be 0.01 to 40 weight percent comonomer based on the total weight of the monomer and the comonomer. In another aspect, the amount of comonomer introduced into the polymerization reactor can be 0.1 to 35 weight percent comonomer based on the total weight of the monomer and the comonomer. However, in another aspect, the amount of comonomer introduced into the polymerization reactor can be 0.5 to 20 weight percent comonomer based on the total weight of the monomer and the comonomer.

[0079] While not intending to be bound by this theory, it is believed that steric hindrance can hinder and / or slow the polymerization reaction when branched, substituted or functionalized olefins are used as reactants. Thus, branches and / or cyclic portions of an olefin that are slightly removed from a carbon-carbon double bond are not expected to hinder the reaction in the same way that the same olefin substituents located closer to the carbon-carbon double bond might.

[0080] According to one aspect, at least one monomer / reactant can be ethylene (or propylene), and thus the polymerization reaction can be a homopolymerization involving only ethylene (or propylene), or a copolymerization with different acyclic, cyclic, terminal, internal, linear, branched, substituted or unsubstituted olefins. In addition, the methods disclosed herein are intended to include olefins that also cover diene compounds, including but not limited to 1,3-butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, etc.

[0081] The olefin polymers covered herein may include any polymer produced by any olefin monomer (and one or more optional comonomers) described herein. For example, the olefin polymer may include 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, etc., including combinations thereof. In one aspect, the olefin polymer may be (or may include) 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 include) 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 olefin polymer may have a unimodal molecular weight distribution.

[0082] Polymerization reactor system and method

[0083] The disclosed catalyst system and preparation method thereof are intended to be used for any olefin polymerization process using various types of polymerization reactors, polymerization reactor systems and polymerization reaction conditions. As used herein, "polymerization reactor" includes any polymerization reactor capable of polymerizing olefin monomers and comonomers (one or more than one comonomer) to produce homopolymers, copolymers, terpolymers, etc. Various types of polymerization reactors include, but are not limited to, those reactors that may be referred to as batch reactors, slurry reactors, gas phase reactors, solution reactors, high pressure reactors, tubular reactors, autoclave reactors, etc., or combinations thereof. Various reactor types use suitable polymerization conditions. The gas phase reactor may include a fluidized bed reactor or a graded horizontal reactor. The slurry reactor may include a vertical or horizontal loop. The high pressure reactor may include an autoclave reactor, a tubular reactor, or a combination thereof in parallel or in series. Reactor types may include intermittent or continuous processes. Continuous processes may use intermittent and / or continuous product discharges. The polymerization reactor system and process may also include partial or complete direct recycling of unreacted monomers, unreacted comonomers and / or diluents.

[0084] The polymerization reactor system may include a single reactor or multiple reactors of the same or different types (e.g., 2 reactors or more than 2 reactors). For example, the polymerization reactor system may include a slurry reactor, a gas phase reactor, a solution reactor, or a combination of two or more of these reactors. Producing polymers in multiple reactors may include several stages in at least two separate polymerization reactors, and the at least two separate polymerization reactors are interconnected by at least one transfer device so that the polymer produced by the first polymerization reactor can be transferred to the second reactor. The desired polymerization conditions in one of the reactors may be different from the operating conditions of the other one or more reactors. Alternatively, the polymerization in multiple reactors may include manually transferring the polymer from one reactor to a subsequent reactor to continue polymerization. The multi-reactor system may include any combination, including but not limited to a plurality of loop reactors, a plurality of gas phase reactors, a combination of a loop reactor and a gas phase reactor, a plurality of high pressure reactors, or a combination of a high pressure reactor and a loop reactor and / or a gas phase reactor. Multiple reactors may be operated in series, in parallel, or in series and in parallel.

[0085] According to one aspect, the polymerization reactor system may include at least one loop slurry reactor, including vertical or horizontal loops. Monomer, diluent, catalyst and comonomer can be continuously fed into the loop reactor where polymerization occurs. Generally speaking, a continuous process may include continuously introducing monomer / comonomer, catalyst and diluent into the polymerization reactor, and continuously removing a suspension comprising polymer particles and diluent from the reactor. The reactor effluent may be flashed to remove solid polymer from a liquid comprising diluent, monomer and / or comonomer. A variety of techniques may be used for this separation step, including but not limited to flashing, which may include any combination of heating and decompression, separation by cyclone action in a cyclone separator or hydrocyclone, or by centrifugation.

[0086] Typical slurry polymerization processes (also referred to as particle formation processes) are disclosed in, for example, U.S. Patent 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 slurry polymerization include, but are not limited to, monomers to be 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, normal butane, normal pentane, isopentane, neopentane and normal hexane. Some loop polymerization reactions can occur under bulk conditions without using a diluent.

[0087] According to another aspect, the polymerization reactor system may include at least one gas phase reactor (e.g., fluidized bed reactor). Such reactor systems may use a continuous recycle stream containing one or more monomers, which is continuously circulated through a fluidized bed under polymerization conditions in the presence of a catalyst. The recycle stream may be discharged from the fluidized bed and recycled back into the reactor. At the same time, the polymer product may be discharged from the reactor, and new or fresh monomers may be added to replace the polymerized monomers. Such gas phase reactors may include a process for the multi-step gas phase polymerization of olefins, wherein the olefins are polymerized in gas phase form in at least two independent gas phase polymerization zones, and the catalyst-containing polymer formed in the first polymerization zone is fed to the 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.

[0088] According to another aspect, the polymerization reactor system may include a high pressure polymerization reactor, for example, a tubular reactor and / or an autoclave reactor. The tubular reactor may have several zones where fresh monomer, initiator or catalyst is added. The monomer may be entrained in an inert gas stream and introduced in one zone of the reactor. The initiator, catalyst and / or catalyst components may be entrained in a gas stream and introduced in another zone of the reactor. The gas streams may be intermixed for polymerization. Heat and pressure may be used appropriately to obtain optimal polymerization conditions.

[0089] According to another aspect, the polymerization reactor system may include a solution polymerization reactor in which the monomer / comonomer is contacted with the catalyst composition by suitable stirring or other means. A carrier comprising an inert organic diluent or excess monomer may be used. If necessary, the monomer / comonomer may be contacted with the catalytic reaction product in the gas phase in the presence or absence of a liquid material. The polymerization zone may be maintained at a temperature and pressure that will form a polymer solution in the reaction medium. Stirring may be used to obtain better temperature control and maintain a uniform polymerization mixture throughout the polymerization zone. Use appropriate means to dissipate the exothermic heat of polymerization.

[0090] The polymerization reactor system may also include at least one feed system, at least one feed system for catalyst or catalyst component and / or any combination of at least one polymer recovery system. Suitable reactor system may also include systems for purification of raw materials, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractional separation, recycling, storage, loading, laboratory analysis and process control. According to the desired properties of olefin polymers, hydrogen may be added to the polymerization reactor as required (for example, continuously or pulsedly).

[0091] The polymerization conditions that can be controlled to improve efficiency and provide the desired polymer properties may include temperature, pressure and the concentration of various reactants. The polymerization temperature can affect the catalyst production rate, polymer molecular weight and molecular weight distribution. According to the Gibbs Free Energy Equation, a suitable polymerization temperature can be any temperature below the depolymerization temperature. Typically, this includes, for example, 60°C to 280°C or 60°C to 120°C, depending on the type of polymerization reactor. In some reactor systems, the polymerization temperature can generally be in the range of 65°C to 110°C, 70°C to about 100°C or 75°C to about 95°C.

[0092] Suitable pressures will also vary depending on the reactor and polymerization type. The pressure for liquid phase polymerization in a loop reactor may generally be less than 1000 psig. The pressure for gas phase polymerization may range from 200 to 500 psig. High pressure polymerization in a tubular reactor or autoclave reactor may generally be carried out at 20,000 to 75,000 psig. Polymerization reactors may also be operated in a supercritical region, which generally occurs at higher temperatures and pressures. Operation above the critical point (supercritical phase) of the pressure / temperature diagram may provide advantages for the polymerization process.

[0093] Also contemplated herein are olefin polymerization processes utilizing any catalyst composition described herein. One such process may include contacting a catalyst composition with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer. Generally speaking, the polymerization process may utilize any olefin monomer and optional comonomer disclosed herein, and the catalyst composition employed may be a single (or dual) metallocene catalyst system utilizing, for example, any metallocene compound disclosed herein, any activator-support, and any organoaluminum compound, and the catalyst system may be prepared by any method disclosed herein. The present invention also relates to and encompasses polymers produced by any polymerization process disclosed herein.

[0094] As another example, an olefin polymerization process encompassed herein may comprise (or consist essentially of, or consist of) contacting an alcohol compound with an organoaluminum compound for a first period of time to form a precontacted mixture, contacting the precontacted mixture with an activator-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 an optional olefin comonomer under polymerization conditions in a polymerization reactor system to produce an olefin polymer.

[0095] In specific aspects, polymerization processes according to the invention can include contacting such a catalyst composition (e.g., a catalyst composition as described herein or prepared as described herein) with ethylene and optional olefin comonomers in a polymerization reactor system under polymerization conditions to produce an ethylene polymer.

[0096] As described herein, unexpectedly, when tested and compared under the same polymerization conditions, the catalyst activity of these catalyst compositions can be higher than the activity of an otherwise identical catalyst system obtained without the use of an alcohol compound (under otherwise identical catalyst preparation conditions) or without the use of a dialkylaluminum alkoxide (and any alkylaluminum dialkoxide and / or aluminum trialkoxide, if present) during catalyst preparation. Thus, the disclosed olefin polymer processes (or catalyst compositions) are characterized in that the activity of the catalyst composition is higher (e.g., at least 10%, at least 20%, at least 25%, at least 30%, or at least 35%, and typically up to and including 50%, 60%, 75%, or 100%) than the activity of an otherwise identical catalyst system obtained without the use of an alcohol compound (or without the use of a dialkylaluminum alkoxide and without the use of an alkylaluminum dialkoxide and / or aluminum trialkoxide, if present) under the same catalyst preparation and polymerization conditions.

[0097] Example

[0098] The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the present invention in any way. Various other aspects, modifications and their equivalents may occur to those of ordinary skill in the art after reading the description herein without departing from the spirit of the present invention or the scope of the appended claims.

[0099] The activator-support (AS) was prepared as follows. 400 mL of water and 100 g of silica-coated alumina (40 wt% alumina with a surface area of ​​450 m 2 / g, pore volume of 1.3 mL / g, and average particle size of 35 microns) to prepare a slurry. Concentrated hydrofluoric acid (5 g HF) solution was mixed into the slurry, and the resulting slurry was then spray dried to a dry flowable powder. The fluorinated silica-coated alumina (4.75 wt. % fluoride) was calcined at 600°C by fluidizing in dry nitrogen for 3 hours, followed by cooling to room temperature while still fluidizing under nitrogen.

[0100] The metallocene compound (MET) used in the examples is methyl(butene-3-yl)methylene (η 5 -cyclopentadienyl)(η 5 -2,7-di-tert-butylfluoren-9-ylidene) zirconium dichloride. The organoaluminum compound (OA) is triisobutylaluminum (TIBA) or triethylaluminum (TEA). The alcohol compound is methanol (MeOH) or isopropyl alcohol (IPA).

[0101] The PL-GPC 220 (Polymer Labs, Molecular weights and molecular weight distributions were obtained using a Polymer Char, Spain, system equipped with an IR4 detector (Polymer Char, Spain) and three (3) HMW-6E GPC column (Waters, MA). The flow rate of the mobile phase 1,2,4-trichlorobenzene (TCB) containing 0.5 g / L 2,6-di-tert-butyl-4-methylphenol (BHT) was set to 1 mL / min, and the polymer solution concentration was approximately 1 mg / mL, depending on the molecular weight. Sample preparation was performed at 150°C, typically for 4 hours, with occasional gentle stirring, before the solution was transferred to the sample vial for injection. An injection volume of approximately 400 μL was used. HDPE polyethylene resin from Chevron Phillips Chemical Company was widely used. BHB5003 was used as a standard and an integral calibration method was used to derive molecular weight and molecular weight distribution. The standard integral table was pre-determined using SEC-MALS in a separate experiment. Mn is the number average molecular weight, Mw is the weight average molecular weight, Mz is the z average molecular weight, and Mp is the peak molecular weight (the molecular weight position of the highest point of the molecular weight distribution curve).

[0102] Melt rheology characterization was performed as follows. Parallel plate geometry was used in Anton Small strain (10%) oscillatory shear measurements were performed on an MCR 501 rheometer. All rheological tests were performed at 190°C. The complex viscosity |η*| versus frequency (ω) data were then curve fitted using a modified three-parameter Carreau-Yasuda (CY) empirical model to obtain the zero shear viscosity -η0, the characteristic viscosity relaxation time -τ η and width parameter -a (CY-a parameter). The simplified Carreau-Yasuda (CY) empirical model is as follows.

[0103]

[0104] Where: |η*(ω)| = magnitude of complex shear viscosity;

[0105] η0=zero shear viscosity;

[0106] τ η = viscous relaxation time (τ(η), in seconds);

[0107] a = "width" parameter (CY-a parameter);

[0108] n = fixed final power law slope (fixed to 2 / 11); and

[0109] ω = angular frequency of the oscillatory shear deformation.

[0110] Detailed information on 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, Vol. 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987).

[0111] Table I summarizes the catalyst composition and polymerization experiments using a one-gallon stainless steel autoclave reactor (containing isobutane as a diluent). First, a mixture of an organoaluminum compound (OA, 1M in hexane) and an alcohol compound was loaded into the reactor at room temperature and mixed / reacted for a period of 30 seconds to 5 minutes. Next, an activator-support (AS, dry powder) was loaded, followed by a toluene solution (1 mg / mL) of a metallocene compound (MET). The reactor was sealed and loaded with 2L of isobutane, and the reactor contents were heated to a target polymerization temperature of 80°C (for a period of about 5 minutes) under stirring. When the reactor contents reached the target temperature, 1-hexene was added, and ethylene was simultaneously loaded into the reactor until the target pressure (320psig, based on 15 wt% 1-hexene of ethylene) was reached. No hydrogen was added. Ethylene and 1-hexene were fed as needed to maintain the target pressure. Throughout the experiment, the reactor was maintained at the target temperature by an automated heating-cooling system. After the reactor was vented, purged, and cooled, the resulting polymer product was dried under reduced pressure.

[0112] As shown in Table I, Examples A1-A9 used a precontacted mixture of TIBA and IPA during catalyst preparation, and Examples B1-B8 used a precontacted mixture of TIBA and MeOH during catalyst preparation - the molar ratio of OH:A1 ranged from about 0.07:1 to 2:1. Examples C1-C3 are repeated comparative examples using TIBA and no added alcohol; the average catalyst activity of Examples C1-C3 is used for comparison with the examples using alcohol. Examples C4-C5 are comparative examples that used TIBA and either IPA or MeOH during catalyst preparation, but no activator-support was used. No polymer was produced in these experiments.

[0113] Likewise, Examples D1-D4 used a precontacted mixture of TEA and IPA during catalyst preparation, and Examples E1-E5 used a precontacted mixture of TEA and MeOH during catalyst preparation - the molar ratio of OH:A1 ranged from about 0.07:1 to 0.8:1. Examples C6-C7 are repeated comparative examples using TEA without the addition of alcohol; the average catalyst activity of Examples C6-C7 is used for comparison with the examples using alcohol.

[0114] Table I summarizes the catalyst activities of the examples based on the amount of metallocene compound (g polymer / g MET / hour) and based on the amount of activator-support (g polymer / g AS / hour). The molecular weight properties and rheological properties of the ethylene polymers produced in the examples are also summarized in Table I.

[0115] Surprisingly, for TIBA and IPA combinations with OH:Al molar ratios of about 0.15:1 to 0.5:1, the catalyst activity increased by 20-70%; for TIBA and MeOH combinations with molar ratios of about 0.07:1 to 0.5:1, the catalyst activity increased by 40-60%; for TEA and IPA combinations with molar ratios of about 0.08:1 to 0.65:1, the catalyst activity increased by 15-55%; and for TEA and MeOH combinations with molar ratios of about 0.15:1 to 0.65:1, the catalyst activity increased by 10-35%. It is worth noting that when the OH:Al molar ratio is high, such as about 0.8:1 and above (and depending on the specific combination of organoaluminum and alcohol compounds), the catalyst activity generally decreases significantly.

[0116] For the above-mentioned examples where the catalyst activity was increased from 10% to 70%, the molecular weight properties of the resulting polymers were not significantly affected. However, the examples of the present invention showed a slight decrease in molecular weight (Mn, Mw and Mz) compared to the corresponding comparative examples. Similarly, and consistent with the lower molecular weight, the high load melt index (HLMI, ASTM D1238, 21,600 g weight at 190°C) of the polymers of the present invention increased, while the zero shear viscosity decreased. Surprisingly, the CY-a parameters of the catalytically active polymers of the examples of the present invention increased by 10 to 70% relative to the corresponding comparative examples, with an average increase of 6% for the combination of TIBA and IPA, an average increase of 15% for the combination of TIBA and MeOH, an average increase of 18% for the combination of TEA and IPA, and an average increase of 8% for the combination of TEA and MeOH.

[0117] Table I. Summary of Examples.

[0118]

[0119] Table I. Summary of Examples (Continued)

[0120]

[0121] Table I. Summary of Examples (Continued)

[0122]

[0123]

[0124] Table I. Summary of Examples (Continued)

[0125]

[0126]

[0127] The present invention has been described above with reference to many aspects and specific examples. Based on the above detailed description, many variations will occur to those skilled in the art. All such obvious variations are within the full intended scope of the appended claims. Other aspects of the present invention may include, but are not limited to, the following aspects (aspects are described as "comprising", but may alternatively be "consisting essentially of" or "consisting of"):

[0128] Aspect 1. A method for producing a composition, the method comprising:

[0129] (i) contacting an alcohol compound with an organoaluminum compound for a first period of time to form a precontacted mixture; and

[0130] (ii) contacting the precontacted mixture with an activator-support and a metallocene compound for a second period of time to form a catalyst composition.

[0131] Aspect 2. The method as defined in aspect 1, wherein the precontacted mixture is contacted with the activator-support before the metallocene compound.

[0132] Aspect 3. The method as defined in aspect 1, wherein the precontacted mixture is contacted with the metallocene compound before the activator-support.

[0133] Aspect 4. The method as defined in any one of aspects 1 to 3, wherein the organoaluminum compound is present in the form of a solution in any suitable hydrocarbon solvent.

[0134] Aspect 5. The method as defined in any one of aspects 1 to 4, wherein the metallocene compound is present in the form of a solution in any suitable hydrocarbon solvent.

[0135] Aspect 6. The method as defined in any one of aspects 1 to 5, wherein the activator-support compound is present in the form of a slurry in any suitable hydrocarbon solvent.

[0136] Aspect 7. The method 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 a combination thereof.

[0137] Aspect 8. A method as defined in any one of aspects 1 to 5, wherein the activator-support is introduced in the form of a dry solid.

[0138] Aspect 9. A method as defined in any one of Aspects 1 to 8, wherein the molar ratio of the hydroxyl group (-OH) of the alcohol compound to the aluminum of the organic aluminum compound (OH:A1) is in any suitable range, for example, 0.05:1 to 0.9:1, 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 to 0.7:1, or 0.2:1 to 0.6:1.

[0139] Aspect 10. The method as defined in any one of aspects 1 to 9, wherein the molar ratio of the alcohol compound to the metallocene compound is in any suitable range, for example, 1:1 to 1000:1, 10:1 to 500:1 or 100:1 to 400:1.

[0140] Aspect 11. The method as defined in any one of aspects 1 to 10, wherein the weight ratio of the alcohol compound to the activator-support is in any suitable range, such as 1:1 to 1:500, 1:2 to 1:250 or 1:5 to 1:150.

[0141] Aspect 12. A method as defined in any one of Aspects 1 to 11, wherein the first time period is any time period sufficient to form the pre-contact mixture, for example 1 second to 15 seconds, 1 second to 10 minutes, 1 second to 48 hours, 10 seconds to 12 hours, 30 seconds to 6 hours, 30 seconds to 5 minutes, at least 5 seconds, at least 15 seconds or at least 1 minute.

[0142] Aspect 13. A method as defined in any one of Aspects 1 to 12, wherein the second time period is any time period sufficient to form the catalyst composition, for example 1 second to 15 seconds, 1 second to 10 minutes, 1 second to 48 hours, 10 seconds to 12 hours, 30 seconds to 6 hours, 30 seconds to 5 minutes, at least 5 seconds, at least 15 seconds or at least 1 minute.

[0143] Aspect 14. A catalyst composition produced by the method as defined in any one of the preceding aspects.

[0144] Aspect 15. A catalyst composition comprising (A) an activator-support, (B) a metallocene compound, (C) an organoaluminum compound, and (D) a dialkylaluminum alkoxide (and optionally, an alkylaluminum dialkoxide and / or an aluminum trialkoxide).

[0145] Aspect 16. A method or composition as defined in any one of Aspects 1 to 15, wherein the activity of the catalyst composition is higher (higher by any amount disclosed herein, e.g., at least 10%, at least 15%, at least 20%, at least 30% or at least 35%, up to 50%, 60%, 75% or 100%) than the activity of an otherwise identical catalyst system obtained without the alcohol compound (or without the dialkylaluminum alkoxide and without the alkylaluminum dialkoxide and / or aluminum trialkoxide, if present) under the same catalyst preparation and polymerization conditions.

[0146] Aspect 17. A method or composition as defined in any one of Aspects 1 to 16, wherein the weight ratio of the metallocene compound to the activator-support is in any suitable range, for example, 1:1 to 1:1,000,000, 1:10 to 1:10,000 or 1:20 to 1:1000.

[0147] Aspect 18. A method or composition as defined in any one of aspects 1 to 17, wherein the weight ratio of the activator-support to the organoaluminum compound is in any suitable range, for example, 1:1 to 100:1, 1:1 to 50:1, or 2:1 to 20:1.

[0148] Aspect 19. A method or composition as defined in any one of aspects 1 to 18, wherein the activator-support comprises a solid oxide treated with an electron-withdrawing anion.

[0149] Aspect 20. The method or composition as defined in any one of aspects 1 to 19, wherein the activator-support comprises a fluorided solid oxide, a sulfated solid oxide, a phosphated solid oxide, or a combination thereof.

[0150] Aspect 21. A method or composition as defined in any one of Aspects 1 to 19, wherein the activator-support comprises fluorided alumina, chlorided alumina, brominated alumina, sulfated alumina, phosphated alumina, fluorided silica-alumina, chlorided silica-alumina, brominated silica-alumina, sulfated silica-alumina, phosphated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, fluorided-chlorinated silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.

[0151] Aspect 22. A method or composition as defined in any one of aspects 1 to 21, wherein the organoaluminum compound comprises any organoaluminum compound disclosed herein.

[0152] Aspect 23. A method 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.

[0153] Aspect 24. A method or composition as defined in aspect 22 or 23, wherein the organoaluminum compound comprises triethylaluminum.

[0154] Aspect 25. A method or composition as defined in aspect 22 or 23, wherein the organoaluminum compound comprises triisobutylaluminum.

[0155] Aspect 26. The method or composition as defined in any one of aspects 1 to 25, wherein the catalyst composition is substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, or combinations thereof.

[0156] Aspect 27. A method or composition as defined in any one of aspects 1 to 26, wherein the alcohol compound comprises any alcohol compound disclosed herein, such as a monool, a diol, a triol or a polyol, and combinations thereof.

[0157] Aspect 28. A method or composition as defined in any one of aspects 1 to 27, wherein the alcohol compound comprises a hydrocarbyl alcohol, such as an alkyl alcohol, a cycloalkyl alcohol, an aryl alcohol or an arylalkyl alcohol, and combinations thereof.

[0158] Aspect 29. A method or composition as defined in any one of aspects 1 to 28, wherein the alcohol compound comprises C1 to C 32 Alcohols, such as C1 to C 18 Alcohol, C1 to C8 alcohol or C1 to C4 alcohol.

[0159] Aspect 30. A method or composition as defined in any one of aspects 1 to 29, wherein the alcohol compound comprises any monohydric alcohol disclosed herein, such as 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, and combinations thereof.

[0160] Aspect 31. A method or composition as defined in any one of aspects 1 to 30, wherein the metallocene compound comprises a bridged metallocene compound, such as any bridged metallocene compound disclosed herein.

[0161] Aspect 32. A method or composition as defined in any one of aspects 1 to 31, wherein the metallocene compound comprises an unbridged metallocene compound, such as any unbridged metallocene compound disclosed herein.

[0162] Aspect 33. A method 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.

[0163] Aspect 34. An olefin polymerization process, the process comprising contacting a catalyst composition as defined in any one of aspects 1 to 33 with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

[0164] Aspect 35. The method as defined in aspect 34, wherein the olefin monomer comprises any olefin monomer disclosed herein, such as any C2-C 20 Olefins.

[0165] Aspect 36. The method as defined in aspect 34, wherein the olefin monomer and the optional olefin comonomer independently comprise C2-C 20 α-Olefins.

[0166] Aspect 37. The method as defined in any one of aspects 34 to 36, wherein the olefin monomer comprises ethylene.

[0167] Aspect 38. A method as defined in any one of aspects 34 to 37, wherein the catalyst composition is reacted with ethylene and a C3-C 10 An olefin comonomer of an alpha-olefin is contacted.

[0168] Aspect 39. The method as defined in any one of aspects 34 to 38, wherein the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene or a mixture thereof.

[0169] Aspect 40. The method as defined in any one of aspects 34 to 39, wherein the polymerization reactor system comprises a batch reactor, a slurry reactor, a gas phase reactor, a solution reactor, a high pressure reactor, a tubular reactor, an autoclave reactor, or a combination thereof.

[0170] Aspect 41. The method as defined in any one of aspects 34 to 40, wherein the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof.

[0171] Aspect 42. The method as defined in any one of aspects 34 to 41, wherein the polymerization reactor system comprises a loop slurry reactor.

[0172] Aspect 43. The method as defined in any one of aspects 34 to 42, wherein the polymerization reactor system comprises a single reactor.

[0173] Aspect 44. The method as defined in any one of aspects 34 to 42, wherein the polymerization reactor system comprises two reactors.

[0174] Aspect 45. The method as defined in any one of aspects 34 to 42, wherein the polymerization reactor system comprises more than two reactors.

[0175] Aspect 46. The method as defined in any one of aspects 34 to 45, wherein the olefin polymer comprises any olefin polymer disclosed herein.

[0176] Aspect 47. The method 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.

[0177] Aspect 48. The method as defined in any one of aspects 34 to 47, wherein the olefin polymer comprises an ethylene / 1-hexene copolymer.

[0178] Aspect 49. The method as defined in any one of aspects 34 to 48, wherein the polymerization conditions comprise a polymerization temperature in the range of 60°C to 120°C, 65°C to 110°C, 70°C to 100°C, or 75°C to 95°C.

[0179] Aspect 50. A method as defined in any one of Aspects 34 to 49, wherein the activity of the catalyst composition is higher (higher by any amount disclosed herein, e.g., at least 10%, at least 20%, at least 25%, at least 30% or at least 35%, up to 50%, 60%, 75% or 100%) than the activity of an otherwise identical catalyst system obtained without the alcohol compound (or without the dialkylaluminum alkoxide and without the alkylaluminum dialkoxide and / or aluminum trialkoxide, if present) under the same catalyst preparation and polymerization conditions.

[0180] Aspect 51. An olefin polymer produced by the olefin polymerization process as defined in any one of aspects 34 to 50.

Claims

1. A method for producing a catalyst composition, the method comprising: (i) contacting an alcohol compound with a trialkylaluminum compound for a first period of time to form a precontacted mixture; as well as (ii) contacting the precontacted mixture with an activator-support and a metallocene compound for a second period of time to form a catalyst composition.

2. The method of claim 1, wherein: The first time period is at least 15 seconds; or A molar ratio of a hydroxyl group (—OH) of the alcohol compound to aluminum of the trialkylaluminum compound is in the range of 0.05:1 to 0.7:

1.

3. The method according to claim 1 or 2, wherein: The alcohol compound includes methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, pentanol, hexanol, heptanol, octanol, decanol, hexadecanol, cyclohexanol, phenol, benzyl alcohol or any combination thereof; The trialkylaluminum compound includes trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum or any combination thereof; or The activator-support comprises a fluorided solid oxide, a sulfated solid oxide, a phosphated solid oxide, or any combination thereof. 4 . The method of claim 3 , wherein a molar ratio of a hydroxyl group (—OH) of the alcohol compound to aluminum of the trialkylaluminum compound is in the range of 0.1:1 to 0.8:

1.

5. The process of claim 1 or 2, wherein the catalyst composition has a higher activity than an otherwise identical catalyst system obtained without the alcohol compound under the same catalyst preparation and polymerization conditions.

6. The method of claim 1, wherein: The trialkylaluminum compound is present in the form of a solution in a hydrocarbon solvent; or The activator-support is present as a slurry in a hydrocarbon solvent; or The metallocene compound is present in the form of a solution in a hydrocarbon solvent; or Any combination thereof.

7. The method of claim 1, wherein: The molar ratio of the alcohol compound to the metallocene compound is in the range of 1:1 to 1000:1; or The weight ratio of the alcohol compound to the activator-support is in the range of 1:1 to 1:

500.

8. The method of claim 1, wherein the metallocene compound comprises a bridged metallocene compound or an unbridged metallocene compound.

9. The process of claim 1 or 8, wherein the catalyst composition comprises a single metallocene compound, two metallocene compounds, or more than two metallocene compounds.

10. The process of claim 1 wherein the precontacted mixture or the catalyst composition comprises trialkylaluminum; dialkylaluminum alkoxide; alkylaluminum dialkoxide and aluminum trialkoxide.

11. The method of claim 10, wherein the dialkylaluminum alkoxide compound has the formula (RZ)2Al(OR A ); the alkyl aluminum dialkoxide compound has the formula (RZ)Al(OR A )2; and / or the aluminum trialkoxide compound has the formula Al(ORA)3; wherein each RZ and each RA may independently be a C1 to C8 alkyl group.

12. An olefin polymerization method, comprising: performing said method to produce the catalyst composition of claim 1; as well as The catalyst composition is contacted with an olefin monomer and optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

13. The olefin polymerization process according to claim 12, wherein: The activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, fluorided-chlorided silica-coated alumina, sulfated alumina, phosphated alumina, or a combination thereof; The polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor or a combination thereof; or The olefin monomer comprises ethylene, and the olefin comonomer comprises C3-C 10 α-Olefins.

14. The olefin polymerization process of claim 13, wherein the polymerization reactor system comprises a single reactor; two reactors; or more than two reactors.

15. The olefin polymerization method of claim 13, wherein the olefin polymer comprises an ethylene homopolymer, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer or an ethylene / 1-octene copolymer.

16. The olefin polymerization process of claim 13, wherein the metallocene compound comprises a bridged metallocene compound or an unbridged metallocene compound.

17. The olefin polymerization process of claim 13, wherein the catalyst composition comprises a single metallocene compound, two metallocene compounds, or more than two metallocene compounds.

18. The olefin polymerization process of any one of claims 13 to 17, wherein the activity of the catalyst composition is higher than the activity of an otherwise identical catalyst system obtained without the alcohol compound under the same catalyst preparation and polymerization conditions.

19. A catalyst composition comprising: (A) activator-support; (B) a metallocene compound; (C) a trialkylaluminum compound; (D) dialkylaluminum alkoxide; and (E) Alkyl aluminum trialkoxide and / or aluminum trialkoxide 。 20. The composition of claim 19, wherein the catalyst composition has a higher activity than an otherwise identical catalyst system lacking the dialkylaluminum alkoxide and the alkylaluminum dialkoxide and aluminum trialkoxide under the same catalyst preparation and polymerization conditions.

21. The composition of claim 19, wherein: The weight ratio of the metallocene compound to the activator-support is in the range of 1:10 to 1:10,000; The weight ratio of the activator-support to the trialkylaluminum compound is in the 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.

22. The composition of claim 19, wherein: The trialkylaluminum compound includes trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum or any combination thereof; or The activator-support comprises a fluorided solid oxide, a sulfated solid oxide, a phosphated solid oxide, or any combination thereof.

23. The method of claim 19, wherein the metallocene compound comprises a bridged metallocene compound or an unbridged metallocene compound.

24. The method of claim 19, wherein the catalyst composition comprises a single metallocene compound, two metallocene compounds, or more than two metallocene compounds.

25. The method of claim 19, wherein the dialkylaluminum alkoxide compound has the formula (RZ)2Al(OR A ); the alkyl aluminum dialkoxide compound has the formula (RZ)Al(OR A )2; and / or the aluminum trialkoxide compound has the formula Al(ORA)3; wherein each RZ and each RA may independently be a C1 to C8 alkyl group.

26. An olefin polymerization process comprising contacting the catalyst composition of claim 19 with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

27. The olefin polymerization process of claim 26, wherein: The activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, fluorided-chlorided silica-coated alumina, sulfated alumina, phosphated alumina, or a combination thereof; The polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor or a combination thereof; or The olefin monomer includes ethylene, and the olefin comonomer includes 1-butene, 1-hexene, 1-octene, or a mixture thereof.

28. The olefin polymerization process of claim 27, wherein the catalyst composition has a higher activity than an otherwise identical catalyst system without the dialkylaluminum alkoxide under the same catalyst preparation and polymerization conditions.

29. The olefin polymerization process of claim 26, wherein: The polymerization conditions include a polymerization temperature in the range of 60°C to 120°C; The polymerization reactor system comprises a loop slurry reactor; or The olefin polymer includes an ethylene homopolymer, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer and / or an ethylene / 1-octene copolymer.

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