ACTIVATING SUPPORTS OF ALUMINES COATED WITH SILICA FOR METALLOCENE CATALYST COMPOSITIONS

专利摘要:
silica-coated alumina activating supports for metallocene catalyst compositions. silica-coated alumina activating supports and catalyst compositions containing these activating supports are disclosed. methods are also provided for preparing silica-coated alumina activator support, for preparing catalyst compositions, and for using catalyst compositions to polymerize olefins.
公开号:BR112012006685B1
申请号:R112012006685-4
申请日:2010-09-22
公开日:2020-03-10
发明作者:Max P. McDaniel；Qing Yang；Randall S. Muninger；Elizabeth A. Benham；Kathy S. Collins
申请人:Chevron Phillips Chemical Company Lp；
IPC主号:

专利说明:

ACTIVATING SUPPORTS OF ALUMINES COATED WITH SILICA FOR METALLOCENE CATALYST COMPOSERS
CROSS REFERENCE TO RELATED APPLICATIONS The application is partly a continuation of co-pending U.S. Patent Application No. 12 / 052,620, filed on March 20, 2008, the disclosure of which is incorporated herein in full by reference.
BACKGROUND OF THE INVENTION The present invention generally relates to the field of olefin polymerization catalysis, catalyst compositions, methods for the polymerization and co-polymerization of olefins and polyolefins. More specifically, this invention relates to chemically treated silica coated alumina activating supports and catalyst compositions employing these activating supports.
SUMMARY OF THE INVENTION The present invention is directed generally towards chemically treated silica coated alumina activating supports, catalyst compositions employing these supports, methods for preparing activating supports and catalyst compositions, methods for using the catalyst compositions to polymerize olefins, the resins of polymer produced using such catalyst compositions, and articles produced using these polymer resins. Specifically, the present invention relates to chemically treated silica coated alumina activating supports and catalyst compositions employing such activating supports. The catalyst compositions containing silica-coated alumina activating supports of the present invention can be used to produce, for example, ethylene-based homopolymers, copolymers, terpolymers and the like.
In the aspects of the present invention, activating supports are disclosed comprising at least one silica-coated alumina treated with at least one electron withdrawing anion. Generally, these silica coated aluminas have an alumina to silica weight ratio of about 1: 1 to about 100: 1, for example, about 2: 1 to about 20: 1. At least one electron withdrawing anion can comprise fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, and the like, or any combination thereof. In addition, two or more electron withdrawing anions can be employed, or any combination thereof. In addition, two or more electron withdrawing anions may be employed, examples of which may include, but are not limited to, fluoride and phosphate, fluoride and sulfate, chloride and phosphate, chloride and sulfate, triflate and sulfate, or triflate and phosphate , and the like.
Catalyst compositions containing these silica coated activator supports are also disclosed in the present invention. In one aspect, the catalyst composition can comprise at least one transition metal compound or metallocene compound and at least one activator support. At least one activator support can comprise at least one silica-coated alumina having a weight ratio of alumina to silica in a range of about 1: 1 to about 100: 1, and is treated with at least one anion removal anion. electrons such as fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate and the like, or combinations thereof. This catalyst composition may further comprise at least one organoaluminium compound. In other respects, the catalyst composition - comprising at least one transition metal or metallocene compound and at least one activating support - can further comprise at least one optional co-catalyst. Optional co-catalysts suitable in this regard may include, but are not limited to, aluminoxane compounds, organoboro or organoborate compounds, ionizing ionic compounds, and the like, or combinations thereof.
Another catalyst composition contemplated herein comprises at least one transition metal or metallocene compound, at least one organoaluminium compound, and at least one activator support. At least one organoaluminium compound may comprise, for example, trimethylaluminum, triethylalumin, tri-n-propylalumin, tri-n-butylalumin, triisobutylalumin, tri-n-hexylalumin, tri-n-octylalumin, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or combinations thereof. At least one activating support comprises at least one silica-coated alumina treated with at least one electron withdrawing anion, such as those electron withdrawing anions described herein. Silica-coated alumina has a weight ratio of alumina to silica in a range of about 1: 1 to about 100: 1, or about 2: 1 to about 20: 1, in aspects of the invention.
The catalyst compositions disclosed herein can be used to polymerize olefins to form homopolymers, copolymers and the like. Such an olefin polymerization process may comprise contacting a catalyst composition of the present invention with at least one olefin monomer and optionally at least one olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises at least a transition metal or metallocene compound and at least one activating support. As disclosed, at least one activating support comprises at least silica-coated alumina treated with at least one electron withdrawing anion, and silica-coated alumina generally has a weight ratio of alumina to silica in a range of about 1: 1 to about 100: 1. Other co-catalysts, including organoaluminium compounds, can be used in the olefin polymerization process.
Polymers produced from the polymerization of olefins, resulting in homopolymers, and the like, can be used to produce various articles of manufacture.
BRIEF DESCRIPTION OF THE FIGURES FIG. 1 presents a graphical representation of catalyst activity, in units of grams of polyethylene per gram of activating support (AS) per hour, versus the concentration of MET 1, in units of micromols of MET 1 per gram of AS, for the activating supports of Examples 1-3. FIG. 2 presents a graphical representation of catalyst activity, in units of grams of polyethylene per gram of MET 1 per hour, versus the concentration of MET 1, in units of micromols of MET 1 per gram of activating support (AS), for activating supports Examples 1-3. FIG. 3 presents a graphical representation of catalyst activity, in units of grams of polyethylene per gram of AS per hour, versus the concentration of MET 2, in units of micromols of MET 2 per gram of AS, for the activating supports of Examples 1-3 . FIG. 4 presents a graphical representation of the catalyst activity, in units of grams of polyethylene per gram of MET 2 per hour, versus the concentration of MET 2, in units of micromols of MET 2 per gram of AS, for the activating supports of Examples 1- 3. FIG. 5 shows a graphical representation of catalyst activity, in units of grams of polyethylene per hour, for the pre-contacted catalyst system and the non-pre-contacted catalyst system of Example 6. FIG. 6 shows a graphical representation of catalyst activity, in units of grams of polyethylene per gram of AS per hour, versus the concentration of MET 3, in units of micromols of MET 3 per gram of AS, for the activating supports of Examples 2-3 .___________________________________ FIG. 7 presents a graphical representation of catalyst activity, in units of grams of polyethylene per gram of MET 3 per hour, versus the concentration of MET 3, in units of micromols of MET 3 per gram of AS, for the activating supports of Examples 2- 3.
DEFINITIONS
To more clearly define the terms used here, the following definitions are provided. To the extent that any definition or use provided by any document incorporated herein by reference conflicts with the definition or use provided here, the definition or use contained herein will prevail. The term "polymer" is used here generally to include homopolymers, copolymers, olefin terpolymers and so on. A copolymer is derived from an olefin monomer and an olefin comonomer, while a terpolymer is derived from an olefin monomer and two olefin comonomers. Accordingly, "polymer" comprises copolymers, terpolymers, etc., derived from any olefin monomer and comonomer (s) disclosed herein. Similarly, an ethylene polymer would include ethylene homopolymers, ethylene copolymers, ethylene terpolymers, and the like. As an example, an olefin copolymer, such as an ethylene copolymer, can be derived from ethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene.
If the monomer and comonomer are ethylene and 1-hexene, respectively, the resulting polymer would be categorized as an ethylene / 1-hexene copolymer.
Similarly, the scope of the term "polymerization" includes homopolymerization, copolymerization, terpolymerization, etc. Therefore, a copolymerization process would involve contacting an olefin monomer (for example, ethylene) and an olefin comonomer (for example, 1-hexene) to produce a copolymer. The term "co-catalyst" is generally used to refer to organoaluminium compounds that can form a component of a catalyst composition. In addition, "co-catalyst" also refers to other optional components of a catalyst composition, including, but not limited to, aluminoxanes, organoboro or organoborate compounds, and ionizing ion compounds, as disclosed herein. The term “co-catalyst” is used regardless of the actual function of the compound or any chemical mechanism by which the compound can operate. In one aspect of this invention, the term "co-catalyst" is used to distinguish that component of the transition metal catalyst composition or metallocene compound .______________________________________________ The term "fluorganoboro compound" is used here with its common meaning to refer to neutral compounds of the BY3 form. The term "fluorgan borate compound" also has its common meaning to refer to the monoanionic salts of a fluorganoboro compound of the form [cation] + [BY4] ", where Y represents a fluorinated organic group. Materials of these types are generally and collectively referred to as “organoboro or organoborate compounds.” The term “contact product” is used here to describe compositions in which components are brought into contact in any order, in any form, and for any period of time. components can be contacted by mixing or mixing In addition, the contact of any component can occur in the presence or absence of any other component of the compositions described here. The combination of additional materials or components can be done by any suitable method. the term “contact product” includes mixtures, solutions, slurries, reaction products, and the like, or their Although “contact product” may include reaction products, the respective components are not required to react with each other. Similarly, the term “contact” is used here to refer to materials that can be mixed, made into slurry, dissolved, reacted, treated, or otherwise brought into contact in some other way. The term "pre-contacted" mixture is used here to describe a first mixture of catalyst components that are contacted for a first period of time before the first mixture is used to form a second mixture or "post-contacted" mixture of catalyst components. who are contacted for a second period of time. The pre-contacted mixture often describes a mixture of metallocene or transition metal compound (or compounds), olefin monomer (or monomers), and organoaluminium compound (or compounds), before this mixture comes into contact with a chemically treated calcined solid oxide (or oxides) and additional organoaluminium compound (s). The pre-contacted mixture can also describe a mixture of metallocene compound or transition metal compound (or compounds), organoaluminium compound (or compounds), and activator support compound (or compounds) that is contacted for a period of time before being fed to a polymerization reactor. Thus, "pre-contacted" describes components that are used to be in contact with each other, but before being brought into contact with the components in the second post-contacted mixture. Consequently, this invention can occasionally distinguish between a component used to prepare the pre-contacted mixture and that component after the mixture has been prepared. For example, in one aspect of this invention, it is possible for a pre-contacted organoaluminium compound, since it is contacted with a metallocene and olefin monomer, to have reacted to form at least one chemical compound, formulation or structure different from the compound of distinct organoaluminium used to prepare the pre-contacted mixture. In this case, the pre-contacted organoaluminium compound or component is described as comprising an organoaluminium compound that was used to prepare the pre-contacted mixture.
In addition, the pre-contacted mixture may describe a mixture of metallocene or transition metal compounds and organoaluminium compounds, before contacting this mixture with chemically treated solid calcined oxides. This pre-contacted mixture can also describe a mixture of metallocene compounds, olefin monomers and chemically treated solid calcined oxides, before the mixture is contacted with an organoaluminium compound or co-catalyst compounds.
Similarly, the term "post-contacted" mixture is used here to describe a second mixture of catalyst components that are contacted for a second period of time, and a constituent of which is the first "pre-contacted" mixture or mixture of catalyst components. who were contacted for a first period of time. For example, the term “post-contacted” mixture is used here to describe the mixture of metallocene or transition metal compounds, olefin monomers, deorganic aluminum compounds, and chemically treated solid calcined oxides formed from contacting the pre-contacted mixture of a portion of these components with any additional components added to form the post-contacted mixture. For example, the additional component added to form the post-contacted mixture may be a chemically treated solid oxide, and optionally, may include an organo-aluminum compound that is the same or different from the organo-aluminum compound used to prepare the pre-contacted mixture, as described here. Consequently, this invention can also occasionally distinguish between a component used to prepare the post-contacted mixture and that component after the mixture has been prepared. ________Q The term "metallocene", as used herein, describes a compound comprising at least a portion of the η3 to q5-cycloalkadienyl type, wherein the η3 ar | 5-cycloalkadienyl moieties include cyclopentadienyl binders, indenyl binders, fluorenyl binders, and the like, including partially saturated or substituted derivatives or analogues of any of these. Possible substitutes for these binders may include hydrogen, so the description "their substituted derivatives" in this invention comprises partially saturated binders such as tetrahydroindenyl, tetrahydrofluorenyl, octahidrofluorenyl, partially saturated idenyl, partially saturated fluorenyl, partially substituted saturated indenyl, partially substituted saturated fluorenyl, and the like. In some contexts, metallocene is referred to simply as the "catalyst", in the same way that "co-catalyst" is used here to refer to, for example, an organoaluminium compound. Metallocene is also used here to include mono-cyclopentadienyl or half-sandwich compounds, as well as compounds containing at least one cyclodienyl ring and compounds containing boratabenzene linkers. In addition, metallocene is also used here to include dinuclear metallocene compounds, for example compounds comprising two metallocene moieties linked by a connector group, such as an alkenyl group resulting from an olefin metathesis reaction or a saturated version resulting from hydrogenation or derivatization. Unless otherwise specified, the following abbreviations are used: Cp for cyclopentadienyl; Ind is indenil; and Flu for fluorenil.
The terms "catalyst composition", "catalyst mixture", "catalyst system" and the like, do not depend on the actual product or composition resulting from contact or reaction of the components of the composition / mixture, the nature of the active catalytic site, or the destination of the co -catalyst, composed of metallocene or transition metal, any olefin monomer used to prepare a pre-contacted mixture, or chemically treated solid oxide, after combining these components. Therefore, the terms "catalyst composition", "catalyst mixture", "catalyst system", and the like, can include both heterogeneous and homogeneous compositions.
The terms "chemically treated solid oxide", "treated solid oxide", and the like, are used here to describe a solid inorganic oxide of relatively high porosity, which exhibits Lewis or Bronsted acidic behavior, and which has been treated with a withdrawal component of electrons, usually an anion, and which is calcined. The electron withdrawal component is generally an anion source compound of electron withdrawal. Thus, the chemically treated solid oxide comprises a calcined contact product of at least one solid oxide with at least one electron withdrawing anion source compound. Generally, the chemically treated solid oxide comprises an ionizing solid acidic oxide. The terms "support" and "activating support" are not used to imply these components that are inert, and such components should not be interpreted as an inert component of the catalyst composition.
Although any methods, devices and materials similar or equivalent to those described here can be used in the practice or testing of the invention, typical methods, devices and materials are described here.
All publications and patents mentioned herein are incorporated by reference for the purpose of describing and disclosing, for example, the interpretations and methodologies that are described in the publications, which can be used in relation to the invention described herein. The publications discussed in the text are provided only for publication before the filing date of this application. Nothing in this document should be construed as an admission that inventors are not entitled to anticipate disclosure by virtue of a previous invention.
For any specific compound disclosed herein, any general or specific structure presented also comprises all the conformational isomers, regioisomers and stereoisomers that may arise from a specific set of substituents. The general or specific structure also comprises all enantiomers, diastereomers, and other optical isomers, in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by those skilled in the art.
Depositors disclose several types of variations on the present invention. These include, but are not limited to, a variation of a series of carbon atoms, a variation of weight ratios, a variation or molar ratios, a variation of surface areas, a variation of pore volumes, a variation of particle sizes , a range of catalytic activities, and so on. When depositors disclose or claim a variation of any kind, their intention is to individually disclose or claim each possible number that a variation could reasonably understand, including end points of the variation as well as any sub-variations and combinations of sub-variations therein. For example, when depositors disclose or claim a weight ratio of alumina to silica or silica coated alumina, their intention is to individually disclose or claim each possible number that a variation could comprise in accordance with the present disclosure. By a disclosure in which the weight ratio of alumina to silica in a silica coated alumina is in a range from about 1: 1 to about 100: 1, depositors intended to state that the weight ratio can be selected from about 1: 1, about 1.1: 1, about 1.2: 1, about 1.3: 1, about 1.4: 1, about 1.5: 1, about 1.6: 1, about 1.7: 1, about 1.8: 1, about 1.9: 1, about 2: 1, about 2.1: 1, about 2.2: 1, about 2.3: 1, about 2.3: 1, about 2.4: 1, about 2.5: 1, about 2.6: 1, about 2.7: 1, about 2.8: 1, about 2.9: 1, about 3: 1, about 3.1: 1, about 3.2: 1, about 3.2: 1, about 3.3 3.4: 1, about 3.5: 1, about 3.6: 1, about 3.7: 1, about 3.8: 1, about 3.9: 1, about 4: 1, about 4.1: 1, about 4.2: 1, about 4.3: 1, about 4.4: 1, about 4.5: 1, about 4.6: 1, about 4.7: 1, about 4.8: 1, about 4.9: 1, about 5: 1, about 5.1: 1, about 5.2: 1, about 5.3: 1, about 5.4: 1, about 5.5: 1, about 5.6: 1, about 5.7: 1, about 5.8: 1, about 5.9: 1, about 6: 1, about 6.5: 1, about 7: 1, about 7: 1, about 7.5: 1, about 8: 1, about 8.5: 1, about 9: 1, about 9.5: 1, about 10: 1, about 11: 1, about 12: 1, about 13: 1, about 14: 1, about 15: 1, about 16: 1, about 17: 1, about 18: 1, about 19: 1, about 20: 1, about 30: 1, about 30: 1, about 40: 1, about 50: 1, about 60: 1, about 70: 1, about 80: 1, about 90: 1, about 95: 1, about 96: 1, about 96: 1, about 97: 1, about 98: 1, about 99: 1, or about 100: 1. In addition, the weight ratio can be in any range from about 1: 1 to about 100: 1 (for example, the weight ratio is in a range from about 2: 1 to about 20: 1), and this also includes any combination of variations from about 1: 1 to about 100: 1 (for example, the weight ratio is in a range of about 1.8: 1 to about 12: 1 or about 20: 1 to about 40: 1). Similarly, all other variations disclosed herein must be interpreted similarly to this example.
Depositors reserve the right to reserve or exclude any individual members of any group, including any sub-variations or combinations of sub-variations in the group, that may be claimed according to a variation or similarly, if for any reason the depositors choose to claim less than the full proportion of this disclosure, for example, consider a reference that Depositors may not be aware of when filing the application. In addition, depositors reserve the right to reserve or exclude any substituents, analogs, compounds, binders, individual structures or groups thereof, or any members of a claimed group, if for any reason the depositors choose to claim less than the full proportion of the disclosure, for example, consider a reference that depositors may not be aware of when filing the application.
The terms "one", "one" and "a" are intended to include plural alternatives, for example, at least one, unless otherwise specified. For example, the disclosure of an "activating support" or "compound" "metallocene" means it comprises one, or mixtures or combinations of more than one activator support or metallocene compound, respectively.
Although the compositions and methods are described in terms of "comprising" various components or steps, the compositions and methods can also "essentially consist of" or "consist of" various components or steps. For example, a catalyst composition in one aspect of the present The invention may comprise: alternatively, it may consist essentially of, or alternatively, (i) at least one transition metal or metallocene compound, (ii) at least one activating support, and (iii) at least one organoaluminium compound.
DETAILED DESCRIPTION OF THE INVENTION The present invention generally relates to chemically treated silica coated alumina activating supports, catalyst compositions employing these supports, methods for preparing activating supports and catalyst compositions, methods for using catalyst compositions to polymerize olefins, resin resins polymer produced using such catalyst compositions, and articles produced using these polymer resins. Specifically, the present invention is directed to chemically treated silica coated alumina activating supports and catalyst compositions employing such activating supports. The catalyst compositions containing the silica-coated alumina supports of the present invention can be used to produce, for example, ethylene-based homopolymers and copolymers.
CATALYST COMPOSITIONS
The catalyst compositions disclosed herein employ at least one silica-coated alumina activating support. According to one aspect of the present invention, a catalyst composition is provided, which comprises: (a) at least one transition metal compound or metallocene compound: e___________________________________________________________________ (b) at least one activator support.
At least one activator support comprises at least one silica-coated alumina, having a weight ratio of alumina to silica ranging from about 1: 1 to about 100: 1, which is treated with at least one electron withdrawing anion . At least one electron withdrawing anion can comprise, for example, fuoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, and the like, or combinations thereof. This catalyst composition may further comprise at least one organoaluminium compound. These catalyst compositions can be used to produce polyolefins - homopolymers, copolymers, and the like - for a variety of end-use applications.
In accordance with this and other aspects of the present invention, it is contemplated that the catalyst compositions disclosed herein may contain more than one transition metal compound and / or more than one metallocene compound and / or more than one activator support. In addition, more than one organoaluminium compound is also contemplated.
In another aspect of the present invention, a catalyst composition is provided that comprises at least one transition metal or metallocene compound, at least one activator support, and, optionally, at least one organoaluminium compound, wherein this catalyst composition is substantially free of aluminoxanes, organoboro or organoborate compounds, and ionizing ionic compounds. In this respect, the catalyst composition has catalytic activity, to be discussed below, in the absence of these additional or optional co-catalysts.
However, in other aspects of this invention, additional co-catalysts can be employed. For example, a catalyst composition comprising at least one metallocene or transition metal compound and at least one activating support can further comprise at least one optional co-catalyst. Suitable co-catalysts in this regard may include, but are not limited to, aluminoxane compounds, or organoboro or organoborate compounds, ionizing ionic compounds, and the like, or combinations thereof. More than one co-catalyst can be present in the catalyst composition.
Another catalyst composition contemplated here comprises: (a) at least one transition metal compound or metallocene compound: __________________________________________________________________________ (b) at least one support-activator; and (c) at least one organoaluminium compound.
At least one activating support comprises at least one silica-coated alumina treated with at least one electron withdrawing anion. At least one silica-coated alumina has a weight ratio of alumina to silica in a range of about 1: 1 to about 100: 1, or about 2: 1 to about 20: 1, in this aspect of the invention . At least one electron withdrawing anion can comprise fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, and the like, or combinations thereof. Often, at least one organoaluminium compound can comprise trimethylaluminum, triethylalumin, tri-n-propylalumin, tri-n-butylalumin, triisobutylalumin, tri-n-hexylalumin, tri-n-octylalumin, diisobutylaluminum hydride, diethylaluminum ethoxide, chloride chloride diethyl aluminum, or any combination of these.
The catalyst compositions of the present invention comprising at least one transition metal or metallocene compound and at least one chemically treated silica coated alumina activating support may further comprise at least one additional or optional activating support. For example, optional activating supports such as fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, chlorinated silica-zirconia -brometted zirconia, sulfated silica-zirconia, fluorinated silica-titania, and the like, or combinations thereof, can be used in catalyst compositions disclosed here. If the additional or optional activating support is a chemically treated silica-alumina, this material will be different from the silica-coated alumina of the present invention, to be discussed below. One or more organoaluminium compounds can also be present in the catalyst composition.
In another aspect, a catalyst composition comprising at least one transition metal or metallocene compound and at least one silica-coated alumina activating support - and optionally, at least one organoaluminium compound - can further comprise at least one additional activating support or optional, in which at least one activating support comprises at least one solid oxide treated with at least one electron withdrawing anion. At least one solid oxide can comprise silica, alumina, silica-alumina, aluminum phosphate, heteropolitungstate, titania, zirconia, magnesia, horia, zinc oxide, any mixed oxide, or any mixture thereof; and at least one electron withdrawing anion may comprise sulfate, bisulfate, fluoride chloride, bromide, iodide, fluorsulfate, fluorborate, phosphate, fluorophosphate, trifluoracetate, triflate, fluorzirconate, fluortitanate, or any combination thereof.
In addition, the activating supports of this invention can comprise a metal or metal ion such as, for example, zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, and the like, or any combination thereof.
In yet another aspect, the catalyst compositions of the present invention may further comprise one or more optional activating supports selected from mineral clay, pillared clay, exfoliated clay, exfoliated clay gelled in another oxide matrix, a layered silicate mineral, a non-layered silicate mineral, a layered aluminosilicate mineral, a non-layered aluminosilicate mineral, and the like, or combinations of these materials. Additional or optional activator support materials will be discussed in more detail below.
In one aspect, the present invention comprises a catalyst composition that comprises at least one transition metal or metallocene compound and at least one activator support. At least one activating support may comprise at least one silica-coated alumina treated with at least one electron withdrawing anion. The weight ratio of alumina to silica in at least one silica coated alumina can vary from about 1: 1 to about 100: 1, for example, from about 1.5: 1 to about 100: 1, from about 2: 1 to about 20: 1, or about 2: 1 to about 12: 1. This catalyst composition may further comprise at least one organoaluminium compound. In addition, this catalyst composition may further comprise at least one optional co-catalyst, wherein at least one optical co-catalyst is at least one aluminoxane compound, at least one organoboro or organoborate compound, at least one ionizing ionic compound, or any combination of these.
This invention further comprises methods for making such catalyst compositions, such as, for example, contacting the respective catalyst components in any order or sequence.
At least one transition metal and / or metallocene compound can be pre-contacted with an olefinic monomer, not necessarily the olefin monomer to be polymerized, and an organoaluminium compound for a first ___________ period of time before contacting this pre- contacted with an activator support. The first time period for contact, the pre-contact time, between the transition metal and / or metallocene compound (or compounds), the olefinic monomer, and the organoaluminium compound generally varies over a time period of about 1 minute to about 24 hours, for example, from about 3 minutes to about 1 hour. Pre-contact times of about 10 minutes to about 30 minutes are also used.
Alternatively, the pre-contact process is carried out in multiple stages, instead of a single stage, in which multiple mixtures are prepared, each comprising a different set of catalyst components. For example, at least two catalyst components are contacted forming a first mixture, followed by contacting the first mixture with at least one other catalyst component forming a second mixture, and so on.
The multiple pre-contact steps can be carried out in a single container or multiple containers. In addition, multiple pre-contact steps can be performed in series (sequentially), in parallel, or in combination. For example, a first mixture of two catalyst components can be formed in a first container, a second mixture comprising the first mixture plus an additional catalyst component can be formed in the first container or in a second container, which is generally placed downstream of the first container.
In another aspect, one or more of the catalyst components can be divided and used in different pre-contact treatments. As an example, part of a catalyst component is fed into a first pre-contact container for pre-contact with at least one other catalyst component, while the rest of that catalyst component is fed into a second pre-contact container for pre-contact with at least one other catalyst component, or is fed directly into the reactor, or a combination of these. Pre-contact can be carried out on any suitable equipment, such as tanks, agitated mixing tanks, various static mixing devices, a flask, a container of any kind, or combinations of these devices.
In another aspect of this invention, the various catalyst components (for example, transition metal or metallocene compound, activator support, organo-aluminum co-catalyst, and optionally an unsaturated hydrocarbon) are contacted in the polymerization reactor simultaneously while the polymerization reaction takes place . Alternatively, any two or more of these catalyst components can be pre-contacted in a container before entering the reaction zone. This pre-contact step can be continuous, in which the pre-contacted product is fed continuously to the reactor, or it can be in a step-by-step process or periodically in which a batch of pre-contacted product is added to make a catalyst composition. This pre-contact step can be performed for a period of time that can vary from a few seconds to several days, or more. In this regard, the continuous pre-contact step generally lasts from about 1 second to about 1 hour. In another aspect, the continuous pre-contact step lasts about 10 seconds to about 45 minutes, or about 1 minute to about 30 minutes.
Once the pre-contacted mixture of transition metal and / or metallocene compounds, olefin monomers, and organoaluminium co-catalysts is brought into contact with the activator support (s), this composition ( with the addition of the activating support) is called a “post-contacted mixture”. The post-contacted mixture optionally remains in contact for a second period of time, the post-contact time, before starting the polymerization process. The post-contact times between the pre-contacted mixture and the activator support generally range from about 1 minute to about 24 hours. In another aspect, the post-contact time can vary from about 1 minute to about 1 hour. The pre-contact step, the post-contact step, or both, can increase the polymer's productivity compared to the same catalyst composition that is prepared without pre-contact or post-contact. However, neither a pre-contact step nor a post-contact step is required. The post-contacted mixture can be heated to a temperature and for a period of time sufficient to allow adsorption, impregnation, or interaction of the pre-contacted mixture and the activating support, so that a portion of the components of the pre-contacted mixture is immobilized. , absorbed, or deposited on it. When heating is employed, the post-contacted mixture is generally heated to a temperature of between about 0 ° F to about 150 ° F, or from about 40 ° F to about 95 ° F.
In another aspect, a metallocene, an organoaluminium, and an activating support can be pre-contacted for a period of time before being contacted with the olefin to be polymerized in the reactor, as shown in Example 6 below.
According to one aspect of this invention, the molar ratio of the transition metal or metallocene compound to the organoaluminium compound in a catalyst composition generally ranges from about 1: 1 to about 1: 10,000. In another aspect, the molar ratio is in a range of about 1: 1 to about 1: 1,000. In yet another aspect, the molar ratio of the metallocene compound or transition metal millis to the organoaluminium compound mills is in a range of about 1: 1 to about 1: 100. These molar ratios reflect the ratio of total mol of transition metal compound (s) and / or metallocene to the total amount of organoaluminium compound (s) in both the pre-contacted mixture and the post-contacted mixture combined, if the pre-contact and / or post-contact steps are used.
When a pre-contact step is used, the molar ratio of mol totals of olefin monomer to mol totals of transition metal compound (s) and / or metallocene in the pre-contacted mixture is generally in a range of about 1:10 to about 100,000: 1. The mol totals of each component are used in this ratio to consider aspects of this invention in which more than one olefin monomer and / or more than one transition metal and / or metallocene compound is employed. In addition, this molar ratio can be in a range from about 10: 1 to about 1,000: 1 in another aspect of the invention.
Generally, the weight ratio of the organoaluminium compound to the activating support is in a range of about 10: 1 to about 1: 1000. If more than one organoaluminium compound and / or more than one activating support is used, this ratio will be based on the total weight of each respective component. In another aspect, the weight ratio of the organoaluminium compound to the activating support is in a range from about 3: 1 to about 1: 100, or from about 1: 1 to about 1:50.
In some aspects of this invention, the weight ratio of the transition metal or metallocene to activator support is in a range from about 1: 1 to about 1: 1,000,000. If more than one transition metal and / or metallocene compound and / or more than one activating support is used, this ratio will be based on the total weight of each respective component. In another aspect, this weight ratio is in a range of about 1: 5 to about 1: 100,000, or from about 1:10 to about 1: 10,000, yet, in another aspect, in another aspect, a The weight ratio of the transition metal and / or metallocene compound (s) to the activator support is in a range from about 1:20 to about 1: 1000.
In yet another aspect of this invention, the concentration of the transition metal or metallocene, in units of micromols of the transition metal or metallocene per gram of the activating support, can be in a range of about 0.5 to about 150. If more than one transition metal and / or metallocene and / or more than one activating support is used, this ratio will be based on the total weight of each respective component. In another aspect, the concentration of the transition metal and / or metallocene, in units of micromols of the transition metal and / or metallocene per gram of the activating support, can be in a range of about 1 to about 120, for example, from about 5 to about 100, from about 5 to about 80, from about 5 to about 60, or from about 5 to about 40. In yet another aspect, the concentration of the transition metal and / the metallocene, in units of micromols of the transition metal and / or metallocene per gram of the activating support, is in a range of about 1 to about 30, from about 1 to about 20, from about 1 to about 15, or from about 1 to about 12.
According to some aspects of this invention, aluminoxane compounds are not required to form the catalyst composition. Thus, polymerization proceeds in the absence of aluminoxanes. Consequently, the present invention can use, for example, organoaluminium compounds and an activating support in the absence of aluminoxanes. While not committing to theory, it is believed that the organoaluminium compound probably does not activate a transition metal or metallocene catalyst in the same way as an organoaluminoxane compound.
In addition, in some respects, organoboro and organoborate compounds are not required to form a catalyst composition of this invention. Nevertheless, aluminoxanes, organoboro or organoborate compounds, ionizing tonic compounds, or combinations thereof can be used in other catalyst compositions contemplated and included in the present invention. Therefore, co-catalysts such as aluminoxanes, organoboro or organoborate compounds, ionizing tonic compounds, or combinations thereof, can be used with the transition metal and / or metallocene compound, in the presence or absence of an organoaluminium compound.
In accordance with one aspect of this invention, a catalyst composition can comprise at least one transition metal or motalocene compound. and at least one activator support. In accordance with another aspect of this invention, a catalyst composition can comprise at least one transition metal or metallocene compound, at least one activator support and at least one organoaluminium compound. Catalyst compositions in these and other aspects of the present invention generally have a catalyst activity greater than about 100 grams of polyethylene (homopolymer, copolymer, etc. as the context requires) per gram of activating support per hour (abbreviated gPE / gA-S / hr). In another aspect, the catalyst activity can be greater than about 200, greater than about 300, greater than about 400, or greater than about 500 gPE / gA-S / hr. In yet another aspect, the catalyst compositions of this invention can be characterized as having a catalyst activity greater than about 750, greater than about 1000, or greater than about 1500 gPE / gA-S / hr. The catalyst activity can be greater than about 2000, greater than about 4000, or greater than about 5000 gPE / gA-S / hr, in certain aspects of this invention. The catalyst activity is measured under slurry polymerization conditions using isobutane as the diluent, at a polymerization temperature of 90 ° C and a reactor pressure of 420 psig. The reactor pressure is largely controlled by the monomer pressure, for example, the ethylene pressure, but other contributors to the reactor pressure may include hydrogen gas (for example, if hydrogen is used), isobutane vapor, and comonomer gas or steam (for example, if a comonomer is used).
Similarly, the catalyst compositions of the present invention may have a catalyst activity greater than about 5000 grams of polyethylene (homopolymer, copolymer, etc., as the context requires) per gram of the transition metal compound or metallocene compound per hour (abbreviated gPE / gMET / hr). For example, the catalyst activity can be greater than about 10,000, greater than about 25,000, or greater than about 50,000 gPE / gMET / hr. In another aspect, the catalyst compositions of this invention can be characterized as having a catalyst activity greater than about 75,000, greater than about 100,000, or greater than about 150,000 gPE / gMET / hr. In yet another aspect of this invention, the catalyst activity can be greater than about 200,000, greater than about 300,000, greater than about 400,000, or greater than about 500,000 gPE / gMET / hr. This catalyst activity is measured under slurry polymerization conditions using isobutane as the diluent, at a polymerization temperature of about 90 ° C and a reactor pressure of about 420 psig.
Catalyst compositions employing silica-coated alumina activating supports - for example, fluorinated silica-coated alumina - can result in significant increases in catalytic activity, for example, compared to a conventional silica-alumina activating support - for example, fluoridated silica-alumina - having an alumina to silica weight ratio of less than 1: 1 (for example, from about 0.05: 1 to about 0.25: 1). These catalytic activities can be compared on a “per gram of activating support” basis or on a “per gram of transition metal or metallocene” basis. In one aspect, the catalyst activity of the present invention is at least twice that of a comparable catalyst composition containing a conventional silica-alumina activating support (ie, under the same reaction conditions, using the same other catalyst components, same chemical treatment of anion etc). In another aspect, the activity of a catalyst composition comprising a silica-alumina activating support (with a weight ratio of alumina to silica in a range of, for example, about 1.5: 1 to about 100: 1) can be at least about 3 times, at least about 4 times, at least about 5 times, at least about 6 times, or at least about 7 times the activity of a comparable catalyst composition comprising a silica-alumina activating support (having a weight ratio of alumina to silica in a range of, for example, about 0.05: 1 to about 0.25: 1). In yet another aspect, the catalyst activity of a catalyst composition comprising a silica-coated alumina activating support can be about 2 times to about 100 times the activity of a comparable catalyst composition comprising a silica-alumina activating support. In yet another aspect, the catalytic activity of a catalyst composition comprising a silica-coated alumina activating support can be from about 2 times to about 80 times; alternatively, from about 3 teams to about 60 times; alternatively, from about 3 teams to about 40 times; or alternatively, from about 4 teams to about 20 times; the activity of a comparable catalyst composition comprising a silica-alumina activating support.
As discussed here, any combination of the metallocene or transition metal compound, activator support, organoaluminium compound, and olefin monomer, can be pre-contacted in some aspects of this invention. When any pre-contact occurs with an olefinic monomer, it is not necessary for the olefin monomer used in the pre-contact step to be the same as the olefin to be polymerized. In addition, when a pre-contact step between any combination of the catalyzed components is employed for a first period of time, this pre-contacted mixture can be used in a subsequent post-contact step between any other combination of catalyst components for a second time period. For example, a metallocene compound, an organoaluminium compound and 1-hexene can be used in a pre-contact step for a first period of time, and this pre-contacted mixture can then be contacted with a chemically treated solid oxide to form a post-contacted mixture which is contacted for a second period of time before starting the polymerization reaction. For example, the first contact time, the pre-contact time, between any combination of the transition metal or metallocene compound, olefinic monomer, activator support and the organoaluminium compound can be about 1 minute to about 24 hours, from about 1 minute to about 1 hour, or from about 10 minutes to about 30 minutes. The post-contacted mixture can optionally remain in contact for a second period of time, the post-contact time, before starting the polymerization process. According to one aspect of this invention, the post-contact times between the pre-contacted mixture and any remaining catalyst component is about 1 minute to about 24 hours, or about 0.1 hour to about 1 hour . ACTIVATING SUPPORTS OF SILICA COATED ALUMINUM The activating supports of the present invention comprise silica coated aluminins and these materials comprise an alumina matrix that is coated, or partially coated, with a layer of silica. These silica-coated alumines generally have a high alumina content, for example, a weight ratio of alumina to silica in silica-coated alumina greater than about 1: 1. The silica coated alumina activating supports provided in this invention may comprise at least one silica coated alumina treated with at least one electron withdrawing anion, at least one silica coated alumina having a weight ratio of alumina to silica that varies, generally from about 1: 1 to about 100: 1. The electron withdrawing anion generally comprises fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate and the like, but combinations of two or more of these anions can also be employed, ________In one aspect of this invention, the alumina weight ratio for silica in silica-coated alumina can be in a range of about 1: 1 to about 100: 1, or about 1.2: 1 to about 25: 1. In another aspect, the weight ratio of alumina to silica in silica coated alumina ranges from about 1.1: 1 to about 100: 1; alternatively, from about 1.1: 1 to about 75: 1; alternatively, from about 1.3: 1 to about 50: 1; alternatively, from about 1.5: 1 to about 20: 1; or alternatively, from about 1.5: 1 to about 15: 1. In yet another aspect, the alumina to silica weight ratio ranges from about 2: 1 to about 100: 1, such as, for example, about 2: 1 to about 50: 1, from about 2: 1 to about 25: 1, or from about 2: 1 to about 20: 1. For example, the weight ratio of alumina to silica in a silica-coated alumina can range from about 2: 1 to about 15: 1, from about 2: 1 to about 12: 1, or from about 2: 1 to about 10: 1. The weight ratio of alumina to silica in silica coated alumina can be about 2.1: 1 to about 9: 1, about 2.2: 1 to about 8: 1, or about 2.3: 1 to about of 6: 1, in other aspects disclosed here.
High alumina silica-coated aluminas of the present invention generally have surface areas ranging from about 100 to about 1000 m2 / g. In some respects, the surface area fits in a range of about 150 to about 750 m2 / g, for example, from about 200 to about 600 m2 / g. The surface area of silica-coated alumina can vary from about 250 to about 500 m2 / g in another aspect of this invention. Alumina coated with silica with a high alumina content having surface areas of about 300 m2 / g, about 350 m2 / g, about 400 m2 / g, or about 450 m2 / g, can be used in some aspects of this invention. The pore volume of silica-coated aluminas is generally greater than about 0.5 mL / g. The pore volume is often greater than about 0.75 mL / g, or greater than about 1 mL / g. In another aspect, the pore volume is greater than about 1.2 ml / g. In yet another aspect, the pore volume fits in a range of about 0.5 ml / g to about 1.8 ml / g, such as, for example, from about 0.8 ml / g to about 1, 7 ml / g, or from about 1 ml / g to about 1.6 ml / g.
The silica coated aluminas disclosed herein generally have a particle size ranging from about 5 microns to about 150 microns. In some aspects of this invention, the average particle size ranges from about 30 microns to about 100 microns. For example, the average particle size of silica-coated aluminas can range from about 40 to about 80 microns.
The silica coated aluminas of the present invention can be produced using various methods, including those disclosed in U.S. Patent No. 5,401,820, which is incorporated herein by reference. In one aspect of this invention, a suitable method for producing a silica-coated alumina can comprise the following steps: (i) providing at least one source of alumina, this source of alumina comprising an alumina, a hydrated alumina, aluminum hydroxide, bohemite , or a combination of these; (ii) contacting the alumina source with a solution or suspension comprising at least one solvent and at least one compound containing silicon capable of producing silica after calcination; (iii) depositing a silicon-containing compound coating on at least a portion of the alumina source; and (iv) removing the solvent.
Alumina sources for silica-coated aluminas may include, but are not limited to, an alumina, a hydrated alumina, aluminum hydroxide, bohemite or a combination thereof.
In one step of the process to produce a silica-coated alumina, the source (or sources) of alumina is / are contacted with a solution or suspension comprising at least one solvent and at least one silicon-containing compound capable of producing silica upon calcination. The alumina source can be wetted or dried before this contact step. Although not limited to any specific solvent, solvents suitable for the solution or suspension (for example, dispersion, emulsion and so on) can include, for example, water and organic solvents such as hexane, heptane, benzene, toluene, xylene, and other hydrocarbons, acetone, alcohols, and the like, or combinations thereof.
One or more silicon-containing compounds can be used to produce a silica coating, for example, a partial coating on alumina, a complete coating on alumina, etc. The silicon-containing compound is generally a material that is capable of producing or releasing silica after calcination, and such materials may include, but are not limited to, silica, sodium silicate, potassium silicate, SiCU, Si (OMe) 4, Si (0Et) 4, siloxane polymers, silica colloids, silyl acid, the like, or combinations thereof.
In some aspects, a coating of the silicon-containing compound is deposited on at least a portion of the alumina source, and the solvent is removed. The solvent can be removed before, or during, a calcination step. The coated alumina can be calcined before and / or during and / or after the coated alumina is contacted with an electron withdrawing anion source. The result of this process is a coating of silica on alumina, for example, partial coating, or a complete coating.
It should be noted that the silica coated aluminas disclosed herein are different from conventional silica-alumina solid oxides (e.g., mixed oxides), both in terms of morphology and in the processes used to produce the respective materials. As noted above, the silica coated aluminas of the present invention both have a high alumina content (for example, a weight ratio of alumina to silica in a range from about 1: 1 to about 100: 1) and a coating of silica (eg partial, complete) in an alumina matrix. Silica-aluminas are known materials generally having a weight ratio of alumina to silica of less than 1: 1, and generally in a range of about 0.05: 1 to about 0.25: 1, as illustrated in example 1 below. Such silica-alumina materials are not the inventive silica-coated aluminas of this invention. It is believed that mixed oxides of silica-alumina can be prepared by co-gelation or co-precipitation methods, which can result in a mixed matrix of silica and alumina (for example, a mixed oxide), or by impregnating a matrix of silica with aluminum ions or alumina. The resulting morphology is different from an alumina matrix with a partial or complete silica coating. The electron withdrawal component used to treat silica-coated alumina solid oxide can be any component that increases the Lewis or Bronsted acidity of the solid oxide after treatment (compared to solid oxide that is not treated with at least one anion of removal of electrons). According to one aspect of the present invention, the electron withdrawing component is an electron withdrawing anion derived from a salt, acid, or other compound, such as a volatile organic compound, which serves as a source or precursor for that anion . Examples of suitable electron withdrawing anions include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorsulfate, phosphate, fluorophosphate, trifluoracetate, triflate, fluorzirconate, fluortitanate, and the like, including mixtures and combinations thereof . In addition, other ionic or non-ionic compounds that serve as sources for these electron withdrawing anions can also be employed in the present invention. It is contemplated that the electron withdrawing anion may be, or comprise, fluoride, chloride, bromide, phosphate, triflate, sulfate, and the like, or any combination thereof, in some aspects of this invention. For example, at least one electron withdrawing anion can comprise fluoide, or, alternatively, can comprise sulfate.
In accordance with an aspect of the present invention, an activating support comprising at least one silica-coated alumina treated with at least one electron withdrawing anion is contemplated. In this regard, at least one silica-coated alumina has a weight ratio of alumina to silica in a range from about 1: 1 to about 100: 1; alternatively, from about 1.5: 1 to about 100: 1; alternatively, from about 2: 1 to about 20: 1; or alternatively, from about 2: 1 to about 12: 1. In addition, in this respect, at least one electron withdrawing anion can comprise fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate or any combination thereof; alternatively, it may comprise chloride, bromide, phosphate, triflate, bisulfate, sulfate or any combination thereof; alternatively, it may comprise chloride, bromide, phosphate, sulfate, or any combination thereof; alternatively, it may comprise chloride; alternatively, it may comprise bromide; alternatively, it may comprise phosphate; or alternatively, it may comprise sulfate.
When the electron withdrawing component comprises a salt from an electron withdrawing anion, the counterion or cation of that salt can be selected from any cation that allows the salt to revert or decompose back to acid during calcination. Factors that dictate the suitability of the specific salt to serve as a source for the electron withdrawing anion include, but are not limited to, the solubility of the salt in the desired solvent, the lack of adverse cation reactivity, the effects of ion matching between the cation and anion, hygroscopic properties transmitted to the salt by the cation, and the like, and thermal stability of the anion. Examples of suitable cations in the electron withdrawing anion salt include, but are not limited to, ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H +, [H (OEt2) 2j +, θ similar.
In addition, combinations of two or more different electron withdrawing anions, in varying proportions, can be used to adapt the specific acidity of the activating support to the desired level. The combinations of electron withdrawal components can be contacted with the oxide materials simultaneously or individually, and in any order that forces the desired acidity of chemically treated solid oxide. For example, one aspect of this invention is to employ two or more electron withdrawing anion source components in two or more separate contact steps. Therefore, in aspects of this invention, an activating support may comprise a silica-coated alumina treated with at least two electron withdrawing anions. Generally, electron withdrawing anions can be selected from fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, and the like. Consequently, at least two electron withdrawing anions can comprise fluoride and phosphate, fluoride and sulfate, chloride and phosphate, chloride and sulfate, triflate and sulfate, or triflate and phosphate, in some aspects of this invention.
Thus, an example of a process by which a chemically treated silica-coated alumina can be prepared is as follows: the selected solid oxide (or a combination of oxides) is contacted with a first source of electron withdrawing anions to form a first mixture, this first mixture is calcined and then contacted with a second compound from the electron withdrawing anion source to form a second mixture; the second mixture is then calcined to form a treated solid oxide. In such a process, the first and second anion source compounds of electron withdrawal are the same or different compounds, comprising the same or different anions (for example, fluoride and sulfate, chloride and phosphate, etc.).
According to one aspect of the present invention, an activating support comprising at least one silica-coated alumina treated with at least two electron withdrawing anions is contemplated. In this regard, at least one silica-coated alumina has a weight ratio of alumina to silica in a range of about 1: 1 to about 100: 1, alternatively, about 1.5: 1 to about 100: 1; alternatively, from about 2: 1 to about 20: 1; or alternatively, from about 2: 1 to about 12: 1. Still, in this respect, at least two electron withdrawing anions can comprise fluoride and phosphate, fluoride and sulfate, chloride and phosphate, chloride and sulfate, triflate and sulfate, or triflate and phosphate; alternatively, it may comprise fluoride and phosphate; alternatively, it may comprise fluoride and sulfate; alternatively, it may comprise chloride and phosphate; alternatively, it may comprise chloride and sulfate; alternatively, it may comprise triflate and sulfate, or alternatively, it may comprise triflate and phosphate. ________According to another aspect of the present invention, a chemically treated silica coated alumina can be treated with a metal source, including metal salts, metal ions, or other metal-containing compounds. Non-limiting examples of the metal or metal ion may include zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, and the like, or combinations thereof. Any method of impregnating the solid oxide with a metal can be used. The method by which the oxide is contacted with a metal source, generally a metal-containing salt or compound, may include, but is not limited to, gelation, co-gelation, impregnation of one compound onto another, and the like. If desired, the metal-containing compound can be added to or impregnated in the solid oxide as a solution, and subsequently in the supported metal after calcination. Accordingly, silica-coated alumina or chemically treated silica-coated alumina may further comprise a metal or metal ion comprising zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, and the like, or combinations of these metals . For example, zinc is often used to impregnate solid oxide because it can provide improved catalyst activity at low cost. The solid oxide can be treated with metal salts or metal-containing compounds before, after or at the same time as the solid oxide is treated with the electron withdrawing anion. Following any contact method, the contacted mixture of oxide, electron withdrawing anion, and the metal ion is usually calcined. Alternatively, the solid oxide material, the source of electron withdrawing anions, and the metal salt or metal-containing compound are contacted and calcined simultaneously. Various processes can be used to form chemically treated solid oxides useful in the present invention. The chemically treated solid oxide may comprise a contact product of at least one solid oxide coated with alumina with one or more electron withdrawing anion sources. Silica-coated alumina solid oxide is not required to be calcined prior to contact with the electron withdrawing anion source. Therefore, the solid oxide can be calcined or, alternatively, the solid oxide can be non-calcined. The contact product is usually calcined during or after the solid oxide is contacted with the electron withdrawing anion source. Various processes for preparing solid oxide activating supports that have been employed in this invention have been reported. For example, such methods are described in U.S. Patent No. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666, 6,524,987, 6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894, 6,667,274, and 6,750,302, the disclosures of which are hereby incorporated by reference in their entirety.
According to one aspect of the present invention, the solid oxide is chemically treated by being contacted with at least one electron withdrawing component, generally a source of electron withdrawing anions.
In addition, the solid oxide is optionally treated with a metal ion, and then calcined to form a solid oxide containing metal or impregnated with chemically treated metal. According to another aspect of the present invention, the solid oxide and electron withdrawing anion source are contacted and calcined simultaneously. The method by which the oxide is contacted with the electron withdrawal component, usually an electron withdrawal anion salt or acid, may include, but is not limited to, gelation, co-gelation, impregnation of a compound on other, and the like. Thus, following any contact method, the contacted mixture of solid oxide, electron withdrawing anion and optional metal ion, can, and often, is calcined. The solid oxide activating support (ie, chemically treated solid oxide), whether the inventive activating supports of this invention or optional additional activating supports (to be discussed below), can thus be produced by a process comprising: 1) contacting at least one oxide solid with at least one electron-withdrawing anion source compound to form a first mixture; and 2) calcining the first mixture to form the solid oxide activating support.
According to another aspect of the present invention, the solid oxide activating support (chemically treated solid oxide) can be produced by a process comprising: 1) contacting at least one solid oxide with a first electron-withdrawing anion source compound for form a first mixture; 2) calcining the first mixture to produce a first calcined mixture; 3) contacting the first calcined mixture with a second electron-withdrawing anion source compound to form a second mixture; and 4) calcining the second mixture to form the solid oxide activating support .______________________________________________________________________________ Generally, at least one electron withdrawing anion source compound is contacted with at least one alumina source (eg, alumina, bohemite) after at least at least one source of alumina is contacted with at least one compound containing silicon capable of producing silica after calcination (for example, silica, silicate). However, it is also contemplated that the compound from the electron withdrawing anion source can be contacted with at least one alumina source before - or, alternatively, at the same time as - at least one alumina source is contacted with at least one compound containing silicon capable of producing silica after calcination.
According to another aspect of the present invention, chemically treated solid oxide is produced by contacting the solid oxide with the electron withdrawing anion source compound, where the solid oxide compound is calcined before, during or after contact with the electron withdrawing anions, and where there is a substantial absence of aluminoxanes, organoboro or organoborate compounds, and ionizing ionic compounds. The calcination of solid oxides and chemically treated solid oxides is carried out in an ambient atmosphere, generally in a dry atmosphere, at a temperature of about 200 ° C to about 900 ° C, and for a period of time of about 1 minute at about 30 hours. The calcination can be conducted at a temperature of about 300 ° C to about 800 ° C, or alternatively, up to a temperature of about 400 ° C to about 700 ° C. The calcination can be conducted for about 30 minutes to about 50 hours, or for about 1 hour to about 15 hours. Thus, for example, calcination can be carried out for about 1 to about 10 hours at a temperature of about 350 ° C to about 550 ° C. Any suitable ambient atmosphere can be used during calcination. Calcination is usually conducted in an oxidizing atmosphere, such as air or oxygen. Alternatively, an inert atmosphere, such as nitrogen or argon, or a reducing atmosphere, such as hydrogen or carbon monoxide, can be used.
According to one aspect of the present invention, the silica-coated alumina solid oxide can be treated with a source of halide ion, sulfate ion, or a combination of anions, optionally treated with a metal ion, and then calcined to provide the chemically treated solid oxide as a specific solid. For example, the solid oxide material can be treated with a sulfate source (called a "sulfating agent"), a chloride ion source (called a "chlorinating agent"), a fluoride ion source (called a “Fluorifying agent”) or a combination of these, and calcined to provide the solid oxide activator.
A chemically treated solid oxide can comprise silica-coated alumina in the form of a specific solid. Fluorinated silica-coated alumina can be formed by contacting a silica-coated alumina with a fluoridating agent. The fluoride ion can be added to the oxide by forming a slurry of the oxide in a suitable solvent such as alcohol or water including, but not limited to, one to three carbon alcohols due to its volatility and low surface tension. Examples of fluoridating agents include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluorborate (NH4BF4), ammonium silicofluoride (hexafluorsilicate) (NH4) 2 (NH4) 2 ), ammonium hexafluorophosphate (NH4PF6), hexafluortitanic acid (H2TiF6), ammonium hexafluoritanic acid ((NH4) 2TiFe), hexafluorzironic acid (H2ZrF6), AIF3, NH4AIF4, their analogs, and combinations thereof. Triflic acid and ammonium triflate can also be used. For example, ammonium bifluoride (NH4HF2) can be used as the fluorifying agent, due to its ease of use and availability.
If desired, the solid oxide can be treated with a fluorifying agent during the calcination step. Any fluorifying agent capable of carefully contacting silica-coated alumina during the calcination step can be used. For example, in addition to those fluoridating agents described above, volatile organic fluorinating agents can be used. Examples of volatile organic fluorifying agents useful in this aspect of the invention include, but are not limited to, freons, perfluorhexane, perfluorbenzene, fluoromethane, trifluorethanol, and the like, and combinations thereof. The calcination temperatures should generally be high enough to decompose the compound and release fluoride. Hydrogen gas fluoride (HF) or fluorine itself (F2) can also be used with silica-coated alumina if fluoridated during calcination. Silicon tetrafluoride (SiF4) and compounds containing tetrafluorborate (BF4 ') can also be used. A convenient method of contacting silica-coated alumina with the fluorifying agent is to vaporize a fluorifying agent in a gas stream used to fluidize the silica-coated alumina during calcination.
Similarly, in another aspect of this invention, the chemically treated solid oxide comprises a chlorinated silica-coated alumina in the form of a specific solid. The chlorinated solid oxide is formed by contacting the silica-coated alumina with a chlorinating agent. The chloride ion can be added to the oxide to form a slurry of the oxide in a suitable solvent. Silica-coated alumina can be treated with a chlorinating agent during the calcination step. Any chlorinating agent capable of serving as a chloride source and carefully contacting the oxide during the calcination step can be used, such as SiCI4, SiMe2Cl2, TiCl4, BCI3, θ similar, including mixtures thereof. Volatile organic chlorinating agents can be used. Examples of suitable volatile organic chlorinating agents include, but are not limited to, certain freons, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, and the like, or any combination thereof. Gaseous hydrogen chloride or chlorine itself can also be used with solid oxide during calcination. A convenient method for contacting silica-coated alumina with the chlorinating agent is to vaporize a chlorinating agent in a gas stream used to fluidize the solid oxide during calcination. The amount of fluoride or chloride ion present before calcining the silica-coated solid oxide is generally about 1 to about 50% by weight, where the weight percentage is based on the weight of the solid oxide before calcination. According to another aspect of this invention, the amount of fluoride or chloride ion present before calcining the solid oxide is about 1 to about 25% by weight, about 2 to about 15%, or about 3% to about 12% by weight. According to another aspect of this invention, the amount of chloride or fluoride ion present before calcining the solid oxide is about 5 to about 10% by weight. Once impregnated with halide, alumina coated silica coated can be dried by any suitable method including, but not limited to, suction filtration followed by evaporation, vacuum drying, spray drying and the like, although it is also possible to start the step calcination immediately without drying the impregnated solid oxide.
A sulfated solid oxide comprises sulfate and a solid oxide component, such as silica-coated alumina, in the form of a particulate solid. Optionally, the sulfated oxide can be further treated with a metal ion so that the calcined sulfated oxide comprises a metal. According to one aspect of the present invention, the sulfated solid oxide comprises sulfate and silica-coated alumina. In some cases, sulfated silica-coated alumina can be formed by a process in which silica-coated alumina is treated with a sulfate source, for example, sulfuric acid or a sulfate salt such as ammonium sulfate. This process is generally carried out by forming a silica-coated alumina slurry in a suitable solvent, such as alcohol or water, to which the desired concentration of the sulfating agent has been added. Suitable organic solvents include, but are not limited to, one to three carbon alcohols due to their volatility and low surface tension.
According to one aspect of this invention, the amount of sulfate ion present before calcination is about 0.5 to about 100 parts by weight of sulfate ion to about 100 parts by weight of solid oxide. According to another aspect of this invention, the amount of sulfate ion present before calcination is from about 1 to about 50 parts by weight of sulfate ion to about 100 parts by weight of solid oxide, and further according to another aspect of this invention, from about 5 to about 30 parts by weight of sulfate ion to about 100 parts by weight of solid oxide. These weight ratios are based on the weight of the solid oxide before calcination. Once impregnated with sulfate, the sulfated silica-coated alumina can be dried by any suitable method including, but not limited to, suction filtration followed by evaporation, vacuum drying, spray drying, and the like, although it is also possible to start the calcination step immediately.
Generally, the silica-coated alumina activating supports of the present invention are calcined. Silica-coated alumina can be calcined before chemical treatment, but this is not a requirement. During or after chemical treatment, the silica-coated alumina activating support can be calcined. Activator supports comprising at least one silica-coated alumina treated with at least one electron withdrawing anion, after calcination, generally have surface areas ranging from about 100 to about 1000 m2 / g. In some aspects, the surface area fits in a range of about 150 to about 750 m2 / g, for example, from about 200 to about 600 m2 / g. The surface area of the activating support can vary from about 200 to about 500 m2 / g in another aspect of this invention. For example, activating supports having surface areas of about 300 m2 / g, about 350 m2 / g, about 400 m2 / g, or about 450 m2 / g, can be employed in this invention.
After calcination, the pore volume of the activator support is generally greater than about 0.5 mL / g. The pore volume is often greater than about 0.75 mL / g, or greater than about 1 mL / g. In another aspect, the pore volume is greater than about 1.2 ml / g. In yet another aspect, the pore volume fits in a range of about 0.8 ml / g to about 1.8 ml / g, such as, for example, from about 1 ml / g to about 1, 6 ml / g.
The calcined activating supports disclosed here generally have average particle sizes ranging from about 5 microns to about 150 microns. In some aspects of this invention, the average particle size ranges from about 30 microns to about 100 microns. For example, the average particle size of the activating supports can be in the range of about 40 to about 80 microns.
In accordance with another aspect of the present invention, one or more of transition metal and / or metallocene compounds can be pre-contacted with an olefin monomer and an organoaluminium compound for a first period of time before contacting this mixture with a activator support (for example, a chemically treated silica coated alumina). Once the pre-contacted mixture of a transition metal and / or metallocene compound, olefin monomer and organoaluminium compound is contacted with the activating support (one or more than one), the composition still comprising the activating support is called “post-contacted” mixture. The post-contacted mixture can remain in further contact for a second period of time before being placed in the reactor where the polymerization process will be carried out.
According to another aspect of the present invention, one or more transition metal and / or metallocene compounds can be pre-contacted with an olefin monomer and an activating support (for example, a chemically treated silica coated alumina) for a first period of time before contacting this mixture with an organoaluminium compound. Once the pre-contacted mixture of the transition metal and / or metallocene compound, olefin monomer, and activating support (one or more than one) is contacted with the organoaluminum compound, the composition still comprising the organoalumin is called a mixture “Post-contacted”. The post-contacted mixture can remain in additional contact for a second period of time before being introduced into the polymerization reactor.
OPTIONAL ACTIVATING SUPPORTS The present invention comprises several catalyst compositions that can include an activating support. For example, a catalyst composition is provided comprising at least one metallocene or transition metal compound and at least one activating support. At least one activator support comprises at least one silica-coated alumina, having a weight ratio of alumina to silica ranging from about 1: 1 to about 100: 1, which is treated with at least one electron withdrawing anion .
Such catalyst compositions further comprise an optional additional activating support, such as a chemically treated solid oxide, which is different from the chemically treated silica coated alumina of the present invention. Alternatively, the catalyst composition may further comprise an activating support selected from a mineral clay, a pillared clay, an exfoliated clay, gelled in another oxide matrix, a layered silicate mineral, a layered silicate mineral, a layered aluminosilicate mineral, an aluminosilicate mineral without layers, and the like, or any combination thereof.
Accordingly, chemically treated solid oxides have improved acidity compared to the corresponding untreated solid oxide compound. The chemically treated oxide solid also functions as a catalyst activator in comparison to the corresponding untreated oxide solid. While the chemically treated solid oxide activates the metallocene in the absence of co-catalysts, it is not necessary to eliminate the co-catalysts from the catalyst composition. The function of activating the activating support is evident in the enhanced activity of the catalyst composition as a whole, compared to the catalyst composition containing the corresponding untreated solid oxide. However, it is believed that the chemically treated solid oxide can function as an activator, even in the absence of organoaluminium compounds, aluminoxanes, organoboro compounds, ionizing ionic compounds, and the like.
Chemically treated solid oxides can comprise at least one solid oxide treated with at least one electron-removing anion. Although not intended to be limited by the following statement, treatment of the solid oxide with an electron-removing component is believed to increase or improve the acidity of the oxide. Therefore, either the activating support has Lewis or Bronsted acidity which is typically greater than the Lewis or Bronsted acidity strength of the untreated solid oxide, or activating support has a greater number of acidic locations than the untreated solid oxide. , or both. One method to quantify the acidity of the chemically treated and untreated solid oxide material is to compare the polymerization activities of treated and untreated oxides under acid catalyzed reactions. The chemically treated solid oxides of this invention are generally formed from an inorganic solid oxide which exhibits Lewis or Bronsted acid behavior and has relatively high porosity. The oxide solid is chemically treated with an electron-removing component, typically an electron-removing anion to form an activating support. The pore volume and the surface area of the silica-coated alumina were discussed in the previous section. The solid oxides used to prepare the additional chemically treated solid oxides generally have a pore volume greater than about 0.1 ml / g. according to another aspect of the present invention the solid oxide has a pore volume greater than about 0.5 ml / g. In accordance with yet another aspect of the invention, the solid oxide has a pore volume greater than about 1 ml / g.
In another aspect, the solid oxide used to prepare the additional chemically treated solid oxide has a surface area of about 100 to about 1000 m2 / g, for example, in the range of about 200 to about 800 m2 / g. In yet another aspect of the present invention, the solid oxide has a surface area in a range from about 250 to about 600 m2 / g.
In yet another aspect, the optional chemically treated solid oxide may comprise a solid inorganic oxide comprising oxygen and at least one element selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 , 13, 14, or 15 of the periodic table, or comprising oxygen and at least one element selected from elements of lanthanide or actnide. (See: Hawley's Condensed Chemical Dictionary, 11th Ed., John Wiley &Sons;1995; Cotton, FA, Wilkinson, G., Murillo, CA, and Bochmann, M., Advanced Inorganic Chemistry, 6th Ed., Wiley-lnterscience, 1999.) For example, inorganic oxide can comprise oxygen and at least one element selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb , Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn and Zr.
Suitable examples of solid oxide materials or compounds that can be used to form chemically treated solid oxide include, but are not limited to, AI2O3, B2O3, BeO, BÍ2O3, CdO, Co3O4, Cr2O3, CuO, Fe2O3, Ga2O3, La2O3, Mn2O3, MoO3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2, V2O5, WO3, Y2O3, ZnO, ZrO2, and the like, including mixed oxides thereof, and combinations thereof. For example, the solid oxide that can be used to prepare the additional chemically treated solid oxide may comprise silica, alumina, silica-alumina, aluminum phosphate, heteropolitungstate, titania, zirconia, magnesia, boron, zinc oxide, their mixed oxides or any combination of these. As noted above, if the solid oxide is a silica-alumina, this material is different from the silica-coated aluminas of the present invention, which have both high alumina content and silica coated in an alumina matrix. These known silica-alumina mixed oxides having an alumina to silica weight ratio of less than 1: 1 can be used to form an additional or optional activating support. For example, the alumina to silica weight ratio in these mixed silica-alumina oxides is often in the range of about 0.05: 1 to about 0.25: 1, as reflected in Example 1. However, these silica- alumina can optionally be used in combination with (ie, or in addition to) the high alumina coated alumina activating supports of the present invention.
The solid oxides of this invention, which can be used to prepare additional chemically treated solid oxides, comprise oxide materials such as alumina, compounds of "mixed oxide" thereof as silica-alumina, and combinations and mixtures thereof. Examples of solid oxides that can be used in the additional activating support of the present invention include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, zeolites, various clay minerals, alumina-titania, alumina-zirconia, zinc-aluminate, and the like.
Suitable electron withdrawal components / anions have been discussed previously. These may include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorsulfate, fluorborate, phosphate, fluorophosphate, trifluoracetate, triflate, fluorzirconate, fluortitanate, and the like, including mixtures and combinations thereof. Thus, for example, the optional activating support (e.g., chemically treated solid oxide) additionally used in the catalyst compositions of the present invention can be, or can comprise, fluoridated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, and the like, or combinations thereof.
In addition, as discussed above, optional chemically treated solid oxides may further comprise a metal or metal ion, such as zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, and the like, or their combinations. Examples of chemically treated solid oxides that contain a metal or metal ion include, but are not limited to, zinc-impregnated chlorinated alumina, titanium-impregnated fluorinated alumina, zinc-impregnated fluorinated alumina, zinc-impregnated chlorinated alumina, silica-silica zinc-impregnated fluoridated alumina, zinc-impregnated sulfated alumina, chlorinated zinc aluminate, fluorinated zinc aluminate, sulfated zinc aluminate, and the like, or any combination thereof.
The methods for preparing, and calcining conditions for, the additional or optional activating supports may be the same as those provided above in the discussion of silica coated alumina activating supports. The pore volume and surface area of the silica coated aluminas were discussed in the previous section, and the variations provided therein may be suitable for the additional optional activating supports.
According to another aspect of the present invention, the catalyst composition may further comprise an exchangeable ion activating support, including, but not limited to, silicate and aluminosilicate compounds or minerals, with layer structures or without layer, and combinations thereof. In another aspect of this invention, exchangeable ion layer aluminosilicates as pillared clays are used as optional activating supports. The exchangeable ion activating support can optionally be treated with at least one electron withdrawing anion like the one disclosed here, although generally the exchangeable ion activating support is not treated with an electron withdrawing anion.
According to another aspect of the present invention, the catalyst composition further comprises clay minerals having exchangeable cations and layers capable of expansion. Common clay mineral activating supports include, but are not limited to, aluminosilicate layers of exchangeable ions such as pillared clays. Although the term "support" is used, it should not be interpreted as an inert component of the catalyst composition, but should be considered an active part of the catalyst composition, due to its close association with the transition metal or metallocene compound.
In accordance with another aspect of the present invention, the clay materials of this invention comprise materials in their natural state or which have been treated with various ions by wetting, ion exchange or piling. Generally, the clay meterial activating support of this invention comprises clays that have ions exchanged for larger cations, including highly charged polynuclear complex cations. However, the clay material activating supports of this invention also comprise clays that have ions exchanged for salts. simple, including, but not limited to, Al (lll), Fe (ll), Fe (lll), and Zn (ll) salts with binders such as halide, acetate, nitrate or nitrite.
According to another aspect of the present invention, the additional activating support comprises a pillared clay. The term “pillarized clay” is used to refer to clay materials that have had ions exchanged for large, highly charged metal complex cations usually polynuclear. Examples of such ions include, but are not limited to, Keggin ions which can have charges such as 7+, various polyoxometalates, and other large ions. Thus, the term pillarization refers to a simple reaction in which the exchangeable cations in a clay material are replaced by large, highly charged ions, such as Keggin ions. These polymeric cations are then immobilized with the clay interlayer and when calcined are converted into metal oxide “pillars”, effectively supporting the clay layers as column-like structures. Thus, as soon as the clay is dried and calcined to produce the supporting pillars between the clay layers, the expanded lattice structure is maintained and the porosity is increased. The resulting pores can vary in shape and size as a function of the pillar material and the main clay material used. Examples of pillar and pillar clays are found in: T.J. Pinnavaia, Science 220 (4595), 365-371 (1983); J.M. Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3, pp. 55-99, Academic Press, Inc., (1972); U.S. Patent No. 4,452,910; U.S. Patent No. 5,376,611; and U.S. Patent No. 4,060,480; whose disclosures are incorporated herein by reference in full. The pillarization process uses clay minerals having exchangeable cations and layers capable of expanding. Any pillarized clay that can increase the polymerization of olefins in the catalyst composition of the present invention can be used. Therefore, clay minerals suitable for pillaring include, but are not limited to, allophanes; smectites, both dioctahedral (Al) and trioctahedral (Mg) and their derivatives such as montmorillonites (bentonites), nontronites, hectorites, or laponites; haloisites; vermiculites; micas; fluorine; chlorites; mixed layer clays; fibrous clays including, but not limited to, sepiolites, atapulgites, and paligorschites; a clay of the serpentine type; illita; laponite; saponite; and any combination of these. In one aspect, the pillared clay activating support comprises bentonite or montmorillonite. The main component of bentonite is montmorillonite, ____________________________________________________________ The pillared clay can be pretreated if desired. For example, a pillarized bentonite is pretreated by drying at about 300 ° C under an inert atmosphere, usually anhydrous nitrogen, for about 3 hours, before being added to the polymerization reactor. Although an example pretreatment is described here, it is to be understood that preheating can be carried out at many other temperatures and times, including any combination of temperature and time steps, all of which are understood by this invention.
The activating supports used to prepare the catalyst compositions of the present invention can be combined with other inorganic support materials, including, but not limited to, zeolites, inorganic oxides, phosphate inorganic oxides and the like. In one aspect, common support materials that are used include, but are not limited to, silica, silica-alumina, alumina, titania, zirconia, magnesia, boron, thorium, aluminum phosphate, aluminum phosphate, silica-titania, silica / titania co-precipitate, their mixtures or any combination thereof.
TRANSITION METAL OR METALOCENE COMPOUNDS
The activating supports of the present invention can be employed in a catalyst composition with one or more transition metal compounds, with one or more metallocene compounds, or combinations thereof (for example, at least transition metal or metallocene compound). Generally, there is no limit on the selection of the transition metal and / or metallocene compounds and / or compounds, which can be used in combination with silica coated alumina activating supports disclosed herein. For example, the transition metal compounds disclosed in U.S. Patent Nos. 7,247,594 and 7,534,842, which are incorporated herein by reference in their entirety, can be used with the silica-coated alumina activating supports of this invention. Non-limiting examples of such transition metal compounds may include, but are not limited to, [bis (2,6-dithercbutylphenolate)] titanium dichloride, [tetrakis (2,6-diisopropylphenolate)] zirconium, dichloride [bis (2 , 6-dimethylphenolate)] zirconium bis (tetrahydrofuran), [zirconium (2,6-dithercbutyl-4-methyl) phenolatej tribenzyl, tetrakis (dimethylamido) zirconium, bis (tert-butylamido) cyclodiphosphazane zirconium dibenzyl, bis (tertiary) ) zirconium cyclodiphosphazane dichloride, 2,2'-methylenebis (6-tert-butyl-4-methylphenoxy) titanium dichloride, 2,2'-thiobis (6-tert-butyl-4-methylphenoxy) titanium dichloride, N- alkoxy - / - titanium tetrahydrofuran quetoiminate dichloride, 2,2 '- [1,2-ethanobis [methylamido-N1methylene1bisf4.6 tert-butylphenoxyflzirconium dibenzyl, N, N' - [(amino-N) di-2,1- zirconium ethanoybis [2-N-2,4,6-trimethylphenyl amidojdibenzyl, and the like, or combinations thereof.
Often, in a metallocene compound, the transition metal is Ti, Zr, Hf, Cr, La, Y, Sc, or V (or it can be more than one, for example, if a dinuclear metallocene compound is used). Some examples of suitable loop-metallocene compounds include, but are not limited to: similar. Depositors used the abbreviations Ph for phenyl, Me for methyl, and t-Bu for tert-butyl.
The following bridged metallocene compounds can also be used in catalyst compositions of the present invention. and the like.
Additional examples of bridged metallocene compounds that are suitable for use in catalyst compositions of the present invention are contemplated. These include, but are not limited to: and the like.
The following non-limiting examples of two-carbon bridged metallocene compounds can also be used in the catalyst composition of the present invention:; and the like. The integer n 'in these metallocene compounds generally range from about 0 to about 10, inclusive. For example, n 'can be 1, 2, 3, 4, 5, 6, 7, or 8.
Other bridged metallocene compounds can be used in catalyst compositions of the present invention, so the scope of the present invention is not limited to the metallocene species provided above.
Likewise, bridged metallocene compounds can be used in catalyst compositions of the present invention, such compounds can include, but are not limited to: Other suitable bridged metallocene compounds include, but are not limited to, the following compounds: bridged metallocene can be used in the catalyst compositions of the present invention, so the scope of the invention is not limited to the bridged metallocene species provided above. Other metallocene compounds, including half-sandwich and cyclodienyl compounds, can be used in catalyst compositions of the present invention, and such compounds may include, but are not limited to, the following:; and the like, where i-Pr is short for isopropyl.
In accordance with one aspect of the invention, at least one transition metal or metallocene compound may comprise a loop-metallocene compound. In another aspect, at least one transition metal or metallocene compound may comprise a bridged metallocene compound. In yet another aspect, at least one transition metal or metallocene compound may comprise a dinuclear metallocene compound. In yet another aspect of the invention, at least one transition metal or metallocene compound may comprise a metallocene compound (or dinuclear compound) containing an alkenyl moiety. For example, a bridged metallocene —or bridged may contain an alkenyl substituent in a Cp, Ind, and / or Flu group .--------- Alternatively, or in addition, a bridged metallocene may contain a alkenyl substituent on the bridged group (or on the bridged atom).
Representative bridged and / or bridged metallocene compounds that can be employed in some aspects of this invention are disclosed in U.S. Patent Nos. 5,498,581, 7,026,494, 7,041,617, 7,119,153, 7,148,298, 7,226,886, 7,294,599, 7,312,283, 7,468,452, 7,517,939, and 7,521,572, the disclosures of which are incorporated herein by reference or in full.
In one aspect of this invention, at least one transition metal or metallocene compound may comprise a bridged metallocene having the following formula: (XI) (X2) (X3) (X4) M1, where: M1 is Ti, Zr, or Hf; (X1) and (X2) independently are a substituted or unsubstituted Cp, Ind, or Flu group; and (X3) and (X4) independently are a halide group (e.g., fluoride, chloride, bromide, iodide) a hydride, an amino, alkoxide, or hydrocarbyl, each having up to 20 carbon atoms.
In another aspect of this invention, at least one transition metal or metallocene compound may comprise a bridged metallocene having the following formula: (X5) (X6) (X7) (X8) M2, where M2 is Ti, Zr, or Hf; (X5) and (X6) independently are a substituted Cp, Ind, or Flu group; (X5) and (X6) are connected by a substituted or unsubstituted group comprising a bridged chain of 2 to 5 carbon atoms, or a bridged atom of carbon, silicon, germanium, tin, boron, nitrogen, or phosphorus; and (X7) and (X8) independently are a halide, hydride, starch, alkoxide or hydrocarbyl group, each having up to 20 carbon atoms.
The bridged and bridged metallocenes represented by the formulas above can comprise a variety of substituents. At each occurrence, any substituent on a substituted Cp, substituted Ind, substituted Flu, and substituted bridged group can independently be an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, germanium group, tin group, lead group, boron group, aluminum group, inorganic group, organometallic group, or a substituted derivative of these, having from 1 to 20 carbon atoms: a halide or hydrogen .
A hydrocarbyl group is used here to specify a radical group that includes, but is not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkylenyl, alkynyl, aralkyl, aralkenyl, aralkynyl, and the like, and includes all of its substituted derivatives. substituted, unsubstituted, branched and linear heteroatom and / or heteroatom. Suitable hydrocarbon groups may include, but are not limited to, methyl, ethyl, propyl, n-butyl, tert-butyl, sec-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl , ethenyl, propenyl, butenyl, pentenyl, hexenyl, phenyl, benzyl, tolyl, xylyl, naphthyl, cyclopentyl, cyclohexyl, and the like.
Examples of halides include fluoride, chloride, bromide and iodide.
Oxygen groups are oxygen-containing groups, examples of which include, but are not limited to, alkoxy or aryloxy (-ORA), -OC (O) RA, -OC (O) H, -OSÍRA3, -OPRA2, -OAIRA2, and similar, including their substituted derivatives, where RA in each case is selected from alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms. Examples of alkoxy or aryloxy groups (-ORA) include, but are not limited to, methoxy, ethoxy, butoxy, phenoxy, substituted phenoxy and the like.
Sulfur groups are sulfur-containing groups, examples of which include, but are not limited to, -SRA, -OSO2RA, -OSO2ORA, -SCN, -SO2RA, and the like, including their substituted derivatives, where RA in each case is selected from alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or substituted aralkyl having from 1 to 20 carbon atoms.
Nitrogen groups are nitrogen-containing groups, which include, but are not limited to, -NH2, -NHRA, -NRA2, -NO2, -CN, and the like, including their substituted derivatives, where RA in each case is selected from alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or substituted aralkyl having from 1 to 20 carbon atoms.
Phosphorus groups are phosphorus-containing groups, which include, but are not limited to, -PH2, -PHRA, -PRA2, -P (O) RA2, -P (ORA) 2, -P (O) (ORA) 2, and the like, including its derivatives, wherein RA in each case is selected from alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or substituted aralkyl having from 1 to 20 carbon atoms.
Arsenic groups are groups containing arsenic, which include, but are not limited to, -AsHRA, -AsRA2, -As (O) RA2, -As (ORA) 2, -As (O) (ORA) 2, and the like, including its substituted derivatives, where RA in each case is selected from alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or substituted aralkyl having from 1 to 20 carbon atoms.
Carbon groups are carbon-containing groups, which include, but are not limited to, alkyl halide groups that comprise alkyl halide groups substituted with I at about 20 carbon atoms, aralkyl groups with 1 at about 20 carbon atoms, -C (O) H, -C (O) RA, -C (O) ORA, cyano, -C (NRA) H, -C (NRA) RA, -C (NRA) ORA, and the like, including derivatives substituted, where RA in each case is selected from alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl or substituted aralkyl having from 1 to 20 carbon atoms.
Silicon groups are groups containing silicon, which include, but are not limited to, silyl groups such as alkylsilyl groups, arylsilyl groups, arylalkylsilyl groups, siloxy groups, and the like, which in each case have 1 to 20 carbon atoms. For example, silicon groups include trimethylsilyl and phenyloctylsilyl groups.
Germanium groups are germanium-containing groups, which include, but are not limited to, germyl groups such as alkylgermyl groups, arylgermyl groups, arylalkylgermyl groups, germyloxy groups, and the like, which in each case have 1 to 20 carbon atoms.
Tin groups are groups containing tin, which include, but are not limited to, stanyl groups such as alkylstannyl groups, arylstannyl groups, arylalkylstannyl groups, stanoxy (or "stanyloxy") groups, and the like, which in each case have from 1 to 20 atoms of carbon. Thus, tin groups include, but are not limited to, stanoxy groups.
Lead groups are groups containing lead, which include, but are not limited to, alkyl lead groups, aryl lead groups, aryl alkyl lead groups, and the like, which in each case have 1 to 20 carbon atoms. Arylalkyl lead groups, and the like, which in each case have 1 to 20 carbon atoms.
Boron groups are groups containing boron, which include, but are not limited to, -BRA2, -BXA2, -BRAXA, where XA is a monoanionic group such as halide, hydride, alkoxide, alkyl thiolate and the like, and where RA in each case is selected from alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms.
Aluminum groups are groups containing aluminum, which include, but are not limited to, -AIRA2, -AIXA2, -AIRAXA, where XA is a monoanionic group such as halide, hydride, alkoxide, alkyl thiolate, and the like, and in which RA in each case it is selected from alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms.
Inorganic groups that can be used as substituents include, but are not limited to, -SO2XA, -OAIXA2, -OSÍXA3, -OPXA2, -SXA, - OSO2XA, -AsXA2, -As (O) XA2, -PXA2, and the like , where XA is a monoanionic group such as halide, hydride, starch, alkoxide, alkyl thiolate, and the like, and where any alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted or substituted aralkyl group in these linkers it has 1 to 20 carbon atoms.
Organometallic groups that can be used as substituents include, but are not limited to, organoboro groups, organoalumin groups, organogalium groups, organosilicon groups, organogermanium groups, organo-tin groups, organocholone groups, transition organo-metal groups, and the like, having from 1 to 20 carbon atoms.
It is also contemplated that at least one transition metal or metallocene compound may comprise one or more dinuclear metallocene compounds. Suitable dinuclear metallocenes include, but are not limited to, those compounds disclosed in US Patent Application No. 12 / 489,630 and US Patent Publication No. 2009/0170690, 2009/0170691 and 2009/0171041, the disclosures of which are incorporated herein by reference in their entirety. .
ORGANOALUMINUM COMPOUNDS
In some respects, the catalyst compositions of the present invention can comprise one or more organoaluminium compounds. Such compounds can include, but are not limited to, compounds having the formula: (RB) 3AI; where RB is an allphatic group having from 1 to 10 carbon atoms. For example, RB can be methyl, ethyl, propyl, butyl, hexyl, or isobutyl.
Other organoaluminium compounds that can be used in catalyst compositions disclosed herein include, but are not limited to, compounds having the formula: AI (X9) m (X10) 3-m, where X9 is a hydrocarbil; X10 is an alkoxide or aryloxide, a halide, or a hydride; and m is 1 to 3, inclusive. Hydrocarbyl is used here to specify a hydrocarbon radical group and includes, but is not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkylenyl, alkynyl, aralkyl, aralkenyl, aralkyl, and the like, and includes all of its substituted derivatives, unsubstituted, branched, linear and / or substituted heteroatom.
In one aspect, X9 is a hydrocarbon having from 1 to about 20 carbon atoms. In another aspect of the present invention, X9 is an alkyl having 1 to 10 carbon atoms. For example, X9 can be methyl, ethyl, propyl, n-butyl, sec-butyl, isobutyl, or hexyl, and the like, in yet another aspect of the present invention.
According to one aspect of the present invention, X10 is an alkoxide or aryloxide, any having from 1 to 20 carbon atoms, a halide or a hydride. In another aspect of this invention, X10 is independently selected from fluorine and chlorine. In yet another aspect, X10 is chlorine.
In the formula, AI (X9) m (X10) 3-m, m is a number from 1 to 3 inclusive, and generally, m is 3. The value of m is not restricted to an integer; therefore, this formula includes sesquihalide compounds or other organo-aluminum agglomeration compounds.
Examples of organoaluminium compounds suitable for use in accordance with the present invention include, but are not limited to, trialkylaluminum compounds, dialkyl aluminum halide compounds, dialkyl aluminum alkoxide compounds, dialkyl aluminum hydride compounds, and combinations thereof. Specific non-limiting examples of suitable organoaluminium compounds include trimethylaluminium (TMA), triethylaluminium (TEA), tri-n-propylaluminium (TNPA), tri-n-butylalumin (TNBA), triisobutylalumin (TIBA), tri-n-hexylalumin, tri-n-octyl aluminum, diisobutyl aluminum hydride, diethyl aluminum ethoxide, diethyl aluminum chloride, and the like, or combinations thereof. The present invention contemplates a method for pre-contacting a transition metal and / or metallocene compound with an organoaluminum compound and an olefin monomer to form a pre-contacted mixture, before contacting this pre-contacted mixture with an activating support. to form a catalyst composition. When the catalyst composition is prepared in this way, generally, although not necessarily, a portion of the organo-aluminum compound is added to the pre-contacted mixture and another portion of the organo-aluminum compound is added to the post-contacted mixture prepared when the pre-contacted mixture is contacted with the solid oxide activating support. However, the entire organoaluminium compound can be used to prepare the catalyst composition in the pre-contact or post-contact stage. Alternatively, all catalyst components are contacted in one step.
In addition, more than one organoaluminium compound can be used in the pre-contact or post-contact stage. When an organo-aluminum compound is added in multiple steps, the amounts of organo-aluminum compound disclosed here include the total amount of organo-aluminum compound used in both pre-contacted and post-contacted mixtures, and any additional organo-aluminum compound added to the reactor. polymerization. Therefore, the total amounts of organoaluminium compounds are disclosed regardless of whether a single organoaluminium compound or more than one organoaluminium compound is used.
ALUMINOXAN COMPOUNDS The present invention contemplates a catalyst composition that can comprise an aluminoxane compound. As used herein, the term "aluminoxane" refers to compounds, compositions, mixtures or distinct species of aluminoxane, regardless of how such aluminoxanes are prepared, formed or otherwise provided. For example, a catalyst composition comprising an aluminoxane compound can be prepared in which the aluminoxane is supplied as a poly (aluminum hydrocarbon oxide), or in which the aluminoxane is provided as the combination of an alkyl aluminum compound and a source of aluminum. active protons like water. Aluminoxanes are also referred to as poly (aluminum hydrocarbon oxides) or organoaluminoxanes.
The other catalyst components are generally contacted with aluminoxane in a saturated hydrocarbon compound solvent, although any solvent that is substantially inert to the reactants, intermediates and products of the activation step can be used. The catalyst composition formed in this way is collected by any suitable method, for example, by filtration. Alternatively, the catalyst composition is introduced into the polymerization reactor being isolated. The aluminoxane compound of this invention can be an oligomeric aluminum compound that comprises linear structures, cyclic structures, or cage structures or mixtures of all three. Cyclic aluminoxane compounds having the formula: where R is a branched or linear alkyl having 1 to 10 carbon atoms, and p is an integer from 3 to 20, are comprised by this invention. The AIRO portion shown here also forms the repeat unit in a linear aluminoxane. Thus, linear aluminoxanes having the formula: where R is a linear or branched alkyl having 1 to 10 carbon atoms, and q is an integer from 1 to 50, are also comprised by this invention.
In addition, aluminoxanes may have cage structures of the formula Rt5r + aRbr-gAI4rO3r, wherein Rt is a linear or branched alkyl group having from 1 to 10 carbon atoms; Rb is a linear or branched bridged alkyl group having 1 to 10 carbon atoms; r is 3 or 4; and a is equal to nAI (3) - nO (2) + nO (4), where nAI (3) is the number of three coordinated aluminum atoms, nO (2) is the number of two coordinated oxygen atoms, and nO (4) is the number of 4 coordinated oxygen atoms.
Thus, the aluminoxanes that can be used in the catalyst compositions of the present invention are generally represented by formulas such as (R-AI-O) p, R (R-AI-O) qAIR2, and the like. In these formulas, the group R is generally a straight or branched C1-C6 alkyl, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. Examples of aluminoxane compounds that can be used in accordance with the present invention include, but are not limited to, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane isane , 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, and the like, or any combination thereof. Methylaluminoxane, ethylaluminoxane, and iso-butylaluminoxane are prepared from trimethylaluminum, triethylalumin, or triisobutylalumin, respectively, and are sometimes referred to as poly (methyl aluminum oxide), poly (ethyl aluminum oxide), and poly (isobutyl oxide) aluminum), respectively. It is also within the scope of the invention to use an aluminoxane in combination with a trialkylaluminum, as disclosed in U.S. Patent No. 4,794,096, incorporated herein in its entirety by reference. The present invention contemplates many values of p and q in the formulas of aluminoxane (R-AI-O) p and R (R-AI-O) qAIR2, respectively. In some respects, p and q are at least 3. However, depending on how organoaluminoxane is prepared, stored and used, the value of p and q can vary within a single sample of aluminoxane, and such combinations of organoaluminoxanes are contemplated here.
In the preparation of a catalyst composition containing an aluminoxane, the molar ratio of the total aluminum moieties in the aluminoxane (or aluminoxanes) to the total moises of the transition metal and / or metallocene compound (or compounds) in the composition is generally between about 1 : 10 and about 100,000: 1. In another aspect, the molar ratio is in a range of about 5: 1 to about 15,000: 1. Optionally, aluminoxane can be added to a polymerization zone in variations from about 0.01 mg / L to about 1000 mg / L, from about 0.1 mg / L to about 100 mg / L, or from about 1 mg / L to about 50 mg / L.
Organoaluminoxanes can be prepared by various procedures. Examples of organoaluminoxane preparations are disclosed in U.S. Patent Nos. 3,242,099 and 4,808,561, the disclosures of which are incorporated herein by reference in their entirety. For example, water in an inert organic solvent can be reacted with an aluminum alkyl compound, such as (RB) 3AI, to form the desired organoaluminoxane compound. While not committing to the theory, it is believed that this synthetic method can provide a mixture of both linear and cyclic R-AI-0 aluminoxane species, both of which are comprised by this invention. Alternatively, organoaluminoxanes are prepared by reacting an aluminum alkyl compound, such as (RB) 3AI, with a hydrated salt, such as hydrated copper sulfate, in an inert organic solvent. ORGANOROUS ORGANOBORATE COMPOUNDS
In accordance with another aspect of the present invention, a catalyst composition further comprising organoboro or organoborate compound is provided. Such compounds include neutral boron compounds, borate salts, and the like, or combinations thereof. For example, fluorganoboro and fluorganoborate compounds are contemplated.
Any fluorganoboro or fluorganoborate compound can be used with the present invention. Examples of fluorganoborate compounds that can be used in the present invention include, but are not limited to, fluorinated aryl borates such as Ν, Ν-dimethylanilinium tetrakis (pentafluorfenyl) borate, triphenylcarbenium tetrakis (pentafluorfenyl) borate, lithium tetrakis (pentafluorfenΝ) , Ν-dimethylanilinium tetrakis [3,5-bis (trifluormethyl) phenyl] borate, triphenylcarbenium tetrakis [3,5-bis (trifluormethyl) phenyljborate, and the like, or mixtures thereof. Examples of fluorganoboro compounds that can be used as co-catalysts in the present invention include, but are not limited to, tris (pentafluorfenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, and the like, or mixtures thereof . Although not intended to be bound by the following theory, these examples of fluorganoborate and fluorganoboro compounds, and related compounds, are considered to form "weakly coordinated" anions when combined with organometal or metallocene compounds, as disclosed in Patent N US 5,919,983, the disclosure of which is incorporated herein in its entirety by reference. Depositors also contemplate the use of diboro or bis-boron compounds, or other bifunctional compounds containing two or more boron atoms in the chemical structure, as disclosed in J. Am. Chem. Soc., 2005, 127, pp. 14756-14768, the content of which is incorporated herein by reference in its entirety.
Generally, any amount of organoboro compound can be used. According to one aspect of this invention, the molar ratio of the mol totals of compound (or compounds) of organoboro or organoborate to the mol totals of compound (or compounds) of transition metal and / or metallocene is in a range of about 0.1: 1 to about 15: 1. Generally, the amount of the boron fluororgane or fluororgane borate compound used is from about 0.5 mol to about 10 mol of boron / borate compound per mol of transition metal and / or metallocene compounds. According to another aspect of this invention, the amount of fluorgan boron or fluorgan borate compound is from about 0.8 mol to about 5 mol of boron / borate compound per mol of transition metal and / or metallocene compounds.
IONIZING IONIC COMPOUNDS The present invention provides a catalyst composition that can further comprise an ionizing ionic compound. An ionizing compound is an ionic compound that can function as a co-catalyst to increase the activity of the catalyst composition. Although not committing to theory, the ionizing ionic compound is believed to be able to react with a metallocene compound and convert the metallocene into one or more cationic metallocene compounds, or incipient cationic metallocene compounds. Again, while not committing to theory, it is believed that the ionizing ionic compound can function as an ionizing compound by extracting completely or partially an anionic binder, possibly a non-alkadienyl binder, from the metallocene. However, the ionizing ionic compound is an activator or co-catalyst independent of ionizing the metallocene, abstracting a ligand to form an ion pair, weakening the metal-ligand bond in the metallocene, simply coordinating with a ligand, or activating metallocene by some other mechanisms.
In addition, it is not necessary for the ionizing ionic compound to activate the transition metal and / or metallocene compound only. The activation function of the ionizing ionic compound may be evident in the enhanced activity of a catalyst composition as a whole, compared to a catalyst composition that does not contain an ionizing ionic compound.
Examples of ionizing ionic compounds 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, tri (n-butyl) ) tetrakis ammonium (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, tri (n-butyl) ammonium tetrakis (pentafluorfenyl) borate, N, N-dimethylanilinium tetrakis (p-tolyl) borate, Ν, Ν-dimethylanilinium tetrakis (m-tolyl) borate, N, N-dimethylanilinium tetrakis (2,4- dimethylphenyl) borate, Ν, Ν-dimethylanilinium tetrakis (3,5-dimethylphenyl) borate, Ν, Ν-dimethylanilinium tetrakis [3,5-bis (trifluormethyl) phenyl] borate, Ν, Ν-dimethylanilinium tetrakis (pentafluorfen, pentafluorfen) tetrakis (p-tolyl) borate, triphenylcarbene tetrakis (m-tolyl) borate, triphenylcarbene tetrakis (2,4-dimethylphenyl) borate, triphenylcarbenium tetrakis (3,5-dimethylphenyl) borate, triphenylcarbene tetrakifor [3,5-bis-bismethyl] phenyl] borate, triphenylcarbenium tetrakis (pentafluorfenil) borate, tropilío tetrakis (p-tolyl) borate, tropilío tetrakis (m-tolyl) borate, tropilío tetrakis (2,4-dimethylphenyl) borate, tropilío tetrakis (3,5-dimethylphenyl) borate 3,5-bis (trifluormethyl) phenyl] borate, tropilío tetrakis (pentafluorfenil) borate, lithium tetrakis (pentafluorfenil) borate, lithium tetrafenilborate, lithium tetrakis (p-tolyl) borate, lithium tetrakis (m-tolyl) borate, lithium (m-tolyl) borate, lithium 2,4-dimethylphenyl) borate, lithium tetrakis (3,5-dimethylphenyl) borate, lithium tetrafluorborate, sodium tetrakis (pentafluorfenyl) borate, sodium tetrafenylborate, sodium tetrakis (p-tolyl) borate, sodium tetrakis (m-tolyl) borate, sodium tetrakis (2,4-dimethylphenyl) borate, sodium tetrakis (3,5-dimethylphenyl) borate, sodium tetrafluorborate, potassium tetrakis (pentafluorfenyl) borate, potassium tetrafenylborate, potassium tetrakis (p-tolyl) borate (potassium tetrakis) ) borate, potassium tetrakis (2,4-dimethyl-phenyl) borate, potassium tetrakis (3,5-dimethyl-phenyl) ) borate, potassium tetrafluorborate, lithium tetrakis (pentafluorfenyl) aluminate, lithium tetrafenylaluminate, lithium tetrakis (p-tolyl) aluminate, lithium tetrakis (m-tolyl) aluminate, lithium tetrakis (2,4-dimethylphenyl), aluminate, 5-dimethylphenyl) aluminate, lithium tetrafluoraluminate, sodium tetrakis (pentafluorfenyl) aluminate, sodium tetrafenylaluminate, sodium tetrakis (p-tolyl) aluminate, sodium tetrakis (m-tolyl) aluminate, sodium tetrakis (2,4-dimethyl aluminate) (3,5-dimethylphenyl) aluminate, sodium tetrafluoraluminate, potassium tetrakis (pentafluorfenyl) aluminate, potassium tetrafenylaluminate, potassium tetrakis (p-tolyl) aluminate, potassium tetrakis (m-tolyl) -aluminate, 2,4-potassium tetrak-dimethyl-tetrak aluminate, potassium tetrakis (3,5-dimethylphenyl) aluminate, potassium tetrafluoraluminate, and the like, or combinations thereof. The ionizing ionic compounds useful in this invention are not limited to these; other examples of ionizing ionic compounds are disclosed in U.S. Patent Nos. 5,576,259 and 5,807,938, the disclosures of which are incorporated herein by reference in their entirety.
OLEFINE MONOMERS
Unsaturated reagents that can be employed with catalyst compositions and polymerization processes of this invention generally include olefin compounds having 2 to 30 carbon atoms per molecule and having at least one olefinic double bond. This invention comprises polymerization processes using a single olefin such as ethylene or propylene, as well as copolymerization, terpolymerization etc. reactions using an olefin monomer with at least one different olefinic compound. For example, the resulting ethylene copolymers, etc., generally contain a greater amount of ethylene (> 50 mol percent) and a smaller amount of comonomer (<50 mol percent), although this is not a requirement. Comonomers that can be polymerized with ethylene generally have 3 to 20 carbon atoms in their molecular chain.
Acyclic, cyclic, polycyclic, terminal (a), internal, linear, branched, substituted, unsubstituted, functionalized and non-functionalized olefins can be employed in this invention. For example, typical unsaturated unsaturated compounds that can be polymerized with the catalyst compositions of this invention include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene , 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3 -heptene, the four normal octenes, the four normal nonenos, the five normal decenos, and similarities, or mixtures of two or more of these compounds. Cyclic and bicyclic olefins, including, but not limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, can also be polymerized as described above. Styrene can also be employed as a monomer in the present invention. In one aspect, the olefin monomer is ethylene; alternatively, the olefin monomer is propylene.
When a copolymer (or alternatively, a terpolymer) is desired, the olefin monomer may comprise, for example, ethylene or propylene, which is copolymerized with at least one comonomer. According to one aspect of this invention, the olefin monomer in the polymerization process comprises ethylene. In this regard, examples of suitable olefin comonomers include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1 -pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, and similar, or combinations thereof. According to one aspect of the present invention, the comonomer can comprise 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or a combination thereof.
Generally, the amount of comonomer introduced into a reactor zone to produce the copolymer is about 0.01 to about 50 weight percent of the comonomer based on the total weight of the monomer and comonomer. According to another aspect of the present invention, the amount of comonomer introduced into a reactor zone is from about 0.01 to about 40 percent by weight of the comonomer based on the total weight of the monomer and comonomer. In yet another aspect, the amount of comonomer introduced into a reactor zone is about 0.1 to about 35 weight percent comonomer based on the total weight of the monomer and comonomer. In yet another aspect, the amount of comonomer introduced into a reactor zone is about 0.5 to about 20 percent by weight of the comonomer based on the total weight of the monomer and comonomer.
Although not committing to the theory, when branched, substituted or functionalized olefins are used as reagents, it is believed that a steric impediment can prevent and / or slow the polymerization process. Thus, the branched and / or cyclic portions of the olefin removed in some way from the carbon-carbon double bond would not be expected to prevent the reaction in the same way as the olefin substituents located closest to the carbon-carbon double bond. According to one aspect of the present invention, at least one monomer / reagent is ethylene, so the polymerizations are polymerizations involving only ethylene, or copolymerizations with a different olefin, acyclic, cyclic, terminal, internal, linear, branched, substituted or not replaced. In addition, the catalyst compositions of this 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.
POLYMERIZATION PROCESS
The catalyst compositions of the present invention can be used to polymerize olefins to form homopolymers, copolymers, terpolymers, and the like. Such an olefin polymerization process comprises contacting a catalyst composition with at least one olefin monomer and optionally at least one olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises at least one metal compound transition or metallocene and at least one activator support. At least one activating support comprises at least one silica-coated alumina treated with at least one electron withdrawing anion, where the silica-coated alumina generally has a weight ratio of alumina to silica in a range of about 1: 1 at about 100: 1. At least one electron withdrawing anion can comprise fluoride, chloride, bromide, phosphate, triflate, sulfate and the like, or any combination thereof.
Often, a catalyst composition of the present invention, employed in an olefin polymerization process, may further comprise at least one organoaluminium compound. Suitable organoaluminum compounds may include, but are not limited to, trimethylaluminum, triethylalumin, tri-n-propylalumin, tri-n-butylalumin, triisobutylalumin, tri-n-hexylalumin, tri-n-octylalumin, diisobutylaluminum hydride, diethylaluminum ethoxide , diethyl aluminum chloride, and the like, or combinations thereof.
The catalyst compositions of the present invention are intended for any method of olefin polymerization using various types of polymerization reactors. As used herein, "polymerization reactor" includes any polymerization reactor capable of polymerizing olefin comonomers (one or more of a comonomer) to produce homopolymers, copolymers, terpolymers, and the like. The various types of reactors include those that can be referred to as batch reactors, slurry, gas phase, solution, high pressure, tubular or autoclave. The polymerization conditions for the various types of reactor are well known to those skilled in the art. Gas phase reactors can comprise fluidized bed reactors or horizontal stage reactors. Slurry reactors can comprise vertical or horizontal circuits. High pressure reactors can comprise autoclave or tubular reactors. For example, the polymerization reaction can be conducted in a gas phase reactor, a circuit reactor, a stirred tank reactor or a combination of these. Reactor types can include batch processes or continuous processes. Continuous processes could use intermittent or continuous product discharge. The processes may also include partial or complete recycling of unreacted monomer, unreacted comonomer and / or diluent.
The polymerization reactor systems of the present invention can comprise one type of reactor in one system or multiple reactors of the same or different type. The production of polymers in multiple reactors can include several stages in at least two separate polymerization reactors interconnected by a transfer device making it possible to transfer the polymers resulting from the first polymerization reactor in the second reactor. The desired polymerization conditions in one of the reactors may differ from the operating conditions of the other reactors. Alternatively, polymerization in multiple reactors may include the manual transfer of polymer from one reactor to subsequent reactors for continued polymerization. Multiple reactor systems may include any combination including, but not limited to, multiple loop reactors, multiple gas reactors, a combination of loop and gas reactors, multiple high pressure reactors or a combination of high pressure reactors with circuit and / or gas. The multiple reactors can be operated in series or in parallel.
According to one aspect of the invention, the polymerization reactor system may comprise at least one circuit slurry reactor comprising vertical or horizontal circuits. Monomer, diluent, catalyst and optionally any comonomer can be continuously fed into a circuit reactor where polymerization takes place. Generally, continuous processes may comprise the continuous introduction of monomer / comonomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal of this reactor from a suspension comprising polymer particles and the diluent. The effluent from the reactor can be evaporated to remove the solid polymer from the liquids that comprise the diluent, monomer and / or comonomer. Various technologies can be used for this separation step including, but not limited to, evaporation which can include any combination of heat addition and pressure reduction; separation by cyclonic action in a cyclone or hydrocyclone; or separation by centrifugation.
A typical slurry polymerization process (also known as the particle form process) is disclosed, for example, in US Patent Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415, each incorporated herein. by reference in full.
Suitable diluents used in slurry polymerization include, but are not limited to, monomer being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some circuit polymerization reactions can occur under volume conditions where no diluent is used. An example is polymerization of propylene monomer as disclosed in U.S. Patent No. 5,455,314, which is incorporated herein by reference in its entirety.
In accordance with yet another aspect of this invention, the polymerization reactor can comprise at least one gas phase reactor. Such systems can employ a continuous recycling stream containing one or more monomers continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions. The recycling stream can be removed from the fluidized bed and recycled back to the reactor. Simultaneously, the polymer product can be removed from the reactor and fresh or free monomer can be added to replace the polymerized monomer. Such gas phase reactors can comprise a process for multi-stage gas phase polymerization of olefins, in which olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones while feeding a polymer containing catalyst formed in a first polymerization zone to a second polymerization zone. A type of gas-gas reactor is disclosed in U.S. Patent No. 5,352,749, 4588,790, and 5,436,304, each of which is incorporated by reference herein in its entirety.
According to another aspect of the invention, a high pressure polymerization reactor can comprise a tubular reactor or an autoclave reactor. Tubular reactors can have several zones in which fresh monomer, initiators or catalysts are added. The monomer can enter an inert gas stream and be introduced into a reactor zone. The initiators, catalysts and / or catalyst components can be inserted into the gas stream and introduced into another area of the reactor. Gas streams can be intermixed for polymerization. Heat and pressure can be used appropriately to obtain optimal polymerization reaction conditions.
According to another aspect of the invention, the polymerization reaction may comprise a solution polymerization reactor in which the monomer / comonomer is contacted with the catalyst composition by suitable stirring or other means. A transpotator comprising an inert organic diluent or excess monomer can be employed. If desired, the monomer / comonomer can be placed in the vapor phase in contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a polymer solution in a reaction medium. Stirring can be used to obtain better temperature control and to maintain uniform polymerization mixes throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat from polymerization.
Polymerization reactors suitable for the present invention may further comprise any combination of at least one raw material feed system, at least one feed system for catalyst or catalyst components and / or at least one polymer recovery system. Reactor systems suitable for the present invention may further comprise systems for purification of raw material, preparation and storage of catalysts, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, unloading, laboratory analysis and process control .
Conditions that are controlled for polymerization effectiveness and to provide desired polymer properties include temperature, pressure and concentrations of various reagents. The polymerization temperature can affect catalyst productivity, polymer molecular weight and molecular weight distribution. The appropriate polymerization temperature can be any temperature below the depolymerization temperature according to the Gibbs Free energy equation. This generally includes from about 60 ° C to about 280 ° C, for example, or from about 60 ° C to about 110 ° C, depending on the type of polymerization reactor. In some reactor systems, the polymerization temperature can be in a range of about 70 ° C to about 100 ° C, or from about 75 ° C to about 90 ° C.
Suitable pressures will also vary according to the type of reactor and polymerization. The pressure for liquid phase polymerizations in a loop reactor is generally less than 1000 psig. The pressure for gas phase polymerization is generally about 200 to 500 psig. High pressure polymerization in tubular or autoclave reactors is generally performed at about 20,000 to 75,000 psig. Polymerization reactors can also be operated in a supercritical region occurring at generally high temperatures and pressures. Operating above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages.
According to one aspect of this invention, the ratio of hydrogen to the olefin monomer in the polymerization process can be controlled. This weight ratio can vary from 0 ppm to about 10,000 ppm of hydrogen, based on the weight of the olefin monomer. For example, the reagent or feed ratio of hydrogen to olefin monomer can be controlled in a weight ratio that fits in a range from about 10 ppm to about 7500 ppm, from about 10 ppm to about 5000 ppm , or from about 10 ppm to about 1000 ppm.
It is also contemplated that monomer, comonomer (or comonomers), and / or hydrogen may be periodically propelled to the reactor, for example, similarly to that employed in US Patent No. 5,739,220 and US Patent Publication No. 2004/0059070, whose disclosures are incorporated herein by reference in full.
In ethylene polymerizations, the ratio of hydrogen feed to ethylene monomer, regardless of the comonomers employed, is generally controlled in a weight ratio ranging from about 0 ppm to about 1000 ppm, but the target weight ratio specificity may depend on the desired molecular weight or melt index (Ml). For ethylene polymers (homopolymers, copolymers, etc.) having an Ml of around 1 g / 10 min, the weight ratio of hydrogen to ethylene can generally range from about 5 ppm to about 300 ppm, as , for example, from about 10 ppm to about 250 ppm, or from about 10 ppm to about 200 ppm. The concentration of the reagents entering the polymerization reactor can be controlled to produce resins with certain physical and mechanical properties. The proposed end-use product that will be formed by the polymer resin and the method of forming that product can ultimately determine the properties and attributes of the desired polymer. Mechanical properties include tensile, impact, bending, creep, stress relaxation, and hardness tests. Physical properties include density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereoregularity, cracking growth, long chain branching and rheological measurements.
This invention is also directed to, and comprises the olefin polymers produced by any of the polymerization processes disclosed herein. Articles of manufacture can be formed from, and can comprise, the olefin polymers produced in accordance with this invention.
POLYMERS AND ARTICLES
If the resulting polymer produced in accordance with the present invention is, for example, an ethylene polymer or copolymer, its properties can be characterized by various analytical techniques known and used in the polyolefin industry. Manufacturing articles can be formed from, and can comprise, ethylene polymers, the typical properties of which are provided below.
Ethylene polymers (homopolymers, copolymers, terpolymers, etc.) produced in accordance with this invention generally have a melt index of about 0.01 to about 100 g / 10 min. Melt rates in the range of about 0.1 to about 50 g / 10 min, or from about 0.3 to about 20 g / 10 min, are contemplated in some aspects of this invention. For example, a polymer of the present invention can have a melt index ranging from about 0.5 to about 10, or from about 0.5 to about 6 g / 10 min. The density of ethylene-based polymers produced using one or more transition metal and / or metallocene compounds and activating supports of the present invention generally falls within the range of about 0.87 to about 0.97 g / cm3. In one aspect of this invention, the density of an ethylene polymer is in a range from about 0.89 to about 0.96 g / cm3. In yet another aspect, the density is in a range from about 0.90 to about 0.95 g / cm3, such as, for example, from about 0.91 to about 0.94 g / cm3.
In one aspect, the polymers of the present invention (e.g., homopolymers, ethylene-based copolymers, etc.) may have low levels of long chain branching, with generally less than about 10 long chain branches (LCB) per total million carbon atoms. In some ways, the number of long chain branches per million total carbon atoms is less than about 9; alternatively, less than about 8; alternatively, less than about 7; alternatively, less than about 6; or alternatively, less than about 5, LCB per million total carbon atoms. In addition, the polymers of the present invention can have less than about 4, less than about 3, or less than about 2, LCB per million total carbon atoms, in other aspects of this invention. For example, the olefin polymers of the present invention can have about 1 LCB per million total carbon atoms, or less than about 1 LCB per million total carbon atoms.
According to another aspect of the current invention, a polymer produced using a catalyst composition that employs a silica-coated alumina activator support - for example, fluorinated silica-coated alumina - can result in a significant decrease in the LCB index, for example. example, in comparison to a polymer produced using a catalyst composition that employs a conventional silica-alumina support-activator - for example, fluorinated silica-alumina - having an alumina to silica weight ratio of approximately 0.05: 1 to approximately 0.25: 1. The number of LCBs in a polymer produced using a catalyst composition of the current invention can be less than approximately 70% of the number of LCBs in a polymer produced using a comparable catalyst composition that contains a conventional silica-alumina activator-support (i.e. it is, under the same reaction conditions, using the same other components of the catalyst, the same chemical treatment of the anion, etc.). For example, the number of LCBs in a polymer produced using a catalyst composition of the current invention can be less than approximately 50%, or less than approximately 35%, of the number of LCBs in a polymer produced using a comparable catalyst composition which contains a conventional silica-alumina activator-support. The number of LCBs per million total carbon atoms can be measured from a graphical representation of the log (ηθ) against the log (Mw). The linear polymers of polyethylene are observed following a relationship of the force law between their zero-shear viscosity, ηθ, and their average-weight molecular weights, Mw, with a force very close to 3.4. This relationship is shown by a straight line with a slope of 3.4 when the logarithm of ηθ is plotted against the logarithm ofo Mw. Deviations from this line of the linear polymer are generally accepted as being caused by the presence of LCB. Janzen and Colby presented a model that predicts the expected deviation of the linear graphical representation of the log (ηθ) against log (Mw) for certain frequencies of LCB as a function of the polymer Mw. See “Diagnosing long-chain branching in polyethylenes,” J. Mol. Struct. 485-486, 569-584 (1999), which is incorporated herein by reference in its entirety. The polymers of this invention may deviate only slightly from the well-known 3.4 law of force "Arnett line" which is used as an indication of a linear polymer (see J. Phys. Chem. 1980, 84, 649 which is incorporated here by reference in its The CY-a parameter for the olefin-based polymers disclosed herein (for example, homopolymers, ethylene-based copolymers) may fall within a range of approximately 0.3 to approximately 0.8 In one aspect, the polymer has a parameter of CY-a on a scale of approximately 0.35 to approximately 0.75 In another aspect, the polymer has a parameter of CY-a on a scale of approximately 0.4 to approximately 0.7. Still in one aspect, the polymer has a parameter of CY- a on a scale of approximately 0.45 to approximately 0.65. In yet another aspect, the polymer has a CY-a parameter on a scale of approximately 0.5 to approximately 0.6.
According to another aspect of the current invention, a polymer produced using a catalyst composition that employs a silica-coated alumina activating support - for example, fluoridated silica-coated alumina - can result in an increase in the CY-a parameter, for example, in comparison to a polymer produced using a catalyst composition that employs a conventional silica-alumina support-activator - for example, fluoridated silica-alumina - having an alumina to silica weight ratio of approximately 0.05: 1 to approximately 0.25 :1. The CY-a parameter for a polymer produced using a catalyst composition of the current invention can be at least approximately 10% greater than the CY-a parameter for a polymer produced using a comparable catalyst composition that contains a conventional activator-support silica-alumina (ie, under the same reaction conditions, using the same other components of the catalyst, the same chemical treatment as the anion, etc.). For example, the CY-a parameter for a polymer produced using a catalyst composition of the current invention can be at least approximately 20%, at least approximately 30%, or at least approximately 50%, greater than the CY- parameter a for a polymer produced using a comparable catalyst composition that contains a conventional silicone-alumina activator support.
Ethylene polymers, both homopolymers, copolymers, terpolymers, and so on, can be formed into various articles of manufacture. Items that may comprise polymers of this invention may include, but are not limited to, an agricultural film, an automobile part, a bottle, a cylinder, a fiber or fabric, a film or a food packaging container, an article of food service, a fuel tank, a geomembrane, a household container, a liner, a molded product, a medical device or material, a pipe, a sheet or an adhesive tape, a toy, and the like. Various processes can be employed to form these items. Non-limiting examples of these processes include injection molding, blow molding, rotational molding, film extrusion, sheet extrusion, profile extrusion, thermoforming, and the like. In addition, additives and modifiers are often added to these polymers in order to provide beneficial polymer processing or end-use product attributes.
Examples This invention is further illustrated by the following examples, which should not be interpreted in a way that imposes limitations on the scope of the invention in any way. Various other aspects, modalities, modifications, and equivalents thereof, which, after reading the description at present, can be suggested by themselves to a person skilled in the art without departing from the principles of the current invention or the scope of the attached claims.
The rheological fusion characterizations were performed as follows. Small-voltage oscillatory shear measurements (10%) were performed on a Rheometrics Scientific, Inc. ARES rheometer using parallel plate geometry. All rheological tests were performed at 190 ° C. The complex viscosity | η * | against the frequency data ((ω) were then suitable on the curve using the modified Carreau-Yasuda (CY) empirical model of three parameters to obtain the zero-shear viscosity -ηθ, characteristics of the viscous relaxation time - τη, and the width parameter - a.The simplified Carreau-Yasuda (CY) empirical model is as follows. where: | η * (ω) | = complex shear viscosity magnitude; ηθ = zero shear viscosity; τη = time of shear viscous relaxation; a = “width” parameter; n = fixes the final inclination of the force law, fixed at 2/11; and ω = angular frequency of oscillatory shear deformation.
Details on the meaning and interpretation of the CY model and derived parameters can be found at: C. A. Hieber and Η. H. Chiang, Rheol. Acta, 28, 321 (1989); C.A. Hieber and H.H. 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. The CY parameter “a” (CY-a) is reported for some of the polymer resins produced in the present.
Molecular weights and molecular weight distributions were obtained using a PL 220 SEC high temperature chromatography unit (Polymer Laboratories) with trichlorobenzene (TCB) as the solvent, with a flow rate of 1 mL / minute at a temperature of 145 ° C. BHT (2,6ditertbutil4methylphenol) at a concentration of 0.5 g / l was used as a stabilizer in the TCB. An injection volume of 200 pL was used with a nominal polymer concentration of 1.5 mg / mL. The dissolution of the sample in stabilized TCB was carried out by heating at 150 ° C for 5 hours with occasional, gentle agitation. The columns used form three PLgel Mixed A LS columns (7.8x300mm) and were calibrated with a wide linear polyethylene standard (Phillips Marlex® BHB 5003) for which the molecular weight was determined. Ethylene was polymerization grade ethylene obtained from Union Carbide Corporation. This ethylene was then further purified through a column of ΊΑ inch spheres of Alcoa Α20Ί alumina, activated at ----------------- approximately 250 ° C in nitrogen. Isobutane was a polymerization class obtained from Phillips Petroleum Company, which was further purified by distillation and then passed through a column of% inch Alcoa A201 spheres, activated in approximately 250 ° C of nitrogen. The 1-hexene was of polymerization grade obtained from the Chevron Chemical Company, which was further purified by purging nitrogen and storage in a 13x molecular sieve activated at approximately 250 ° C. Triisobutylaluminium (TIBA) was obtained from Akzo Corporation as a solution of a molar in heptane.
All polymerizations were carried out in a stirred one-gallon reactor. First, the reactor was purged with nitrogen and heated to approximately 120 ° C. After cooling below approximately 40 ° C and purging with isobutane steam, the metallocene compound was charged into the reactor under nitrogen. The amount of metallocene varied based on the ratio of metallocene to the activator support, but was generally on the scale of 0.1 to 3.5 milligrams. Approximately 100 mg of the activator support (A-S) was then added to the reactor, followed by approximately 0.3 mL of the 1M triisobutyl aluminum co-catalyst (TIBA). The reactor was then closed and, if noted, approximately 48 g of 1-hexene was injected into the reactor. Two liters of the isobutane were added under pressure, and the reactor was subsequently heated to approximately 90 ° C. The reactor contents were mixed at 700 RPM. Ethylene was then added to the reactor and fed on demand to maintain a constant total pressure of approximately 420 psig. The reactor was maintained and controlled at 90 ° C during the entire 60-minute operating time of the polymerization. Upon completion, isobutane and ethylene were exhaled from the reactor, the reactor was opened, and the polymer product was collected and dried.
Example 1: The synthesis of activated support of fluoridated silica-alumina Silica-alumina was obtained from W.R. Grace Company containing about 13% alumina by weight and having a surface area of approximately 400 m2 / g and a pore volume of approximately 1.2 ml / g. This material was obtained as a powder having an average particle size of approximately ru microns. Approximately 100 grams of this material were impregnated with a solution containing approximately 200 mL of water and approximately 10 grams of ammonia hydrogen fluoride, resulting in a wet powder that has the consistency of wet sand. This mixture was then placed on a flat tray and allowed to dry under vacuum at approximately 110 ° C for approximately 16 hours.
To calcinate the support, approximately 10 grams of this pulverized mixture were placed in a 1.75 inch quartz tube accommodated with a sintered quartz disc at the bottom. As the powder was supported on the disc, the air (nitrogen can be replaced) dried by passing through a 13X molecular sieve column, was blown upwards through the disc at the standard rate of approximately 1.6 to 1.8 cubic feet per hour. An electric oven around the quartz tube was then turned on, and the temperature was raised at the rate of approximately 400 ° C per hour to the desired calcination temperature of approximately 450 ° C. At this temperature, the powder was allowed to fluidize for approximately three hours in dry air. Later, fluoridated silica-alumina was collected and stored under anhydrous nitrogen, and was used without exposure to the atmosphere. The fluoridated silica-alumina activating support of Example 1 is abbreviated A-S1. The weight ratio of alumina to silica in A-S1 is approximately 0.15: 1.
Example 2: Synthesis of a Bohemite sulfated alumina activating support was obtained from W.R. Grace Company under the name “Alumina A” and having a surface area of approximately 300 m2 / g and a pore volume of approximately 1.3 mL / g. This material was obtained as a powder that has an average particle size of approximately 100 microns. This material was impregnated to incipient humidity with an aqueous solution of ammonium sulfate to equal approximately 15% sulfate. This mixture was then placed on a flat tray and allowed to dry under vacuum at approximately 110 ° C for approximately 16 hours.
To calcinate the support, approximately 10 grams of this pulverized mixture were placed in a 1.75 inch quartz tube accommodated with a sintered quartz disc at the bottom. As the powder was supported on the disc, the air (nitrogen can be replaced) dried by passing through a 13X molecular sieve column, was blown upwards through the disc at the standard rate of approximately 1.6 to 1.8 cubic feet per hour. An electric oven around the quartz tube was then switched on, and the temperature was raised at a rate of approximately 400 ° C per hour to the desired calcination temperature of approximately 600 ° C. At this temperature, the powder was allowed to fluidize for approximately three hours in dry air. Later, sulfated alumina was collected and stored under anhydrous nitrogen, and was used without exposure to the atmosphere. The sulfated alumina activating support of Example 2 is abbreviated A-S2.
Example 3 Synthesis of silica-coated fluoridated alumina activator support A silicon-coated alumina was obtained from Sasol Company under the designation “Siral 28M” which contains approximately 72% alumina by weight and has a surface area of approximately 340 m2 / g and a pore volume of approximately 1.6 mL / g. This material was obtained as a powder that has an average particle size of approximately 70 microns. Additional information on Siral materials can be found in W. Daniell et al., “Enhanced surface acidity in mixed alumina-silicas: a low temperature FTIR study,” in Applied Catalysis A: General 196 (2000) 247-260, whose Disclosure is hereby incorporated by reference in its entirety. Siral 28M was first calcined at 600 ° C for approximately 6 hours, then impregnated with incipient moisture with a 10% solution of ammonium bifluoride in methanol. This mixture was then placed on a flat tray and allowed to dry under vacuum at approximately 110 ° C for approximately 16 hours.
To calcinate the support, approximately 10 grams of this pulverized mixture were placed in a 1.75 inch quartz tube accommodated with a sintered quartz disc at the bottom. As the powder was supported on the disc, the air (nitrogen can be replaced) dried by passing through a 13X molecular sieve column, was blown upwards through the disc at the standard rate of approximately 1.6 to 1.8 cubic feet per hour. An electric oven around the quartz tube was then switched on, and the temperature was raised at a rate of approximately 400 ° C per hour to the desired calcination temperature of approximately 600 ° C. At this temperature, the powder was allowed to fluidize for approximately three hours in dry air. Later, silica-coated fluoridated alumina was collected and stored under anhydrous nitrogen, and was used without exposure to the atmosphere. The silica-coated fluoridated alumina activator support of Example 3 is abbreviated A-S3. The weight ratio of alumina to silica in A-S3 is approximately 2.6: 1.
Example 4.
Comparison of polymerization catalyst activity using MET 1 and the activating supports of Examples 1-3 The metallocene compound of Example 4, abbreviated “MET 1,” has the following structure (Ph = phenyl; t-Bu = tert-butyl) : The metallocene compound MET 1 can be prepared according to any appropriate method. Such a technique is described in U.S. Patent Publication No. 2007-0179044, the disclosure of which is incorporated herein by reference in its entirety.
The activating supports of examples 1-3 were loaded in separate experiments in the reactor with the various levels of MET 1 along with a constant amount of TIBA co-catalyst. No hexene was introduced. FIG. 1 illustrates the activity resulting from the polymerization catalyst for each of the three activating supports, as a function of the ratio of MET 1 to the activating support. Activity is measured in units of grams of polyethylene produced per gram of A-S per hour. The concentration of MET 1 varied from approximately 5 to approximately 20 micromoles of MET 1 per gram of A-S. FIG. 1 shows that A-S3 provided the best activity at low levels of MET 1, well above that of A-S1 and almost twice as high as that of A-S2. Therefore, less metallocene would be required in a catalyst system that employs A-S3 to provide the same catalyst activity achieved with greater loading of the metallocene with the A-S2 activator support. Since the metallocene compound used in a polymerization catalyst system can be an expensive component, reducing the amount of metallocene can be a significant benefit. FIG. 1 also indicates that the activity using A-S3 was comparable to that of A-S2 in the largest metallocene load. FIG. 2 illustrate the same data of the activity of the polymerization catalyst, but preferably, the activity is measured in units of grams of polyethylene produced per gram of MET 1 per hour. The activity of the catalyst using A-S2 is relatively constant across the MET 1 concentration range from approximately 5 to approximately 20 micromoles of MET 1 per gram of A-S. The increased catalyst activity of a system that employs A-S3 in lower loads of lower MET 1 COM is also shown in FIG. 2. The molecular weight and other properties of the polymer resins produced using A-S3 are compared to those produced using A-S2, in a loading found with magnesium 3.5 per 100 grams of the activator-support, in table I below. The polymer produced using A-S3 had a lower molecular weight than that produced using A-S2.
Table I. Comparison of the property of polymers produced using A-S2 and A-S3.
Notes in table I: - Mn - average number of molecular weight. - Mw - average weight of the molecular weight. - Mz - z-average of the molecular weight. - PDI - polydispersity index, Mw / Mn. - ηθ - zero shear viscosity at 190 ° C. - CY-a - Carreau-Yasuda width parameter.
Example 5.
Comparison of polymerization catalyst activity using MET 2 and the activating supports of Examples 1-3 The metallocene compound of example 5 was hafnium bis dichloride (n-butylcyclopentadienyl) (abbreviated “MET 2”), which can be prepared from according to the appropriate method to synthesize metallocene compounds.
The activating supports of examples 1-3 were loaded in separate experiments in the reactor with the various levels of MET 2 together with a constant amount of TIBA co-catalyst. For example 5, the reactor was maintained and controlled at 95 ° C during the entire 60 minute operating time of the polymerization. No hexene was introduced. FIG. 3 compares the activity resulting from the polymerization catalyst for each of the three activating supports, as a function of the ratio of MET 2 to the activating support. Activity is measured in units of grams of polyethylene produced per gram of A-S per hour. The concentration of MET 2 varied from approximately 5 to approximately 40 micromoles of MET 2 per gram of A-S. FIG. 3 demonstrated that A-S3 provided more than twice the activity of the catalyst at all levels of metallocene loading when compared to the activity of the catalyst obtained using A-S1 or A-S2. FIG. 4 illustrates the same data of the activity of the polymerization catalyst, but preferably, the activity is measured in units of grams of polyethylene produced per gram of MET 2 per hour. Not only is the catalyst activity in all MET 2 loads (micromoles of MET 2 per gram of AS) greater for the catalyst system containing A-S3, but the activity in the lowest metallocene loading is greater than 100,000 grams of polyethylene (per gram of MET 2 per hour) greater than that activity of the catalyst systems using A-S1 or A-S2. Thus, less metallocene can be used in a catalyst system that employs A-S3 to provide the same catalyst activity as that obtained with much larger metallocene loads using the A-S1 or A-S2 activator support.
Example 6 Effect of pre-contact on the catalyst activity of the polymerization of a catalyst system containing MET 2 and A-S3 FIG. 5 compares the grams of polyethylene produced per hour for a pre-contacted catalyst system and for a catalyst system that was not pre-contacted. The polymerization procedure used for the catalyst system that was not pre-contacted was substantially the same as that employed in example 5. In this case, however, a fixed amount of approximately 0.3 milligrams of MET 2 was used. For the pre-contacted catalyst system, MET-2, A-S3 and TIBA were first mixed in a separate container for approximately 30 minutes before being introduced into the reactor and exposed to ethylene. As shown in FIG. 5, the pre-contacted catalyst system generated a significant improvement in polymerization activity against the non-pre-contacted catalyst system.
Example 7: Comparison of polymerization catalyst activity using MET 3 and the activating supports of Examples 2-3 The metallocene compound of example 7, abbreviated “MET 3,” has the following structure: The metallocene compound MET 3 can be prepared in according to any appropriate method. Such a technique is described in U.S. Patent 7,064,225, the disclosure of which is incorporated herein by reference in its entirety.
The activating supports of examples 2-3 were loaded in separate experiments in the reactor with the various levels of MET 3 together with a constant amount of TIBA co-catalyst. No hexene was introduced. FIG. 6 compares the activity resulting from the polymerization catalyst for A-S2 and A-S3, depending on the ratio of MET 3 to the activator support. Activity is measured in units of grams of polyethylene produced per gram of A-S per hour. MET 3 ranged from approximately 5 to approximately 120 micromoles of MET 3 per gram of A-S. FIG. 6 demonstrates that A-S3 provided greater catalyst activity at lower metallocene loads on the activator support compared to A-S2. FIG. 7 illustrates the same data of the activity of the polymerization catalyst, but preferably, the activity is measured in units of grams of polyethylene produced per gram of MET 3 per hour. In metallocene shipments of approximately 60 and above (micromoles of MET 3 per gram A-S), the activities of the catalyst systems containing A-S2 and A-S3 appeared very similar. However, at low metallocene loads, the activity of the catalyst was much greater for the catalyst system that employs A-S3. As mentioned above, less metallocene can be used in a catalyst system that employs A-S3 to provide the same catalyst activity as that obtained with much larger loads of metallocene using the A-S1 or A-S2 activator support.
Examples 8-10 The effect of fluoride concentration on the activity of the silica-coated fluoridated alumina activator support The silica-coated alumina support used in Examples 8-10 was the same as the high-content of silica-coated alumina employed in the example 3, containing about 72% alumina by weight. For examples 8-10, this non-calcined material was impregnated to incipient humidity with a 5%, 10%, or 15% ammonium bifluoride solution in methanol, followed by calcination at a temperature of approximately 600 ° C by approximately three hours, in the manner described in example 3.
Polymerizations of ethylene were carried out as described in example 7, except that in this case, the loading of MET 3 was fixed at 3.5 milligrams per 100 g of the activating support.
Table II summarizes the catalyst activity data for examples 8-10. For this set of circumstances, the fluoride level at approximately 10 percentage weight NH4HF2 provided the greatest activity of the catalyst. The results in Table II also indicate that precalcination of the silica-coated alumina activating support before fluoride treatment can also provide an improvement in activity. For example, the activities of the catalyst in FIGS. 6-7, using the pre-calcined support, were significantly higher than that achieved with example 9, which did not pre-calcined the support before fluoride treatment ._______ Table II. Examples 8-10 using the metallocene MET 3 compound.
Notes in Table II: - Fluoride added is the percentage weight of the hf4nh2 solution. - The activity is based on A-S is in units of grams of polyethylene produced per gram of A-S per hour. - MET 3-based activity is in units of kilograms of polyethylene per gram of MET 3 per hour.
Examples 11-17 The effect of the alumina to silica weight ratio on the activity of fluoridated silica-coated alumina activating supports Table III lists the supports of silica, alumina, silica-alumina, or silica-coated alumina with different alumina ratios for silica, used in Examples 11-17. The grade of silica-alumina used in example 16 was the same as that used in example 1, and the grade of alumina used in example 11 was the same as that used in example 2. The grade of silica used in example 17 was grade silica. 952 WR Grace Company. The silicone-coated alumines used in examples 12-15 were obtained from Sasol, each made by the same technique, but with a different ratio of alumina to silica.
Each support was pre-calcined at 600 ° C, and then impregnated with 10% ammonium bifluoride in methanol, then calcined again at 600 ° C, in the manner described in example 3. The polymerisations of ethylene were carried out as described in example 7 (for example, 100 mg AS, 0.3 mmol TIBA), except that in this case, the loading of MET 3 was fixed at approximately 3.5 mg, and approximately 48 grams of 1-hexene were loaded into the reactor.
As shown in Table III, the activities of the catalyst in Examples 12-15 were superior to the activities of the catalyst in Examples 11 and 16-17. Due to the excess of MET 3 that was used, activities based on the amount of MET 3 that was used, in units of kilograms of polyethylene per gram of MET 3 per hour, are low.
Table III. Examples 11-17 using the metallocene MET 3 compound.
Notes in Table III: - The ratio of alumina to silica is the weight ratio in the support of silica-alumina or silica-coated alumina. - The activity is based on A-S is in units of grams of polyethylene produced per gram of A-S per hour. - MET 3-based activity is in units of kilograms of polyethylene per gram of MET 3 per hour. EXAMPLES 18-24 Catalyst compositions containing MET 3 and silica-coated alumina activating support with single and double anions The metallocene compound, MET 3, was used in Examples 18-24. Table IV lists the activator support employed in examples 18-24, and the respective catalyst activity, the CY-a parameter, and Tan Delta (at 0.1 / sec) for each example. The sulfated alumina in example 18 was prepared in the same manner as in example 2. The fluoridated alumina in example 19 was prepared as in example 1, except that the support was W.R. “Alumina A”. Grace Company. The chlorinated alumina in example 20 was prepared as follows. Approximately 10 grams of W.R. Grace Company were placed in a 2 inch quartz tube suspended in a sintered glass frit. The nitrogen was then passed through the alumina bed at a rate of 0.1 feet / sec. An electric oven around the quartz tube was turned on and the temperature was raised to approximately 600 ° C for 1.5 hours, then approximately 1 mL of the CCI4 liquid was injected and evaporated into the nitrogen flow, and contacted with the alumina bed. The calcination step was continued for 2 hours, and then chlorinated alumina was cooled and stored without exposure to the atmosphere. The fluorinated silica-alumina in example 21 was prepared as in example 1. The fluoridated silica-coated alumina in example 22 was prepared as in example 3. The double anion silica-coated alumina in examples 23-24 was prepared as follows. The silal-coated alumina Siral 28M from example 3 was used for examples 23-24, after first calcined in air at 600 nC .--------- For the sulfated-fluorinated activator support, approximately 10 grams of silica alumina -calcined coatings were made into a methanol slurry containing approximately 0.5 grams of ammonium bifluoride and approximately 0.8 grams of sulfuric acid. The methanol was then vaporized, and the dry support was calcined in nitrogen at 600 ° C 600 for three hours. The phosphate-fluoride activator support was prepared using the same procedure, except that 0.8 grams of phosphoric acid were used in place of sulfuric acid.
Polymerizations of ethylene were conducted as described in example 7 (for example, 100 mg AS, 0.3 mmol TIBA), except that in this case, the loading of MET 3 was fixed at approximately 3.5 mg, and approximately 48 grams of 1-hexene were loaded in the reactor.
As shown in Table IV, the activities of the catalyst in Examples 22-24 were superior to the activities of the catalyst in Examples 18-27. The CY-a parameter in Table IV can be an indicator of the LCB index. Examples 22-24 shows significant increases in the CY-a parameter compared to Example 21.
Tan delat is the loss module divided by the storage module at a shear frequency. The data in Table IV were taken at a low shear frequency of 0.1 / sec. Tan delta can be sensitive to the effects of LCB. Generally, a higher tan delta means that the polymer relaxes easily, with little stress storage, and that the polymer has a relatively lower LCB, assuming all other considerations are the same (for example, molecular weight, molecular weight distribution , etc.). Table IV. Examples 18-24 using the MET 3 meta-ocene compound.
Notes in Table IV: - The ratio of alumina to silica is the weight ratio in the support of silica-alumina or silica-coated alumina. - The activity is based on A-S is in units of grams of polyethylene produced per gram of A-S per hour. - CY-a - Carreau-Yasuda width parameter. EXAMPLES 25-32 Catalyst compositions containing MET 4 and silica-coated alumina activating support with single and double anions The metallocene compound of examples 25-32 was bis-indenyl zirconium ethylene dichloride (abbreviated “MET 42”) , which can be prepared according to any appropriate method for synthesizing metallocene compounds. Table IV lists the activating support used in examples 25-32, and the respective catalyst activity, the CY-a parameter, and Tan Delta (at 0.1 / sec) for each example. The activating support of examples 25-27 and 29-32 were prepared as listed for the respective activating support in examples 18-24. The phosphate-fluoride alumina of example 28 was prepared in a similar manner to examples 23-24, except that "Alumina A" by W.R. Grace Company was the starting material.
Polymerizations of ethylene were conducted in the same manner as Examples 18-24 (eg, 100 mg AS, 0.3 mmol TIBA), except that in this case, the MET 4 loading was fixed at approximately 3.5 mg, and approximately 48 grams of 1-hexene were loaded into the reactor.
As shown in Table V, the activities of the catalyst in Examples 30-32 were superior to the activities of the catalyst in Examples 25-29. Examples 30-32 also demonstrated significant increases in tan delta (at 0.1 / sec) and the CY-a parameter compared to example 29.
Table V. Examples 25-32 using the metallocene MET 4 compound ._________________ Notes in table V: - The ratio of alumina to silica is the weight ratio in the support of silica-alumina or silica-coated alumina. - The activity is based on A-S is in units of grams of polyethylene produced per gram of A-S per hour. - CY-a - Carreau-Yasuda width parameter. EXAMPLES 33-39 The synthesis of silica-coated alumina activator support having weight ratios ranging from alumina to silica The fluoridated activator supports of Examples 33-39 were prepared as follows. Example 33 was prepared as in example 26. For examples 34-39, “Alumina A” by W.R. Grace, having a surface area of approximately 300 m2 / g and a pore volume of 1.3 mL / g, was used as the starting material. The alumina was first calcined at 600 ° C. Then, the samples of 10 grams of calcined alumina were treated with varying amounts of silica tetraethoxide (ortho), as follows. Each respective 10-gram alumina sample was poured into 50 mL of methanol, which contained a target amount of Si (OEt) 4- Methanol was evaporated, and 1 gram of ammonium bifluoride dissolved in 30 mL of methanol was then added to create a wet sand consistency. The methanol was evaporated again and the chemically treated solid oxide was calcined at 600 ° C 600 for 3 hours in nitrogen. After cooling, the fluorinated silica-coated alumina was cooled, and stored without exposure to the atmosphere.
These activating supports fluorinated alumina or silica-coated alumina - flnnretarlo were tpstarlnq for the polymerization activity with 3 ma of MET 3 and 1 ml of 1 M TIBA in heptane (Example 35 used 1.8 mg of MET 3). The amounts of activating support were in the range of 25 mg to 55 mg. Polymerizations in 1L of the isobutane were carried out for approximately 30 minutes at 80 ° C, at a reactor pressure of 450 psig, and in a 40 mL load of 1-hexene.
The weight ratios of alumina to silica of the fluoridated activating supports used in examples 33-39, and the resulting activity of the polymerization catalyst, are shown in Table VI. Due to the excess of MET 3 that was used, the activities based on the amount of MET 3 that was used, in units of kilograms of polyethylene per gram of MET 3 per hour, are low - compare example 35 (1.8 mg MET 3) with Example 36 (3 mg MET 3). Table VI. Examples 33-39 using the metallocene MET 3 compound.
Notes in Table VI: - The alumina to silica ratio is the weight ratio on the silica-coated alumina support. - Activity based on A-S is in units of grams of polyethylene per gram of A-S per hour. - Activity based on MET 3 is in units of kilograms of polyethylene per gram of MET 3 per hour.

权利要求:
Claims (14)
[1]
1. Catalyst composition, characterized by the fact that it comprises: (a) a metallocene compound comprising a transition metal selected from Ti, Zr or Hf; and (b) an activating support; wherein this activating support comprises a silica-coated alumina treated with an electron-removing anion, in which: the silica-coated alumina has a weight ratio of alumina to silica in the range of 2: 1 to 20: 1 and the anion Electron remover comprises fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, or any combination thereof.
[2]
2. Catalyst composition according to claim 1, characterized by the fact that the metallocene comprises Zr, or Hf.
[3]
3. Catalyst composition according to claim 1, characterized by the fact that the metallocene compound comprises a bridged metallocene with the following formula: (X1) (X2) (X3) (X4) M1, where: M2 is Ti , Zr, or Hf; (X5) and (X6) are independently a substituted Cp, Ind or Flu group; (X5) and (X6) are connected by a substituted or unsubstituted bridge group, comprising a bridge chain of 2 to 5 carbon atoms, or a bridge atom of carbon, silicon, germanium, tin, boron, nitrogen or phosphor; and (X7) and (X8) are independently a halide, hydride, starch, alkoxide or hydrocarbyl group, any of which have up to 20 carbon atoms.
[4]
4. Catalyst composition according to claim 1, characterized in that the activator support comprises a silica-coated alumina treated with two or more electron-withdrawing anions and in which the electron-withdrawing anions comprise fluoride and phosphate, fluoride and sulphate, chloride and phosphate, chloride and sulphate, triflate and sulphate, or triflate and phosphate, or where silica-coated alumina has a surface area in the range of 100 to 1000 m2 / g, a pore volume greater than 0, 5 mL / g, and a particle size in the range of 5 microns to 150 microns.
[5]
5. Catalyst composition according to claim 1, characterized in that it comprises a silica-coated alumina is produced by a process: in which the alumina-coated silica is produced by a process which comprises: providing an alumina source, the alumina source, comprising an alumina, hydrated alumina, aluminum hydroxide, bohemite, or a combination thereof; contacting the alumina source with a solution or suspension comprising a solvent and a silicon-containing compound capable of producing silica upon calcination; depositing a coating of the silicon-containing compound on a portion of the alumina source; and removing the solvent.
[6]
6. Catalyst composition according to claim 1, characterized by the fact that it additionally comprises an organoaluminic compound having the formula: Al (X9) m (X10) 3-m; where: x9 is a hydrocarbon; X10 is an alkoxide or an aryloxide, a halide, or a hydride; and m is 1 to 3, inclusive.
[7]
7. Catalyst composition according to claim 1, characterized by the fact that it still comprises at least one optional co-catalyst, in which the optional co-catalyst is aluminoxane compound, an organoboro compound or organoborate, an ionic compound of ionization, or any combination thereof, or further comprising an optional activating support, wherein the optional activating support is fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, silica -sulfated alumina, fluoridated silica-zirconia, chlorinated silica-zirconia, silica-zirconia bromidated, sulfated silica-zirconia, fluorinated silica-titanium or any combination thereof.
[8]
8. Catalyst composition according to claim 1, characterized by the fact that a catalyst activity of the catalyst composition is greater than 1000 grams of polyethylene per gram of activating support per hour under circumstances of slurry polymerization, using isobutane as a diluent, with a polymerization temperature of 90 oC and a reactor pressure of 2997kPa (420 psig) or where a catalyst activity of the catalyst composition is greater than 25,000 grams of polyethylene per gram of metallocene compound per hour in paste polymerization conditions, using isobutane as a diluent, with a polymerization temperature of 90 ° C and a reactor pressure of 2997 kPa (420 psig).
[9]
9. Catalyst composition according to claim 1, characterized in that a metallocene compound comprises a loop-metallocene compound or a metallocene compound comprises a bridgeless compound.
[10]
10. Catalyst composition according to claim 1, characterized in that the catalyst composition comprises: (a) a metallocene compound; (b) an activating support; and (c) an organoaluminium compound; wherein triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, diisobutyl aluminum hydride, diethyl aluminum ethoxide, diethyl aluminum chloride, or any combination thereof; wherein the activating support comprises an electron-removing anion treated with silica-coated alumina, where: silica-coated alumina has a weight ratio of alumina to silica in the range of 2: 1 to 20: 1, and the removing anion electron electron comprises fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate or any combination thereof.
[11]
11. Olefin polymerization process, characterized by the fact that the process comprises: contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under the polymerization conditions to produce an olefin polymer, in which the composition of the catalyst comprises metallocene compound, in which the metallocene comprises a transition metal selected from Ti, Zr or Hf, and an activating support, in which: the activating support comprises a silica-coated alumina treated with an electron-removing anion, in which : silica-coated alumina has a weight ratio of alumina to silica on a scale of approximately 2: 1 to 20: 1, and the electron-removing anion comprises fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, or any combination of these.
[12]
Process according to claim 11, characterized in that the olefin monomer is ethylene, and the olefin comonomer comprises 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, or a combination thereof.
[13]
13. Olefin polymer, characterized by the fact that it is produced according to the process of claim 11.
[14]
14. Article, characterized by the fact that it comprises the olefin polymer as defined in claim 13.

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-02| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-09-17| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-01-21| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-03-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/09/2010, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US12/565,257|2009-09-23|

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PCT/US2010/049779|WO2011037971A1|2009-09-23|2010-09-22|Silica-coated alumina activator-supports for metallocene catalyst compositions|

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