High porosity fluorinated silica-coated alumina activator-supports and their use in metallocene-based catalyst systems for olefin polymerization

Abstract

The fluorinated silica-coated alumina activator-support has a bulk density of from 0.15 to 0.37 g / mL, a total pore volume of from 0.85 to 2 mL / g, a BET surface area of from 200 to 500 m2 / g, an average pore size of from 10 to 25 nm, and a pore volume of from 80% to 99% of pores having a diameter greater than 6 nm. Methods of making fluorinated silica-coated alumina activator-supports and using fluorinated silica-coated alumina in catalyst compositions and olefin polymerization processes are also described. Representative ethylene-based polymers produced using the compositions and methods have a melt index of from 0.1 to 10 g / 10 min and a density of from 0.91 to 0.96 g / cm3, and contain from 70 to 270 ppm of solid oxides and from 2 to 18 ppm of fluorine.

Description

[0001] Citation of Related Applications

[0002] This application was filed as a PCT international patent application on June 1, 2023, and claims the benefit and priority of U.S. Provisional Patent Application No. 63 / 348,044 filed on June 2, 2022, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure generally relates to fluorinated solid oxide activator-supports, methods for preparing the activator-supports, metallocene-based catalyst compositions containing the activator-supports, methods for polymerizing olefins using the catalyst compositions, and polymer resins produced using the catalyst compositions. More specifically, the present disclosure relates to fluorinated silica-coated alumina activator-supports having relatively high pore volume and porosity and having an average pore size greater than 10 nm in diameter. Background Art

[0004] It would be beneficial to produce a solid activator-support having increased catalytic activity in olefin polymerization processes, such as the production of vinyl polymers using metallocene-based catalyst systems. The increased catalytic activity of the solid activator-support would allow a reduction in the amount of metallocene component required in the catalyst system, which could result in significant cost savings. The present invention is therefore generally directed to these objectives. Summary of the invention

[0005] 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.

[0006] Aspects of the present invention relate to fluorinated silica-coated alumina activator-supports. For example, in one aspect, the fluorinated silica-coated alumina can have (or can be characterized by) a bulk density of 0.15 to 0.37 g / mL, a total pore volume of 0.85 to 2 mL / g, a pore volume of 200 to 500 m 2 / g BET surface area and an average pore size of 10 to 25 nm. In another aspect, the fluorinated silica-coated alumina can have (or can be characterized by) a bulk density of 0.15 to 0.37 g / mL, a total pore volume of 0.85 to 2 mL / g, a pore volume of 200 to 500 m 2 The fluorinated silica-coated alumina has a BET surface area of ​​1.1777 W / g and 80% to 99% of the pore volume in pores with a diameter greater than 6 nm.

[0007] Catalyst compositions are also provided herein, and such catalyst compositions can comprise a metallocene compound, any of the fluorinated silica-coated alumina activator-supports disclosed herein, and an optional cocatalyst. Olefin polymerization methods are also contemplated, and such methods can comprise contacting any of the catalyst compositions provided herein with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

[0008] Another aspect of the invention is a method of producing a fluorinated silica-coated alumina, and in this aspect, the method may include contacting a fluoriding agent with a silica-coated alumina to produce a fluorinated silica-coated alumina. The silica-coated alumina may have (or may be characterized by) a bulk density of 0.15 to 0.37 g / mL, a total pore volume of 1.1 to 2.5 mL / g, a pore volume of 250 to 600 m 2 / g and an average pore size of 10 to 25 nm.

[0009] In another aspect, a supported metallocene catalyst is provided, and such catalyst may comprise a metallocene compound and a fluorinated silica-coated alumina. The amount of metallocene compound adsorbed per gram of fluorinated silica-coated alumina may be at least 55 μmol / g (e.g., 60 to 130 μmol / g) and / or the number of molecules of metallocene compound adsorbed per square nanometer surface area of ​​the fluorinated silica-coated alumina may be at least 0.1 molecules / nm 2 (e.g. 0.1 to 0.3 molecules / nm 2 ).

[0010] Other aspects of the invention are directed to ethylene polymers, typically in pellet or bead form, characterized by a melt index (MI) in the range of 0.1 to 10 g / 10 min and a viscosity in the range of 0.91 to 0.96 g / cm 3 The density of these ethylene polymers can be within the range of 70 to 270 ppm of solid oxide (e.g., silica-coated alumina) and 2 to 18 ppm of fluorine. In addition, such ethylene polymers can also contain 0.5 to 5 ppm of zirconium or hafnium.

[0011] The foregoing summary of the invention and the following detailed description all provide examples and are illustrative only. 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 be directed to various feature combinations and sub-combinations described in the detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1Presented is a graph of the pore volume distribution of silica-coated alumina as a function of pore size (nm) for Comparative Example 1 (CE-1) and Inventive Example 1 (IE-1).

[0014] Figure 2 Presented are plots of the surface area distribution of silica-coated alumina as a function of pore size (nm) for CE-1 and IE-1.

[0015] Figure 3 Presented is a graph of the pore volume distribution as a function of pore size (nm) for the fluorinated silica-coated alumina of Comparative Example 2 (CE-2) and Inventive Example 2 (IE-2).

[0016] Figure 4 Presented are plots of surface area distribution of fluorinated silica-coated alumina as a function of pore size (nm) for CE-2 and IE-2.

[0017] Figure 5 Particle size distribution graphs of the fluorinated silica-coated aluminas of CE-2 and IE-2 are presented.

[0018] definition

[0019] 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 the term is used in the present disclosure, but is not specifically defined in this article, the definition in IUPAC Compendium of Chemical Terminology, the 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 will not be uncertain or invalid. If any definition or usage provided by any file incorporated herein by reference conflicts with the definition or usage provided herein, then the definition or usage provided herein shall prevail.

[0020] Herein, the features of the subject matter are described so that within a particular aspect, a combination of different features can be envisioned. For each aspect and each feature disclosed herein, it is expected that all combinations of compounds, compositions, processes or methods described herein will not be adversely affected when a particular combination is explicitly described or not explicitly described. In addition, unless otherwise explicitly described, any aspect or feature disclosed herein can be combined to describe compounds of the present invention, compositions, processes or methods consistent with the present disclosure.

[0021] Typically, element groups are referred to using the numbering scheme indicated in the version of the periodic table published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, a group of elements may be referred to using the common name assigned to the group; for example, alkali metals are referred to as Group 1 elements, alkaline earth metals are referred to as Group 2 elements, transition metals are referred to as Groups 3-12 elements, and halogens or halides are referred to as Group 17 elements.

[0022] Although compositions and methods / processes are described herein as "comprising / including" various components or steps, compositions and methods / processes may also "consist essentially of" or "consist of" the various components or steps unless otherwise specified. For example, a catalyst composition consistent with various aspects of the present invention may comprise; alternatively, may consist essentially of; or alternatively, may consist of: a metallocene compound, a fluorinated silica-coated alumina, and a cocatalyst.

[0023] Unless otherwise stated, the terms "a", "an", "the", etc. are intended to include multiple alternatives, such as at least one. For example, unless otherwise stated, disclosures about "metallocene compounds" or "comonomers" are intended to cover one metallocene compound or cocatalyst, or a mixture or combination of more than one metallocene compound or cocatalyst, respectively.

[0024] For any particular compound disclosed herein, unless otherwise indicated, the general structure or name presented is also intended to cover all structural isomers, conformational isomers, and stereoisomers that can be generated by a specific set of substituents. Thus, unless otherwise explicitly indicated, a general reference to a compound includes all structural isomers; for example, a general reference to pentane includes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while a general reference to butyl includes n-butyl, sec-butyl, isobutyl, and tert-butyl. In addition, when the context permits or requires, the general structure or name mentioned covers all enantiomers, diastereomers, and other optical isomers (whether in enantiomeric or racemic form), as well as mixtures of stereoisomers. For any specific formula or name provided, any general formula or name provided also covers all conformational isomers, regioisomers, and stereoisomers that can be generated by a specific set of substituents.

[0025] The term "substituted" when used to describe a group, for example, when referring to a substituted analog of a particular group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in the group, and is intended to be non-limiting. A group or groups may also be referred to herein as "unsubstituted," or referred to by equivalent terms such as "non-substituted," which refers to the original group in which the non-hydrogen moiety does not replace the hydrogen in the group. Unless otherwise indicated, it will be understood by those of ordinary skill in the art that "substituted" is intended to be non-limiting and includes inorganic or organic substituents.

[0026] The term "polymer" is generally used herein to include olefin homopolymers, copolymers, terpolymers, etc., and their alloys and blends. The term "polymer" also includes impact, block, graft, random and alternating copolymers. Copolymers are derived from olefin monomers and an olefin comonomer, while terpolymers are derived from olefin monomers and two olefin comonomers. Therefore, "polymer" encompasses copolymers and terpolymers derived from any olefin monomer and comonomer disclosed herein. Similarly, the scope of the term "polymerization" includes homopolymerization, copolymerization and trimerization. Therefore, ethylene polymers include ethylene homopolymers, ethylene copolymers (e.g., ethylene / α-olefin copolymers), ethylene terpolymers, etc., and their blends or mixtures. Therefore, ethylene polymers encompass polymers commonly referred to in the art as LLDPE (linear low density polyethylene) and HDPE (high density polyethylene). As an example, olefin copolymers such as 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. Unless otherwise specified, the term "polymer" also includes all possible geometric configurations, and such configurations may include isotactic, syndiotactic, and random symmetries. In addition, unless otherwise specified, the term "polymer" is also intended to include polymers of all molecular weights.

[0027] The term "co-catalyst" is used herein generally to refer to compounds that, when used, can constitute a component of the catalyst composition in addition to the fluorinated silica-coated alumina activator-support, for example, aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, and the like. The term "co-catalyst" is used without regard to the actual function of the compound or any chemical mechanism by which the compound may act.

[0028] As used herein, the term "metallocene" describes a metallocene comprising at least one 3 To 5 -cyclodiene-type moiety, wherein n 3 To 5-Cycloalkadienyl moieties include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, and the like, including partially saturated or substituted derivatives or analogs of any of these. Possible substituents on these ligands may include H, and thus the present invention includes ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted partially saturated indenyl, substituted partially saturated fluorenyl, and the like. In some contexts, metallocenes are simply referred to as "catalysts," in much the same way as the term "cocatalyst" is used herein to refer to, for example, organoaluminum compounds.

[0029] 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 these components after combining with a co-catalyst, metallocene compound, or fluorinated silica-coated alumina. Thus, the terms "catalyst composition", "catalyst mixture", "catalyst system", etc. encompass the initial starting components of the composition, as well as any products that may result from contacting these initial starting components, and this includes both heterogeneous and homogeneous catalyst systems or compositions. The terms "catalyst composition", "catalyst mixture", "catalyst system", etc. may be used interchangeably throughout this disclosure.

[0030] Unless otherwise indicated, the terms "contacting" and "combining" are used herein to describe compositions, processes and methods in which materials or components are contacted or combined together in any order, in any manner and for any length of time. For example, the materials or components can be blended, mixed, slurried, dissolved, reacted, treated, compounded or otherwise contacted or combined in some other manner or by any suitable method or technique.

[0031] The present invention discloses several types of scopes. When disclosing or claiming any type of scope, it is intended to disclose or claim each possible number that such scope can reasonably cover separately, including the endpoints of the scope and any sub-ranges and combinations of sub-ranges covered therein. As a representative example, the total pore volume of fluorinated silica-coated alumina can be within a certain range in various aspects of the present invention. According to the disclosure that the pore volume can be within the range of 0.85 to 2mL / g, it is intended to show that the pore volume can be any amount within the range, and for example, 0.85 to 2mL / g can be included, such as 0.85 to 1.6mL / g, 0.9 to 1.8mL / g, 0.9 to 1.5mL / g or 1 to 1.7mL / g, etc. Any range or range combination. Similarly, all other ranges disclosed herein should be interpreted in a manner similar to this example.

[0032] 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.

[0033] 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.

[0034] 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

[0035] Disclosed herein are methods for preparing fluorinated silica-coated alumina and metallocene-based catalyst compositions containing the fluorinated silica-coated alumina. Also provided are polymerization processes for producing olefin polymers using the metallocene-based catalyst compositions.

[0036] Advantageously, the fluorinated silica-alumina activator-support has a high pore volume and increased porosity, as well as a higher adsorption for metallocene compounds, enabling a significant increase in catalytic activity.

[0037] Fluorinated silica coated alumina activator-support

[0038] The fluorinated silica-coated alumina activator-support contemplated herein may have (or may be characterized by) a bulk density of 0.15 to 0.37 g / mL, a total pore volume of 0.85 to 2 mL / g, a pore volume of 200 to 500 m 2 / g BET surface area and an average pore size of 10 to 25 nm. Another fluorinated silica-coated alumina contemplated herein may have (or may be characterized by) a bulk density of 0.15 to 0.37 g / mL, a total pore volume of 0.85 to 2 mL / g, a pore volume of 200 to 500 m 2 / g BET surface area and 80% to 99% pore volume in pores with diameters greater than 6nm. Unless otherwise stated, these illustrative and non-limiting examples of fluorinated silica-coated aluminas consistent with the present invention may also have any of the properties listed below in any combination.

[0039] Generally, the fluorinated silica-coated alumina can have a bulk density of 0.15 to 0.37 g / mL. Other representative and non-limiting bulk density ranges include 0.15 to 0.32 g / mL, 0.17 to 0.3 g / mL, 0.18 to 0.28 g / mL, or 0.18 to 0.25 g / mL, etc. The total pore volume of the fluorinated silica-coated alumina can be in the range of 0.85 to 2 mL / g, and the BET surface area can be in the range of 200 to 500 m 2 In some aspects, the total pore volume can range from 0.85 to 1.6 mL / g; alternatively, 0.9 to 1.8 mL / g; alternatively, 0.9 to 1.5 mL / g; alternatively, 1 to 1.7 mL / g. Likewise, in some aspects, the BET surface area can range from 250 to 450 m 2 / g; alternatively, 200 to 425m 2 / g; alternatively, 270 to 425m 2 / g.

[0040] Advantageously, the fluorinated silica-coated alumina activator-support has a significant amount of mesopores (pores with a pore size greater than or equal to 10 nanometers in diameter). One test to quantify the significant amount of larger pores is the average pore size in nanometers (4000*PV / SA, where PV is in mL / g and SA is in m 2 For example, the total pore volume is 0.96 mL / g and the total BET surface area is 330 m 2 / g of fluorinated silica-coated alumina converts to an average pore size of 11.6 nm. Although not limited thereto, the fluorinated silica-coated alumina disclosed herein may have an average pore size of 10 to 20 nm in one aspect, an average pore size of 10.5 to 22 nm in another aspect, an average pore size of 11 to 22 nm in another aspect, and an average pore size of 11 to 19 nm in yet another aspect.

[0041] Another indicator of a significant amount of larger pores is the percentage of the pore volume in pores with a diameter greater than 6 nm. The fluorinated silica-coated alumina can have, for example, 80% to 97%, 82% to 99%, 82% to 97%, 83% to 98%, or 84% to 99% of the pore volume in pores with a diameter greater than 6 nm.

[0042] Another indicator of the amount of larger pores of the fluorinated silica-coated alumina is a significant amount of pore volume in pores with diameters greater than 20 nm and / or greater than 40 nm. In one aspect, the amount of pore volume in pores with diameters greater than 20 nm may fall within the range of 9.5 to 30%, 10 to 30%, 10 to 27%, 10.5 to 28%, or 11 to 26%, but is not limited thereto. Additionally or alternatively, the fluorinated silica-coated alumina may be characterized by having 3.5 to 15%, 3.5 to 13%, 4 to 15%, 4 to 13%, or 5 to 15% of the pore volume in pores with diameters greater than 40 nm.

[0043] Another indicator of a significant amount of larger pores is the amount of pore volume present in pores with diameters greater than 6 nm. Although not limited thereto, the fluorinated silica-coated alumina can have a pore volume of at least 0.7 mL / g, at least 0.8 mL / g, or at least 0.85 mL / g in pores with diameters greater than 6 nm, with representative ranges including 0.7 to 1.6 mL / g, 0.7 to 1.4 mL / g, 0.75 to 1.5 mL / g, 0.8 to 1.6 mL / g, or 0.8 to 1.4 mL / g, etc. Similarly, the fluorinated silica-coated alumina can have a pore volume of at least 0.09 mL / g or at least 0.1 mL / g in pores with diameters greater than 20 nm, with representative ranges including 0.09 to 0.4 mL / g, 0.09 to 0.34 mL / g, 0.1 to 0.4 mL / g, 0.1 to 0.36 mL / g, or 0.11 to 0.34 mL / g, etc.

[0044] Referring now to the characterization of the fluorinated silica-coated alumina based on surface area, the vast majority of the surface area belongs to pores with a diameter greater than 6 nm. Although not limited thereto, the fluorinated silica-coated alumina can have 65 to 98%, 65 to 94%, 65 to 91%, 68 to 94%, 70 to 98%, or 70 to 91% of the surface area in pores with a diameter greater than 6 nm. Additionally or alternatively, the fluorinated silica-coated alumina can be characterized by having 19.5 to 55%, 20 to 55%, 20 to 50%, 21 to 55%, or 21 to 50% of the surface area in pores with a diameter greater than 10 nm, but is not necessarily limited thereto.

[0045] Another indicator of the greater amount of surface area attributable to larger pores is the amount of surface area of ​​the fluorinated silica-coated alumina in pores greater than 6 nm in diameter. Although not limited thereto, the fluorinated silica-coated alumina may have at least 250 nm in pores greater than 6 nm in diameter. 2 / g or at least 275m 2 The surface area of ​​​​the sample is 250 to 475 m / g, with a typical range of 250 to 475 m 2 / g, or 275 to 450 m2 / g, etc. Similarly, the fluorinated silica-coated alumina can have at least 78 m 2 / g or at least 85m 2 / g range, with a representative range of 78 to 200 m 2 / g or 85 to 180m 2 / g, etc.

[0046] Those skilled in the art will recognize that the fluorided silica-coated alumina may have any suitable particle size. Exemplary and non-limiting ranges of average particle size (d50) of the fluorided silica-coated alumina may include 30 to 150 microns, 40 to 100 microns, or 45 to 85 microns, etc.

[0047] The silica content of the fluorided silica-coated alumina, while not necessarily limited, is typically in the range of 10 to 80 weight percent based on the weight of the silica-coated alumina. More typically, the fluorided silica-coated alumina contains 20 to 60 weight percent silica in one aspect, 25 to 55 weight percent silica in another aspect, and 35 to 45 weight percent silica in yet another aspect. These percentages are based on the weight of the silica-coated alumina.

[0048] Likewise, although not limited thereto, the fluorided silica-coated alumina may contain 0.5 to 18 wt % F, although any suitable amount may be used. In many cases, the fluorided silica-coated alumina described herein contains 1 to 13 wt % F, 2 to 9 wt % F, 3 to 16 wt % F, or 3 to 10 wt % F, etc. These weight percentages are based on the weight of the fluorided silica-coated alumina.

[0049] Catalyst composition

[0050] The present invention encompasses catalyst compositions comprising metallocene compounds and fluorinated silica-coated alumina activator-supports. These catalyst compositions can be used to produce polyolefins (homopolymers, copolymers, etc.) to meet various end-use applications. In various aspects of the present invention, it is contemplated that the catalyst composition may contain a metallocene compound (or two or more metallocene compounds). In addition, more than one fluorinated silica-coated alumina may also be utilized. Those skilled in the art will readily recognize that loading one or more metallocene compounds on fluorinated silica-coated alumina will not affect the total pore volume and surface area, pore volume distribution, and surface area distribution, so these features of the supported metallocene catalyst are actually the same as those disclosed above for fluorinated silica-coated alumina (based on the amount of adsorbed metallocene, as shown in the Examples section below).

[0051] In one aspect of the invention, the supported metallocene catalyst may comprise a metallocene compound and a fluorinated silica-coated alumina, and the amount of the metallocene compound adsorbed per gram of the fluorinated silica-coated alumina may be at least 55 μmol / g or at least 60 μmol / g, with representative ranges including 55 to 155 μmol / g, 60 to at least 130 μmol / g, etc. In another aspect of the invention, the supported metallocene catalyst may comprise a metallocene compound and a fluorinated silica-coated alumina, and the number of molecules of the metallocene compound adsorbed per square nanometer surface area of ​​the fluorinated silica-coated alumina may be at least 0.1 molecules / nm 2 or at least 0.12 molecules / nm 2 , with a representative range of 0.1 to 0.3 molecules / nm 2 , 0.1 to 0.24 molecules / nm 2 or 0.12 to 0.22 molecules / nm 2 wait.

[0052] The catalyst compositions of the present invention comprise a metallocene compound and a fluorinated silica-coated alumina, and optionally, these catalyst compositions may also comprise one or more co-catalyst compounds (suitable co-catalysts, such as organoaluminum compounds, are discussed herein). Thus, the catalyst compositions of the present invention may comprise a metallocene compound, a fluorinated silica-coated alumina, and an organoaluminum compound. Thus, a catalyst composition consistent with various aspects of the present invention may comprise (or consist essentially of, or consist of): a metallocene compound, a fluorinated silica-coated alumina, and an organoaluminum compound.

[0053] In another aspect of the present invention, a catalyst composition is provided, the catalyst composition comprising a metallocene compound, a fluorinated silica-coated alumina, and an organoaluminum compound, wherein this catalyst composition is substantially free of aluminoxane, an organoboron or organoborate compound, an ionizing ionic compound, or a combination thereof; alternatively, substantially free of aluminoxane; alternatively, substantially free of organoboron or organoborate compounds; 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 of aluminoxane, organoboron or organoborate compound, and ionizing ionic compound. In these aspects, the catalyst composition has the catalytic activity discussed below in the absence of these additional materials. For example, the catalyst composition of the present invention may consist essentially of a metallocene compound, a fluorinated silica-coated alumina, and an organoaluminum compound, wherein no other material is present in the catalyst composition, and the other material will increase / decrease the activity of the catalyst composition by more than about 10% compared to the catalytic activity of the catalyst composition in the absence of the material.

[0054] However, in other aspects of the invention, these cocatalysts may be employed. For example, a catalyst composition comprising a metallocene complex and a fluorinated silica-coated alumina may further comprise a cocatalyst. In this regard, suitable cocatalysts may include, but are not limited to, aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, and the like, or any combination thereof; alternatively, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, or any combination thereof. More than one cocatalyst may be present in the catalyst composition.

[0055] In specific aspects of catalyst compositions containing cocatalysts and polymerization methods using cocatalysts, the cocatalyst may comprise an aluminoxane compound (e.g., a supported aluminoxane), an organoboron or organoborate compound, an ionizing ionic compound, an organoaluminum compound, an organozinc compound, an organomagnesium compound, or an organolithium compound, and this includes any combination of these materials. In one aspect, the cocatalyst may comprise an organoaluminum compound. In another aspect, the cocatalyst may comprise an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof. In yet another aspect, the cocatalyst may comprise an aluminoxane compound; alternatively, an organoboron or organoborate compound; alternatively, an ionizing ionic compound; alternatively, an organozinc compound; alternatively, an organomagnesium compound; alternatively, an organolithium compound.

[0056] Specific non-limiting examples of suitable organoaluminum compounds may include trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), tri-isobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, etc., or combinations thereof. Representative and non-limiting examples of aluminoxanes include methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, tert-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, etc., or any combination thereof. Representative, non-limiting examples of organoboron / organoborate compounds include N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron, and the like, or mixtures thereof.

[0057] Examples of ionizing ionic compounds may include, but are not limited to, the following compounds: tri(n-butyl)ammonium tetra(p-tolyl)borate, tri(n-butyl)ammonium tetra(m-tolyl)borate, tri(n-butyl)ammonium tetra(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium tetra(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetra(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetra(3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammonium tetra(pentafluorophenyl)borate, N,N-dimethylanilinium tetra(p-tolyl)borate, N,N-dimethylanilinium tetra(m-tolyl)borate, N,N-dimethylanilinium tetra(2,4-dimethylphenyl)borate, N,N-dimethylanilinium tetra(3,5-dimethylphenyl)borate, [(trifluoromethyl)phenyl]borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis(p-tolyl)borate, triphenylcarbonium tetrakis(m-tolyl)borate, triphenylcarbonium tetrakis(2,4-dimethylphenyl)borate, triphenylcarbonium tetrakis(3,5-dimethylphenyl)borate, triphenylcarbonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbonium tetrakis(pentafluorophenyl)borate, churnium tetrakis(p-tolyl)borate, churnium tetrakis(m-tolyl)borate, churnium tetrakis(2,4-dimethylphenyl)borate, churnium tetrakis(3,5-dimethylphenyl)borate, churnium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, churnium tetrakis(pentafluorophenyl)borate phenyl) borate, tetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithium tetrakis(2,4-dimethylphenyl)borate, lithium tetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodium tetrakis(pentafluorophenyl)borate, sodium tetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodium tetrakis(2,4-dimethylphenyl)borate, sodium tetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetrakis(pentafluorophenyl)borate, potassium tetrakis(pentafluorophenyl)borate, potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate, potassium tetrakis(2,4-dimethylphenyl)borate, potassium tetrakis(3,5-dimethylphenyl)borate, tetrafluoroborate The invention also includes the following: potassium, lithium tetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate, lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate, lithium tetrakis(2,4-dimethylphenyl)aluminate, lithium tetrakis(3,5-dimethylphenyl)aluminate, lithium tetrakisfluoroaluminate, sodium tetrakis(pentafluorophenyl)aluminate, sodium tetrakis(p-tolyl)aluminate, sodium tetrakis(m-tolyl)aluminate, sodium tetrakis(2,4-dimethylphenyl)aluminate, sodium tetrakis(3,5-dimethylphenyl)aluminate, sodium tetrakisfluoroaluminate, potassium tetrakis(pentafluorophenyl)aluminate, potassium tetrakis(p-tolyl)aluminate, potassium tetrakis(m-tolyl)aluminate, potassium tetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrakisfluoroaluminate, the like, or a combination thereof.

[0058] Exemplary organozinc compounds that may be used as co-catalysts may include, but are not limited to, dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, dineopentylzinc, bis(trimethylsilyl)zinc, bis(triethylsilyl)zinc, bis(triisopropylsilyl)zinc, bis(triphenylsilyl)zinc, bis(allyldimethylsilyl)zinc, bis(trimethylsilylmethyl)zinc, and the like, or combinations thereof.

[0059] Similarly, exemplary organomagnesium compounds can include, but are not limited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, dineopentylmagnesium, bis(trimethylsilylmethyl)magnesium, methylmagnesium chloride, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesium bromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide, ethylmagnesium iodide, propylmagnesium iodide , butylmagnesium iodide, neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide, methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesium ethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide, trimethylsilylmethylmagnesium ethoxide, methylmagnesium propoxide, ethylmagnesium propoxide, propylmagnesium propoxide, butylmagnesium propoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesium propoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide, propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesium phenoxide, trimethylsilylmethylmagnesium phenoxide, etc., or any combination thereof.

[0060] Likewise, exemplary organolithium compounds can include, but are not limited to, methyllithium, ethyllithium, propyllithium, butyllithium (e.g., tert-butyllithium), neopentyllithium, trimethylsilylmethyllithium, phenyllithium, tolyllithium, xylyllithium, benzyllithium, (dimethylphenyl)methyllithium, allyllithium, and the like, or combinations thereof.

[0061] The cocatalysts that can be used in the catalyst composition and polymerization method of the present invention are not limited to the above cocatalysts. Other suitable cocatalysts are well known to those skilled in the art, including, for example, those disclosed in U.S. Pat. Nos. 3,242,099, 4,794,096, 4,808,561, 5,576,259, 5,807,938, 5,919,983, 7,294,599, 7,601,665, 7,884,163, 8,114,946 and 8,309,485.

[0062] Any suitable metallocene compound can be used in the catalyst composition. For example, in some aspects, the metallocene component of the catalyst system provided herein may include an unbridged metallocene; alternatively, an unbridged zirconium or hafnium-based metallocene compound; alternatively, an unbridged zirconium and / 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. These cyclopentadienyls and indenyls can be independently unsubstituted, or can be substituted by any suitable substituent (one or more substituents). Illustrative and non-limiting examples of unbridged metallocene compounds (e.g., with zirconium or hafnium) that can be used in catalyst systems that meet various aspects of the present invention are described in U.S. Patent Nos. 7,199,073, 7,226,886, 7,312,283 and 7,619,047.

[0063] In other aspects, the metallocene component of the catalyst composition provided herein 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; or alternatively, a bridged zirconium or hafnium metallocene compound with a cyclopentadienyl group and a fluorenyl group. These cyclopentadienyl groups and fluorenyl groups may be independently unsubstituted, or may be substituted with any suitable substituent (one or more substituents). For example, such bridged metallocenes may contain alkenyl substituents (e.g., terminal alkenyl groups) on a bridging group, on a cyclopentadienyl group-type group (e.g., cyclopentadienyl or fluorenyl group), or on a bridging group and a cyclopentadienyl group-type group. In some aspects, the metallocene catalyst component may include a bridged zirconium or hafnium metallocene compound with a fluorenyl group and an aryl group on the bridging group; alternatively, a bridged zirconium or hafnium metallocene compound with a cyclopentadienyl group and a fluorenyl group and an aryl group on the bridging group; alternatively, a bridged zirconium metallocene compound with a fluorenyl group and an aryl group on the bridging group; or alternatively, a bridged hafnium metallocene compound with a fluorenyl group and an aryl group on the bridging group. In these and other aspects, the aryl group on the bridging group can be a phenyl group. Optionally, these bridged metallocenes can contain alkenyl substituents (e.g., terminal alkenyl groups) in the bridging group, on the cyclopentadienyl-type group, or on the bridging group and the cyclopentadienyl group. Illustrative and non-limiting examples of bridged metallocene compounds (eg, with zirconium or hafnium) useful in catalyst systems consistent with 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.

[0064] The catalyst composition may be made in any manner, such as by contacting the metallocene compound, fluorided silica-coated alumina, and cocatalyst (if used) in any order or sequence.

[0065] In general, the weight ratio of the co-catalyst (e.g., organoaluminum compound) to the fluorinated silica-coated alumina can be in the range of 10:1 to 1:1000. If more than one co-catalyst compound and / or more than one fluorinated silica-coated alumina is used, this ratio is based on the total weight of each corresponding component. On the other hand, the weight ratio of the co-catalyst to the fluorinated silica-coated alumina can be in the range of 3:1 to 1:500 or 1:10 to 1:350.

[0066] In some aspects of the invention, the weight ratio of the metallocene complex to the fluorinated silica-coated alumina can be in the range of 1:1 to 1:1,000,000. If more than one metallocene compound and / or more than one fluorinated silica-coated alumina is used, this ratio is based on the total weight of the corresponding components. In another aspect, this weight ratio can be in the range of 1:5 to 1:100,000 or 1:10 to 1:10,000. Again, in another aspect, the weight ratio of the metallocene to the fluorinated silica-coated alumina can be in the range of 1:20 to 1:1000.

[0067] The catalyst compositions of the present invention generally have a catalyst activity of greater than 2,000 grams, greater than 3,000 grams, greater than 4,000 grams, greater than 5,000 grams, etc., of ethylene polymer (homopolymer or copolymer, as the context requires) per gram of fluorinated silica-coated alumina per hour (abbreviated as g / g / hr). On the other hand, the catalyst activity range can be 3,000 to 20,000 grams, 4,000 to 15,000 grams, or 4,000 to 9,000 grams of polyethylene per gram of fluorinated silica-coated alumina per hour (g / g / hr). These activities are measured under slurry polymerization conditions, in the presence of triisobutylaluminum cocatalyst, using isobutane as a diluent, a polymerization temperature of 75 to 100° C. (e.g., 95° C.), and a reactor pressure of 300 (2.07 MPa) to 500 psig (3.45 MPa), such as 400 psig (2.76 MPa). Additionally, an excess of a metallocene compound (eg, 1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)methanezirconium dichloride) may be used in the catalyst composition.

[0068] Additionally or alternatively, the catalyst compositions of the present invention generally have a catalyst activity of greater than 100,000 grams, greater than 150,000 grams, greater than 200,000 grams, etc., of ethylene polymer (homopolymer or copolymer, as the context requires) per gram of metallocene compound per hour (abbreviated as g / g / hr). On the other hand, the catalyst activity range can be 100,000 to 1,000,000 g / g / hr, 150,000 to 600,000 g / g / hr or 200,000 to 500,000 g / g / hr. These activities are measured under slurry polymerization conditions, in the presence of triisobutylaluminum cocatalyst, using isobutane as diluent, 75 to 100° C. (e.g., 95° C.) polymerization temperature and 300 (2.07 MPa) to 500 psig (3.45 MPa) (e.g., 400 psig (2.76 MPa)) reactor pressure.

[0069] Aggregation methods

[0070] Olefin polymers (e.g., ethylene polymers) can be produced by the disclosed catalyst compositions using any suitable polymerization process, using various types of polymerization reactors, polymerization reactor systems, and polymerization reaction conditions. The polymerization process may be included in a polymerization reactor system, contacting any catalyst composition disclosed herein with an olefin monomer and an optional olefin comonomer under polymerization conditions to produce an olefin polymer. The present invention also encompasses any olefin polymer (e.g., ethylene polymer) produced by the polymerization process disclosed herein.

[0071] 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 those 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; or alternatively, the polymerization reactor system may include a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof. The polymerization conditions of various reactor types are well known to those skilled in the art. The gas phase reactor may include a fluidized bed reactor or a graded horizontal reactor. The slurry reactor may include vertical and / or horizontal loops. The high pressure reactor may include an autoclave and / or a tubular reactor. Reactor types may include batch 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.

[0072] The polymerization reactor system may include a single reactor or multiple reactors (2 reactors, more than 2 reactors) of the same or different types. 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 interconnected by a transfer device, making it possible to transfer the polymer obtained from the first polymerization reactor to the second reactor. The desired polymerization conditions in one reactor may be different from the operating conditions of other reactors. Alternatively, the polymerization occurring in multiple reactors may include manually transferring the polymer from one reactor to a subsequent reactor for continued polymerization. The multi-reactor system may include any combination, including but not limited to multiple loop reactors, multiple gas phase reactors, a combination of loop reactors and gas phase reactors, multiple high-pressure reactors, or a combination of high-pressure reactors and loop reactors and / or gas phase reactors. Multiple reactors may be operated in series, in parallel, or in series and in parallel. Therefore, the present invention encompasses polymerization reactor systems including a single reactor, including two reactors, and including more than two reactors. In certain aspects of the present invention, the polymerization reactor system may include a slurry reactor, a gas phase reactor, a solution reactor, and a combination of multiple reactors thereof.

[0073] According to one aspect, the polymerization reactor system may include at least one loop slurry reactor including vertical or horizontal loop flow. Monomer, diluent, catalyst and comonomer can be continuously fed into the loop reactor where polymerization occurs. Typically, 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 this 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 cyclonic action in a cyclone separator or hydrocyclone, or by centrifugation.

[0074] 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 polymerizations include, but are not limited to, the monomers being polymerized and hydrocarbons that are liquid under the reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some loop polymerization reactions can occur under bulk conditions without the use of a diluent.

[0075] 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 employ a continuous recycle stream containing one or more monomers, which is continuously circulated through a fluidized bed in the presence of a catalyst under polymerization conditions. 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 multi-step gas phase polymerization process for olefins, wherein the olefins are gas phase polymerized in at least two independent gas phase polymerization zones, while 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. Patent Nos. 5,352,749, 4,588,790, 5,436,304, 7,531,606, and 7,598,327.

[0076] According to another aspect, the polymerization reactor system may include a high pressure polymerization reactor, for example, a tubular reactor 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.

[0077] 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.

[0078] 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).

[0079] 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 may affect the catalyst production rate, polymer molecular weight and molecular weight distribution. For example, in order to produce a specific grade of olefin polymer (or ethylene polymer), various polymerization conditions can be kept substantially constant (for example, within + / -20%, + / -10% or + / -5%). 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 70°C to about 105°C or 75°C to 100°C.

[0080] Suitable pressures will also vary depending on the reactor and polymerization type. The pressure for liquid phase polymerization in a loop reactor is typically less than 1000 psig (6.9 MPa). The pressure for gas phase polymerization is typically at about 200 to 500 psig (1.4 MPa to 3.4 MPa). High pressure polymerization in a tubular reactor or autoclave reactor is typically carried out at 20,000 to 75,000 psig (138 to 517 MPa). Polymerization reactors may also be operated in supercritical regions, which typically occur at higher temperatures and pressures. Operations above the critical point (supercritical phase) of the pressure / temperature diagram may provide advantages for the polymerization process.

[0081] The olefin monomers that can be used in the catalyst compositions and polymerization processes of the present invention typically can include olefin compounds having 2 to 30 carbon atoms per molecule and having at least one olefin double bond, such as ethylene or propylene. In one aspect, the olefin monomers can include C2-C 20 Olefins; alternatively, C2-C 20 α-olefins; alternatively, C2-C 10 Olefins; alternatively, C2-C 10 α-olefin; alternatively, the olefin monomer may include ethylene; or alternatively, the olefin monomer may include propylene (eg, to produce a polypropylene homopolymer or a propylene-based copolymer).

[0082] When a copolymer (or alternatively, a terpolymer) is desired, the olefin monomers and olefin comonomers may independently include, for example, C2-C 20 In some aspects, the olefin monomer may include ethylene or propylene, which is co-polymerized with at least one comonomer (e.g., C2-C 20 α-olefins or C3-C 20 According to one aspect of the present invention, the olefin monomer used in the polymerization process may include ethylene. In this regard, the comonomer may include C3-C10 α-olefins; alternatively, the comonomer may include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof; alternatively, the comonomer may include 1-butene, 1-hexene, 1-octene, or any combination thereof; alternatively, the comonomer may include 1-butene; alternatively, the comonomer may include 1-hexene; or alternatively, the comonomer may include 1-octene.

[0083] Polymers and products

[0084] The olefin polymers encompassed herein may include any polymer produced by any olefin monomer and optional comonomer described herein. For example, the olefin polymer may include ethylene homopolymers, ethylene copolymers (e.g., ethylene / α-olefins, ethylene / 1-butene, ethylene / 1-hexene, ethylene / 1-octene, etc.), propylene homopolymers, propylene copolymers, ethylene terpolymers, propylene terpolymers, etc., including any combination thereof. In one aspect, the olefin polymer may be (or may include) ethylene / 1-butene copolymers, ethylene / 1-hexene copolymers or ethylene / 1-octene copolymers, and on the other hand, the olefin polymer may be (or may include) ethylene / 1-hexene copolymers.

[0085] If the resulting polymer produced according to the present invention is, for example, an ethylene polymer, its properties can be characterized by various analytical techniques known and used in the polyolefin industry. Articles can be formed from and / or can include the olefin polymers (e.g., ethylene polymers) of the present invention, and their typical properties are provided below.

[0086] The ethylene-based polymers disclosed herein generally have a density greater than or equal to 0.90 g / cm 3 , and less than or equal to 0.97g / cm 3 However, in certain aspects, the density can be between 0.91 and 0.965 g / cm 3 , 0.91 to 0.93 g / cm 3 , 0.92 to 0.96 g / cm 3 , 0.93 to 0.955 g / cm 3 or 0.94 to 0.955 g / cm 3In the range of . Although not limited thereto, the ethylene polymer may have a high load melt index (HLMI) in the following range: 0 to 100 g / 10 min; alternatively, 1 to 80 g / 10 min; alternatively, 2 to 40 g / 10 min; alternatively, 2 to 30 g / 10 min; alternatively, 1 to 20 g / 10 min; or alternatively, 50 to 100 g / 10 min. In one aspect, the ethylene polymers described herein may have a Mw / Mn ratio or polydispersity index in the range of 2 to 40, 5 to 40, 7 to 25, 8 to 15, 2 to 10, 2 to 6, or 2 to 4. Additionally or alternatively, ethylene polymers can have a weight average molecular weight (Mw) in the range of 75,000 to 700,000, 75,000 to 200,000, 100,000 to 500,000, 150,000 to 350,000 or 200,000 to 320,000 g / mol. In addition, olefin polymers can be produced by a single or dual metallocene catalyst system containing zirconium and / or hafnium. In this case, olefin polymers or ethylene polymers can contain Mg, V, Ti and Cr of measurable amount, that is, its amount is less than 0.1ppm by weight. In other respects, olefin polymers or ethylene polymers can independently contain Mg, V, Ti and Cr that are less than 0.08ppm, less than 0.05ppm or less than 0.03ppm.

[0087] Illustrative and non-limiting examples of specific ethylene polymers (e.g., ethylene / α-olefin copolymers) encompassed herein produced using supported fluorinated silica-coated aluminas having porosity and other properties disclosed herein can have a melt index (MI) in the range of 0.1 to 10 g / 10 min and a MI in the range of 0.91 to 0.96 g / cm 3 The density of the fluorinated silica-coated alumina is within the range of 100 ppm and the ethylene polymer may contain 70 to 270 ppm of solid oxide and 2 to 18 ppm of fluorine. The fluorine content is measured by weight of the F element, and generally, the fluorine comes from an inorganic source used when preparing the fluorinated silica-coated alumina. Since the disclosed fluorinated silica-coated alumina has unexpectedly high catalytic activity and catalyst productivity, the resulting ethylene polymer has an advantageously lower amount of catalyst residues.

[0088] The melt index of ethylene polymers is in the range of 0.1 to 10 g / 10 min, but more typically, the melt index is in the range of 0.3 to 8, 0.5 to 5, 0.8 to 3, or 0.5 to 2 g / 10 min, etc. The density of ethylene polymers can typically be 0.91 to 0.96 or 0.915 to 0.958 g / cm 3 In one aspect, the density can be between 0.916 and 0.956 g / cm 3In the range of 0.917 to 0.954 g / cm 3 In the range of 0.915 to 0.952 g / cm 3 within the range.

[0089] In one aspect, the ethylene polymer can have a Mw in the range of 25,000 to 400,000 g / mol, 40,000 to 300,000 g / mol, 50,000 to 250,000 g / mol, or 80,000 to 200,000 g / mol. Additionally or alternatively, the ethylene polymer can have a Mw / Mn ratio in the range of 2 to 25, 2.1 to 20, 2.3 to 20, 2 to 5, or 8 to 25. The ethylene polymer can have a unimodal molecular weight distribution, such as can be produced using a single metallocene catalyst, and therefore generally has a narrower MWD. ​​Alternatively, the ethylene polymer can have a bimodal molecular weight distribution, such as can be produced using two metallocene catalysts, and therefore generally has a broader MWD.

[0090] As discussed herein, ethylene polymers can be produced in the presence of metallocene catalysts, so chromium and Ziegler-Natta catalyst systems are not required. Therefore, ethylene polymers may not contain measurable amounts of magnesium, vanadium, titanium or chromium (catalyst residues), i.e., amounts less than 0.1 ppm by weight. In some aspects, ethylene polymers may independently contain less than 0.08 ppm, less than 0.05 ppm or less than 0.03 ppm of magnesium (or vanadium, or titanium, or chromium). The amounts of these elements can be determined by ICP analysis on a PerkinElmer Optima 8300 instrument. Polymer or product samples can be ashed overnight with sulfuric acid in a Thermolyne furnace, followed by acid digestion with HCl and HNO3 (3:1 v:v) in a HotBlock.

[0091] In fact, ethylene polymers contain 70 to 270ppm of solid oxide (for example silicon dioxide coated alumina) and 2 to 18ppm of fluorine (by weight) conventionally.Other exemplary ranges of the fluorine content of ethylene polymers include but are not limited to 2 to 16ppm, 2 to 14ppm, 2 to 12ppm, 2 to 10ppm, 3 to 16ppm, 3 to 12ppm, 4 to 12ppm or 4 to 10ppm of fluorine.Other exemplary ranges of the solid oxide content of ethylene polymers include but are not limited to 70 to 250ppm, 100 to 250ppm, 100 to 200ppm, 100 to 150ppm, 120 to 250ppm, 120 to 200ppm or 120 to 170ppm of solid oxide.The solid oxide content of polymer is to be quantitatively tested by the ash content discussed below. Although not required, the solid oxide can contain any suitable relative amounts of silica and alumina, and exemplary weight ratios of silica:alumina can include 20:80 to 80:20, 20:80 to 60:40, 25:75 to 55:45, or 35:65 to 45:55, etc. The ethylene polymer also contains residual metals from the metallocene compound, such as zirconium and / or hafnium (or titanium, if used). Generally, the ethylene polymer can contain 0.5 to 5 ppm, 0.5 to 4 ppm, 0.5 to 3 ppm, 0.6 to 5 ppm, 0.6 to 4 ppm, 0.6 to 3 ppm, 0.7 to 4 ppm, or 0.7 to 2.5 ppm of zirconium (or hafnium, or titanium).

[0092] Ethylene polymers, whether homopolymers, copolymers, etc., can be formed into various products. Products that can contain the polymers of the present invention include, but are not limited to, agricultural films, automotive parts, bottles, barrels, fibers or fabrics, food packaging films or containers, food service products, fuel tanks, geomembranes, household containers, liners, molded products, medical devices or materials, pipes, sheets or tapes, toys, etc. Various processes can be used to form these products. Non-limiting examples of these processes include injection molding, blow molding, rotational molding, film extrusion, sheet extrusion, profile extrusion, thermoforming, etc. In addition, additives and modifiers are usually added to these polymers to provide beneficial polymer processing or end-use product properties. Such processes and materials are described in Modern Plastics Encyclopedia, mid-November 1995, Volume 72, Issue 12; and Film Extrusion Manual-Process, Materials, Properties, TAPPI Press, 1992. In some aspects of the invention, an article may comprise any of the olefin polymers (or ethylene polymers) described herein, and the article may be or may comprise a film (eg, blown film), a pipe, or a shaped product (eg, a blow molded product).

[0093] Preparation of fluorinated silica-coated alumina

[0094] A method for making a fluorinated silica-coated alumina activator-support is described herein. This method may comprise (or consist essentially of, or consist of) contacting a fluoriding agent with a silica-coated alumina to produce a fluorided silica-coated alumina. Prior to combining with the fluoriding agent, the silica-coated alumina has (or is characterized by) the following properties: a bulk density of 0.15 to 0.37 g / mL, a total pore volume of 1.1 to 2.5 mL / g, a pore volume of 250 to 600 m 2 / g BET surface area and an average pore size of 10 to 25 nm. In general, features of the present method (e.g., fluorinating agent, silica-coated alumina and its characteristics, fluorinated silica-coated alumina and its characteristics, etc.) have been described independently herein, and these features can be combined in any combination to further describe the disclosed method. In addition, unless otherwise stated, other method steps can be performed before, during and / or after any step listed in the disclosed method. In addition, the fluorinated silica-coated alumina activator-support produced according to the disclosed method is within the scope of the present disclosure and is encompassed herein.

[0095] Typically, the silica-coated alumina starting material has a bulk density of 0.15 to 0.37 g / mL. Other representative and non-limiting bulk density ranges include 0.15 to 0.32 g / mL, 0.17 to 0.3 g / mL, 0.18 to 0.28 g / mL, or 0.18 to 0.25 g / mL, etc. The total pore volume of the fluorinated silica-coated alumina can be in the range of 1.1 to 2.5 mL / g, and the BET surface area can be in the range of 250 to 600 m 2 In some aspects, the total pore volume can range from 1.2 to 2.2 mL / g; alternatively, 1.3 to 2.4 mL / g; alternatively, 1.4 to 2 mL / g; or alternatively, 1.3 to 1.8 mL / g. Likewise, in some aspects, the BET surface area can range from 300 to 550 m 2 / g; alternatively, 300 to 500m 2 / g; or alternatively, 325 to 475 m 2 / g.

[0096] Silica coated alumina has a significant amount of larger pores, and one particularly measurable parameter is the average pore size in nanometers (4000*PV / SA, where PV is in mL / g and SA is in m 2 For example, the total pore volume is 1.6 mL / g and the total BET surface area is 410 m2 / g of fluorinated silica-coated alumina converts to an average pore size of 15.6 nm. Although not limited thereto, the silica-coated alumina starting material can have an average pore size of 10 to 20 nm in one aspect, an average pore size of 11 to 19 nm in another aspect, an average pore size of 12 to 20 nm in another aspect, and an average pore size of 12 to 18 nm in yet another aspect.

[0097] The silica-coated alumina can contain any suitable amount of silica based on the weight of the silica-coated alumina. Representative ranges include 10 to 80 weight percent silica, 20 to 60 weight percent silica, 25 to 55 weight percent silica, or 35 to 45 weight percent silica, and the like.

[0098] Although not limited thereto, the method of producing a fluorinated silica-coated alumina activator-support can be carried out by contacting a fluoriding agent with a silica-coated alumina in water to form an aqueous mixture containing the fluorided silica-coated alumina. The order in which the components are combined to produce the aqueous mixture is not particularly limited. In one aspect, for example, the fluoriding agent can be contacted with water first, and then the silica-coated alumina can be introduced; while on the other hand, the silica-coated alumina can be contacted with water first, and then the fluoriding agent can be introduced. Again, on the other hand, the components can be contacted substantially simultaneously, in which case this means that the fluoriding agent, the silica-coated alumina, and the water are contacted together as soon as commercially feasible, for example within 15 minutes, within 5 minutes, or within 1 minute of contacting the two components (e.g., water with the fluoriding agent or the silica-coated alumina).

[0099] Any suitable fluorinating agent or fluorine-containing compound can be used to produce fluorinated silica-coated alumina. Exemplary and non-limiting examples of fluorinating agents include hydrogen fluoride (HF), ammonium bifluoride (NH4HF2), trifluoromethanesulfonic acid (CF3SO3H), tetrafluoroboric acid (HBF4), hexafluorosilicic acid (H2SiF6), hexafluorophosphoric acid (HPF6), zinc tetrafluoroborate (Zn(BF4)2), etc. If desired, a combination of two or more fluorinating agents can be used. In one aspect, the fluorinating agent can comprise (or consist essentially of, or consist of) hydrogen fluoride (HF); alternatively, ammonium bifluoride (NH4HF2); alternatively, trifluoromethanesulfonic acid (CF3SO3H); alternatively, tetrafluoroboric acid (HBF4); alternatively, hexafluorosilicic acid (H2SiF6); alternatively, hexafluorophosphoric acid (HPF6); or alternatively, zinc tetrafluoroborate (Zn(BF4)2).

[0100] The fluorinating agent and silica-coated alumina may be contacted or combined at any suitable pH, various temperatures, and time periods. In general, ambient temperatures are conveniently used, and elevated temperatures are generally avoided to prevent the release of gaseous fluorine compounds.

[0101] The process for making the fluorided silica-coated alumina activator-support may also include a step of drying the fluorided silica-coated alumina, and any suitable technique may be utilized. For example, excess liquid may be removed from the fluorided silica-coated alumina (e.g., drained, filtered, decanted, pressed, centrifuged, etc.), and the wet fluorided silica-coated alumina may be subjected to a wide range of drying times, drying temperatures, and drying pressures. For example, the drying time may be in the range of 15 minutes to 48 hours, 30 minutes to 24 hours, or 1 to 12 hours, and the drying temperature may be in the range of 50°C to 300°C, 95°C to 300°C, or 100°C to 275°C. The drying pressure may be atmospheric pressure or about atmospheric pressure, but in many cases, the drying step may be performed under vacuum conditions at any suitable subatmospheric pressure, such as less than 100 Torr (13.3 kPa), less than 50 Torr (6.67 kPa), or less than 10 Torr (1.33 kPa).

[0102] Various types of drying devices can be used for the drying step, such as, but not limited to, a tray dryer, a rotary dryer, a fluidized bed dryer, and a spray dryer. In a particular aspect of the invention, the drying step comprises spray drying the (wet) fluorinated silica-coated alumina (e.g., a slurry or suspension of fluorinated silica-coated alumina in water) into a dry granular or powder form. For spray drying, the drying time is different from the time described above, wherein the drying time is less than 30 minutes, less than 20 minutes, less than 10 minutes, less than 5 minutes, or even less than 1 minute.

[0103] Optionally, after drying, the fluorinated silica-coated alumina may be calcined, which may be performed at a variety of temperatures and time periods. Typical peak calcination temperatures are generally in the range of 400°C to 1000°C, such as 400°C to 900°C, 500°C to 800°C, or 550°C to 700°C. In these and other aspects, these temperature ranges are also intended to encompass the case where the calcination step is performed at a series of different temperatures within the corresponding ranges rather than a single fixed temperature, wherein at least one temperature is within the corresponding range.

[0104] The duration of the calcining step is not limited to any particular time period. Thus, the calcining step may be performed, for example, for a time period as short as 30-45 minutes to as long as 36-48 hours or longer. The appropriate calcining time may depend, for example, on the initial / peak calcining temperature and other variables. However, in general, the calcining step may be performed for a time period in the range of 30 minutes to 48 hours, such as 1 hour to 24 hours, 1 hour to 12 hours, 2 hours to 12 hours, or 2 hours to 8 hours.

[0105] The calcining step can be carried out in a calcining gas stream comprising (or consisting essentially of, or consisting of): an inert gas (e.g., nitrogen), oxygen, air, or any mixture or combination thereof. In some aspects, the calcining gas stream can comprise air, while in other aspects, the calcining gas stream can comprise a mixture of air and nitrogen. Again, in certain aspects, the calcining gas stream can be an inert gas, such as nitrogen and / or argon.

[0106] The calcining step can be performed using any suitable technique or equipment, whether intermittent or continuous. For example, the calcining step can be performed in a belt calciner, or alternatively, in a rotary calciner. In some aspects, the calcining step can be performed in an intermittent or continuous calcining vessel including a fluidized bed. Those skilled in the art will recognize that other suitable techniques and equipment can be used for the calcining step, and such techniques and equipment are encompassed herein.

[0107] The fluorinated silica-coated alumina produced by the disclosed method can have any of the properties or characteristics disclosed above, such as a bulk density of 0.15 to 0.37 g / mL, a total pore volume of 0.85 to 2 mL / g, a pore volume of 200 to 500 m 2 / g BET surface area, an average pore size of 10 to 25 nm, 80 to 99% of the pore volume in pores with a diameter greater than 6 nm, etc. In addition, the resulting fluorinated silica-coated alumina can have any target amount of fluorine, such as 0.5 to 18 wt% F, 1 to 13 wt% F, 2 to 9 wt% F, 3 to 16 wt% F, or 3 to 10 wt% F, based on the weight of the fluorinated silica-coated alumina.

[0108] Example

[0109] 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. After reading the description herein, those of ordinary skill in the art can conceive of various other aspects, modifications and their equivalents without departing from the spirit of the present invention or the scope of the appended claims.

[0110] For the characterization of silica-coated alumina and fluorinated silica-coated alumina, Quantachrome Instruments Surface area and pore volume analyzer, degas about 0.2 grams of sample in the physical adsorption tube. In order to prevent some fine particles from boiling into the area of ​​the sample tube that is not in the heating zone, the pressure is gradually reduced and the temperature is gradually increased. Initially, the sample is kept at 30°C at a controlled rate of 5mm Hg / s while the pressure is reduced from ambient pressure to 1mm Hg. After reaching a sufficient vacuum (about 0.1mm Hg), the temperature is raised to 80°C and maintained for 30 minutes, then raised to 150°C and maintained for 30 minutes, then raised to 250°C and maintained for 720 minutes, and the final vacuum reaches a pressure of about 1 millitorr. After cooling to ambient temperature, the sample is backfilled with nitrogen and analyzed on the same physical adsorption instrument. About 39 adsorption points are collected to construct an isotherm, and the software package provided with the instrument is used to determine the surface area, pore volume and generate a pore size distribution curve. The surface area was determined by the adsorption isotherm with a P / Po value of 0.0 to 0.2 using the BET method (Brunauer, J. Am Chem. Soc., 1938, 60, 309). The pore volume value was calculated by the isotherm with a P / Po value closest to 0.982. The pore size distribution was generated from the desorption isotherm data using the BJH method (J. Am. Chem. Soc., 1951, 73, 373), and the thickness curve was generated using the Halsey equation (J. Chem. Phys., 1948, 16, 931). The total pore volume was determined according to Halsey (J. Chem. Phys., 1948, 16, 931).

[0111] Bulk density measurements are measured according to ASTM D6683-19. The d50 particle size, or median or average particle size, refers to the particle size at which 50% of the sample has a smaller size and 50% of the sample has a larger size. Particle size distribution (including d10, d50 and d90) is determined according to ISO 13320 using laser diffraction.

[0112] Melt rheology characterization was performed as follows. Small strain (less than 10%) oscillatory shear measurements were performed on an MCR rheometer using parallel plate geometry. 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 viscous relaxation time –τ η and width parameter – a (CY-a parameter). The simplified Carreau-Yasuda (CY) empirical model is as follows.

[0113]

[0114] Where: |η*(ω)| = magnitude of complex shear viscosity;

[0115] η0=zero shear viscosity;

[0116] τ η = viscous relaxation time (τ(η));

[0117] a = "width" parameter (CY-a parameter);

[0118] n = fixed final power law slope (fixed to 2 / 11); and

[0119] ω = angular frequency of the oscillatory shear deformation.

[0120] Detailed information on the -CY model and the meaning and interpretation of the 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 ed., John Wiley & Sons (1987).

[0121] Melt index (MI, g / 10 minutes) can be determined according to ASTM D1238 at 190°C with a 2,160 gram weight. Density is determined according to ASTM D1505 and ASTM D4703 on compression molded specimens cooled at 15°C per minute and conditioned at room temperature for 40 hours, in grams per cubic centimeter (g / cm 3 ) as the unit.

[0122] Molecular weights and molecular weight distributions were obtained using a PL-GPC 220 (Polymer Labs, Agilent Company) system equipped with an IR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns (Waters, MA) operated at 145°C. 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 at 1 mL / min, and the polymer solution concentration was in the range of 1.0-1.5 mg / mL depending on the molecular weight. Sample preparation was performed at 150°C, typically for 4 hours with occasional gentle stirring, and the solution was subsequently transferred to a sample vial for injection. An injection volume of approximately 400 μL was used. HDPE polyethylene resin from Chevron Phillips Chemical Company was used. BHB5003 was used as a broad standard and the molecular weight and molecular weight distribution were derived using an integral calibration method. The integral table for the broad standard was pre-determined in a separate experiment using SEC-MALS. Mn is the number average molecular weight, Mw is the weight average molecular weight, Mz is the z average molecular weight, Mv is the viscosity average molecular weight, and Mp is the peak molecular weight (the molecular weight position of the highest point of the molecular weight distribution curve).

[0123] In this article, the ASTM ash content of the polymer (measured according to ASTM D5630-13, Procedure B) includes the amount of solid oxide (e.g., silica-coated alumina), metallocene transition metal and fluorine. Since the metallocene transition metal and fluorine account for a very small proportion of the ash content, the ash content is very close to the solid oxide content, but the solid oxide content in this article is equal to the ash content minus the metallocene transition metal content, and then minus the fluorine content.

[0124] Metal content, such as transition metal content of metallocene compounds, can be determined by ICP analysis on a PerkinElmer Optima 8300 instrument. Polymer or article samples can be ashed with sulfuric acid overnight in a Thermolyne furnace, followed by acid digestion with HCl and HNO3 (3:1 v:v) in a HotBlock.

[0125] The fluoride content was determined by weighing the added fluoride compound directly. Alternatively, the fluoride content was determined by X-ray fluorescence using calibration samples with known fluoride content. In all cases, the added fluoride remained on the support after calcination, indicating no losses due to evaporation.

[0126] Comparative Examples and Inventive Examples 1-2

[0127] Obtained from Sasol Olefins & Surfactants GmbH 40 (Comparative Example 1, CE-1) and Two silica-coated alumina supports of 40 HPV (Inventive Example 1, IE-1) and each support contained 40 wt% silica and 60 wt% alumina based on the dry weight of the composition. The two supports were then treated with aqueous hydrofluoric acid to obtain about 5 wt% fluorine based on the dry weight of the support. The particles were dried to obtain a white powder. A 10 gram sample of each powdered product was then calcined at 600° C. in dry air in a fluidized bed for three hours, cooled to room temperature, and purged with dry nitrogen for 30 minutes. The fluorinated silica-coated alumina powdered products (Comparative Example 2 (CE-2) and Inventive Example 2 (IE-2)) were stored under nitrogen for later use.

[0128] Figure 1-2 The pore volume distribution and surface area distribution of silica-coated alumina of CE-1 and IE-1 are shown as a function of pore size (nm), respectively. Figure 3-4 The pore volume distribution and surface area distribution of the fluorinated silica-coated aluminas of CE-2 and IE-2 are shown as a function of pore size (nm). Figure 1-4 Some of the data presented graphically are listed in Table I. Table I shows the raw data obtained using nitrogen desorption curves, summarizing the pore volume and surface area into several pore size categories. The data are expressed as percentages and absolute values: pore volume is mL / g, surface area is m 2 / g. Figure 3-4 The particle size tests of the fluorided silica-coated aluminas of CE-2 and IE-2 shown in Table I were conducted after drying and calcining the corresponding fluorided silica-coated aluminas.

[0129] Looking first at the silica coated aluminas of CE-1 and IE-1 in the figures and data tables, the total pore volume of IE-1 is significantly increased relative to CE-1, but in addition there is also a substantial increase in the average pore size, peak pore size, and the amount of pore volume and surface area present in the larger pores.

[0130] After fluorination, drying and calcination, the graph and data table also show that the fluorinated silica-coated alumina of IE-2 has the same beneficial improvements as CE-2. Although the increase in overall pore volume is not as significant as that of the silica-coated alumina base material, IE-2 has a large increase in average pore size and peak pore size (over 20%) compared to CE-2, and the amount of pore volume and surface area in the larger pores is also significantly increased. Advantageously, the amount of mesopores (generally pores with a pore size greater than or equal to 10 nm) in the fluorinated silica-coated alumina of IE-2 is much greater than that of CE-2, while the amount of small pores (e.g., less than 6 nm in diameter) is significantly less.

[0131] Figure 5 The particle size distributions of IE-2 and CE-2 are shown, and the key particle size distribution metrics for IE-2 are summarized in Table II. Very small particles, often referred to as fines, can cause problems in a polymerization reactor system. Helpfully, although the particle size distribution of IE-2 is slightly wider than that of CE-2, only a very small fraction of IE-2 has a particle size less than 10 μm (d10 particle size is 24.6 μm). The d50 average particle size of the fluorinated silica-coated alumina of IE-2 is 63 μm, the d90 / d10 ratio is 5.4, the d90 / d50 ratio is 2.1, and the span is 1.7.

[0132] In addition, the ability of IE-2's fluorinated silica coated alumina (FSCA) to adsorb metallocene compounds was compared to CE-2. The metallocene compound (MET) was 1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)methanezirconium dichloride (a bridged cyclopentadienyl-fluorenyl metallocene compound in which the carbon bridge is substituted with a methyl group and a terminal butenyl group). First, a MET stock solution was prepared by dissolving 80 mg of the metallocene compound (MET) in a solvent mixture containing 8 mL of toluene and 80 mL of heptane. The concentration of MET in the stock solution was 0.91 mg / mL or 1.56 μmol / mL.

[0133] The adsorption experiment was performed in the following manner: 8 mL of MET stock solution was mixed with IE-2 and CE-2 respectively at room temperature, and the mixture was then shaken for 1 minute and allowed to stand for 15 minutes. The supernatant of the mixture was measured at a wavelength of 582 nm using the UV-visible method to determine the amount of MET in the supernatant. The amount of MET adsorbed on IE-2 or CE-2 was calculated by subtracting the amount of MET remaining in the supernatant from the amount of MET in the stock solution used in the experiment.

[0134] Table III summarizes the adsorption experiments performed using IE-2 and CE-2. CE-2 adsorbed only 51 micromoles of MET metallocene compound per gram of CE-2, while IE-2 unexpectedly adsorbed 98 micromoles of MET per gram of IE-2 (a 92% increase). In other words, CE-2 adsorbed only 0.087 molecules of MET metallocene compound per square nanometer surface area, while IE-2 unexpectedly adsorbed 0.178 molecules of MET per square nanometer surface area (a 104% increase). Using the BET surface area in Table I, the adsorption amount (in μmol / g) in Table III, and Avogadro's number, the number of MET molecules adsorbed on the corresponding FSCA per square nanometer surface area was determined.

[0135] While not wishing to be bound by the following theory, it is believed that IE-2 has better contact (or dispersion) between silica and alumina, thereby creating more acid sites, thereby increasing the absorptivity (and catalytic activity, as discussed below). Thus, IE-2 actually has a greater number of acid sites or a greater number of "ionized" sites than CE-2, and each site can adsorb a base molecule (the MET metallocene compound is a weak base), which then ionizes the metallocene base.

[0136] Polymerization Examples 3-12

[0137] The general procedure for the polymerization experiments is as follows. The polymerization experiments are summarized in Table IV and were conducted in a 1-gallon autoclave reactor, with isobutane diluent (approximately 2 L) used for all experiments. Fluorinated silica-coated alumina (approximately 50 mg), 1 mmol TIBA (1 M solution in hexane), and 0.5-1.0 mg of a metallocene compound (i.e., 1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)methane zirconium dichloride; 1 mg / mL toluene solution) were loaded into the reactor, followed by the addition of isobutane. An excess of metallocene was used so that the activity of the fluorinated silica-coated alumina could be evaluated. The contents of the reactor were stirred and heated to the desired polymerization temperature of 90°C. Ethylene was then introduced into the reactor (without the addition of hydrogen or comonomer), and ethylene was fed as needed to maintain the target pressure at 390 psig (2.69 MPa) for the desired reaction time of 30 minutes. During the whole operation, the temperature of the reactor was maintained at 90° C. by an automatic heating-cooling system. After the reactor was vented, purged and cooled, the resulting polymer product was dried under reduced pressure.

[0138] Table IV summarizes the results of polymerization experiments, where Examples 3-8 used CE-2 fluorinated silica-coated alumina and Examples 9-12 used IE-2 fluorinated silica-coated alumina, the catalyst activity is expressed in grams of polymer produced per gram of fluorinated silica-coated alumina per hour (g / g / hr), and the CY-a parameter of the resulting polymer is measured. Unexpectedly, the catalytic activity using IE-2 fluorinated silica-coated alumina increased by more than 100% on average relative to CE-2.

[0139] The Carreau-Yasuda "a" parameter (CY-a parameter) is particularly sensitive to subtle changes in the polymer, such as long chain branch (LCB) content. Surprisingly, given the significant differences in catalytic activity between Examples 3-8 and Examples 9-12, there is no difference in the CY-a parameter, indicating that the basic polymer properties have not changed significantly.

[0140] Invention Examples 13-16

[0141] Similar to IE-1, Inventive Examples 14A-15A each contained 40 wt% silica and 60 wt% alumina, while Inventive Example 13A contained 28 wt% silica and 72 wt% alumina. Using the same fluorination and calcination procedures as described above, IE-13A was treated with aqueous HBF4 to give 12.5 wt% F (IE-13B), while IE-14A was treated with aqueous HBF4 to give 5 wt% F (IE-14B). IE-15A was first calcined at 600°C for three hours and then treated with aqueous HBF4 to give 7 wt% F (IE-15B). The bulk density of these examples ranged from 0.18 to 0.32 g / mL.

[0142] As in Table I, Table V also shows the raw data obtained using nitrogen desorption curves, summarizing the pore volume and surface area results for several particle size categories. The data are expressed as percentages and absolute values: pore volume is mL / g, surface area is m 2 / g. After fluorination, drying and calcination, Table V shows the same beneficial improvements as shown in Table I for the fluorinated silica-coated alumina of IE-2 compared to CE-2. The fluorinated silica-coated alumina materials of IE-13B, IE-14B and IE-15B have higher pore volumes and much larger average pore sizes than CE-2. Advantageously, the amount of mesopores (generally pores with a pore size greater than or equal to 10 nm) in the fluorinated silica-coated aluminas of IE-13B, IE-14B and IE-15B is much greater than that of CE-2, while the amount of small pores (e.g., less than 6 nm in diameter) is significantly less.

[0143] Similar to Table III, Table VI summarizes adsorption experiments performed using IE-13B, IE-14B, IE-15B, and IE-16B (IE-16B was prepared similarly to IE-15B, but using 14 wt% F). Unexpectedly, for these inventive fluorinated silica-coated alumina support materials, 60 to over 120 micromoles of MET were adsorbed per gram of the corresponding support. CE-2 adsorbed only 0.087 molecules of MET metallocene compound per square nanometer surface area, while the inventive fluorinated silica-coated alumina support materials in Table VI unexpectedly adsorbed 0.13 to 0.21 molecules of MET per square nanometer surface area on the corresponding support.

[0144] Table I

[0145]

[0146]

[0147] Table II

[0148]

[0149]

[0150] Table III

[0151]

[0152] Table IV

[0153]

[0154]

[0155] Table V

[0156]

[0157] Table VI

[0158] Example IE-13B IE-14B IE-15B IE-16B Silicon dioxide, weight % 28 40 40 40 Total PV, mL / g 1.22 1.39 1.46 1.40 Pre-calcination no no yes yes Fluorine, weight % 12.5 5 7 14 Adsorbed MET, μmol / g 59.6 122.1 117.7 107.3 <![CDATA[BET surface area, m 2 / g]]> 270 424 381 310 <![CDATA[Adsorbed MET, molecule / nm 2 > 0.133 0.173 0.186 0.208

[0159] The present invention has been described above with reference to many aspects and specific embodiments. 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 (these aspects are described as "comprising", but alternatively, may be "essentially composed of" or "consisting of"):

[0160] Aspect 1. A fluorinated silica-coated alumina having (or characterized by) a bulk density of 0.15 to 0.37 g / mL, a total pore volume of 0.85 to 2 mL / g, a pore volume of 200 to 500 m 2 / g and an average pore size of 10 to 25 nm.

[0161] Aspect 2. A fluorinated silica-coated alumina having (or characterized by) a bulk density of 0.15 to 0.37 g / mL, a total pore volume of 0.85 to 2 mL / g, a pore volume of 200 to 500 m 2 / g BET surface area and 80% to 99% of the pore volume is in pores with a diameter greater than 6nm.

[0162] Aspect 3. The fluorinated silica-coated alumina as described in Aspect 1 or 2, wherein the fluorinated silica-coated alumina contains any suitable amount of silica or an amount of silica within any range disclosed herein, for example, 10 to 80 wt. % silica, 20 to 60 wt. % silica, 25 to 55 wt. % silica, or 35 to 45 wt. % silica, based on the weight of the silica-coated alumina.

[0163] Aspect 4. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the fluorinated silica-coated alumina contains any suitable amount of fluorine or an amount of fluorine within any range disclosed herein, for example, 0.5 to 18 wt. % F, 1 to 13 wt. % F, 2 to 9 wt. % F, 3 to 16 wt. % F, or 3 to 10 wt. % F, based on the weight of the fluorinated silica-coated alumina.

[0164] Aspect 5. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the fluorinated silica-coated alumina has any suitable average (d50) particle size or an average particle size within any range disclosed herein, for example, 30 to 150 microns, 40 to 100 microns, or 45 to 85 microns.

[0165] Aspect 6. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the bulk density is in any suitable range or in any range disclosed herein, for example, 0.15 to 0.32 g / mL, 0.17 to 0.3 g / mL, 0.18 to 0.28 g / mL, or 0.18 to 0.25 g / mL.

[0166] Aspect 7. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the total pore volume is in any suitable range or in any range disclosed herein, for example, 0.85 to 1.6 mL / g, 0.9 to 1.8 mL / g, 0.9 to 1.5 mL / g, or 1 to 1.7 mL / g.

[0167] Aspect 8. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the BET surface area is within any suitable range or within any range disclosed herein, for example, 250 to 450 m 2 / g, 200 to 425m 2 / g or 270 to 425m 2 / g.

[0168] Aspect 9. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the fluorinated silica-coated alumina has an average pore size in any suitable range or in any range disclosed herein, for example, 10 to 20 nm, 10.5 to 22 nm, 11 to 22 nm, or 11 to 19 nm.

[0169] Aspect 10. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the fluorinated silica-coated alumina has any suitable pore volume percentage or amount within any range disclosed herein in pores having a diameter greater than 6 nm, for example 80 to 97%, 82 to 99%, 82 to 97%, 83 to 98% or 84 to 99%.

[0170] Aspect 11. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the fluorinated silica-coated alumina has any suitable pore volume percentage or amount within any range disclosed herein in pores having a diameter greater than 20 nm, for example 9.5 to 30%, 10 to 30%, 10 to 27%, 10.5 to 28% or 11 to 26%.

[0171] Aspect 12. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the fluorinated silica-coated alumina has any suitable pore volume percentage or amount within any range disclosed herein in pores having a diameter greater than 40 nm, for example, 3.5 to 15%, 3.5 to 13%, 4 to 15%, 4 to 13% or 5 to 15%.

[0172] Aspect 13. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the fluorinated silica-coated alumina has any suitable pore volume in pores having a diameter greater than 6 nm or an amount within any range disclosed herein, for example at least 0.7 mL / g, at least 0.8 mL / g, at least 0.85 mL / g, 0.7 to 1.6 mL / g, 0.7 to 1.4 mL / g, 0.75 to 1.5 mL / g, 0.8 to 1.6 mL / g or 0.8 to 1.4 mL / g.

[0173] Aspect 14. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the fluorinated silica-coated alumina has any suitable pore volume in pores having a diameter greater than 20 nm or an amount within any range disclosed herein, for example at least 0.09 mL / g, at least 0.1 mL / g, 0.09 to 0.4 mL / g, 0.09 to 0.34 mL / g, 0.1 to 0.4 mL / g, 0.1 to 0.36 mL / g, or 0.11 to 0.34 mL / g.

[0174] Aspect 15. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the fluorinated silica-coated alumina has any suitable surface area percentage in pores having a diameter greater than 6 nm or an amount within any range disclosed herein, for example 65 to 98%, 65 to 94%, 65 to 91%, 68 to 94%, 70 to 98% or 70 to 91%.

[0175] Aspect 16. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the fluorinated silica-coated alumina has any suitable surface area percentage in pores having a diameter greater than 10 nm or an amount within any range disclosed herein, for example, 19.5 to 55%, 20 to 55%, 20 to 50%, 21 to 55% or 21 to 50%.

[0176] Aspect 17. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the fluorinated silica-coated alumina has any suitable surface area in pores greater than 6 nm in diameter or an amount within any range disclosed herein, such as at least 250 m 2 / g, at least 275m 2 / g, 250 to 475m 2 / g or 275 to 450m 2 / g.

[0177] Aspect 18. A fluorinated silica-coated alumina as defined in any of the preceding aspects, wherein the fluorinated silica-coated alumina has any suitable surface area in pores greater than 10 nm in diameter or an amount within any range disclosed herein, such as at least 78 nm. 2 / g, at least 85m 2 / g, 78 to 200m 2 / g or 85 to 180m 2 / g.

[0178] Aspect 19. A catalyst composition comprising a metallocene compound, the fluorinated silica-coated alumina defined in any one of the preceding aspects, and optionally a co-catalyst.

[0179] Aspect 20. The composition as defined in aspect 19, wherein the metallocene compound comprises any suitable metallocene compound or any metallocene compound disclosed herein.

[0180] Aspect 21. The composition as defined in aspect 19 or 20, wherein the metallocene compound comprises an unbridged zirconium or hafnium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or one cyclopentadienyl group and one indenyl group.

[0181] Aspect 22. The composition as defined in any one of aspects 19 to 21, wherein the metallocene compound comprises a bridged zirconium or hafnium-based metallocene compound having a fluorenyl group.

[0182] Aspect 23. The composition as defined in any one of aspects 19 to 21, wherein the metallocene compound comprises a bridged zirconium or hafnium-based metallocene compound having a cyclopentadienyl group and a fluorenyl group.

[0183] Aspect 24. The composition as defined in any one of aspects 19 to 23, wherein the catalyst composition comprises only one metallocene compound.

[0184] Aspect 25. The composition as defined in any one of aspects 19 to 23, wherein the catalyst composition comprises two or more metallocene compounds.

[0185] Aspect 26. The composition as defined in any one of aspects 19-25, wherein the catalyst composition comprises the co-catalyst, such as any co-catalyst disclosed herein.

[0186] Aspect 27. The composition as defined in aspect 26, wherein the co-catalyst comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an organoaluminum compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof.

[0187] Aspect 28. The composition as defined in aspect 26, wherein the co-catalyst comprises any suitable organoaluminum compound or any organoaluminum compound disclosed herein.

[0188] Aspect 29. The composition as defined in any one of aspects 19-26, wherein the catalyst composition is substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, or combinations thereof.

[0189] Aspect 30. A composition as defined in any one of aspects 19 to 29, wherein the catalyst composition has a catalyst activity of 0.05 % under slurry polymerization conditions in the presence of triisobutylaluminum cocatalyst using isobutane as a diluent at a polymerization temperature of 75 to 100° C. (e.g., 95° C.) and a reactor pressure of 300 psig (2.07 MPa) to 500 psig (3.45 MPa) (e.g., 400 psig (2.76 MPa)). Within any range disclosed herein, for example, 3,000 to 20,000 grams, 4,000 to 15,000 grams, or 4,000 to 9,000 grams of ethylene polymer per gram of the fluorinated silica-coated alumina per hour (in addition or alternatively, 100,000 to 1,000,000 grams, 150,000 to 600,000 grams, or 200,000 to 500,000 grams of ethylene polymer per gram of the metallocene compound per hour).

[0190] Aspect 31. An olefin polymerization process, comprising contacting the catalyst composition defined in any one of aspects 19-30 with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

[0191] Aspect 32. The olefin polymerization process as defined in aspect 31, wherein the olefin monomer comprises any olefin monomer disclosed herein, such as any C2-C 20 Olefins.

[0192] Aspect 33. The olefin polymerization process as defined in aspect 31, wherein the olefin monomer and the optional olefin comonomer independently comprise C2-C 20 α-Olefins.

[0193] Aspect 34. The olefin polymerization process as defined in any one of aspects 31 to 33, wherein the olefin monomer comprises ethylene.

[0194] Aspect 35. An olefin polymerization process as defined in any one of aspects 31 to 34, wherein the catalyst composition is contacted with ethylene and an olefin comonomer comprising C3-C 10 α-Olefins.

[0195] Aspect 36. The olefin polymerization process as defined in any one of aspects 31 to 35, wherein the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene or a mixture thereof.

[0196] Aspect 37. An olefin polymerization process as defined in any one of aspects 31 to 36, 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.

[0197] Aspect 38. The olefin polymerization process as defined in any one of aspects 31 to 37, wherein the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof.

[0198] Aspect 39. An olefin polymerization process as defined in any one of aspects 31 to 38, wherein the polymerization reactor system comprises a loop slurry reactor.

[0199] Aspect 40. The olefin polymerization process of any one of aspects 31-39, wherein the polymerization reactor system comprises a single reactor.

[0200] Aspect 41. The olefin polymerization process as defined in any one of aspects 31 to 39, wherein the polymerization reactor system comprises 2 reactors.

[0201] Aspect 42. An olefin polymerization process as defined in any one of aspects 31 to 39, wherein the polymerization reactor system comprises more than 2 reactors.

[0202] Aspect 43. An olefin polymerization process as defined in any one of aspects 31-42, wherein the olefin polymer comprises any olefin polymer disclosed herein.

[0203] Aspect 44. The olefin polymerization process as defined in any one of aspects 31 to 43, 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.

[0204] Aspect 45. An olefin polymerization process as defined in any one of aspects 31-44, wherein the polymerization conditions include a polymerization reaction temperature in the range of 60°C to 120°C and a reaction pressure in the range of 200 to 1000 psig (1.4 to 6.9 MPa).

[0205] Aspect 46. An olefin polymerization process as defined in any one of aspects 31 to 45, wherein the polymerization conditions are substantially constant, for example within a range of + / - 20%, + / - 10% or + / - 5% for a particular polymer grade.

[0206] Aspect 47. The olefin polymerization process as defined in any one of aspects 31 to 46, wherein no hydrogen is added to the polymerization reactor system.

[0207] Aspect 48. The olefin polymerization process as defined in any one of aspects 31 to 46, wherein hydrogen is added to the polymerization reactor system.

[0208] Aspect 49. An olefin polymer produced by the olefin polymerization process defined in any one of aspects 31-48.

[0209] Aspect 50. A method of producing a fluorinated silica-coated alumina, the method comprising contacting a fluorinating agent with a silica-coated alumina to produce the fluorinated silica-coated alumina, wherein the silica-coated alumina has (or is characterized by) a bulk density of 0.15 to 0.37 g / mL, a total pore volume of 1.1 to 2.5 mL / g, a pore volume of 250 to 600 m 2 / g BET surface area and an average pore size of 10 to 25 nm.

[0210] Aspect 51. The method as defined in aspect 50, wherein the fluorinating agent and the silica-coated alumina are contacted in water to form an aqueous mixture of the fluorided silica-coated alumina.

[0211] Aspect 52. The method as defined in aspect 50 or 51, further comprising a step of drying the fluorided silica-coated alumina, a step of calcining the fluorided silica-coated alumina, or both.

[0212] Aspect 53. A method as defined in any one of Aspects 50-52, wherein the fluorinating agent comprises hydrogen fluoride (HF), ammonium bifluoride (NH4HF2), trifluoromethanesulfonic acid (CF3SO3H), tetrafluoroboric acid (HBF4), hexafluorosilicic acid (H2SiF6), hexafluorophosphoric acid (HPF6), zinc tetrafluoroborate (Zn(BF4)2) or any combination thereof.

[0213] Aspect 54. A method as defined in any one of aspects 50 to 52, wherein the fluorinating agent comprises hydrogen fluoride (HF).

[0214] Aspect 55. The method as defined in any one of aspects 50-54, wherein the fluorinated silica-coated alumina is as defined in any one of aspects 1-18.

[0215] Aspect 56. A supported metallocene catalyst comprising a metallocene compound and a fluorinated silica-coated alumina, wherein the amount of the metallocene compound adsorbed per gram of the fluorinated silica-coated alumina is in any suitable range or in any range disclosed herein, for example, at least 55 μmol / g, at least 60 μmol / g, 55 to 155 μmol / g, or 60 to at least 130 μmol / g.

[0216] Aspect 57. A supported metallocene catalyst comprising a metallocene compound and a fluorinated silica-coated alumina, wherein the number of molecules of the metallocene compound adsorbed per square nanometer surface area of ​​the fluorinated silica-coated alumina is within any suitable range or within any range disclosed herein, such as at least 0.1 molecules / nm 2 , at least 0.12 molecules / nm 2 , 0.1 to 0.3 molecules / nm 2 , 0.1 to 0.24 molecules / nm 2 or 0.12 to 0.22 molecules / nm 2 .

[0217] Aspect 58. The catalyst defined in aspect 56 or 57, wherein the supported metallocene catalyst (or the fluorinated silica-coated alumina) is defined by any one of aspects 1-18.

[0218] Aspect 59. An ethylene polymer having (or characterized by) a melt index (MI) in the range of 0.1 to 10 g / 10 min and a viscosity in the range of 0.91 to 0.96 g / cm 3 The invention relates to a polymer having a density within a range of about 100 to about 200 ppm, wherein the ethylene polymer contains 70 to 270 ppm of solid oxide and 2 to 18 ppm of fluorine.

[0219] Aspect 60. A polymer as defined in aspect 59, wherein the MI is in any range disclosed herein, such as 0.3 to 8, 0.5 to 5, 0.8 to 3, or 0.5 to 2 g / 10 min.

[0220] Aspect 61. A polymer as defined in aspect 59 or 60, wherein the density is within any range disclosed herein, for example, 0.915 to 0.958, 0.916 to 0.956, 0.917 to 0.954, or 0.915 to 0.952 g / cm 3 .

[0221] Aspect 62. A polymer as defined in any one of Aspects 59-61, wherein the ethylene polymer contains 70 to 250 ppm, 100 to 250 ppm, 100 to 200 ppm, 100 to 150 ppm, 120 to 250 ppm, 120 to 200 ppm, or 120 to 170 ppm of solid oxide.

[0222] Aspect 63. A polymer as defined in any one of Aspects 59-62, wherein the ethylene polymer contains 2 to 16 ppm, 2 to 14 ppm, 2 to 12 ppm, 2 to 10 ppm, 3 to 16 ppm, 3 to 12 ppm, 4 to 12 ppm, or 4 to 10 ppm of fluorine.

[0223] Aspect 64. A polymer as defined in any of Aspects 59-63, wherein the solid oxide contains silica and alumina in any suitable relative amounts or silica:alumina ratio within any range disclosed herein, for example, 20:80 to 80:20, 20:80 to 60:40, 25:75 to 55:45, or 35:65 to 45:55.

[0224] Aspect 65. A polymer as defined in any one of Aspects 59-64, wherein the ethylene polymer contains 0.5 to 5 ppm, 0.5 to 4 ppm, 0.5 to 3 ppm, 0.6 to 5 ppm, 0.6 to 4 ppm, 0.6 to 3 ppm, 0.7 to 4 ppm, or 0.7 to 2.5 ppm of chromium (or hafnium, or titanium).

[0225] Aspect 66. A polymer as defined in any one of aspects 59-65, wherein the ethylene polymer independently contains less than 0.1 ppm (by weight), less than 0.08 ppm, less than 0.05 ppm, or less than 0.03 ppm of Mg, V, Ti, or Cr.

[0226] Aspect 67. A polymer as defined in any of aspects 59-66, wherein the ethylene polymer has an Mw in any range disclosed herein, for example, 25 to 400, 40 to 300, 50 to 250, or 80 to 200 kg / mol.

[0227] Aspect 68. A polymer as defined in any of Aspects 59-67, wherein the ethylene polymer has a Mw / Mn ratio in any range disclosed herein, such as 2 to 25, 2.1 to 20, 2.3 to 20, 2 to 5, or 8 to 25.

[0228] Aspect 69. A polymer as defined in any one of aspects 59 to 68, wherein the ethylene polymer has a unimodal molecular weight distribution.

[0229] Aspect 70. A polymer as defined in any one of aspects 59 to 68, wherein the ethylene polymer has a bimodal molecular weight distribution.

[0230] Aspect 71. The polymer as defined in any one of aspects 59-70, wherein the ethylene polymer comprises an ethylene homopolymer and / or an ethylene / α-olefin copolymer.

[0231] Aspect 72. A polymer as defined in any one of aspects 59 to 71, wherein the ethylene polymer comprises an ethylene homopolymer, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer and / or an ethylene / 1-octene copolymer.

[0232] Aspect 73. A polymer as defined in any one of aspects 59 to 72, wherein the ethylene polymer comprises an ethylene / 1-hexene copolymer.

[0233] Aspect 74. The polymer as defined in any one of aspects 59-73, wherein the polymer is produced by the olefin polymerization process defined in any one of aspects 31-48.

[0234] Aspect 75. An article (eg, a film, a pipe, or a shaped product) comprising an ethylene polymer as defined in any one of aspects 59-74.

[0235] Aspect 76. An article comprising an ethylene polymer as defined in any one of Aspects 59-74, wherein the article is an agricultural film, an automotive part, a bottle, a chemical container, a barrel, a fiber or fabric, a food packaging film or container, a food service article, a fuel tank, a geomembrane, a household container, a liner, a formed product, a medical device or material, an outdoor storage product, an outdoor play equipment, a pipe, a sheet or tape, a toy, or a traffic barrier.

Claims

1. A fluorinated silica-coated alumina having: Bulk density of 0.15 to 0.37 g / mL; Total pore volume from 0.85 to 2 mL / g; 200 to 500m 2 / g BET surface area; and An average pore size of 10 to 25 nm and / or 80% to 99% of the pore volume is pores with a diameter greater than 6 nm.

2. The fluorinated silica-coated alumina of claim 1, wherein the fluorinated silica-coated alumina comprises: 10 to 80 wt % silica, based on the weight of the silica-coated alumina; and 0.5 to 18 wt% F based on the weight of the fluorided silica-coated alumina.

3. The fluorided silica-coated alumina of claim 1 or 2, wherein the fluorided silica-coated alumina has an average (d50) particle size of 30 to 150 microns.

4. The fluorinated silica-coated alumina according to any one of claims 1 to 3, wherein: The bulk density is 0.17 to 0.3 g / mL; The total pore volume is 0.9 to 1.5 mL / g; The BET surface area is 250 to 450 m 2 / g; The average pore size is 10 to 20 nm; and Between 83% and 98% of the pore volume is in pores with a diameter greater than 6 nm.

5. The fluorinated silica-coated alumina according to any one of claims 1 to 4, wherein: 9.5% to 30% of the pore volume is in pores with a diameter greater than 20nm; 3.5% to 15% of the pore volume is in pores with a diameter greater than 40nm; The fluorinated silica-coated alumina has a pore volume of 0.7 to 1.6 mL / g in pores having a diameter greater than 6 nm; and The fluorinated silica-coated alumina has a pore volume of 0.09 to 0.4 mL / g in pores with diameters greater than 20 nm.

6. The fluorinated silica-coated alumina according to any one of claims 1 to 5, wherein: 65% to 98% of the surface area is in pores with a diameter greater than 6nm; 19.5% to 55% of the surface area is in pores with a diameter greater than 10 nm; The fluorinated silica-coated alumina has a diameter of 250 to 475 nm in pores greater than 6 nm. 2 / g surface area; and The fluorinated silica-coated alumina has a diameter of 78 to 200 nm in pores greater than 10 nm. 2 / g of surface area.

7. A catalyst composition comprising a metallocene compound, the fluorinated silica-coated alumina according to any one of claims 1 to 6, and an optional co-catalyst.

8. The catalyst composition of claim 7, wherein the catalyst composition comprises a metallocene compound.

9. The catalyst composition of claim 7, wherein the catalyst composition comprises two or more metallocene compounds.

10. An olefin polymerization process comprising contacting the catalyst composition of any one of claims 7 to 9 with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

11. The method of claim 10, wherein: The catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof; and The polymerization reactor system comprises a loop slurry reactor, a fluidized bed reactor, a solution reactor or a combination thereof.

12. A method of producing the fluorinated silica-coated alumina of any one of claims 1 to 6, the method comprising contacting a fluorinating agent with a silica-coated alumina to produce the fluorinated silica-coated alumina, wherein the silica-coated alumina has: Bulk density of 0.15 to 0.37 g / mL; Total pore volume from 1.1 to 2.5 mL / g; 250 to 600m 2 / g BET surface area; and Average pore size of 10 to 25 nm.

13. A supported metallocene catalyst comprising: metallocene compounds; and Fluorinated silica coated alumina; wherein: The amount of the metallocene compound adsorbed per gram of the fluorinated silica-coated alumina is at least 55 μmol / g; or The number of molecules of the metallocene compound adsorbed per square nanometer surface area of ​​the fluorinated silica-coated alumina is at least 0.1 molecules / nm 2 ;or Both.

14. The catalyst of claim 13, wherein: The amount of the metallocene compound adsorbed per gram of the fluorinated silica-coated alumina is 55 to 155 μmol / g; and The number of molecules of the metallocene compound adsorbed per square nanometer surface area of ​​the fluorinated silica-coated alumina is 0.1 to 0.3 molecules / nm 2 .

15. The catalyst according to claim 13 or 14, wherein the catalyst has: Bulk density of 0.15 to 0.37 g / mL; Total pore volume from 0.85 to 2 mL / g; 200 to 500m 2 / g BET surface area; and An average pore size of 10 to 25 nm and / or 80% to 99% of the pore volume is pores with a diameter greater than 6 nm.

16. An ethylene polymer having: A melt index (MI) in the range of 0.1 to 10 g / 10 min; and 0.91 to 0.96 g / cm 3 Density within range; wherein the ethylene polymer comprises: 70 to 270 ppm solid oxides; and 2 to 18 ppm fluorine.

17. The polymer of claim 16, wherein the ethylene polymer comprises: 100 to 200 ppm solid oxide; and 4 to 12 ppm fluorine.

18. A polymer as claimed in claim 16 or 17 wherein the ethylene polymer further comprises 0.5 to 5 ppm of zirconium and / or hafnium.

19. The polymer of any one of claims 16-18, wherein the ethylene polymer independently contains less than 0.1 ppm of Mg, V, Ti and Cr.

20. The polymer of any one of claims 16-19, wherein the solid oxide comprises silica and alumina, the weight ratio of silica:alumina being from 20:80 to 60:

40.

21. The polymer of any one of claims 16-20, wherein the ethylene polymer comprises an ethylene homopolymer and / or an ethylene / α-olefin copolymer.

22. An article comprising the polymer of any one of claims 16-21.

Images