RU2782224C1 - Methods for production of fluorinated solid oxides and their use in metallocene-based catalytic systems - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present document proposes methods for the production of fluorinated solid oxides by bringing into contact of a fluor-containing compound with an inorganic base to obtain an aqueous mixture, pH of which is at least 4, with subsequent bringing of solid oxide into contact with the specified aqueous mixture to obtain fluorinated solid oxide. Methods are also proposed for the production of fluorinated solid oxides by bringing of an acidic fluor-containing compound into contact with solid oxide to obtain a mixture with subsequent bringing of the specified mixture into contact with the inorganic base to obtain fluorinated solid oxide with pH of at least 4. The invention also relates to fluorinated solid oxide obtained by the specified methods, catalytic systems, and methods for olefin polymerization. Fluorinated solid oxide is used as an activator component in a catalytic system for olefin polymerization.

EFFECT: obtainment of fluorinated solid oxides in a safer way, low corrosion activity of fluorinated solid oxide relatively to equipment, absence of emission into the atmosphere of potentially dangerous vapors of fluorine hydride during spraying drying.

22 cl, 2 dwg, 5 tbl, 32 ex

Description

LINK TO RELATED APPLICATION

This application claims priority from U.S. Provisional Application No. 62/737,157, filed September 27, 2018, the contents of which are incorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION

The present invention relates generally to the field of olefin polymerization catalysis, supported catalyst compositions, olefin polymerization processes, and polyolefins. More specifically, the present invention relates to fluorinated solid oxides, methods for producing fluorinated solid oxides, as well as to catalyst compositions and polymerization methods that use these fluorinated solid oxides.

Fluorine compounds such as hydrogen fluoride and hydrofluoric acid are highly corrosive and can release harmful gases during processing. Thus, it would be reasonable to use fluorine compounds to produce fluorinated solid oxides in a safer manner and with little or no emissions. Accordingly, the present invention, in General, is directed to solving just such problems.

SUMMARY OF THE INVENTION

This Brief Description of the Invention is provided to introduce, in a simplified form, a selection of concepts that are further presented below in the Detailed Description. It is implied that this summary is not intended to identify the required or key features of the claimed subject matter. It is also understood that this brief description does not limit the scope of the claimed subject matter.

This document proposes and describes methods for producing fluorinated solid oxides. The first method for producing a fluorinated solid oxide may include (a) contacting an acidic fluorine compound and an inorganic base to form an aqueous mixture having a pH of at least about 4, and (b) contacting the solid oxide with said aqueous mixture to form a fluorinated solid oxide. The second method for producing a fluorinated solid oxide may include (A) contacting an acidic fluorine-containing compound with a solid oxide to obtain a mixture; and (B) contacting said mixture with an inorganic base to form a fluorinated solid oxide at a pH of at least about 4. According to non-limiting aspects of the present invention, the acidic fluorine compound may include tetrafluoroboric acid (HBF ₄ ) and/or hexafluorosilicic acid (H ₂ SiF ₆ ), the inorganic base may include a zinc-containing base such as ZnO, and the solid oxide may include silica-alumina and/or silica-coated alumina.

The present invention also provides catalyst compositions containing said fluorinated solid oxides. One such catalyst composition may contain a metallocene compound, a fluorinated solid oxide, and an optional co-catalyst. The catalyst compositions of the present invention can be used to polymerize olefins to form homopolymers, copolymers, terpolymers, and the like. The process for polymerizing olefins in the presence of a catalyst composition according to the present invention may include contacting the catalyst composition with an olefin monomer and optionally an olefin comonomer in a polymerization reactor system under polymerization conditions to form an olefin polymer.

The polymers obtained from the polymerization of olefins, which form, for example, homopolymers or copolymers based on ethylene or propylene, can be used for the production of various industrial products.

In both the above summary and the following detailed description, examples are given, the descriptions themselves being illustrative only. Accordingly, the foregoing summary and the following detailed description should not be construed as limiting. In addition, features or variations in addition to those set forth herein may be provided. For example, some aspects may relate to various combinations and subcombinations of the features discussed in the detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a particle size distribution plot of the fluorinated solid oxide prepared according to Example 15.

Fig. 2 is a SEM image of the fluorinated solid oxide of Example 15.

DEFINITIONS

For a clearer understanding of the terms used in this document, the following definitions are provided. Unless otherwise indicated, the following definitions apply to the present description. If any term is used in the description which is not specifically defined herein, the definition given in the IUPAC Compendium of Chemical Terminology, 2nd ^Ed (1997) may be used, provided that such definition does not conflict with any other description or definition. used herein, or does not render undefined or invalidate any claim to which this definition refers. In the event that any definition or use given in any document incorporated herein by reference conflicts with the definition or use given herein, the definition or use given herein shall take precedence.

In this document, the features of the subject matter are described in such a way that a combination of different features can be envisaged within specific aspects. For each and every aspect and/or feature described herein, all combinations that do not adversely affect the devices, compositions, processes and/or methods described herein are discussed with or without a detailed description of the specific combination. In addition, unless expressly stated otherwise, any aspect and/or feature described herein can be combined to describe the devices, compositions, processes and/or methods proposed in the invention that do not contradict the present invention.

Although compositions and methods/processes are described herein in terms of "comprising" various components or steps, compositions and methods/processes may also "consist essentially of" or "consist of" various components or steps, unless otherwise indicated. For example, a catalyst composition corresponding to aspects of the present invention may contain; alternatively may consist essentially of; or alternatively may consist of; a metallocene compound, a fluorinated solid oxide, and a co-catalyst.

Singular terms are meant to include plural alternatives, such as at least one, unless otherwise noted. For example, the description of "metallocene compound" or "comonomer" is intended to include a single metallocene compound or comonomer, or mixtures or combinations of more than one metallocene compound or comonomer, respectively, unless otherwise indicated.

In general, groups of elements are indicated using the numbering scheme given in the version of the Periodic Table of the Elements published in Chemical and Engineering News , 63(5), 27, 1985. In some cases, a group of elements may be indicated using the common name adopted for a given groups; for example, alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, transition metals for Group 3-12 elements, and halogens or halides for Group 17 elements.

For any particular compound described herein, the general structure or name given is also intended to include all structural isomers, conformational isomers, and stereoisomers that may result from a particular set of substituents, unless otherwise indicated. Thus, a general reference to a compound includes all structural isomers unless explicitly stated otherwise; for example, a generic reference to pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane, while a generic reference to a butyl group includes an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. In addition, reference to a general structure or name includes all enantiomers, diastereomers and other optical isomers, whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as circumstances permit or require.

As used herein, the term "polymer" generally includes olefin homopolymers, copolymers, terpolymers, and the like, as well as alloys and mixtures thereof. The term "polymer" also includes impact copolymers, block copolymers, graft, random and alternating copolymers. The copolymer is made from an olefin monomer and one olefin comonomer, while the terpolymer is made from an olefin monomer and two olefin comonomers. Accordingly, "polymer" includes copolymers and terpolymers derived from any of the olefin monomer and comonomer(s) described herein. Similarly, the scope of the term "polymerization" includes homopolymerization, copolymerization and terpolymerization. Therefore, an ethylene polymer includes ethylene homopolymers, ethylene copolymers (eg, ethylene/α-olefin copolymers), ethylene terpolymers, and the like, as well as combinations or mixtures thereof. Thus, ethylene polymer includes polymers often referred to in the art as LLDPE (Linear Low Density Polyethylene) and HDPE (High Density Polyethylene). For example, an olefin copolymer such as an ethylene copolymer can be prepared from ethylene and a comonomer such as 1-butene, 1-hexene, or 1-octene. If the monomer and comonomer were ethylene and 1-hexene, respectively, the resulting polymer can be classified as an ethylene/1-hexene copolymer. The term "polymer" also includes all possible geometric configurations, unless otherwise indicated, such configurations may include isotactic, syndiotactic and random symmetries. In addition, the "polymers" described herein (eg, polymers of ethylene) may also be referred to as "polymer compositions".

In this document, the term "co-catalyst" is generally used to refer to compounds such as aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, and the like, which, when used, may be one component of the catalyst composition, for example, in addition to the fluorinated solid oxide. The term "co-catalyst" is used regardless of the actual function of the compound or any chemical mechanism by which said compound may act.

The terms "catalyst composition", "catalyst mixture", "catalyst system", etc. do not depend on the actual product or composition resulting from bringing into contact or interaction of the starting components of the described or claimed catalyst composition/mixture/system, the nature of the active catalytic site, or the behavior of the co-catalyst, metallocene compound or fluorinated solid oxide after combining these components. Therefore, the terms "catalyst composition", "catalyst mixture", "catalyst system", etc. include the original starting components of the composition, as well as any product(s) that can be obtained as a result of bringing into contact of these initial starting components, while these terms include both heterogeneous and homogeneous catalyst systems or compositions. In the present description, the terms "catalyst composition", "catalyst mixture", "catalyst system" and the like. can be used interchangeably.

As used herein, the term “contacting” refers to substances or components that can be mixed, agitated, suspended, dissolved, immersed, brought into contact, processed, sprayed, impregnated, compounded, or otherwise brought into contact or combined in any other way. manner or by any suitable method. Substances or components can be brought into contact or combined together in any order, in any way and for any period of time, unless otherwise indicated.

Although any methods, devices and materials similar or equivalent to the methods, devices and materials described herein can be used in the practice or testing of the present invention, exemplary methods, devices and materials are described in this application.

All publications and patents referenced herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the concepts and methodologies described in the publications that can be used in conjunction with the invention described herein.

The present invention provides several types of ranges. If a range of any type is described or claimed, it is provided to describe or claim individually each possible numerical value that can reasonably be included in the specified range, including the end values of the range, as well as any subranges and combinations of subranges. included in the specified range. As a typical example, according to various aspects of the present invention, the pH of the aqueous mixture may be within certain ranges. When stating that the pH may be in the range of about 4 to about 8, the purpose is to indicate that the pH may be any value within the specified range and, for example, may be about 4, about 4.5, about 5 , about 5.5, about 6, about 6.5, about 7, about 7.5, or about 8. In addition, the pH can be in any range from about 4 to about 8 (for example, from about 4 to about 7, 5), which range also includes any combination of the ranges from about 4 to about 8 (for example, the pH may be from about 4.2 to about 6.8, or from about 4.5 to about 6.5). In addition, in all cases where "about" a specific value is indicated, such value is described in itself. Thus, the statement that the pH is from about 4 to about 8 also indicates a pH range of 4 to 8 (for example, from 4 to 7.5), while the specified range also includes any combination of ranges from 4 to 8 (for example , the pH can be from 4.2 to 6.8 or from 4.5 to 6.5). Likewise, all other ranges described herein should be interpreted in the same way as the example provided.

The term "about" means that quantities, sizes, compositions, parameters and other quantitative indicators and characteristics are not and should not be exact, but may have an approximate value, including more or less, if necessary, reflecting tolerances, conversion factors , rounding off, measurement errors, and the like, as well as other factors known to those skilled in the art. In general, an amount, size, composition, parameter, or other quantity or characteristic is "exemplary" or "approximate" whether or not it is expressly stated. The term "about" also includes amounts that differ due to different equilibrium conditions for the composition obtained from a particular initial mixture. Claims, whether modified by the term "about" or not, include equivalent amounts. The term "about" may mean "within 10%" of the specified numerical value, preferably "within 5%" of the specified numerical value.

DETAILED DESCRIPTION OF THE INVENTION

The present invention generally relates to fluorinated solid oxides, methods for producing fluorinated solid oxides, catalyst compositions using fluorinated solid oxides, methods for using such catalyst compositions for the polymerization of olefins, polymer resins obtained using such catalyst compositions, and articles of industrial production, made using such polymeric resins.

Commercially produced fluorinated solid oxides, such as fluorinated silica coated alumina, are typically prepared by immersing the solid oxide in a strongly acidic HF (or hydrofluoric acid) solution, allowing the fluorine time to soak and react with the solid oxide. Such a process, carried out before spray drying, usually takes 12 hours. Otherwise, if the reaction is not completely completed, HF vapor may be released into the atmosphere. The neutralized slurry is then spray-dried to produce very fine fluorinated solid oxide particles, typically with an average particle size d50 of less than 40 µm and in some cases less than 35 µm. In addition, due to fluorine emissions and safety concerns, this process for producing fluorinated solid oxides is not practiced in the United States.

The processes described herein for producing fluorinated solid oxides have several advantages. In one method, an acidic fluorine compound reacts with an inorganic base such that the resulting aqueous fluoride mixture does not release potentially hazardous hydrogen fluoride fumes into the atmosphere during spray drying. Moreover, by raising the pH of the aqueous mixture to a relatively neutral pH (>4.0), not only is the possibility of hydrogen fluoride evolution prior to spray drying eliminated, but the corrosivity of the aqueous fluorine mixture is also significantly reduced. In addition, the time needed to neutralize the acid is significantly reduced, resulting in a more economical process. In addition, fluorinated solid oxides with an average particle size d50 of more than 40 microns, and in some cases more than 50 microns, can be easily obtained.

In another method, an acidic fluorine compound is first contacted with a solid oxide and then an inorganic base is added to raise the pH to a relatively neutral level. Thus, as mentioned above, potentially hazardous hydrogen fluoride vapors are not released into the atmosphere during spray drying, and the corrosivity of the fluorinated solid oxide to spray drying equipment and other equipment is also significantly reduced.

Another potential advantage of the described methods, although not a necessary requirement, is that an inorganic base can also be chosen to increase the overall catalytic activity of the fluorinated solid oxide, for example by adding zinc or other suitable metal.

FLUORINATED SOLID OXIDES

The present document proposes and describes various methods for producing a fluorinated solid oxide. The first process for producing a fluorinated solid oxide may include (or consist essentially of, or consist of) (a) contacting an acidic fluorine compound and an inorganic base to form an aqueous mixture having a pH of at least about 4, and (b) bringing solid oxide in contact with the specified aqueous mixture to obtain a fluorinated solid oxide. The second method for producing a fluorinated solid oxide may include (or consist essentially of, or consist of) (a) contacting an acidic fluorine-containing compound with a solid oxide to form a mixture; and (B) contacting said mixture with an inorganic base to form a fluorinated solid oxide at a pH of at least about 4.

In general, the features of any of the processes proposed in the present invention (for example, but not limited to, acid fluorine compound, inorganic base, pH, solid oxide, and the conditions under which the steps are carried out) are independently described herein, while such features can be combined in any combination to further describe the proposed methods. Moreover, other process steps can be performed before, during and/or after any of the steps listed in the proposed methods, unless otherwise indicated. In addition, fluorinated solid oxides (also referred to as carrier activators or chemically treated solid oxides) obtained in accordance with the proposed methods are within the scope of the present invention and are included therein.

Considering now step (a) of the first process, the acidic fluoro compound and the inorganic base can be brought into contact to form an aqueous mixture having a pH of at least about 4. The order in which the components in step (a) are combined to form an aqueous mixture, especially not limited. In one aspect, for example, to form an aqueous mixture, the acidic fluorine compound may first be contacted with water and then with an inorganic base, while in another aspect, the inorganic base may be first contacted with water and then with the acidic fluorine compound, to obtain an aqueous mixture.

In step (a), any suitable acidic fluorine compound can be used. Illustrative and non-limiting examples of the acidic fluorine compound include hydrogen fluoride (HF), acidic ammonium fluoride (NH ₄ HF ₂ ), triflate acid (CF ₃ SO ₃ H), tetrafluoroboric acid (HBF ₄ ), hexafluorosilicic acid (H ₂ SiF ₆ ), hexafluorophosphoric acid (HPF ₆ ) and the like. To obtain an aqueous mixture, combinations of two or more acidic fluorine compounds can be used. In one aspect, the acidic fluoro compound may comprise (or consist essentially of, or consist of) hydrogen fluoride (HF), acidic ammonium fluoride (NH ₄ HF ₂ ), triflate acid (CF ₃ SO ₃ H), tetrafluoroboric acid (HBF ₄ ), hexafluorosilicic acid (H ₂ SiF ₆ ), hexafluorophosphoric acid (HPF ₆ ), or any combination thereof. According to another aspect, the acidic fluorine compound may include (or consist essentially of, or consist of) hydrogen fluoride (HF); alternatively acidic ammonium fluoride (NH ₄ HF ₂ ); alternatively triflate acid (CF ₃ SO ₃ H); alternatively tetrafluoroboric acid (HBF ₄ ); alternatively hexafluorosilicic acid (H ₂ SiF ₆ ); or alternatively hexafluorophosphoric acid (HPF ₆ ). According to another aspect, the acidic fluorine compound may include tetrafluoroboric acid (HBF ₄ ), hexafluorosilicic acid (H ₂ SiF ₆ ), or both.

Similarly, various inorganic bases can be used, with said inorganic bases typically containing a metal. For example, the inorganic base may contain Zn, Al, Fe, Mn, Ca, Mg, or combinations thereof (zinc-containing inorganic base, aluminum-containing inorganic base, iron-containing inorganic base, manganese-containing inorganic base, calcium-containing inorganic base, magnesium-containing inorganic base, or combinations thereof). Thus, typical examples of inorganic bases that can be used in the proposed methods may include, but are not limited to, ZnO, Zn(OH) ₂ , ZnCO ₃ , Al(OH) ₃ , Al ₂ O ₃ , AlOOH, Fe ₂ O ₃ , Fe(OH) ₃ , Fe(OH) ₂ , MnO ₂ , Mn(OH) ₂ , Ca(OH) ₂ , CaCO ₃ , Mg(OH) ₂ , MgCO etc. Combinations of two or more inorganic bases can be used to form an aqueous mixture. According to one aspect of the present invention, the inorganic base may include ZnO, Zn(OH) ₂ and/or ZnCO ₃ while according to another aspect, the inorganic base may include Al(OH) ₃ , Al ₂ O ₃ and/or AlOOH, while according to in another aspect, the inorganic base may include Fe ₂ O ₃ , Fe(OH) ₃ , and/or Fe(OH) ₂ , and according to another aspect, the inorganic base may include MnO ₂ and/or Mn(OH) ₂ , while according to another aspect, the inorganic base may include Ca(OH) ₂ and/or CaCO ₃ and according to another aspect, the inorganic base may include Mg(OH) ₂ and/or MgCO ₃ .

The acidic fluoro compound and the inorganic base can be combined to form an aqueous mixture having a pH of at least about 4. Among other things, the pH can often be generally neutral, and typically can range from about 4 to about 8, for example, about 4 to about 7.5, about 4 to about 6, about 4 to about 5.5, about 4 to about 5, about 4.2 to about 7.5, about 4.2 to about 6.8, about 4.2 to about 5.5, about 4.5 to about 7.5, about 4.5 to about 6.5, about 5 to about 8, about 5 to about 7 or from about 5 to about 6.

The relative number of equivalents of acid in the acid fluoro compound to the number of equivalents of base in the inorganic base that are combined in step (a) may be chosen to maintain a pH of at least about 4. Depending on the particular acid fluoro compound and inorganic used, base, among other factors, the ratio of acid:base equivalents (acidic fluoro compound to inorganic base) is generally from about 1.3:1 to about 1:3. Thus, according to one aspect of the present invention, the ratio of acid:base equivalents can be from about 1.2:1 to about 1:2, and according to another aspect, such a ratio can be from about 1:1 to about 1:2, and according to in yet another aspect, the ratio may be from about 1:1.1 to about 1:1.8. For example, 1 mole of Zn(OH) ₂ (or ZnO, or ZnCO ₃ ) contains 2 equivalents of a base, while 1 mole of HF (or HBF ₄ ) contains 1 equivalent of an acid.

The corresponding molar amount of F relative to the number of equivalents of the base in the inorganic base in the aqueous mixture is not particularly limited. In general, this ratio may be from about 0.5:1 to about 8:1, from about 0.8:1 to about 7:1, or from about 1:1 to about 6:1.

In addition, depending on the pH and the particular acid fluoride compound and inorganic base used, among other factors, the aqueous mixture may be a solution or the aqueous mixture may be a suspension (eg, with a visible precipitate). Step (a) - and step (b) - of the proposed process can be carried out in any suitable vessel, such as a stirred tank.

Stage (a) of the proposed method can be carried out at different temperatures and for different periods of time. For example, an acidic fluorine compound and an inorganic base can be combined to form an aqueous mixture having a pH of at least about 4 at a temperature in the range of about 10°C to about 60°C; alternatively from about 10°C to about 40°C; alternatively from about 10°C to about 30°C; alternatively from about 15°C to about 45°C; alternatively from about 15°C to about 35°C; alternatively from about 20°C to about 40°C; or alternatively from about 20°C to about 30°C. According to these and other aspects, such temperature ranges are meant to include cases where step (a) is carried out at several different temperatures, and not at one fixed temperature, lying within the respective ranges, while at least one of the temperatures is within the listed ranges. . In general, ambient temperature is usually used and high temperatures are generally avoided to prevent evolution of gaseous fluorine compounds.

The duration of step (a) is not limited to any particular time period, provided that the acidic fluoro compound and the inorganic base have been sufficiently mixed to form an aqueous mixture having a pH of at least about 4. However, in general, step (a ) can be carried out for a period of time that can be from about 30 seconds to about 8 hours, for example, from about 1 minute to about 2 hours, from about 1 minute to about 30 minutes, from about 5 minutes to about 4 hours, from about 5 minutes to about 3 pm, etc.

Consider now stage (b) of the first method, in which the aqueous mixture is brought into contact with a solid oxide to obtain a fluorinated solid oxide. Step (b) of the first method can be carried out at various temperatures and for various periods of time, such as, but not limited to, the temperatures and periods described for step (a) herein. Non-limiting examples of suitable fluorinated solid oxides are described in, for example, US Pat.

The fluorinated solid oxide may include any suitable solid oxide, such as a solid oxide containing a metal ion capable of reacting with a Lewis acid. The solid oxide may include oxide materials such as alumina, their "mixed oxides" such as silica-alumina, coatings of one oxide deposited on another, and combinations and mixtures thereof. Mixed oxides such as silica-alumina may be one or more chemical phases containing more than one metal combined with oxygen to form a solid oxide. Examples of mixed oxides that can be used to form an activator-carrier, alone or in combination, may include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, alumina-titania , alumina-zirconium dioxide, zinc aluminate, alumina-boron oxide, silicon dioxide-boron oxide, aluminophosphate-silicon dioxide, titanium dioxide-zirconium dioxide, and the like. The solid oxide as used herein may also include oxide materials such as the silica coated alumina described in US Pat. etc.).

In one aspect, the solid oxide may include alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminum phosphate, heteropolytungstate, titanium dioxide, zirconia, magnesium oxide, boron oxide, any mixed oxide thereof, or any their combination. In another aspect, the solid oxide may include alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminum phosphate, heteropolytungstate, titanium dioxide, zirconia, magnesium oxide, or boron oxide, and any mixed oxide or oxide thereof. any mixture of them. In another aspect, the solid oxide may include alumina, titania, zirconia, magnesium oxide, boron oxide, any mixed oxide or any combination thereof, while in another aspect, the solid oxide may include silica-alumina, coated alumina. silicon dioxide, silicon dioxide-titanium dioxide, silicon dioxide-zirconium dioxide, alumina-boron oxide, or any combination thereof. According to another aspect, the solid oxide may include alumina, titania, zirconia, magnesium oxide, boron oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, oxide aluminum-boron oxide, etc. or any combination of them. In yet another aspect, the solid oxide may include alumina, silica-alumina, silica-coated alumina, or any mixture thereof; alternatively alumina; alternatively silica-alumina; or alternatively silica-coated alumina.

The content of silicon dioxide in solid oxide materials based on silicon dioxide-alumina or alumina coated with silicon dioxide, which can be used, can be from about 5 to about 95% of the mass. In one aspect, the silica content of said solid oxides may be from about 10% to about 80%, or from about 20% to about 70% by weight. In another aspect, the silica content of such materials may be from about 15% to about 60%, from about 25% to about 50%, or from about 25% to about 45% by weight. The solid oxides contemplated herein may have any suitable surface area, pore volume, and particle size, as will be understood by those skilled in the art.

In one aspect, the fluorinated solid oxide may include (or consist essentially of, or consist of) fluorinated alumina, fluorinated titania, fluorinated zirconia, fluorinated magnesium oxide, fluorinated boron oxide, fluorinated silica-alumina, fluorinated alumina with a fluorinated silica coating, a fluorinated silica-titania, a fluorinated silica-zirconium dioxide, a fluorinated alumina-boron oxide, and the like; and any mixture or combination thereof. In another aspect, the fluorinated solid oxide may include fluorinated alumina, fluorinated silica-alumina, fluorinated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, and the like, and any mixture or combination thereof. According to another aspect, the fluorinated solid oxide may include fluorinated alumina; alternatively fluorinated titanium dioxide; alternatively fluorinated zirconia; alternatively fluorinated magnesium oxide; alternatively fluorinated boron oxide; alternatively fluorinated silica-alumina; alternatively fluorinated silica coated alumina; alternatively fluorinated silica-titanium dioxide; alternatively fluorinated silica-zirconium dioxide; or alternatively fluorinated alumina-boron oxide.

Without being limited to this, the fluorinated solid oxide may generally contain from about 0.5 to about 15% of the mass. F based on the mass of fluorinated solid oxide (in terms of dry matter, excluding water). According to specific aspects provided herein, the fluorinated solid oxide may contain from about 1 to about 12% by weight, from about 1 to about 8% by weight, from about 2 to about 15% by weight, from about 2 to about 9 % wt., from about 2 to about 7% wt., from about 3 to about 12% of the mass. or from about 3 to about 7% of the mass. F based on the total weight of the fluorinated solid oxide.

If the fluorine-containing compound includes boron, for example, HBF ₄ fluorinated solid oxide can often contain from about 0.2 to about 1.2% of the mass. B, and according to some aspects from about 0.3 to about 1% of the mass. B, or from about 0.4 to about 0.9% of the mass. B based on the total weight of the fluorinated solid oxide (in terms of dry matter, excluding water).

Similarly, although not limited to this, the fluorinated solid oxide may also contain from about 0.5 to about 15% of the mass. metal of an inorganic base (for example, Zn, Fe, Mn, Ca and Mg, individually or in any combination) based on the weight of the fluorinated solid oxide (in terms of dry matter, excluding water). For example, when using ZnO as an inorganic base, the fluorinated solid oxide may contain from about 0.5 to about 15% of the mass. Zn. Similarly, if Mg(OH) ₂ is an inorganic base, the fluorinated solid oxide may contain from about 0.5 to about 15 wt%. mg. If necessary, you can use a mixture of inorganic bases, for example, a mixture of ZnO and MgCO ₃ ; in such cases, the total content of Zn and Mg in the fluorinated solid oxide is in the range from about 0.5 to about 15% of the mass. In specific aspects provided herein, the fluorinated solid oxide may contain from about 0.5 to about 5% by weight, from about 1 to about 12% by weight, from about 1 to about 10% by weight, from about 1 to about 8 wt%, from about 1 to about 5 wt%, from about 1 to about 3.5 wt%, from about 1.5 to about 8 wt%. or from about 1.5 to about 5% of the mass. inorganic base metal, based on the total weight of the fluorinated solid oxide.

Such appropriate amounts of fluorine, boron (if any) and metal (for example, Zn, Fe, Mn, Ca and Mg, individually or in any combination) in the fluorinated solid oxide may be present after drying and before calcining the fluorinated solid oxide, as well as after calcining the fluorinated solid oxide.

Before calcination, the fluorinated solid oxide can also be characterized by the presence of a reaction product of an acid fluorine compound and an inorganic base. In one aspect, for example, when the acidic fluorine compound is tetrafluoroboric acid (HBF ₄ ) and the inorganic base is a zinc base such as ZnO, the fluorinated solid oxide may include a solid oxide and contain from about 1 to about 18 wt. (or from about 3 to about 13% wt., or from about 4 to about 10% wt., or from about 5 to about 9% wt.) Zn(BF ₄ ) ₂ . In another aspect, when the acidic fluorine compound is hexafluorosilicic acid (H ₂ SiF ₆ ) and the inorganic base is a zinc base such as ZnO, the fluorinated solid oxide may include a solid oxide and contain from about 1 to about 18 wt. (or from about 3 to about 13% wt., or from about 4 to about 10% wt., or from about 5 to about 9% wt.) ZnSiF ₆ .

The fluorinated solid oxide may have any suitable total pore volume, BET surface area, and particle size. As a non-limiting example, according to one aspect, the fluorinated solid oxide may have a total pore volume in the range of from about 0.5 to about 2.5 ml/g, according to another aspect from about 0.5 to about 2 ml/g, and according to still one of the aspects from about 0.7 to about 1.5 ml/g. The BET specific surface area of the fluorinated solid oxide is not particularly limited, and in one aspect may be from about 150 to about 700 m ² /g, in another aspect from about 200 to about 700 m ² /g, and in another aspect from about 250 up to about 500 m ² /g. Similarly, the average particle size (d50) of the fluorinated solid oxide particles is not particularly limited, and in one aspect may be from about 10 to about 500 microns, in another aspect from about 25 to about 200 microns, and in another aspect from about 20 to about 100 microns.

Optionally, the fluorinated solid oxide may be impregnated with additional metal or metals. Among other things, such impregnation can be carried out by bringing the metal-containing compound into contact with an acidic fluorine-containing compound and an inorganic base. The metal compound may contain a metal and an organic group (eg acetate) or the metal compound may be inorganic (eg nitrate). Illustrative metals may include, but are not limited to, zinc, nickel, cobalt, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, and the like. or their combinations. The metal in the inorganic base and the metal in the metal-containing compound may be the same (eg zinc) or different (eg zinc and cobalt). In one aspect, the metal-containing compound may include an organozinc compound such as zinc acetate and/or zinc formate.

When impregnated with additional metal, the fluorinated solid oxide may contain any suitable amount of the metal of the metal-containing compound, often ranging from about 0.5 to about 10% by weight. based on the mass of fluorinated solid oxide (in terms of dry matter, excluding water). In specific aspects provided herein, the fluorinated solid oxide may contain from about 0.5 to about 5% by weight, from about 1 to about 12% by weight, from about 1 to about 10% by weight, from about 1 to about 8% wt., from about 1 to about 4% wt., from about 1.5 to about 8% of the mass. or from about 1.5 to about 5% of the mass. the metal of the metal-containing compound, based on the total weight of the fluorinated solid oxide.

Consider now a second process for producing a fluorinated solid oxide, which may include (A) contacting an acidic fluorine compound with a solid oxide to form a mixture, and (B) contacting the resulting mixture with an inorganic base to form a fluorinated solid oxide at a pH of at least about 4. In the second method, the selection of the acid fluorine compound, the solid oxide, the inorganic base, and the fluorinated solid oxide is similar to the selection described herein for the first method. Similarly, the pH conditions, acid-base equivalents, molar ratios of F to base equivalents, and other features described herein for the first method also apply to the second method. In addition, step (A) and step (B) of the second method can be carried out at different temperatures and for different periods of time, such as the temperatures and periods described herein for step (a) of the first method, but not limited to them.

The first method and the second method may further include the step of drying the fluorinated solid oxide, any suitable method or any suitable method described herein may be used. For example, excess liquid can be removed from the fluorinated solid oxide (eg, by draining, filtering, etc.), while the wet fluorinated solid oxide can be exposed to a wide range of drying times, drying temperatures, and drying pressures. For example, the drying time may be from about 15 minutes to about 48 hours, from about 30 minutes to about 24 hours, or from about 1 to about 12 hours, and the drying temperature may be from about 50°C to about 300°C, from about 95°C to about 300°C or from about 100°C to about 275°C. The drying pressure may be at or near atmospheric pressure, but in many cases the drying step may be carried out under vacuum at any suitable subatmospheric pressure, e.g. less than 100 Torr (13.3 kPa), less than 50 Torr (6.67 kPa) or less than 10 Torr (1.33 kPa).

Various types of dryers can be used for the drying step, such as rotary dryers, rotary dryers, fluid bed dryers, and spray dryers, although applicable dryers are not limited to those listed. Similarly, the flow of the drying medium (gas flow) with respect to the fluorinated solid oxide is not particularly limited, and includes cocurrent flow, countercurrent flow, and through flow (such as in a fluidized bed, for example).

According to some aspects of the present invention, the drying step may include spray drying the fluorinated solid oxide. In general, spray drying can be used to convert a wet fluorinated solid oxide (e.g., a slurry or slurry of the fluorinated solid oxide in water) into dried particles or powder form by spraying a feed stream containing the wet fluorinated solid oxide into a device containing a hot drying gas. (usually air) in which residual water evaporates from the fluorinated solid oxide.

In the spray drying process, the feed stream can be sprayed into the drying chamber in the form of droplets and brought into contact with a large volume of hot gas which is in direct contact with the wet solid oxide. Typical inlet gas temperatures are from 95°C to about 800°C, or from about 100°C to about 500°C, but are not limited to these temperatures. The gas flow relative to the solids flow to the spray dryer may be co-current flow, counter-current flow or mixed flow. After drying, the gas stream and the dried fluorinated solid oxide are separated. If necessary, fine particles can be removed in trap filters or cyclones. The dried fluorinated solid oxide may be in the form of free flowing solid particles.

The raw material supplied to the spray dryer can be subjected to a spraying process, which can use, for example, a high pressure nozzle, a two-fluid nozzle, or a high-speed centrifugal disk. High pressure nozzles provide atomization by forcing a high pressure solid carrier slurry through a small nozzle orifice, the size of which may depend on, among other factors, the pressure required and the size of the solids in the slurry. Long-term use may cause wear of the nozzle opening and clogging; therefore, regular maintenance may be advisable to ensure proper atomization. Two-fluid nozzles have an advantage over low operating pressure applications and can often be used when the feed stream is a thick or high solids slurry that does not work well in high pressure nozzle systems. The spray liquid may be steam or air.

The high speed centrifugal disks make it possible to atomize the fluorinated solid oxide slurry by bringing said slurry into contact with a rapidly rotating disk. To obtain a suitable droplet size for drying, the disc diameter and disc speed (eg 3000 rpm and above) can be varied. The advantage is that disc spraying is not subject to wear and clogging like nozzle systems. The rotation of the disk can be caused by any suitable motor or technical means.

Regardless of the spraying method, the spray drying method can be carried out so as to maintain the spherical shape of the fluorinated solid oxide. In many cases, the average particle size of the solid material can be maintained, with the overall average particle size depending on the spray method, the solids content of the solid oxide feed stream, the viscosity of the feed stream, and the feed rate, among other factors. Similarly, the bulk density of the dried fluorinated solid oxide can be adjusted based on spray dryer operating conditions such as droplet size, inlet gas temperature, and air turbulence, among other factors.

The mixing of the gas stream (eg air) and the droplet in the drying chamber can be carried out, for example, using a co-current flow of gas and solids (eg horizontal or vertical spray dryers) or a countercurrent flow of gas and solids. In the latter case, the upward airflow may carry fine particles to the top of the chamber for easy removal. Mixed flow spray dryers combine countercurrent and cocurrent drying with complex hydrodynamic profiles and high turbulence for efficient heat and mass transfer.

The advantage of spray drying may be the short contact time of the fluorinated solid oxide with elevated temperatures in the drying chamber. Thus, in addition to the average particle size, the spray drying process can be carried out in such a way as to obtain dried fluorinated solid oxides with a surface area and pore volume comparable to the starting material (ie before spray drying).

Optionally, after drying, the fluorinated solid oxide can be subjected to a calcination (to obtain a calcined fluorinated solid oxide), which can be carried out at various temperatures and for various periods of time. Typical maximum calcination temperatures often range from about 400°C to about 1000°C, for example, from about 400°C to about 900°C, from about 500°C to about 800°C, or from about 550°C to about 700°C. According to these and other aspects, such temperature ranges are also intended to include cases where the calcination step is carried out at several different temperatures (eg, initial calcination temperature, maximum calcination temperature) rather than at one fixed temperature within the respective ranges.

The duration of the calcination step is not limited to any particular time period. Therefore, the calcination step can be carried out, for example, for a period of time ranging from 30-45 minutes to 36-48 hours or more. A suitable calcination time may depend, among other variables, on, for example, the initial/maximum calcination temperature. However, in general, the calcination step can be carried out over a period of time that can be from about 30 minutes to about 48 hours, for example, from about 1 hour to about 24 hours, from about 1 hour to about 12 hours, from about 2 hours to about 12 hours, or from about 2 hours to about 8 hours.

The calcination step can be carried out in a calcination gas stream containing (or consisting essentially of, or consisting of) an inert gas (eg, nitrogen), oxygen, air, or any mixture or combination thereof. In some aspects, the calcination gas stream may contain air, while in other aspects, the calcination gas stream may contain a mixture of air and nitrogen. However, in some aspects, the calcining gas stream may be an inert gas such as nitrogen and/or argon.

The calcination step can be carried out using any suitable method and equipment, either batchwise or continuously. For example, the calcination step can be carried out in a belt kiln or alternatively in a rotary kiln. In some aspects, the calcination step may be carried out in a batch or continuous calcination vessel containing a fluidized bed. As will be appreciated by those skilled in the art, other suitable methods and equipment may be used for the calcination step, and such methods and equipment are included herein.

CATALYTIC COMPOSITIONS

In some aspects, the present invention uses catalyst compositions containing a metallocene compound and a fluorinated solid oxide as an activator. Such catalyst compositions can be used to produce polyolefins, homopolymers, copolymers, and the like. - for various purposes. According to aspects of the present invention, it is contemplated that the proposed catalyst composition may contain more than one metallocene compound (two or more metallocene compounds). Moreover, it is also possible to use more than one fluorinated solid oxide activator.

In general, the catalyst compositions of the present invention comprise a metallocene compound and a fluorinated solid oxide. Optionally, such catalyst compositions may further comprise one or more co-catalyst compounds or compounds (suitable co-catalysts such as organoaluminum compounds are also discussed herein). Thus, the catalyst composition according to the present invention may contain a metallocene compound, a fluorinated solid oxide, and an organoaluminum compound. For example, the fluorinated solid oxide may include (or consist essentially of, or consist of) fluorinated alumina, fluorinated silica-alumina, fluorinated silica-zirconia, fluorinated silica-titania, fluorinated alumina coated with fluorinated dioxide silicon, etc. In addition, the organoaluminum compound may include (or consist essentially of, or consist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride , diethylaluminum ethoxide, diethylaluminum chloride, and the like. or their combinations. Accordingly, the catalyst composition corresponding to aspects of the present invention may contain (or consist essentially of, or consist of) a metallocene compound; fluorinated alumina (or fluorinated silica-alumina or fluorinated silica coated alumina); and triethylaluminum (or triisobutylaluminum).

According to another aspect of the present invention, there is provided a catalyst composition comprising a metallocene compound, a fluorinated solid oxide, and an organoaluminum compound, said catalyst composition being substantially free of aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, or combinations thereof; alternatively essentially free of aluminoxanes; alternatively essentially free of organoboron or organoborate compounds; or alternatively substantially free of ionizing ionic compounds. In such aspects, the catalyst composition has the catalytic activity discussed below in the absence of said additional materials. For example, the catalyst composition of the present invention may consist essentially of a metallocene compound, a fluorinated solid oxide, and an organoaluminum compound, with no other materials present in the catalyst composition that would increase/decrease the activity of the catalyst composition by more than about 10% relative to the catalytic activity of the catalyst composition in the absence of these substances.

However, according to other aspects of the present invention, such activators/co-catalysts can be used. For example, a catalyst composition containing a metallocene complex and a fluorinated solid oxide may further comprise a co-catalyst. Suitable cocatalysts according to this aspect 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; or alternatively organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, or any combination thereof. More than one co-catalyst may be present in a catalyst composition.

Any suitable metallocene compound may be used in the catalyst composition. For example, in some aspects, the metallocene component of the catalyst systems provided herein may include a non-bridged metallocene; alternatively, a non-bridging metallocene compound based on zirconium or hafnium; alternatively, a non-bridging metallocene compound based on zirconium or hafnium containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group; alternatively, a non-bridging zirconium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group. Such cyclopentadienyl groups and indenyl groups may independently be unsubstituted or may contain any suitable substituent (one or more than one). Illustrative and non-limiting examples of non-bridged metallocene compounds (e.g., with zirconium or hafnium) that can be used in catalyst systems corresponding to aspects of the present invention are described in US Pat. document through a link.

In other aspects, the metallocene component of the catalyst compositions provided herein may comprise a bridged metallocene compound with, for example, titanium, zirconium, or hafnium, such as a bridged metallocene compound based on zirconium or hafnium with a fluorenyl group; or alternatively a bridged metallocene compound based on zirconium or hafnium with a cyclopentadienyl group and a fluorenyl group. Such cyclopentadienyl groups and fluorenyl groups may independently be unsubstituted or may contain any suitable substituent (one or more than one). For example, such bridged metallocenes may contain an alkenyl substituent (eg, terminal alkenyl) on the bridge group, on the cyclopentadienyl type group (eg, cyclopentadienyl group or fluorenyl group), or on the bridge group and the cyclopentadienyl 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 in the bridge group; alternatively, a zirconium or hafnium-based bridged metallocene compound with a cyclopentadienyl group and a fluorenyl group and an aryl group in the bridged group; alternatively, a zirconium-based bridging metallocene compound with a fluorenyl group and an aryl group in the bridging group; or alternatively a hafnium-based bridged metallocene compound with a fluorenyl group and an aryl group in the bridged group. According to these and other aspects, the aryl group in the bridging group may be a phenyl group. Optionally, such bridged metallocenes may contain an alkenyl substituent (eg, terminal alkenyl) on the bridge group, on the cyclopentadienyl type group, or on both the bridge group and the cyclopentadienyl group. Illustrative and non-limiting examples of bridged metallocene compounds (for example, with zirconium or hafnium) that can be used in catalyst systems corresponding to aspects of the present invention are described in US patents Nos. scope is incorporated herein by reference.

The catalyst composition may be prepared in any manner, for example by bringing into contact the metallocene compound, the fluorinated solid oxide and the co-catalyst (if used) in any order.

In general, the weight ratio of co-catalyst (eg, organoaluminum compound) to fluorinated solid oxide may be from about 10:1 to about 1:1000. When using more than one co-catalyst and/or more than one fluorinated solid oxide, this ratio is based on the total weight of each respective component. In another aspect, the weight ratio of co-catalyst to fluorinated solid oxide may be from about 3:1 to about 1:500, or from about 1:10 to about 1:350.

According to some aspects of the present invention, the weight ratio of metallocene complex to activator (fluorinated solid oxide) can be from about 1:1 to about 1:1,000,000. When more than one metallocene compound and/or more than one fluorinated solid oxide is used, this ratio is based on the total weight of the respective components. In another aspect, said weight ratio may be from about 1:5 to about 1:100,000, or from about 1:10 to about 1:10,000. But at the same time, according to another aspect, the mass ratio of metallocene to fluorinated solid oxide can be from about 1:20 to about 1:1000.

The catalytic activity of the catalyst compositions of the present invention is generally greater than about 1000 grams, greater than about 2000 grams, greater than 3000 grams, greater than about 4000 grams, and so on. ethylene polymer (homopolymer or copolymer as the case may be) per gram of fluorinated solid oxide per hour (abbreviated g/g/h). In another aspect, the catalytic activity may be greater than about 6,000, greater than about 8,000, or greater than about 10,000 g/g/h, and may often be as high as 13,000 to 18,000 g/g/h. Such activities are measured under slurry polymerization conditions using triisobutylaluminum as a co-catalyst and isobutane as diluent at a polymerization temperature of 95° C. and a reactor pressure of 400 psig (about 2758 kPa). In addition, an excess of a metallocene compound (1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)zirconium dichloride) can be used, while the fluorinated the solid oxide may include, but is not limited to, fluorinated silica coated alumina.

JOINT CATALYSTS

According to certain aspects relating to catalyst compositions comprising a co-catalyst and co-catalyst polymerization processes, said co-catalyst may comprise a metal hydrocarbyl compound, examples of which include non-halogen metal hydrocarbyl compounds, non-halogen metal hydrocarbyl compounds, non-halogen metal alkyl compounds, alkyl halide metal compounds and so on. The hydrocarbyl group (or alkyl group) may be any hydrocarbyl (or alkyl) group described herein. Moreover, in some aspects, the metal hydrocarbyl metal can be a Group 1, 2, 11, 12, 13, or 14 metal; alternatively a Group 13 or 14 metal; or alternatively a Group 13 metal. Therefore, in some aspects, the metal hydrocarbyl metal (or nonhalogen metal hydrocarbyl or metal hydrocarbyl halide) can be lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, boron, aluminum, or tin ; alternatively lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum or tin; alternatively lithium, sodium or potassium; alternatively magnesium or calcium; alternatively lithium; alternatively sodium; alternatively potassium; alternatively magnesium; alternatively calcium; alternatively zinc; alternatively boron; alternatively aluminum; or alternatively tin. In some aspects, a metal hydrocarbyl or metal alkyl, with or without a halide, may include lithium hydrocarbyl or lithium alkyl, magnesium hydrocarbyl or magnesium alkyl, boron hydrocarbyl or boron alkyl, zinc hydrocarbyl or zinc alkyl, or aluminum hydrocarbyl or aluminum alkyl.

According to specific aspects related to catalyst compositions containing a cocatalyst and cocatalyst polymerization processes, said cocatalyst may include an aluminoxane compound (e.g., a supported aluminoxane), an organoboron compound or an organoborate compound, an ionizing ionic compound, an organoaluminum compound, an organozinc a compound, an organomagnesium compound, or an organolithium compound, wherein said co-catalyst includes any combination of the listed substances. In one aspect, the co-catalyst may include an organoaluminum compound. In another aspect, the co-catalyst may include 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. According to another aspect, the co-catalyst may include an aluminoxane compound; alternatively an organoboron or organoborate compound; alternatively an ionizing ionic compound; alternatively an organozinc compound; alternatively an organomagnesium compound; or alternatively an organolithium compound.

Specific non-limiting examples of suitable organoaluminum compounds may include trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n -octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and the like. or their combinations. Типичные и неограничивающие примеры алюминоксанов включают метилалюминоксан, модифицированный метилалюминоксан, этилалюминоксан, н-пропилалюминоксан, изопропилалюминоксан, н-бутилалюминоксан, трет-бутилалюминоксан, втор-бутилалюминоксан, изобутилалюминоксан, 1-пентилалюминоксан,2-пентилалюминоксан, 3-пентилалюминоксан, изопентилалюминоксан, неопентилалюминоксан и т .P. or any combination of them. Representative and non-limiting examples of organoboron/organoborate compounds include tetrakis(pentafluorophenyl)borate N,N-dimethylanilinium, tetrakis(pentafluorophenyl)triphenylcarbenium borate, lithium tetrakis(pentafluorophenyl)borate, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate N,N -dimethylanilinium, tetrakis[3,5-bis(trifluoromethyl)phenyl]triphenylcarbenium borate, tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron and the like. or mixtures thereof.

Examples of ionizing ionic compounds may include, but are not limited to, the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl)ammonium tetrakis(m-tolyl)borate, tetrakis(2,4 tri(n-butyl)ammonium -dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tetrakis(pentafluorophenyl)tri(n-butyl)ammonium borate, tetrakis(p-tolyl)borate N, N-dimethylanilinium, tetrakis(m-tolyl)borate N, N-dimethylanilinium, tetrakis(2,4-dimethylphenyl)borate N, N-dimethylanilinium, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, tetrakis triphenylcarbenium (p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate, triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate, tetrakis[3,5-bis(trifluoromethyl)phenyl ]triphenylcarbenium borate, tetrakis(pentafluorophenyl)borate tri phenylcarbenium, tropylium tetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropylium tetrakis(2,4-dimethylphenyl)borate, tropylium tetrakis(3,5-dimethylphenyl)borate, tetrakis[3,5-bis( tropylium trifluoromethyl)phenyl]borate, tropylium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, tetrakis(2,4-dimethylphenyl) lithium borate, lithium tetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodium tetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodium tetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, tetrakis(2,4 -dimethylphenyl)sodium borate, sodium tetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetrakis(pentafluorophenyl)borate, potassium tetraphenylborate, potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate, tetrakis( 2,4-dimethylphenyl)potassium borate, potassium tetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithium tetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate, tetrakis(p lithium -tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate, lithium tetrakis(2,4-dimethylphenyl)aluminate, lithium tetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate, sodium tetrakis(pentafluorophenyl)aluminate, sodium tetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodium tetrakis(m-tolyl)aluminate, sodium tetrakis(2,4-dimethylphenyl)aluminate, sodium tetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate, potassium tetrakis(pentafluorophenyl)aluminate, potassium tetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassium tetrakis(m-tolyl)aluminate, potassium tetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate, and the like. or their combinations.

Examples of organozinc compounds that can be used as co-catalysts may include, but are not limited to, dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc, di(triethylsilyl)zinc, di(triisoproplysilyl)zinc, di( triphenylsilyl)zinc, di(allyldimethylsilyl)zinc, di(trimethylsilylmethyl)zinc, and the like. or their combinations.

Similarly, exemplary organomagnesium compounds may include, but are not limited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, dineopentylmagnesium, di(trimethylsilylmethyl)magnesium, methylmagnesium chloride, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, propylmagnesium bromide, butyl неопентилмагнийбромид, триметилсилилметилмагнийбромид, метилмагнийиодид, этилмагнийиодид, пропилмагнийиодид, бутилмагнийиодид, неопентилмагнийиодид, триметилсилилметилмагнийиодид, метилмагний этоксид, этилмагний этоксид, пропилмагний этоксид, бутилмагний этоксид, неопентилмагний этоксид, триметилсилилметилмагний этоксид, метилмагний пропоксид, этилмагний пропоксид, пропилмагний пропоксид, бутилмагний пропоксид, неопентилмагний пропоксид, триметилсилилметилмагний propoxide, methyl magnesium phenoxide, ethyl magnesium phenoxide, propyl magnesium phenoxide, butyl magnesium phenoxide, neopentyl magnesium phenoxide, trimethylsilylmethylmagnesium phenoxide, and the like. or any combination of them.

Similarly, exemplary organolithium compounds may include, but are not limited to, methyllithium, ethyllithium, propyllithium, butyllithium (e.g., t-butyllithium), neopentyllithium, trimethylsilylmethyllithium, phenyllithium, tolyllithium, xylyllithium, benzyllithium, (dimethylphenyl)methyllithium, allyllithium, etc. P. or their combinations.

The cocatalysts that can be used in the catalyst compositions of the present invention are not limited to the cocatalysts described above. Other suitable cocatalysts are well known to those skilled in the art, including, for example, the catalysts described in US Pat. incorporated herein by reference in its entirety.

POLYMERIZATION METHODS

The catalyst compositions of the present invention can be used to polymerize olefins to form homopolymers, copolymers, terpolymers, and the like, and such catalyst compositions are discussed herein. One of the proposed methods for the polymerization of olefins in the presence of a catalyst composition according to the present invention may include bringing the catalyst composition into contact with an olefin monomer and optionally an olefin comonomer (one or more) in a polymerization reactor system under polymerization conditions to obtain an olefin polymer, while the specified catalyst composition can contain a metallocene compound, a fluorinated solid oxide, and an optional co-catalyst. Suitable metallocene complexes, fluorinated solid oxides as activators and cocatalysts are described herein. Therefore, aspects of the present invention relate to a process for the polymerization of olefins in the presence of a catalyst composition, wherein the proposed method comprises contacting the catalyst composition with ethylene and optionally an olefin comonomer (one or more) under polymerization conditions to form an ethylene polymer. Similarly, the present invention includes olefin polymerization processes comprising any of the processes for producing a fluorinated solid oxide described herein (for example, comprising (a) contacting an acid fluorine compound and an inorganic base to form an aqueous mixture having a pH of at least about 4, and (b) contacting a solid oxide with said aqueous mixture to form a fluorinated solid oxide; or comprising (A) contacting an acidic fluorine compound with a solid oxide to form a mixture, and (B) contacting the resulting mixture with an inorganic base to form a fluorinated solid oxide at a pH of at least about 4), contacting a metallocene compound, a fluorinated solid oxide, and an optional co-catalyst to form a catalyst composition, and contacting said catalyst composition with an olefin monomer and n optionally, one or more olefin comonomers in a polymerization reactor system under polymerization conditions to form an olefin polymer.

The catalyst compositions of the present invention are intended for any olefin polymerization process using various types of polymerization reactor systems and reactors. The polymerization reactor system may include any polymerization reactor capable of polymerizing olefin monomers and comonomers (one or more than one comonomer) to produce homopolymers, copolymers, terpolymers, and the like. The various types of reactors include what may be called a loop reactor, a slurry reactor, a gas phase reactor, a solution reactor, a high pressure reactor, a tubular reactor, an autoclave reactor, and the like, or combinations thereof. Suitable polymerization conditions are used for different types of reactors. Gas phase reactors may include fluidized bed reactors or multi-stage horizontal reactors. Slurry reactors may contain vertical or horizontal loops. High pressure reactors may include autoclave or tubular reactors. In reactors of various types, batch or continuous processes can be used. When using continuous processes, you can use batch or continuous unloading of the product. The processes may also include partial or complete direct recycling of unreacted monomer, unreacted comonomer and/or diluent.

The polymerization reactor systems of the present invention may comprise one type of reactor in the system, or multiple reactors of the same or different types (eg, single reactor, double reactor, more than two reactors). The production of polymers in multiple reactors may include several stages in at least two separate polymerization reactors connected to each other by means of a transfer device that allows the resulting polymers to be transferred from the first polymerization reactor to the second reactor. The required polymerization conditions in one of the reactors may differ from the operating conditions in the other reactor(s). Alternatively, multi-reactor polymerization may involve manually transferring polymer from one reactor to subsequent reactors to continue the polymerization. Multiple reactor systems may include any combination, including, but not limited to, multiple loop reactors, multiple gas phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors, or a combination of high pressure reactors with loop and/or gas phase reactors. Several reactors may be operated in series or in parallel or/and in series and in parallel. Accordingly, the present invention includes polymerization reactor systems containing one reactor, containing two reactors, and containing more than two reactors. According to some aspects of the present invention, the polymerization reactor system may comprise a slurry reactor, a gas phase reactor, a solution reactor, as well as combinations of several reactors thereof.

According to one aspect of the present invention, the polymerization reactor system may comprise at least one slurry loop reactor containing vertical or horizontal loops. The monomer, diluent, catalyst and comonomer can be continuously fed into the loop reactor in which the polymerization takes place. In general, continuous processes may include the continuous introduction of monomer/comonomer, catalyst and diluent into a polymerization reactor and the continuous removal from such reactor of a suspension containing polymer particles and diluent. The reactor effluent may be flashed to remove solid polymer from liquids containing diluent, monomer and/or comonomer. Various technologies can be used for such a separation step, including, but not limited to, flash evaporation, which may include any combination of heat and pressure reduction, separation by cyclonic action in either a cyclone or a hydrocyclone, or separation by centrifugation.

An exemplary slurry polymerization process (also known as a particle process) is described, for example, in US Pat.

Suitable diluents for use in slurry polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquids under the polymerization 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 reactor polymerization reactions can take place under high volume conditions that do not use a diluent, such as can be used in the bulk polymerization of propylene to form polypropylene homopolymers.

According to another aspect of the present invention, the polymerization reactor system may comprise at least one gas phase reactor. Such reactor systems may use a continuous recycle stream containing one or more monomers circulating continuously through a fluidized bed in the presence of a catalyst under polymerization conditions. The recycle stream can be removed from the fluidized bed and returned back to the reactor. Simultaneously, the polymer product can be removed from the reactor and new or fresh monomer added to replace the polymerized monomer. Such gas phase reactors may include a multistage gas phase olefin polymerization process in which olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones while simultaneously feeding the catalyst-containing polymer produced in the first polymerization zone to the second polymerization zone. One type of gas phase reactor is described in US Pat. Nos. 5,352,749; 4,588,790; 5,436,304;

According to another aspect of the present invention, the high pressure polymerization reactor may include a tubular reactor or an autoclave reactor. Tubular reactors may have multiple zones to which fresh monomer, initiators or catalysts are added. The monomer can be entrained in an inert gas flow and introduced into one of the zones of the reactor. The initiators, catalysts and/or catalyst components can be entrained in the gas stream and introduced into another zone of the reactor. For polymerization, the gas streams can be stirred. Heat and pressure can be used appropriately to ensure optimal polymerization reaction conditions.

According to another aspect of the present invention, the polymerization reactor system may comprise a solution polymerization reactor in which the monomer (and comonomer, if used) is brought into contact with the catalyst composition by suitable agitation or other means. A carrier containing an inert organic diluent or an excess of monomer may be used. If necessary, the monomer/comonomer can be brought into contact in the vapor phase with the product of the catalytic reaction in the presence or absence of liquid material. Temperature and pressure are maintained in the polymerization zone to provide a polymer solution in the reaction medium. Agitation can be used to provide better temperature control and maintain uniformity of polymerization mixtures throughout the polymerization zone. Suitable means are used to remove the exothermic heat of polymerization.

Polymerization reactor systems suitable for the present invention may further include any combination of at least one feedstock supply system, at least one catalyst supply system or catalyst components, and/or at least one polymer recovery system. Reactor systems suitable for the present invention may further include feed purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, offloading, laboratory analysis, and process control.

The polymerization conditions controlled to provide the efficiency and desired properties of the polymer may include temperature, pressure, and concentrations of various reagents. The polymerization temperature can affect catalyst performance, polymer molecular weight and molecular weight distribution. A suitable polymerization temperature may be any temperature below the depolymerization temperature according to the Gibbs free energy equation. Typically, such a temperature is, for example, from about 35°C to about 280°C, or from about 50°C to about 175°C, depending on the type of polymerization reactor(s). In some reactor systems, the polymerization temperature may generally range from about 60°C to about 120°C, or from about 70°C to about 100°C. Various polymerization conditions can be maintained substantially constant, for example, to obtain a certain grade of olefin polymer.

Suitable pressures will also vary depending on the type of reactor and polymerization. The pressure for carrying out liquid phase polymerization in a loop reactor is typically less than 1000 psig (6.9 MPa). The pressure for conducting gas phase polymerization is typically from about 200 to 500 psig (1.4 MPa to 3.4 MPa). High pressure polymerization in tubular or autoclave reactors is generally carried out at pressures from about 20,000 to 75,000 psig (138 to 517 MPa). Polymerization reactors can also operate in the supercritical region occurring at typically higher temperatures and pressures (eg, above 92° C. and 700 psig). Operating at conditions above the critical point in the pressure/temperature diagram (supercritical phase) can provide advantages to such a polymerization reaction method.

Aspects of the present invention relate to olefin polymerization processes carried out in the absence of added hydrogen. The process for polymerizing olefins according to the present invention may include contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer in a polymerization reactor system under polymerization conditions to form an olefin polymer, said catalyst composition may contain a metallocene compound, a fluorinated solid oxide, and an optional co-catalyst, and wherein the polymerization process is carried out in the absence of added hydrogen (hydrogen is not added to the polymerization reactor system). As one skilled in the art will appreciate, hydrogen can be generated in situ with catalyst compositions in various olefin polymerization processes, and the amount generated may vary depending on the particular catalyst composition and metallocene compound used, the type of polymerization process used, the polymerization reaction conditions employed, and etc.

In other aspects, it may be desirable to carry out the polymerization process in the presence of a certain amount of added hydrogen. Accordingly, the olefin polymerization process of the present invention may include contacting the catalyst composition with an olefin monomer and optionally an olefin comonomer in a polymerization reactor system under polymerization conditions to form an olefin polymer, said catalyst composition may contain a metallocene compound, a fluorinated solid oxide, and an optional co-polymer. catalyst, wherein the polymerization process is carried out in the presence of added hydrogen (hydrogen is added to the polymerization reactor system). For example, the ratio of hydrogen to olefin monomer can be controlled during polymerization, often by the ratio of hydrogen feed to olefin monomer entering the reactor. The ratio of added hydrogen to olefin monomer in this process can be controlled at a weight ratio of from about 25 ppm to about 1500 ppm, from about 50 to about 1000 ppm, or from about 100 ppm to about 750 ppm.

In accordance with some aspects of the present invention, the ratio of hydrogen in the feed or reactant to olefin monomer can be kept substantially constant during the polymerization cycle to produce a particular grade of polymer. That is, you can choose a specific value of the ratio of hydrogen:olefin monomer within the range from about 5 ppm to about 1000 ppm or so, and maintain this ratio during the polymerization cycle within about +/- 25%. For example, if the target ratio is 100 ppm, then maintaining the hydrogen:olefin monomer ratio substantially constant means maintaining the feed ratio at about 75 ppm to about 125 ppm. In addition, to obtain a particular grade of polymer, the addition of comonomer (or comonomers) can be, and usually is, substantially constant throughout the polymerization cycle.

However, in other aspects, it is contemplated that the monomer, comonomer (or comonomers), and/or hydrogen may be intermittently fed to the reactor in an intermittent manner, for example, in a manner similar to that used in US Patent No. 5,739,220 and US Patent Publication No. 2004/0059070, which are incorporated herein by reference in their entirety.

The concentration of reactants entering the polymerization reactor system can be controlled in such a way as to obtain resins with certain physical and mechanical properties. The intended end use product to be made from the polymer resin and the method for making such a product may ultimately determine the desired properties and characteristics of the polymer. Mechanical properties include testing for tensile strength, bending, impact strength, creep, stress relaxation and hardness. Physical properties include measurements of density, molecular weight, molecular weight distribution, melting point, glass transition temperature, crystallization temperature, density, stereoregularity, cracking, long chain branching, and rheological measurements.

The present invention also relates to polymers (eg, ethylene/α-olefin copolymers, ethylene homopolymers, etc.) obtained using any of the polymerization methods described herein, and includes these polymers. Products of industrial production can be made from polymers obtained according to the present invention, and/or may contain them.

OLEFIN MONOMERS

Unsaturated reactants that can be used with the catalyst compositions and polymerization processes of the present invention can generally include olefinic compounds containing from 2 to 30 carbon atoms per molecule and having at least one olefinic double bond. The present invention includes homopolymerization processes using a single olefin, such as ethylene or propylene, as well as copolymerization, terpolymerization, and the like. using an olefin monomer with at least one other olefin compound. For example, the resulting copolymers, ethylene terpolymers, etc. may generally contain a major amount of ethylene (> 50 mole percent) and a minor amount of comonomer (<50 mole percent), although this is not a requirement. The comonomers that can be copolymerized with ethylene can often have 3 to 20 carbon atoms or 3 to 10 carbon atoms in their molecular chain.

According to the present invention, acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched, substituted, unsubstituted, functionalized and non-functionalized olefins can be used. For example, typical unsaturated compounds that can be polymerized with the catalyst compositions of the present invention may include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1- pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, four normal octenes (eg 1-octene), four normal nonenes, five normal decenes, and the like. or mixtures of two or more of the listed compounds. Cyclic and bicyclic olefins, including but not limited to cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, can also be polymerized as described herein. Styrene can also be used as the monomer according to the present invention. In one aspect, the olefin monomer may include a C ₂ -C ₂₀ olefin; alternatively C ₂ -C ₂₀ alpha-olefin; alternatively C ₂ -C ₁₀ olefin; alternatively C ₂ -C ₁₀ alpha-olefin; alternatively, the olefin monomer may include ethylene; or alternatively, the olefin monomer may include propylene.

If a copolymer (or alternatively a terpolymer) is desired, the olefin monomer and olefin comonomer may independently include, for example, a C ₂ -C ₂₀ alpha olefin. In some aspects, the olefin monomer may include ethylene or propylene that is copolymerized with at least one comonomer (eg, C ₂ -C ₂₀ alpha olefin, C ₃ -C ₂₀ alpha olefin, etc.). According to one aspect of the present invention, the olefin monomer used in the polymerization process may include ethylene. In this aspect, examples of suitable olefin comonomers may include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene , 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, etc. . or their combinations. According to another aspect of the present invention, the olefin monomer may include ethylene, and the comonomer may include a C ₃ -C ₁₀ alpha olefin; 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.

In general, the amount of comonomer introduced into the polymerization reactor system to form the copolymer may be from about 0.01 to about 50 weight percent, based on the combined weight of monomer and comonomer. According to another aspect of the present invention, the amount of comonomer introduced into the polymerization reactor system may be from about 0.01 to about 40 weight percent based on the total weight of monomer and comonomer. In yet another aspect, the amount of comonomer introduced into the polymerization reactor system may be from about 0.1 to about 35 weight percent, based on the combined weight of monomer and comonomer. But at the same time, according to another aspect, the amount of comonomer introduced into the polymerization reactor system may be from about 0.5 to about 20 weight percent based on the total weight of monomer and comonomer.

Without wishing to be bound by such a theory, when branched, substituted, or functionalized olefins are used as reactants, it is believed that steric hindrance may interfere with and/or slow down the polymerization process. Thus, branched and/or cyclic olefin moiety(s) further away from the carbon-carbon double bond would not be expected to interfere with the reaction in the same way that the same olefinic substituents closer to the carbon double bond might. -carbon.

According to one aspect of the present invention, at least one monomer/reagent may be ethylene (or propylene), so the polymerization reaction may be a homopolymerization involving only ethylene (or propylene), or a copolymerization with another acyclic, cyclic, terminal, internal, linear, branched, substituted or unsubstituted olefin. In addition, the catalyst compositions of the present invention can be used in the polymerization of diolefin compounds, including, but not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

POLYMERS AND PRODUCTS

The olefin polymers provided herein may include any polymer derived from any of the olefin monomer and comonomer(s) described herein. For example, the olefin polymer may include ethylene homopolymer, propylene homopolymer, ethylene copolymer (e.g., ethylene/α-olefin, ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene, etc.), propylene copolymer, ethylene terpolymer, propylene terpolymer, and the like, including combinations thereof. In one aspect, the olefin polymer may be (or may comprise) an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer; or alternatively an ethylene/1-hexene copolymer. According to another aspect, the olefin polymer may be (or may contain) a polypropylene homopolymer or a propylene-based copolymer.

If the resulting polymer obtained according to the present invention is, for example, an ethylene polymer, its properties can be characterized by various analytical methods known and used in the polyolefin industry. Industrial articles may be made from and/or contain the ethylene polymers of the present invention, the typical properties of said polymers being given below.

In general, the density of an ethylene polymer (e.g., an ethylene homopolymer and/or an ethylene/α-olefin copolymer, such as an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer) can range from about 0, 87 to about 0.96 g/cm ³ . According to one aspect of the present invention, the density of the ethylene polymer may be from about 0.89 to about 0.96, or from about 0.87 to about 0.94 g/cm ³ . But at the same time, according to another aspect, the density can be from about 0.90 to about 0.96 g/cm ³ , for example, from about 0.91 to about 0.96 g/cm ³ , from about 0.91 to about 0.95 g/cm ³ , or from about 0.91 to about 0.94 g/cm ³ .

Suitable non-limiting ranges for the melt flow index (MI) of the ethylene polymer may include an MI less than or equal to about 25, less than or equal to about 10, less than or equal to about 5, or less than or equal to about 2 g/10 min. In some aspects, the ethylene polymer may have an MI in the range of 0 to about 25, about 0.1 to about 10, about 0.25 to about 5, about 0.5 to about 3, or about 0.5 to about 2 g/10 minutes.

Among other things, the ethylene polymer may have a number average molecular weight (Mn) in the range of from about 5,000 to about 150,000, from about 5,000 to about 50,000, from about 10,000 to about 100,000, or from about 15,000 to about 75,000 g/mol. Additionally or alternatively, the ethylene polymer may have a weight average molecular weight (Mw) in the range of about 50,000 to about 700,000, about 60,000 to about 600,000, about 75,000 to about 500,000, or about 100,000 to about 400,000 g/mol.

Ethylene polymers, be they homopolymers, copolymers, etc., can be molded into a variety of industrial products. Articles that may contain the polymers of the present invention include, but are not limited to, agricultural film, automobile part, bottle, drum, fiber or fabric, food packaging film or container, food service product, fuel tank, geomembrane, a household container, a lining material, a molded article, a medical device or material, a pipe, a sheet or tape, a toy, and the like. For the manufacture of these products, you can use various methods. Non-limiting examples of such methods include injection molding, blow molding, spin molding, film extrusion, sheet extrusion, shaped extrusion, thermoforming, and the like. In addition, additives and modifiers are often added to these polymers to provide efficient processing of the polymer or beneficial properties of the final product. Such methods and materials are described in the Modern Plastics Encyclopedia , Mid-November 1995 Issue, Vol. 72, no. 12; and Film Extrusion Manual - Process, Materials, Properties , TAPPI Press, 1992; the contents of which are incorporated herein by reference in their entirety.

In addition, the present document provides a method for molding or manufacturing an article of industrial production containing a polymer obtained by any of the polymerization methods described herein. For example, the proposed method may include (i) contacting the catalyst composition with an olefin monomer and an optional olefin comonomer under polymerization conditions in a polymerization reactor system to form an olefin polymer, said catalyst composition may contain a metallocene compound, a fluorinated solid oxide as an activator, and an optional co-catalyst (eg, an organoaluminum compound); and (ii) molding an article of industrial production containing an olefin polymer. The molding step may include mixing, melt spinning, extrusion, casting or thermoforming, and the like, including combinations thereof.

EXAMPLES

The present invention is further illustrated by the following examples, which should in no way be construed as limiting the scope of the present invention. Upon reading the description provided herein, one skilled in the art will be able to suggest various other aspects, modifications, and equivalents without departing from the spirit of the present invention or the scope of the appended claims.

Melt flow index (MI, g/10 min) can be determined according to ASTM D1238 at 190 ºC with a load of 2160 grams, and Melt flow index at high load (HLMI, g/10 min) can be determined according to ASTM D1238 at 190 ºC with a load of 21600 gram. Density can be determined in grams per cubic centimeter (g/cm ³ ) using a molded sample that has been cooled at 15 ºC per hour and conditioned for 40 hours at room temperature according to ASTM D1505 and ASTM D4703.

Molecular weights and molecular weight distributions can be determined using a PL-GPC 220 system (Polymer Labs, Agilent Company) equipped with an IR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns (Waters, MA) operating at 145 °C. The flow rate of the mobile phase of 1,2,4-trichlorobenzene (TCB) containing 0.5 g/l of 2,6-di-tert-butyl-4-methylphenol (BHT) was set at 1 ml/min, at the polymer solution concentrations ranged from 1.0 to 1.5 mg/ml depending on the molecular weight. Sample preparation was performed at 150° C. for nominally 4 hours with occasional and gentle agitation, after which the solutions were transferred to sample vials for injection. A sample volume of approximately 200 μl was used. An integral calibration method was used to determine molecular weights and molecular weight distributions using MARLEX® high density polyethylene (HDPE) resin BHB5003 from Chevron Phillips Chemical Company as a standard. In a separate experiment using SEC-MALS, a table with integrated values ​​for the standard was preliminarily generated. Mn is the number average molecular weight, Mw is the weight average molecular weight, Mz is the z-average molecular weight.

The determination of the rheological characteristics of the melt was carried out as follows. Vibrational shear measurements at low strain (10%) were carried out on an Anton Paar MCR 501 rheometer using parallel plate geometry. All rheological tests were carried out at 190°C. Then, the data were substituted into the complex viscosity curve |ƞ * | on frequency (ω) using a modified three-parameter empirical Carro-Yasuda (CY) model to obtain a zero shear viscosity value - ƞ ₀ , a characteristic viscous relaxation time - τ _ƞ and a rheological width parameter - a (parameter CY-a). A simplified empirical Carro-Yasuda (CY) model is presented as follows.

where: : | ƞ* ( ω ) | = magnitude of complex shear viscosity;

ƞ ₀ = viscosity at zero shear;

τ _ƞ = viscous relaxation time (Tau(η) in sec);

a = parameter "rheological width" (parameter CY-a);

n =adjusts the final slope of the exponential function, setpoint 2/11; and

ω = angular frequency of deformation in oscillatory shear.

A detailed description of the significance and explanation of the CY model and the parameters derived from it 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 R. B. Bird, R. C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics , 2nd Edition, John Wiley & Sons (1987); each of which is incorporated herein by reference in its entirety.

Particle size d ₅₀ , or median or average particle size, refers to the particle size at which 50% of the particles in the sample are smaller and 50% of the particles in the sample are larger. Particle size distribution (including d10, d50 and d90) was determined by laser diffraction according to ISO 13320.

The BET specific surface areas described herein were determined using the BET nitrogen adsorption method described in Brunaur et al., J. Am. Chem. soc. , 60, 309 (1938). Total pore volume was determined according to Halsey, GD, J. Chem. Phys. (1948), 16, pp. 931.

EXAMPLES A1-A2

Preparation of Fluorinated Solid Oxide

In example A1, a fluorinated solid oxide was obtained using HBF ₄ , and in example A2, a fluorinated solid oxide was obtained using H ₂ SiF ₆ . ZnO was used as the inorganic base, while the solid oxide was alumina coated with silicon dioxide (Siral® (Siral) 40), containing 40% of the mass. silicon dioxide and 60% of the mass. aluminum oxide. The results of composition calculations for (A1) tetrafluoroboric acid (HBF ₄ ) and (A2) hexafluorosilicic acid (H ₂ SiF ₆ ) are shown in Table I for 5% wt. F or 5 grams F per 100 grams (dry weight) solid oxide. Approximately 1.25 equivalents of ZnO were used for each equivalent of acid, and after the addition of solid oxide, the percentage of solids in the aqueous mixture was 20% by weight.

In these examples, water was first charged into the vessel, then the acidic fluorine compound, and then ZnO, and stirring was carried out until dissolution, which took about 10 minutes. If necessary, an acid-base indicator (eg, methyl orange) can be added to confirm that sufficient ZnO has been added to achieve a generally neutral pH, in this case a pH of approximately 4.5. Depending on the specific conditions, not all of the ZnO may dissolve. After completion of the ZnO addition, the solid oxide was added and stirred for 30 minutes at 25°C to obtain an aqueous suspension. Next, the fluorinated solid oxides were subjected to spray drying.

Table I. Preparation of Fluorinated Solid Oxide

Example A1 A2 Alumina coated with silicon dioxide, dry weight, g 100 100 Measured weight loss (dry/wet) 0.95 0.95 Wet mass of silicon dioxide-alumina, g 105.3 105.3 Target amount of solids twenty% twenty% Required amount of water, g 500 500 Source of fluoric acid HBF ₄ H ₂ SiF ₆ Specified amount of fluoride, % 5% 5% Specified amount of fluoride, g F 5 5 Mw of fluoride source 88 144 % fluoride in source 86.4% 79.2% Required amount of F acid, g 5.79 6.32 Acid source concentration 48% 22.5% Required amount g of acid solution 12.1 28.1 Acid solution density 1.4 1.22 ml of desired acid solution 8.6 23.0 Applicable acid equivalents 0.0658 0.0877 Given excess ZnO 1.25 1.25 Required Zinc Oxide Equivalents 0.0822 0.1096 The required number of moles of zinc oxide 0.0411 0.0548 Mw zinc oxide 81 81 Required amount g
zinc oxide 3.33 4.44 mmol Zn/g silica-alumina 0.41 0.55

EXAMPLES A3-A4

Obtaining a fluorinated solid oxide using an additional amount of metal

Sample A3 was a fluorinated solid oxide obtained according to example A1 using additional impregnation with zinc, and sample A4 was a fluorinated solid oxide obtained according to example A2 using additional impregnation with zinc. The protocol used to prepare samples A3-A4 was the same as in examples A1-A2, except that in examples A3-A4, additional zinc acetate was added after completion of the addition of ZnO to provide a total amount of Zn of about 1 mmol/g solid oxide as shown in Table II.

Table II. Obtaining a fluorinated solid oxide using an additional amount of metal

Example A3 A4 Number of added moles of zinc oxide 0.0411 0.0548 Addition of X Zn added as acetate 1.50 1.00 Number of added moles of zinc acetate 0.0617 0.0548 Mw Zn(OAc) ₂ 183.48 183.48 g added zinc acetate 11.32 10.06 Total mmol Zn/g silica coated alumina 1.028 1.096

EXAMPLES 1-15 and C1-C6

Polymerization experiments with fluorinated solid oxides

In examples 1-14 and C1-C5, the general procedure for polymerization experiments was as follows. The results of the polymerization experiments are summarized in Table III, the experiments themselves being carried out in a 2.2 L autoclave reactor using isobutane (1.2 L) in all experiments. Fluorinated solid oxide, TIBA solution and 3 mg of the metallocene compound (which was 1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)methane dichloride zirconium, a bridged cyclopentadienyl-fluorenylmetallocene compound with a carbon bridge containing methyl and terminal butenyl as substituents) was loaded into the reactor, followed by the addition of isobutane. An excess of metallocene was used so that the activity of the fluorinated solid oxide could be assessed. The contents of the reactor were stirred and heated to the desired polymerization temperature of 95 ^° C. Ethylene was then introduced into the reactor (hydrogen or comonomer was not added) with ethylene added as needed to maintain the set pressure of 400 psig (about 2758 kPa) for the desired reaction time. The temperature in the reactor was maintained at 95°C throughout the cycle using an automatic heating and cooling system. After venting the reactor, purging and cooling, the resulting polymer product was dried under reduced pressure. Examples 15 and C16 used a 4 L steel reactor with 2 L of isobutane, but only 1 mg of the metallocene compound was used.

In examples 1-15, fluorinated solid oxides were prepared as generally described in examples A1-A4, except that ZnO was combined first with water, and then an acidic fluorine compound was added, which was neutralized with ZnO (to a pH in the range from 4 to 5). Most, if not all, of the ZnO has dissolved. In Examples 3-4, additional zinc acetate was added to the aqueous mixture. Silica-coated alumina (40 wt % silica) was then added and mixed for 30 minutes at 25°C followed by spray drying at approximately 100°C. After drying, the catalyst was calcined for 3 hours in air at the appropriate maximum calcination temperature shown in Table III.

In FIG. 1 shows the particle size distribution of the fluorinated solid oxide product prepared according to Example 15, said fluorinated solid oxide product (fluorinated silica coated alumina) having a d10 of 17 µm, a d50 of 49 µm and a d90 of 78 µm in total.

Fig. 2 is a SEM image of the fluorinated solid oxide of Example 15. As shown in FIG. 2 , both fluorine and zinc are well distributed on the surface of the fluorinated solid oxide, which indicates a uniform distribution and efficient use of both fluorine and zinc components in the preparation of the fluorinated solid oxide.

The fluorinated solid oxides in Control Examples C1-C3 were prepared by contacting the silica-coated alumina with an acidic HF solution to allow the fluorine to be absorbed into the solid oxide, and then by spray drying in a commercial spray dryer. The particle size d50 was 37 μm.

The fluorinated solid oxides in Controls C4-C6 were prepared by impregnating silica-coated alumina with a solution of ammonium hydrogen fluoride (C4 and C6) or a solution of HBF ₄ (C5) in methanol (no inorganic base added), drying, and then calcining for 3 hours as shown in Table III. Samples C4-C5 were spray dried while C6 was dried in a drying oven.

To prepare the fluorinated solid oxide, Table III lists the spray drying and calcination conditions, the fluorine compound used and its amount (mmol per gram of solid oxide), the amount of ZnO, the amount of zinc acetate (if used), and the surface area of the fluorinated silica coated alumina. (SA) and total pore volume (PV). For the polymerization experiments, Table III lists the amount of TIBA (triisobutylaluminum) co-catalyst, the amount of fluorinated silica coated alumina (FSCA), the amount of polyethylene produced (g), reaction time (min), catalyst yield (grams PE (polyethylene) per gram FSCA) and catalytic activity (grams PE per gram FSCA per hour).

Samples C1-C3 showed typical catalytic activity - averaging 8600 g/g/hr - using standard HF-formed FSCA. Using the fluorinated solid oxides prepared as described herein, examples 1-14 used laboratory spray drying, and the data appear to indicate that a slightly elevated 650° C. calcination temperature results in higher catalytic activity, in different from the standard 600 °C used in examples C1-C3. It is important to note that samples calcined at 650 ^° C. showed activity comparable, if not better - averaging 9,900 g/g/hr - to that of samples C1-C3.

To determine the effect of ZnO (an inorganic base) on catalytic activity, samples C4-C5 were prepared using standard ammonium hydrogen fluoride as a fluoride source and using HBF ₄ as a fluoride source (as in examples 1-14), but in both cases without adding zinc. Although the main purpose of adding the inorganic base is not related to catalytic activity, it appears that the addition of ZnO resulted in a slight increase in catalytic activity.

Example 15 was a larger scale FSCA study using both spray drying and calcination in pilot plants, this study was conducted under different polymerization conditions which resulted in lower catalytic activity than in examples 1-14. In Example C6, the control catalyst was run under the same conditions, which demonstrated that the catalytic activity of Sample 15 was much higher.

In general, the above examples show that the described processes for the preparation of fluorinated solid oxides provide an activator comparable, if not better, with standard fluorinated solid oxide activators obtained by other methods. However, it is advantageous that such fluorinated solid oxides can be produced at a relatively neutral pH (>4) without the release of potentially hazardous and corrosive hydrogen fluoride fumes.

Table III. Results of the study of samples 1-15 and C1-C6

Example Spray drying
at 100 °C Ignition (air, 3 hours, laboratory) Fluorine compound Fluorine Compound (mmol/g) ZnO
(mmol/g) zinc acetate
(mmol/g) C1 Industrial HF 2.632 0 0 C2 Industrial HF 2.632 0 0 C3 Industrial HF 2.632 0 0 one Lab - Party HBF ₄ 0.658 0.411 0 2 Lab - Party HBF ₄ 0.658 0.411 0 3 Lab - Party HBF ₄ 0.658 0.411 0.589 four Lab - Party HBF ₄ 0.658 0.411 0.589 5 Lab - Party HBF ₄ 0.658 0.411 0 6 Lab - Party HBF ₄ 0.658 0.411 0 7 Lab - Party HBF ₄ 0.658 0.411 0 eight Lab - Party HBF ₄ 0.658 0.411 0 9 Lab - Party HBF ₄ 0.658 0.411 0 ten Lab - Party HBF ₄ 0.658 0.411 0 eleven Lab - Party HBF ₄ 0.658 0.411 0 12 Lab - Party HBF ₄ 0.658 0.411 0 13 Lab - Party HBF ₄ 0.658 0.411 0 fourteen Lab - Party HBF ₄ 0.658 0.411 0 C4 Laboratory _{NH4HF2 _} 0.368 0 0 C5 Laboratory HBF ₄ 0.658 0 0 fifteen Pilot plant Pilot plant - 600 °C HBF ₄ 0.658 0.411 0 C6 Laboratory - drying in a drying oven _{NH4HF2 _} 0.368 0 0

Table III. Results of the study of samples 1-15 and C1-C6 (continued)

Example Solution 1M TIBA FSCA
(G) PE outlet
(G) Time
(min) Exit
(y/y) Activity
(g/g/h) SA
(m ² /g) PV (ml/g) C1 0.5 ml 0.0430 179 26 4163 9606 C2 0.5 ml 0.0295 136 thirty 4610 9220 C3 0.5 ml 0.0497 210 36 4225 7042 one 0.5 ml 0.0267 107 thirty 4007 8015 392 0.961 2 0.5 ml 0.0287 129 31 4495 8700 3 0.5 ml 0.0411 92 17 2238 7900 314 0.908 four 0.5 ml 0.0336 177 32 5268 9877 5 0.5 ml 0.0335 135 37 4030 6535 386 0.932 6 0.5 ml 0.0297 97 33 3266 5938 7 0.5 ml 0.0488 163 thirty 3340 6680 eight 0.5 ml 0.0280 150 43 5357 7475 9 0.5 ml 0.0423 39 63 922 878 ten 0.5 ml 0.0104 52 35 5000 8571 eleven 0.5 ml 0.0138 108 34 7826 13811 12 0.5 ml 0.0339 168 29 4956 10253 13 0.5 ml 0.0291 151 35 5189 8895 343 0.923 fourteen 0.5 ml 0.0210 122 36 5810 9683 C4 0.5 ml 0.0305 136 28 4459 9555 366 0.988 C5 0.5 ml 0.0161 78 32 4845 9084 fifteen 0.4 ml 0.0300 97 thirty 3233 6467 C6 0.4 ml 0.0300 52 thirty 1733 3467

EXAMPLES 16-23

Obtaining a Fluorinated Solid Oxide Using a Sodium Base

Alumina coated with silicon dioxide (Siral® (Siral) 40) was impregnated with hydrofluoric acid to provide 5% of the mass. F, and added sodium carbonate in water to neutralize the acid in an amount equal to the level of sodium indicated in table IV. Sodium was added to neutralize acidity during production of fluorinated silica coated alumina (FSCA). These FSCA supports were then calcined in air at 600° C. for three hours, cooled to room temperature, and purged with dry nitrogen for 30 minutes. A 100 mg sample of each FSCA was introduced into a 4 L stainless steel autoclave along with 0.4 ml of triisobutylaluminum (TIBA) and 0.2 mg of the bridged metallocene compound dichloride (1-(methyl)-1-(3-butenyl)-1 -(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)methane zirconium, a bridged cyclopentadienyl-fluorenylmetallocene compound with a carbon bridge containing methyl and terminal butenyl as substituents.Two liters of liquid isobutane were then added, and the temperature of the reactor was raised to 90°C and maintained at this temperature throughout the experiment.Ethylene was added at a pressure of 390 psig (about 2689 kPa), while it was supplied as needed at the indicated pressure for 30 minutes.After venting the reactor, purging and cooling, the resulting polymer the product was dried under reduced pressure.

Table IV summarizes the results obtained in examples 16-23. Activity was calculated based on the amount of polymer produced per gram of FSCA and time allowed. The addition of sodium led to a change in the molecular weight and rheological properties of the resulting polymer. Although sodium carbonate reduced the acidity, it also unacceptably reduced the activity of the catalyst when increasing amounts of sodium were added.

EXAMPLES 24-30

Obtaining a fluorinated solid oxide using magnesium.

In examples 24-30, the same procedure was used as in examples 16-23, except that during the preparation of FSCA, magnesium nitrate was added rather than sodium base. After preparation, the FSCA supports were dried and calcined at 475°C, and then polymerization experiments were carried out similar to examples 16-23. Table V summarizes the results obtained in examples 24-30. Surprisingly, the addition of magnesium nitrate did not affect activity, regardless of the amount added. In addition, this addition did not affect the molecular weight and rheological properties of the polymer.

EXAMPLES 31-32

Obtaining Fluorinated Solid Oxide Using Various Magnesium Bases

In example 31, 6.9 ml of a solution of 22.5% of the mass. H ₂ SiF ₆ was added to 30 ml of water to obtain an acidic solution with a pH of approximately 1.0. Magnesium carbonate was added to neutralize the acidity, which generated CO ₂ gas. The addition was continued until the formation of gas ceased, which occurred with the introduction of 2.2 g of MgCO ₃ , which is approximately 2 mol of Mg per mol of acid H ₂ SiF ₆ used. The addition of magnesium carbonate raised the pH of the resulting mixture to about 5.1. 30 g of Siral® (Siral) 40 silica coated alumina was then added to this mixture. After stirring for 5 minutes, the FSCA was removed, dried in a vacuum oven at 110° C. overnight, and passed through a 35 mesh sieve. Then a sample of this powder weighing 10 g was calcined in a fluidized bed at 600°C for three hours, similarly to how it was done in examples 16-23. Next, polymerization experiments were carried out similar to examples 16-23 using 100 mg of FSCA, 0.4 ml of 1M TIBA and 2 mg of bridged metallocene. In Example 31, three experiments were carried out with FSCA prepared using MgCO ₃ and unexpectedly high activity values were obtained: 7160 g/g/h, 7600 g/g/h and 7740 g/g/h.

Example 32 used the same procedure as in example 31, except that the same molar amount of Mg was introduced into hexafluorosilicic acid in the form of magnesium hydroxide. The polymerization conditions were the same. Two experiments were carried out with FSCA prepared using Mg(OH) ₂ and, analogously to Example 31, unexpectedly high activity values were obtained in Example 32: 6840 g/g/h and 6400 g/g/h.

Table IV. Results of the study of samples 16-23

Example Na
(% mass) Activity (g/g/h) Mn (kg/mol) Mw (kg/mol) Mz (kg/mol) 16 0 4160 150 369 720 17 0.02 3905 150 371 726 eighteen 0.05 3285 153 374 724 19 0.10 3221 150 371 725 twenty 0.15 2685 150 368 717 21 0.20 2431 152 375 734 22 0.25 2262 151 381 748 23 0.30 1854 152 384 764

Table IV. Results of the study of samples 16-23 (continued)

Example η ₀ (Pa-sec) τ _η (sec) CY-a MI
(g/10 min) HLMI
(g/10 min) Tan-d @1/sec 16 261764 0.398 0.448 0.035 0.647 4.024 17 317233 0.484 0.458 0.029 0.520 3.811 eighteen 351600 0.540 0.458 0.026 0.476 3.654 19 416833 0.595 0.461 0.022 0.391 3.546 twenty 528850 0.847 0.478 0.017 0.297 3.209 21 720100 0.959 0.482 0.012 0.200 3.088 22 849700 1.123 0.503 0.010 0.158 3.009 23 991800 1.510 0.521 0.008 0.137 2.743

Table V. Results of the study of samples 24-30

Example mg
(% mass) Activity (g/g/h) Mn (kg/mol) Mw (kg/mol) Mz (kg/mol) 24 0 1680 160 421 895 25 0.02 1060 174 461 998 26 0.05 1700 153 412 874 27 0.10 1660 150 424 942 28 0.15 1160 167 464 1019 29 0.22 1940 139 406 987 thirty 0.30 1260 132 462 1104

Table V. Results of the study of samples 24-60 (continued)

Example η ₀ (Pa-sec) τ _η (sec) CY-a MI
(g/10 min) HLMI
(g/10 min) Tan-d @ 0.1/sec 24 8.39E+05 1.40 0.474 0.011 0.193 2.63 25 1.39E+06 2.10 0.464 0.006 0.115 2.24 26 9.34E+05 1.29 0.463 0.009 0.166 2.67 27 1.09E+06 1.55 0.433 0.009 0.162 2.39 28 1.31E+06 1.91 0.470 0.007 0.118 2.34 29 7.09E+06 1.19 0.448 0.013 0.253 2.67 thirty 1.47E+06 2.17 0.447 0.006 0.115 2.17

The present invention has been described above with reference to numerous aspects and specific examples. Those skilled in the art can offer many options in view of the above detailed description. All such obvious variations are within the intended full scope of the appended claims. Other aspects of the present invention may include, but are not limited to, the following aspects (aspects are described as "comprising" but alternatively may "consist essentially of" or "consist of"):

Aspect 1. A method for producing a fluorinated solid oxide, comprising:

(a) contacting an acidic fluorine compound and an inorganic base to form an aqueous mixture having a pH of at least about 4; and

(b) contacting the solid oxide with said aqueous mixture to form a fluorinated solid oxide.

Aspect 2. The method defined according to aspect 1 wherein the acidic fluoro compound and the inorganic base are brought into contact at any suitable acid:base equivalent ratio or acid:base equivalent ratio within any of the ranges recited herein, e.g., from about 1, 3:1 to about 1:3, about 1.2:1 to about 1:2, about 1:1 to about 1:2, about 1:1.1 to about 1:1.8, etc. d.

Aspect 3. The method defined according to aspect 1 or 2, wherein said aqueous mixture is a solution.

Aspect 4. The method defined according to aspect 1 or 2, wherein said aqueous mixture is a suspension.

Aspect 5. The method defined according to any one of aspects 1-4, wherein in step (a) the acidic fluoro compound is first contacted with water and then with an inorganic base to form an aqueous mixture.

Aspect 6. The method defined according to any one of aspects 1-4, wherein in step (a) the inorganic base is first contacted with water and then with an acidic fluorine compound to form an aqueous mixture.

Aspect 7 A method as defined in any of the preceding aspects, wherein in step (a) a metal-containing compound is contacted with an acidic fluorine-containing compound and an inorganic base.

Aspect 8 The method defined according to aspect 7, wherein the metal-containing compound comprises any suitable organozinc compound or any organozinc compound described herein, eg, zinc acetate, zinc formate, etc.

Aspect 9. The method defined according to aspect 7 or 8, wherein the fluorinated solid oxide contains any suitable amount of a metal of a metal-containing compound (for example, zinc) or an amount of a metal of a metal-containing compound (for example, zinc) in any of the ranges given herein, for example, from about 0.5 to about 10% wt., from about 1 to about 8% wt., from about 1 to about 4% wt. etc. based on the weight of the fluorinated solid oxide.

Aspect 10. A method for producing a fluorinated solid oxide, comprising:

(A) bringing the acidic fluorine compound into contact with a solid oxide to obtain a mixture; and

(B) contacting the resulting mixture with an inorganic base to form a fluorinated solid oxide at a pH of at least about 4.

Aspect 11. The method defined according to aspect 10, characterized in that said method comprises any suitable acid:base equivalent ratio of the acid fluoride compound and the inorganic base or acid:base equivalent ratio within any of the ranges provided herein, e.g., from about 1 3:1 to about 1:3, about 1.2:1 to about 1:2, about 1:1 to about 1:2, about 1:1.1 to about 1:1.8, etc. .d.

Aspect 12 The method defined according to aspect 10 or 11 wherein the metal-containing compound is contacted with said mixture and an inorganic base in step (B).

Aspect 13 The method defined according to aspect 12, wherein the metal-containing compound comprises any suitable organozinc compound or any organozinc compound described herein, eg, zinc acetate, zinc formate, etc.

Aspect 14. The method defined according to aspect 12 or 13, wherein the fluorinated solid oxide contains any suitable amount of a metal of a metal-containing compound (for example, zinc) or an amount of a metal of a metal-containing compound (for example, zinc) in any of the ranges given herein, for example, from about 0.5 to about 10% wt., from about 1 to about 8% wt., from about 1 to about 4% wt. etc. based on the weight of the fluorinated solid oxide.

Aspect 15 The method as defined in any of the preceding aspects, wherein the acidic fluoride compound comprises any suitable acidic fluoride compound or any acidic fluorine compound described herein, e.g., hydrogen fluoride (HF), acid ammonium fluoride (NH ₄ HF ₂ ), triflate acid (CF ₃ SO ₃ H), tetrafluoroboric acid (HBF ₄ ), hexafluorosilicic acid (H ₂ SiF ₆ ), hexafluorophosphoric acid (HPF ₆ ), etc. or any combination of them.

Aspect 16 The method as defined in any of the preceding aspects, wherein the acidic fluoro compound comprises tetrafluoroboric acid (HBF ₄ ), hexafluorosilicic acid (H ₂ SiF ₆ ), or both.

Aspect 17. The method defined according to any of the preceding aspects, wherein the inorganic base includes any suitable inorganic base or any inorganic base described herein, for example, a zinc-containing inorganic base, an aluminum-containing inorganic base, an iron-containing inorganic base, a manganese-containing inorganic base, a calcium-containing an inorganic base, a magnesium-containing inorganic base, or any combination thereof.

Aspect 18. The method defined according to any of the preceding aspects, wherein the inorganic base includes any suitable inorganic base or any inorganic base described herein, for example, ZnO, Zn(OH) ₂ , ZnCO ₃ , Al(OH) ₃ , Al ₂ O ₃ , AlOOH, Fe ₂ O ₃ , Fe(OH) ₃ , Fe(OH) ₂ , MnO ₂ , Mn(OH) ₂ , Ca(OH) ₂ , CaCO ₃ , Mg(OH) ₂ , MgCO ₃ etc. or any combination of them.

Aspect 19 The method as defined in any of the preceding aspects, wherein the inorganic base comprises ZnO, Zn(OH) ₂ , ZnCO ₃ or any combination thereof.

Aspect 20. A method as defined in any of the preceding aspects, wherein the pH is in any suitable range or any range provided herein, for example, from about 4 to about 8, from about 4 to about 7.5, from about 4 to about 6, from about 4 to about 5.5, from about 4 to about 5, from about 4.2 to about 7.5, from about 4.2 to about 6.8, from about 4.2 to about 5 .5, about 4.5 to about 7.5, about 4.5 to about 6.5, about 5 to about 8, about 5 to about 7, about 5 to about 6, etc.

Aspect 21. The method defined according to any of the preceding aspects, wherein the solid oxide comprises any suitable solid oxide or any solid oxide described herein, for example, alumina, titanium dioxide, zirconia, magnesium oxide, boron oxide, silicon dioxide -alumina, silica-coated alumina, silica-titanium dioxide, silica-zirconia, alumina-boron oxide, etc. or any combination of them.

Aspect 22 The method as defined in any of the preceding aspects, wherein the fluorinated solid oxide comprises any suitable fluorinated solid oxide or any fluorinated solid oxide described herein, e.g., fluorinated alumina, fluorinated titania, fluorinated zirconia, fluorinated oxide magnesium, fluorinated boron oxide, fluorinated silica-alumina, fluorinated silica-coated alumina, fluorinated silica-titanium dioxide, fluorinated silica-zirconia, fluorinated alumina-boron oxide, etc. or any combination of them.

Aspect 23 A method as defined in any of the preceding aspects wherein the solid oxide comprises silica coated alumina.

Aspect 24 The method as defined in any of the preceding aspects wherein the fluorinated solid oxide comprises fluorinated silica coated alumina.

Aspect 25 The method as defined in any one of aspects 21-24, wherein the silica coated alumina comprises any suitable amount of silica, or an amount of silica within any of the ranges recited herein, such as from about 10 to about 80 % wt., from about 20 to about 70% wt., from about 25 to about 50% wt. etc. based on the mass of alumina coated with silicon dioxide.

Aspect 26. The method defined according to any of the preceding aspects, wherein the fluorinated solid oxide contains any suitable amount of fluorine or an amount of fluorine in any range given herein, for example, from about 0.5 to about 15% wt., from about 1 to about 12% wt., from about 2 to about 9% wt. etc. based on the weight of the fluorinated solid oxide.

Aspect 27 The method as defined in any of the preceding aspects, wherein the fluorinated solid oxide comprises any suitable amount of an inorganic base metal (e.g., Zn, Fe, Mn, Ca, and Mg, alone or in any combination) or an amount of an inorganic base metal in any range given in this document, for example, from about 0.5 to about 15 wt. -%, from about 1 to about 10 wt. -%, from about 1.5 to about 8% of the mass. etc. based on the weight of the fluorinated solid oxide.

Aspect 28. The method defined according to any of the preceding aspects, wherein the fluorinated solid oxide has any suitable pore volume or pore volume in any range given herein, for example, from about 0.5 to about 2.5 ml/g, from about 0.5 to about 2 ml/g, from about 0.7 to about 1.5 ml/g, etc.

Aspect 29 The process as defined in any of the preceding aspects, wherein the fluorinated solid oxide has any suitable BET surface area or BET specific surface area in any of the ranges provided herein, for example, from about 150 to about 700 m ² /g, from about 200 to about 700 m ² /g, from about 250 to about 500 m ² /g, etc.

Aspect 30. A process as defined in any of the preceding aspects, wherein the fluorinated solid oxide has any suitable average particle size (d50) or average particle size in any of the ranges herein, such as from about 10 to about 500 microns, from about 25 to about 200 microns, from about 20 to about 100 microns, etc.

Aspect 31. The method defined according to any of the preceding aspects, further comprising the step of drying the fluorinated solid oxide using any suitable method or any method described herein, for example, subjecting the fluorinated solid oxide to elevated temperature and optionally subatmospheric pressure, spray drying fluorinated solid oxide, etc.

Aspect 32. A method as defined in any of the preceding aspects, further comprising the step of calcining the fluorinated solid oxide at any suitable maximum calcination temperature or temperature within any range recited herein, for example, from about 400°C to about 1000°C, from about 400° C. to about 900 ^° C., from about 500° C. to about 800° C., etc.

Aspect 33 A fluorinated solid oxide prepared by a method defined in accordance with any one of the preceding aspects.

Aspect 34 A catalyst composition comprising a metallocene compound, a fluorinated solid oxide as defined in Aspect 33, and an optional co-catalyst.

Aspect 35 A composition as defined in aspect 34 wherein the metallocene compound includes any suitable metallocene compound or any metallocene compound described herein.

Aspect 36 A composition as defined in Aspect 34 or 35 wherein the metallocene compound comprises a zirconium or hafnium based non-bridged metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group.

Aspect 37 A composition as defined in any one of aspects 34-36 wherein the metallocene compound comprises a bridged zirconium or hafnium metallocene compound with a fluorenyl group.

Aspect 38 A composition as defined in any one of aspects 34-37 wherein the metallocene compound comprises a zirconium or hafnium bridged metallocene compound with a cyclopentadienyl group and a fluorenyl group.

Aspect 39 A composition as defined in any one of aspects 34-38, wherein said catalyst composition contains only one metallocene compound.

Aspect 40 A composition as defined in any one of aspects 34-38, wherein said catalyst composition contains two or more metallocene compounds.

Aspect 41 A composition as defined in any one of aspects 34-40, wherein said catalyst composition comprises a cocatalyst, for example any cocatalyst described herein.

Aspect 42 The composition as defined in Aspect 41 wherein the cocatalyst 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.

Aspect 43 The composition as defined in aspect 41 wherein the cocatalyst comprises any suitable organoaluminum compound or any organoaluminum compound described herein.

Aspect 44 A composition as defined in any one of aspects 34-41, wherein said catalyst composition is substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, or combinations thereof.

Aspect 45 A composition as defined in any one of aspects 34-44, wherein the catalyst activity of the catalyst composition is within any of the ranges recited herein, such as greater than about 2000 grams, greater than about 4000 grams, greater than about 6000 grams, etc. polyethylene per gram of fluorinated solid oxide per hour under slurry polymerization conditions using triisobutylaluminum as a co-catalyst and isobutane as a diluent and at a polymerization temperature of 95° C. and a reactor pressure of 400 psig (about 2758 kPa).

Aspect 46. A process for polymerizing olefins comprising contacting the catalyst composition defined in any one of aspects 34-45 with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to form an olefin polymer.

Aspect 47. A process for the polymerization of olefins, comprising:

the method defined according to any one of aspects 1-32;

contacting a fluorinated solid oxide, a metallocene compound, and an optional co-catalyst to form a catalyst composition; and

contacting the catalyst composition with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to form an olefin polymer.

Aspect 48 The olefin polymerization process as defined in aspect 46 or 47, wherein the olefin monomer comprises any olefin monomer described herein, for example, any C ₂ -C ₂₀ olefin.

Aspect 49 A process for the polymerization of olefins as defined in any one of aspects 46-48, wherein the olefin monomer and the optional olefin comonomer independently comprise a C ₂ -C ₂₀ alpha olefin.

Aspect 50. A process for the polymerization of olefins as defined in any one of aspects 46-49, wherein the olefin monomer comprises ethylene.

Aspect 51 An olefin polymerization process as defined in any one of aspects 46-50, wherein the catalyst composition is contacted with ethylene and an olefin comonomer comprising a C ₃ -C ₁₀ alpha olefin.

Aspect 52 An olefin polymerization process as defined in any one of aspects 46-51, wherein the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Aspect 53 A process for the polymerization of olefins as defined in any one of aspects 46-49, wherein the olefin monomer comprises propylene.

Aspect 54. An olefin polymerization process as defined in any one of aspects 46-53, 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.

Aspect 55. An olefin polymerization process as defined in any one of aspects 46-54, wherein the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof.

Aspect 56. An olefin polymerization process as defined in any one of aspects 46-55, wherein the polymerization reactor system comprises a slurry loop reactor.

Aspect 57. An olefin polymerization process as defined in any one of Aspects 46-56, wherein the polymerization reactor system comprises a single reactor.

Aspect 58 An olefin polymerization process as defined in any one of Aspects 46-56, wherein the polymerization reactor system comprises 2 reactors.

Aspect 59. An olefin polymerization process as defined in any one of Aspects 46-56, wherein the polymerization reactor system comprises more than 2 reactors.

Aspect 60. A process for the polymerization of olefins as defined in any one of aspects 46-59, wherein the olefin polymer includes any of the olefin polymers described herein.

Aspect 61. An olefin polymerization process defined according to any one of aspects 46-52 or 54-60, 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 .

Aspect 62 The process for polymerizing olefins as defined in any one of aspects 46-49 or 53-60, wherein the olefin polymer comprises a polypropylene homopolymer and/or a propylene-based copolymer.

Aspect 63. An olefin polymerization process as defined in any one of aspects 46-62, wherein the polymerization conditions comprise a polymerization reaction temperature in the range of about 60°C to about 120°C and a reaction pressure in the range of about 200 to about 1000 psig. about 1.4 to about 6.9 MPa).

Aspect 64 A process for the polymerization of olefins as defined in any one of aspects 46-63, wherein the polymerization conditions are substantially constant, for example, to produce a specific grade of polymer.

Aspect 65 An olefin polymerization process as defined in any one of aspects 46-64, wherein no hydrogen is added to the polymerization reactor system.

Aspect 66 An olefin polymerization process as defined in any one of aspects 46-64, wherein hydrogen is added to the polymerization reactor system.

Aspect 67. A process for polymerizing olefins as defined in any one of aspects 46-66, wherein the number average molecular weight (Mn) of the olefin polymer is in any of the ranges recited herein, such as from about 5,000 to about 150,000 g/mol, from about 5,000 to about 50,000 g/mol, about 10,000 to about 100,000 g/mol, etc.

Aspect 68. A process for polymerizing olefins as defined in any one of aspects 46-67, wherein the weight average molecular weight (Mw) of the olefin polymer is within any of the ranges recited herein, such as from about 50,000 to about 700,000 g/mol, from about 75,000 to about 500,000 g/mol, from about 100,000 to about 400,000 g/mol, etc.

Aspect 69. An olefin polymerization process as defined in any one of aspects 46-68, wherein the density of the olefin polymer is in any of the ranges provided herein, such as from about 0.89 to about 0.96 g/cm ³ , from about 0.91 to about 0.95 g/cm ³ , about 0.91 to about 0.94 g/cm ³ , etc.

Aspect 70. A process for polymerizing olefins as defined in any one of aspects 46-69, wherein the melt flow index (MI) of the olefin polymer is in any of the ranges recited herein, such as from 0 to about 25 g/10 min, from about 0.1 to about 10 g/10 min, about 0.5 to about 3 g/10 min, etc.

Aspect 71 An olefin polymer obtained from an olefin polymerization process as defined in any one of Aspects 46-70.

Aspect 72 An article of manufacture comprising an olefin polymer as defined in Aspect 71.

Claims (53)

1. A method for producing a fluorinated solid oxide, including: (a) contacting an acidic fluorine compound and an inorganic base to form an aqueous mixture having a pH of at least 4; and (b) contacting the solid oxide with said aqueous mixture to form a fluorinated solid oxide. 2. The method according to claim 1, in which: the acidic fluoro compound and the inorganic base are brought into contact with an acid:base equivalent ratio ranging from 1:1 to 1:2; and in step (a) the acidic fluorine compound is first contacted with water and then with an inorganic base to obtain an aqueous mixture, or in step (a) the inorganic base is first contacted with water and then with the acidic fluorine compound to obtain water mixture. 3. The method according to claim 1 or 2, in which: additionally, the metal-containing compound is brought into contact with an acidic fluorine-containing compound and an inorganic base in step (a); and fluorinated solid oxide additionally contains from 0.5 to 10% of the mass. the metal of the metal-containing compound, based on the weight of the fluorinated solid oxide. 4. A method for producing a fluorinated solid oxide, including: (A) bringing the acidic fluorine compound into contact with a solid oxide to obtain a mixture; and (B) contacting the resulting mixture with an inorganic base to form a fluorinated solid oxide at a pH of at least 4. 5. The method according to claim 4, characterized in that said method comprises an equivalent ratio of acid : base of the acidic fluoro compound to an inorganic base in the range of 1:1 to 1:2. 6. The method according to claim 4 or 5, in which: additionally, the metal-containing compound is brought into contact with said mixture and an inorganic base in step (B); and fluorinated solid oxide additionally contains from 0.5 to 10% of the mass. the metal of the metal-containing compound, based on the weight of the fluorinated solid oxide. 7. The method according to any one of the preceding claims, wherein the inorganic base includes a zinc-containing inorganic base, an aluminum-containing inorganic base, an iron-containing inorganic base, a manganese-containing inorganic base, a calcium-containing inorganic base, a magnesium-containing inorganic base, or any combination thereof. 8. A method according to any one of the preceding claims, wherein: the acidic fluorine compound includes hydrogen fluoride (HF), ammonium acid fluoride (NH ₄ HF ₂ ), triflate acid (CF ₃ SO ₃ H), tetrafluoroboric acid (HBF ₄ ), hexafluorosilicic acid (H ₂ SiF ₆ ), hexafluorophosphoric acid (HPF ₆ ) or any combination thereof; and inorganic base includes ZnO, Zn(OH) ₂ , ZnCO ₃ , Al(OH) ₃ , Al ₂ O ₃ , AlOOH, Fe ₂ O ₃ , Fe(OH) ₃ , Fe(OH) ₂ , MnO ₂ , Mn(OH ) ₂ , Ca(OH) ₂ , CaCO ₃ , Mg(OH) ₂ , MgCO ₃ or any combination thereof. 9. A method according to any one of the preceding claims, wherein: the acidic fluorine compound includes tetrafluoroboric acid (HBF ₄ ), hexafluorosilicic acid (H ₂ SiF ₆ ), or both; the inorganic base includes ZnO, Zn(OH) ₂ , ZnCO ₃ or any combination thereof; and fluorinated solid oxide contains from 0.5 to 15% of the mass. Zn based on the weight of the fluorinated solid oxide. 10. A method according to any one of the preceding claims, wherein: pH is from 4 to 8; and fluorinated solid oxide contains from 0.5 to 15% of the mass. F based on the weight of the fluorinated solid oxide. 11. A method according to any one of the preceding claims, wherein: the fluorinated solid oxide has a total pore volume of 0.5 to 2.5 ml/g, a BET specific surface area of 150 to 700 m ² /g, and an average particle size (d50) of 20 to 100 microns; and the fluorinated solid oxide includes fluorinated alumina, fluorinated titanium dioxide, fluorinated zirconia, fluorinated magnesium oxide, fluorinated boron oxide, fluorinated silica-alumina, fluorinated silica-coated alumina, fluorinated silica-titania, fluorinated silica -zirconia, fluorinated alumina-boron oxide, or any combination thereof. 12. A method according to any one of the preceding claims, wherein the solid oxide comprises silica-coated alumina. 13. The method according to p. 12, in which the alumina coated with silicon dioxide contains from 25 to 50% of the mass. silicon dioxide based on the mass of alumina coated with silicon dioxide. 14. A method according to any one of the preceding claims, further comprising the step of spray drying the fluorinated solid oxide. 15. A method according to any one of the preceding claims, further comprising the step of calcining the fluorinated solid oxide. 16. Fluorinated solid oxide obtained by the method according to any one of the preceding paragraphs. 17. An olefin polymerization catalyst composition comprising a metallocene compound, the fluorinated solid oxide of claim 16, and an optional co-catalyst. 18. A method for producing a catalytic composition, including: (i) a method according to any one of paragraphs. 1-13; (ii) drying and calcining the fluorinated solid oxide; and (iii) contacting a fluorinated solid oxide, a metallocene compound, and a co-catalyst to form a catalyst composition. 19. The method of polymerization of olefins, including: contacting the catalyst composition of claim 17 with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to form an olefin polymer. 20. The method according to claim 19, in which: the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof; and the olefin monomer includes ethylene, and the olefin comonomer includes 1-butene, 1-hexene, 1-octene, or a combination thereof. 21. The method according to claim 19 or 20, in which: the olefin polymer includes an ethylene homopolymer and/or an ethylene/α-olefin copolymer; and the catalytic composition contains an organoaluminum cocatalyst. 22. The method of polymerization of olefins, including: (i) a method according to any one of paragraphs. 1-13; (ii) drying and calcining the fluorinated solid oxide; (iii) contacting a fluorinated solid oxide, a metallocene compound, and an optional co-catalyst to form a catalyst composition; and (iv) contacting the catalyst composition with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to form an olefin polymer.

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